Glass containers with improved delamination resistance and damage tolerance

专利摘要:
GLASS CONTAINERS WITH DELAMINATION RESISTANCE AND IMPROVED DAMAGE TOLERANCE The present invention relates to glass containers that have at least two performance attributes selected from delamination resistance, improved strength and increased damage resistance. In one embodiment, a glass container may include a body having an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A tough inorganic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tough inorganic coating may have a coefficient of friction less than or equal to 0.7.
公开号:BR112015012289B1
申请号:R112015012289-2
申请日:2013-11-22
公开日:2022-02-01
发明作者:Paul Stephen Danielson；Steven Edward Demartino；Robert Michael Morena；Robert Anthony Schaut；Theresa Chang；John Stephen Peanasky；Santona Pal；Natesan Venkataraman；Ronald Luce Verkleeren；Andrei Gennadyevich Fadeev；Christopher Lee Timmons；Dana Craig Bookbinder
申请人:Corning Incorporated；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[0001] This descriptive report claims priority to provisional patent application no. of U.S. series 61/731,767 filed on November 30, 2012 and entitled “Glass Containers With Improved Attributes”, the entirety of which is incorporated herein by reference. This descriptive report also claims priority to patent application no. of U.S. series 13/912,457 filed on June 7, 2013 entitled “Delamination Resistant Glass Containers”, patent application no. of U.S. series 13/780,754 filed on February 28, 2013 entitled “Glass Articles With Low-Friction Coatings” and patent application no. of U.S. series 14/075,620 filed November 8, 2013 entitled “Glass Containers With Delamination Resistance And Improved Damage Tolerance”, all of which are incorporated herein by reference. BACKGROUNDFIELD
[0002] The present specification refers generally to glass containers and more specifically to glass containers for use in the storage of pharmaceutical formulations. BACKGROUND OF THE TECHNIQUE
[0003] Historically, glass has been used as the material of choice for packaging pharmaceuticals due to its airtight capability, optical clarity, and excellent chemical durability over other materials. Specifically, the glass used in pharmaceutical packaging needs to have adequate chemical durability so that it does not affect the stability of the pharmaceutical formulations contained therein. Glasses that have adequate chemical durability include those glass compositions within the ASTM standard, “Type IA” and “Type IB” glass compositions that have a proven record of chemical durability.
[0004] Although Type IA and Type IB glass compositions are commonly used in pharmaceutical packaging, they suffer from several shortcomings, which include a tendency of the inner surfaces of pharmaceutical packaging to loosen particulate glass or “delaminate” upon exposure to solutions. pharmaceuticals.
[0005] In addition, the use of glass in pharmaceutical packaging may also be limited by the mechanical performance of glass. Specifically, the high processing speeds used in manufacturing and filling glass pharmaceutical packaging can result in mechanical damage to the packaging surface, such as abrasions, as the packaging comes into contact with processing equipment, handling equipment, and /or other packaging. This mechanical damage significantly decreases the strength of the pharmaceutical glass package resulting in an increased likelihood that cracks will develop in the glass, potentially compromising the sterility of the pharmaceutical contained in the package or causing the package to fail completely.
[0006] Consequently, there is a need for alternative glass containers for use as pharmaceutical packaging that exhibit a combination of at least two of improved delamination resistance, increased strength and/or damage tolerance. SUMMARY
[0007] According to a first embodiment, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A tough inorganic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tough inorganic coating may have a coefficient of friction less than or equal to 0.7.
[0008] In another embodiment, a glass container may include a body that has an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A transient coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the transient coating may have a coefficient of friction less than or equal to 0.7.
[0009] In another embodiment, a glass container may include a body that has an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body has a delamination factor of less than or equal to 10. A tough organic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tough organic coating may have a coefficient of friction less than or equal to 0.7.
[0010] In another embodiment, a glass container may include a body having an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. The body can be formed from a Type I, Class B glass in accordance with ASTM E438-92. A barrier coating may be positioned on the inner surface of the body such that a composition contained in the glass container does not come into contact with the inner surface of the body. A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0011] In another embodiment, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends from the outer surface to the inner surface. The body may have a hydrolytic resistance of at least HGB2 or better in accordance with the ISO 719 standard. The body may be formed from a glass composition that is free of constituent components that form species that volatilize significantly at temperatures corresponding to at a viscosity in the range from about 200 poise to about 100 kilopoise. A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0012] In another embodiment, a glass container may include a body having an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. The body can be formed from a Type I, Class B glass in accordance with ASTM E438-92. The body can be formed under processing conditions that attenuate the vaporization of volatile species in the glass composition. A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0013] Additional features and advantages of the glass container modalities described herein will be set forth in the detailed description that follows, and in part will be readily apparent to those skilled in the art from this description or recognized by practice of the modalities described in present document, which includes the following detailed description, the claims, as well as the accompanying drawings.
[0014] It should be understood that both the aforementioned general description and the following detailed description describe various modalities and are intended to provide an overview or framework for understanding the nature and character of the claimed subject. The attached drawings are included to provide additional understanding of the various modalities, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein and together with the description serve to explain the principles and operations of the claimed subject. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 schematically represents a cross-section of a glass container, according to one or more embodiments described herein;
[0016] Figure 2 schematically represents a layer compressively tensioned in a portion of the side wall of the glass container of Figure 1;
[0017] Figure 3 schematically represents a portion of the side wall of the glass container formed from laminated glass;
[0018] Figure 4 schematically represents a horizontal compression apparatus to test the horizontal compression force of a glass container;
[0019] Figure 5 schematically depicts a glass container having a barrier coating positioned on at least a portion of the inner surface of the glass container, in accordance with one or more embodiments shown and described herein;
[0020] Figure 6 schematically represents a portion of a side wall of a glass container that has a persistent layer homogeneity;
[0021] Figure 7 schematically represents a portion of a side wall of a glass container that has a persistent surface homogeneity;
[0022] Figure 8 schematically represents a glass container with a lubricious coating positioned on the outer surface of the glass container;
[0023] Figure 9 schematically represents a test template to determine the coefficient of friction between two glass containers;
[0024] Figure 10 schematically represents an apparatus for evaluating the thermal stability of a coating applied to a glass container;
[0025] Figure 11 graphically represents light transmittance data for coated and uncoated conceptacles measured in the visible light spectrum from 400 to 700 nm, in accordance with one or more embodiments shown and described herein;
[0026] Figure 12A schematically depicts a tenacious organic lubricious coating positioned on the outer surface of a glass container in accordance with one or more embodiments shown and described herein;
[0027] Figure 12B schematically depicts a tenacious organic lubricious coating positioned on the outer surface of a glass container in accordance with one or more embodiments shown and described herein;
[0028] Figure 13 schematically represents the chemical structure of a diamine monomer that can be used to form a polyimide coating layer;
[0029] Figure 14 schematically represents the chemical structure of another diamine monomer that can be used to form a polyimide coating layer;
[0030] Figure 15 schematically represents the chemical structures of some monomers that can be used as polyimide coatings applied to glass containers;
[0031] Figure 16 graphically represents the effect of composition and temperature on volatilization for a Type IB glass and a boron-free glass;
[0032] Figure 17 schematically represents the reaction steps of a silane that binds to a substrate, according to one or more embodiments shown and described herein;
[0033] Figure 18 schematically represents the reaction steps of a polyimide that binds to a silane, according to one or more embodiments shown and described herein;
[0034] Figure 19 graphically represents the failure probability as a function of the applied load in a horizontal compression test for conceptacles, according to one or more modalities shown and described in this document;
[0035] Figure 20 contains a Table that reports the load and coefficient of friction measured for Type IB glass conceptacles and conceptacles formed from a reference glass composition that underwent ion exchange and were coated in accordance with with one or more embodiments shown and described herein;
[0036] Figure 21 graphically represents the failure probability as a function of applied stress in four-point bending for tubes formed from a reference glass composition in as-received condition, in ion exchange condition (uncoated), in ion exchange condition (coated and ground), in ion exchange condition (uncoated and ground) and for tubes formed from Type IB glass in as received condition and in ion exchange condition in accordance with a or more modalities shown and described herein;
[0037] Figure 22 schematically represents the mass spectrometer-gas chromatograph output data for an APS/Novastrat® 800 coating, according to one or more embodiments shown and described herein;
[0038] Figure 23 graphically represents mass spectrometer-gas chromatography output data for a DC806A coating, in accordance with one or more embodiments shown and described herein;
[0039] Figure 24 is a Table that reports different lubricious coating compositions that were tested under lyophilization conditions, according to one or more embodiments shown and described herein;
[0040] Figure 25 is a graph reporting the coefficient of friction for uncoated and weak glass conceptacles that have a silicone resin coating tested on a template of concepta upon conceptacle, in accordance with one or more embodiments shown and described in this document;
[0041] Figure 26 is a graph that reports the friction coefficient for conceptculae coated with an APS/PMDA-ODA (poly(4,4'-oxydiphenylene-pyromelithimide) polyimide coating and ground multiple times under different loads applied to a jig from conceptcar to conceptacle, in accordance with one or more embodiments shown and described herein;
[0042] Figure 27 is a graph that reports the coefficient of friction for conceptacles coated with an APS coating and ground multiple times under different loads applied in a jig from concepta to conceptacle, in accordance with one or more embodiments shown and described herein. ;
[0043] Figure 28 is a graph that reports the friction coefficient for conceptculae coated with an APS/PMDA-ODA (poly(4,4'-oxydiphenylene-pyromelithimide) polyimide coating and ground multiple times under different loads applied to a jig concept car on concept car after the concept car has been exposed to 300°C for 12 hours in accordance with one or more embodiments shown and described herein;
[0044] Figure 29 is a graph reporting the coefficient of friction for conceptacles coated with an APS coating and ground multiple times under different loads applied to a conceptacle jig on conceptacle after the conceptacles were exposed to 300°C for 12 hours, according to one or more embodiments shown and described herein;
[0045] Figure 30 is a graph reporting the friction coefficient for Type IB conceptculae coated with a polyimide PMDA-ODA (poly(4,4'-oxydiphenylene-pyromelithimide) coating and ground multiple times under different loads applied to a template from concept to conceptacle, in accordance with one or more embodiments shown and described herein;
[0046] Figure 31 graphically represents the coefficient of friction for conceptculae coated with APS/Novastrat® 800 before and after lyophilization, according to one or more embodiments shown and described herein;
[0047] Figure 32 graphically represents the friction coefficient for conceptculae coated with APS/Novastrat® 800 before and after autoclaving, according to one or more modalities shown and described herein;
[0048] Figure 33 graphically represents the coefficient of friction for coated glass containers exposed to different temperature conditions and for an uncoated glass container;
[0049] Figure 34 graphically represents the failure probability according to a load function applied in a horizontal compression test for conceptacles, according to one or more modalities shown and described in this document;
[0050] Figure 35 is a Table illustrating the change in friction coefficient with variations in coupling agent composition of a lubricious coating applied to a glass container as described herein;
[0051] Figure 36 graphically represents the coefficient of friction, applied force and friction force for coated glass containers before and after depyrogenization;
[0052] Figure 37 graphically represents the coefficient of friction, applied force and friction force for coated glass containers before and after depyrogenization, according to one or more embodiments shown and described herein;
[0053] Figure 38 graphically represents the failure probability according to a load function applied in a horizontal compression test for conceptacles, according to one or more modalities shown and described in this document;
[0054] Figure 39 graphically represents the coefficient of friction, applied force and friction force for coated glass containers before and after depyrogenization, according to one or more embodiments shown and described herein;
[0055] Figure 40 graphically represents the coefficient of friction, applied force and friction force for coated glass containers for different depyrogenization conditions;
[0056] Figure 41 graphically represents the coefficient of friction after varying heat treatment times, according to one or more modalities shown and described herein;
[0057] Figure 42 graphically represents light transmittance data for coated and uncoated conceptculae measured in the visible light spectrum from 400 to 700 nm, in accordance with one or more embodiments shown and described herein;
[0058] Figure 43 graphically represents the coefficient of friction, applied force and friction force for coated glass containers before and after depyrogenization, in accordance with one or more embodiments shown and described herein;
[0059] Figure 44 graphically represents the failure probability according to a load function applied in a horizontal compression test for conceptacles, according to one or more modalities shown and described in this document;
[0060] Figure 45 is a micrograph of a coating, in accordance with one or more embodiments shown and described herein;
[0061] Figure 46 is a micrograph of a coating, in accordance with one or more embodiments shown and described herein;
[0062] Figure 47 is a micrograph of a coating, in accordance with one or more embodiments shown and described herein;
[0063] Figure 48 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the conceptacles as coated in a comparative example;
[0064] Figure 49 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the heat-treated conceptacles of a comparative example;
[0065] Figure 50 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the conceptacles as coated in a comparative example;
[0066] Figure 51 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the heat-treated conceptacles of a comparative example:
[0067] Figure 52 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for conceptacles with an adhesion-promoting layer in conforming condition coated;
[0068] Figure 53 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for conceptacles with an adhesion-promoting layer in a conforming condition coated;
[0069] Figure 54 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for conceptacles with an adhesion-promoting layer after depyrogenization ;
[0070] Figure 55 graphically represents the coefficient of friction, scratch penetration, applied perpendicular force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for conceptacles with an adhesion-promoting layer after depyrogenization ;
[0071] Figure 56 graphically represents the failure probability as a function of load applied in a horizontal compression test for conceptacles with an adhesion promoting layer, according to one or more modalities shown and described herein; and
[0072] Figure 57 graphically represents the failure probability as a function of load applied in a horizontal compression test for conceptacles with an adhesion promoting layer, according to one or more modalities shown and described in this document. DETAILED DESCRIPTION
[0073] Reference will now be made in detail to the modalities of glass containers, examples of which are illustrated in the attached drawings. Whenever possible, the same reference numbers will be used throughout the drawings to refer to similar or equal parts. The glass containers described herein have at least two performance attributes selected from delamination resistance, enhanced strength and increased damage resistance. For example, glass containers can have a combination of delamination resistance and improved strength; improved strength and increased damage resistance; or increased delamination resistance and damage resistance. In a particular embodiment, a glass container may include a body having an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A tough inorganic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tough inorganic coating may have a coefficient of friction less than or equal to 0.7. Glass containers with various combinations of delamination resistance, enhanced strength and increased damage resistance will be described in more detail herein with specific reference to the accompanying drawings.
[0074] In the embodiments of glass compositions described herein, the concentration of constituent components (eg, SiO2, Al2O3, B2O3 and the like) is specified in mol percent (mol %) on an oxide base, except where specified in contrary.
[0075] The term "substantially free", when used to describe the concentration and/or absence of a particular constituent component in a glass composition, means that the constituent component is not intentionally added to the glass composition. However, the glass composition may contain traces of the constituent component as a contaminant or loose elements in amounts less than 0.1 mol%.
[0076] The term "chemical durability", for use in the present invention, refers to the ability of the glass composition to resist degradation under exposure to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein can be evaluated according to three established material testing standards: DIN 12116 dated March 2001 and entitled “Testing of glass - Resistance to attack by a boiling aqueous solution of hydrochloric acid - Method of test and classification”; ISO 695: 1991 entitled “Glass—Resistance to attack by a boiling aqueous solution of mixed alkali—Method of test and classification”; ISO 720: 1985 entitled “Glass—Hydrolytic resistance of glass grains at 121 degrees C—Method of test and classification”; and ISO 719: 1985 “Glass — Hydrolytic resistance of glass grains at 98 degrees C — Method of test and classification”. Each standard and the classifications within each standard are described in further detail in this document. Alternatively, the chemical durability of a glass composition can be assessed according to USP <660> entitled “Surface Glass Test” and/or European Pharmacopeia 3.2.1 entitled “Glass containers For Pharmaceutical Use”, which assess surface durability of the glass.
[0077] The term "strain point" and "Tstrain", for use in the present invention, refers to the temperature at which the viscosity of the glass is 3x1014 poise.
[0078] The term "softening point", for use in the present invention, refers to the temperature at which the viscosity of the glass composition is 1x107.6 poise.
[0079] Conventional glass containers used to store pharmaceuticals and/or other consumables may experience damage during filling, packaging and/or shipping. Such damage can be in the form of scratches, abrasions and/or surface scratches which, when sufficiently deep, can result in a through crack or even complete failure of the glass container, thus compromising the contents of the glass package.
[0080] In addition, some conventional glass containers may be susceptible to delamination, particularly when the glass container is formed from alkali borosilicate glasses. Delamination refers to a phenomenon in which glass particles are released from the glass surface after a series of leaching, corrosion and/or weathering aging reactions. In general, glass particles are silica-rich glass flakes that originate from the inner surface of the package as a result of leaching of modifier ions into a solution contained within the package. These flakes can generally be from about 1 nm to about 2 microns (μm) in thickness with a width greater than about 50 μm. As these flakes are primarily composed of silica, the conceptacles generally do not further degrade after being released from the glass surface.
[0081] It was previously assumed that delamination is due to the phase separation that occurs in alkali borosilicate glasses when the glass is exposed to the elevated temperatures used to reform the glass into a container shape.
[0082] However, it is now believed that adelamination of the silica-rich glass flakes from the inner surfaces of the glass containers is due to the compositional characteristics of the glass container immediately after formation. Specifically, the high silica content of alkali borosilicate glasses causes the glass to have relatively high forming and melting temperatures. However, the alkali and borate components in the glass composition melt and/or vaporize at much lower temperatures. In particular, borate species in glass are highly volatile and evaporate from the glass surface at the high temperatures necessary to shape and reform glass.
[0083] Specifically, the glass stock is reformed into glass containers at high temperatures and in direct flame. The high temperatures required at higher equipment speeds cause the more volatile borate species to evaporate from portions of the glass surface. When this evaporation occurs within the inner volume of the glass vessel, volatilized borate species are redeposited in other areas of the glass vessel surface causing compositional inhomogeneities on the glass vessel surface, particularly with respect to surface regions close to the inside the glass container (i.e. those regions on or directly adjacent to the inner surfaces of the glass container). For example, as one end of a glass tube is closed to form the bottom or base of the container, borate species may evaporate from the bottom portion of the tube and be redeposited elsewhere in the tube. Evaporation of material from the base and heel portions of the container is particularly prominent as these areas of the container undergo more extensive reforming and, as such, are exposed to higher temperatures. As a result, areas of the container exposed to higher temperatures may have silica-rich surfaces. Other areas of the container that are sensitive to boron deposition may have a boron-rich layer on the surface. Areas sensitive to boron deposition that are at a temperature greater than the annealing point of the glass composition, but less than the hottest temperature to which the glass is subjected during reforming can lead to boron incorporation onto the glass surface. The solutions contained in the container can leach boron from the boron-rich layer. As the boron-rich layer is leached from the glass, a high silica (gel) glass network remains, which swells and deforms during hydration and eventually breaks away from the surface.
[0084] The glass containers described in this document alleviate at least two of the aforementioned problems. Specifically, glass containers have at least two performance attributes selected from delamination resistance, enhanced strength, and increased damage resistance. For example, glass containers can have a combination of delamination resistance and improved strength; improved strength and increased damage resistance; or increased delamination resistance and damage resistance. Each performance attribute and methods for achieving the performance attribute will be described in further detail in this document.
[0085] Referring now to Figures 1 and 2, an embodiment of a glass container 100 for storing a pharmaceutical formulation is schematically represented in cross section. The glass container 100 generally comprises a body 102. The body 102 extends between an inner surface 104 and an outer surface 106 and generally encloses an inner volume 108. In the embodiment of the glass container 100 shown in Figure 1, the body 102 generally comprises a wall portion 110 and a base portion 112. The wall portion 110 passes into the base portion 112 through a heel portion 114. The body 102 has a wall thickness Tw that extends between the inner surface 104 to the outer surface 106, as shown in Figure 1.
[0086] While the glass container 100 is depicted in Figure 1 as having a specific shape (i.e., conceptacle), it should be understood that the glass container 100 may have other shapes that include, without limitation, Vacutainers®, cartridges, syringes, ampoules, bottles, vials, flasks, tubes, beakers, or the like. Additionally, it is to be understood that the glass containers described herein can be used for a variety of applications which include, without limitation, pharmaceutical packaging, beverage containers, or the like. FORCE
[0087] Still referring to Figures 1 and 2, in some embodiments described herein, the body 102 includes a compressively tensioned layer 202 that extends from at least the outer surface 106 of the body 102 to wall thickness Tw to a DOL layer depth from the outer surface 106 of the body 102. The compressively tensioned layer 202 generally increases the strength of the glass container 100 and also improves the damage tolerance of the glass container. Specifically, a glass container having a compressively tensioned layer 202 is generally capable of withstanding a greater degree of surface damage, such as scratches, chips, or the like, without failure compared to an unreinforced glass container, as that the compressively tensioned layer 202 mitigates the propagation of cracks from surface damage in the compressively tensioned layer 202.
[0088] In the embodiments described herein, the layer depth of the compressively stressed layer may be greater than or equal to about 3 μm. In some embodiments, the depth of can be greater than 10 μm or even greater than 20 μm. In some embodiments, the layer depth may be greater than or equal to about 25 μm or even greater than or equal to about 30 μm. For example, in some embodiments, the layer depth can be greater than or equal to about 25 μm and up to about 150 μm. In some other embodiments, the layer depth may be greater than or equal to about 30 μm and less than or equal to about 150 μm. In further embodiments, the layer depth may be greater than or equal to about 30 µm and less than or equal to about 80 µm. In some other embodiments, the layer depth may be greater than or equal to about 35 μm and less than or equal to about 50 μm.
[0089] The compressively stressed layer 202 generally has a surface compressive stress (ie, a compressive stress as measured on the outer surface 106) greater than or equal to 150 MPa. In some embodiments, the surface compression stress may be greater than or equal to 200 MPa, or even greater than or equal to 250 MPa. In some embodiments, the surface compression stress may be greater than or equal to 300 MPa, or even greater than or equal to 350 MPa. For example, in some embodiments, the surface compression stress can be greater than or equal to about 300 MPa and less than or equal to about 750 MPa. In some other embodiments, the surface compressive stress may be greater than or equal to about 400 MPa and less than or equal to about 700 MPa. In still other embodiments, the surface compression stress may be greater than or equal to about 500 MPa and less than or equal to about 650 MPa. Stress in ion-exchanged glassware can be measured with an FSM (Fundamental Stress Meter) instrument. This instrument couples light inside and outside the birefringent glass surface. The measured birefringence is then related to stress through a material constant, the photoelastic coefficient or optical stress (SOC or PEC). Two parameters are obtained: the maximum surface compression stress (CS) and the exchange layer depth (DOL). Alternatively, compressive stress and layer depth can be measured using refractive near-field stress measurement techniques.
[0090] While the compressively tensioned layer 202 has been shown and described herein as extending from the outer surface 106 in the thickness Tw of the body 102, it should be understood that in some embodiments the body 102 may additionally comprise a second compressively tensioned layer extending from the inner surface 104 in the thickness Tw of the body 102. In this embodiment, the layer depth and surface compressive stress of the compressively tensioned second layer may reflect those of the compressively tensioned layer 202 over the centerline the thickness Tw of the body 102.
[0091] Several different techniques can be used to form the compressively tensioned layer 202 on the body 102 of the glass container 100. For example, in embodiments where the body 102 is formed from ion exchanged glass, the compressively tensioned layer 202 can be formed in body 102 by ion exchange. In these embodiments, the compressively stressed layer 202 is formed by placing the glass vessel in a bath of molten salt to facilitate the exchange of relatively large ions in the molten salt for relatively smaller ions in the glass. Several different exchange reactions may be used to achieve the compressively stressed layer 202. In one embodiment, the bath may contain molten KNO3 salt, while the glass from which the glass vessel 100 is formed contains lithium ions and/or or sodium. In this embodiment, the potassium ions in the bath are exchanged for the relatively smaller lithium and/or sodium ions in the glass, thus forming the compressively stressed layer 202. In another embodiment, the bath may contain NaNO3 salt and the glass a from which the glass container 100 is formed contains lithium ions. In this embodiment, the sodium ions in the bath are exchanged for the relatively smaller lithium ions in the glass, thus forming the compressively stressed layer 202.
[0092] In a specific embodiment, the compressively stressed layer 202 can be formed by submerging the glass vessel in a bath of molten salt of 100% KNO3 or, alternatively, a mixture of KNO3 and NaNO3. For example, in one embodiment, the molten salt bath may include KNO3 with up to about 10% NaNO3. In this embodiment, the glass from which the container is formed may include sodium ions and/or lithium ions. The temperature of the molten salt bath can be greater than or equal to 350 °C and less than or equal to 500 °C. In some embodiments, the temperature of the molten salt bath may be greater than or equal to 400°C and less than or equal to 500°C. In still other embodiments, the temperature of the molten salt bath can be greater than or equal to 450°C and less than or equal to 475°C. The glass vessel can be kept in the molten salt bath for a period of time sufficient to facilitate the exchange of the relatively large ions in the salt bath for relatively smaller ions in the glass and thus achieve the surface and depth compression stress of desired layer. For example, glass can be kept in the molten salt bath for a period of time that is greater than or equal to 0.05 hours to less than or equal to about 20 hours in order to achieve layer depth and compression stress. of desired surface. In some embodiments, the glass vessel may be kept in the molten salt bath for more than or equal to 4 hours and less than or equal to about 12 hours. In other embodiments, the glass vessel may be kept in the molten salt bath for more than or equal to about 5 hours and less than or equal to about 8 hours. In an exemplary embodiment, the glass vessel may be ion exchanged in a molten salt bath comprising 100% KNO3 at a temperature greater than or equal to about 400 °C and less than or equal to about 500 °C for a period of time. period of time greater than or equal to about 5 hours and less than or equal to about 8 hours.
[0093] Typically, the ion exchange process is carried out at temperatures more than 150 °C below the strain point (Tstrain) of the glass, in order to minimize stress relaxation due to elevated temperatures. However, in some embodiments, the compressively stressed layer 202 is formed in a bath of molten salt that is at a temperature greater than the strain point of the glass. This type of ion exchange reinforcement is referred to in this document as “high temperature ion exchange reinforcement”. In high temperature ion exchange reinforcement, the relatively smaller ions in the glass are exchanged for relatively larger ions from the molten salt bath as described above. As relatively smaller ions are exchanged for relatively larger ions at temperatures above the strain point, the resulting stress is released or “relaxed”. However, replacing smaller ions in the glass with larger ions creates a surface layer on the glass that has a lower coefficient of thermal expansion (CTE) than the rest of the glass. As the glass cools, the CTE differential between the glass surface and the rest of the glass creates the compressively stressed layer 202. This high temperature ion exchange technique is particularly well suited to reinforcing glass articles such as glass containers, which have complex geometries and typically shortens the reinforcement process time over typical ion exchange processes and also allows for a greater layer depth.
[0094] Still referring to Figures 1 and 2, in an alternative embodiment, the compressively stressed layer 202 may be introduced into the body 102 of the glass container 100 by thermal quenching. Compressively stressed layers are formed by thermal tempering by heating the glass container and differentially cooling the surface of the glass with respect to most of the glass. Specifically, a glass that is rapidly cooled has a greater molar volume (or lower density) than a more slowly cooled glass. Consequently, if the surface of the glass is intentionally rapidly cooled, the surface of the glass will have a greater volume and the inner part of the glass (that is, the rest of the glass below the outer surface) will necessarily cool at a slower rate than the as the heat needs to escape most of it through the surface. By creating a continuous gradient in molar volume (or history/thermal density) from the outer surface 106 at the wall thickness Tw of the body 102, a compressively stressed layer 202 is produced that has a parabolic stress profile (i.e., the compressive stress decreases parabolic with increasing distance from the outer surface 106 of the body 102). Thermal quenching processes are generally faster and less expensive than ion exchange processes. However, surface compression stresses due to the fact that thermal quenching processes are generally less than surface compression stresses due to ion exchange processes. In embodiments where the glass container is thermally tempered, the resulting compressively stressed layer extends from the outer surface 106 to a layer depth DOL that is up to 22% of the wall thickness Tw of the glass containers. For example, in some embodiments, the DOL can be from about 5% to about 22% of wall thickness Tw or even from about 10% to about 22% of wall thickness Tw.
[0095] In a typical thermal tempering process, the glass vessel 100 is first heated to its softening point, and subsequently the outer surface 106 of the body 102 is rapidly cooled to below the softening point with a fluid, such as with a jet of gas, or the like, to create a temperature differential between the outer surface 106 of the body 102 and the remainder of the body 102, as described above. The temperature differential between the outer surface 106 and the remaining body surface 106 produces a compressively tensioned layer 202 that extends the wall thickness Tw of the body 102 from the outer surface 106. For example, the glass may be initially heated to 50 to 150°C. °C above its softening point and then rapidly cooled to room temperature by directing a fluid over the glass. The fluid may include, without limitation, air, oil or oil-based fluids.
[0096] Now referring to Figures 1 to 3, in another embodiment, the glass container 100 may be formed from laminated glass tubing that facilitates the formation of a compressively tensioned layer 202 at least on the outer surface 106 of the body 102. Laminated glass generally comprises a core layer of glass 204 and at least one protective layer of glass 206a. In the embodiment of the glass container 100 shown in Figure 3, the laminated glass includes a pair of protective glass layers 206a, 206b. In that embodiment, the glass core layer 204 generally comprises a first surface 205a and a second surface 205b that is opposite the first surface 205a. A first protective glass layer 206a is fused to the first surface 205a of the core layer of glass 204 and a second protective layer of glass 206b is fused to the second surface 205b of the core layer of glass 204. The protective layers of glass 206a, 206b are fused to the glass core layer 204 without any additional materials, such as adhesives, coating layers, or the like, disposed between the glass core layer 204 and the protective glass layers 206a, 206b.
[0097] In the embodiment shown in Figure 3, the glass core layer 204 is formed from a first glass composition having a CTEcore average core thermal expansion coefficient and the protective glass layers 206a, 206b are formed at from a second different glass composition that has an average coefficient of thermal expansion CTEclad. In the embodiments described herein, CTEcore is not the same as CTEclad such that a compression stress layer is present in at least one of the core layer or the protective layer. In some embodiments, CTEcore is larger than CTEclad, which results in the protective glass layers 206a, 206b being compressively stressed without having ion exchange or being thermally tempered. In some other embodiments, such as when laminated glass comprises a single core layer and a single protective layer, CTEclad may be larger than CTEcore, which results in the glass core layer being compressively stressed without having ion exchange or be thermally tempered.
[0098] The laminated glass tubing from which the glass container is formed can be formed as described in patent no. U.S. 4,023,953, which is incorporated herein by reference. In embodiments, the glass forming the glass core layer 204 is formed from a glass composition that has a CTEcore average thermal expansion coefficient that is greater than the CTEclad average thermal expansion coefficient of any of the protective layers. of glass 206a, 206b. As the glass core layer 204 and the glass protective layers 206a, 206b cool, the difference in the average thermal expansion coefficients of the glass core layer 204 and the protective glass layers 206a, 206b causes a compressively stressed layer develops in protective glass layers 206a, 206b. When laminated glass is used to form a container, these compressively stressed layers extend from the outer surface 106 of the glass container 100 at wall thickness Tw and form the inner surface 104 of the glass container at wall thickness Tw. In some embodiments, the compressively stressed layer may extend from the outer surface of the glass container body at wall thickness Tw to a layer depth that is from about 1 μm to about 90% of the wall thickness. Tw. In some other embodiments, the compressively stressed layer may extend from the outer surface of the glass container body at wall thickness Tw to a layer depth that is from about 1 μm to about 33% of the thickness of wall Tw. In still other embodiments, the compressively tensioned layer may extend from the outer surface of the glass container body at wall thickness Tw to a layer depth that is from about 1 µm to about 10% of the thickness of wall Tw.
[0099] After the laminated tube is formed, the tube can be formed into a container shape using conventional tube converting techniques.
[0100] In some embodiments where the glass container is formed from laminated glass, the at least one protective layer forms the inner surface of the body of the glass container such that the at least one protective layer of glass is in direct contact with the product stored in the glass container. In such embodiments, the at least one protective layer may be formed from a glass composition that is resistant to delamination, as described in further detail herein. Consequently, it should be understood that the at least one protective layer may have a delamination factor of less than or equal to 10, as described in further detail in this document.
[0101] In another alternative embodiment, the glass container can be reinforced by applying a coating to the glass body. For example, a coating of an inorganic material, such as titania, can be applied to at least a portion of the outer surface of the glass body by soot deposition or vapor deposition processes. The titania coating has a lower coefficient of thermal expansion than the glass on which it is deposited. As the coating and glass cool, the titania shrinks less than the glass, and as a result, the surface of the glass body is in tension. In such embodiments, it should be understood that the surface compressive stress and layer depth are measured from the surface of the coating rather than the surface of the coated glass body. Although the inorganic coating material has been described herein as comprising titania, it should be understood that other inorganic coating materials with suitably low coefficients of thermal expansion are also contemplated. In embodiments, the inorganic coating may have a coefficient of friction of less than 0.7 relative to a similar coated container. The inorganic coating may also be thermally stable at temperatures greater than or equal to 250°C, as described further herein.
[0102] In another alternative embodiment, the glass body may be reinforced by the glass body with a high modulus coating that has a coefficient of thermal expansion equal to or greater than the underlying glass body. Reinforcement is achieved by the difference in elastic modulus which imparts resistance to damage, while the difference in thermal expansion imparts a compressive stress on the glass surface (balancing stress in the high modulus coating). In such embodiments, it should be understood that the surface compressive stress and layer depth are measured from the surface of the glass body rather than the surface of the coated glass body. The high modulus makes it difficult for scratches and damage to be introduced and the underlying compressive layer prevents scratches and cracks from propagating. An exemplary material pairing to demonstrate this effect is a sapphire coating on 33 expansion borosilicate glass or a zirconium oxide coating deposited on 51 expansion borosilicate glass.
[0103] Based on the foregoing, it should be understood that, in some embodiments, glass containers may include a compressively tensioned layer that extends from at least the outer surface of the body in the wall thickness of the glass container. . The compressively tensioned layer improves the mechanical strength of the glass container over a glass container that does not include a compressively tensioned layer. The compressively tensioned layer also improves the damage tolerance of the glass container such that the glass container is able to withstand greater surface damage (i.e. scratches, chips, etc., which extend deeper into the thickness of wall of the glass container) without fault with respect to a glass container which does not include a compressively tensioned layer. Additionally, it is also to be understood that, in these embodiments, the compressively stressed layer may be formed on the glass container by ion exchange, by thermal tempering, by forming the glass container from laminated glass, or by applying a coating. to the glass body. In some embodiments, the compressively stressed layer may be formed by a combination of these techniques. RESISTANCE TO DELAMINATION
[0104] In some embodiments, the glass containers 100 can also resist delamination after long-term exposure to certain chemical compositions stored in the container. As noted above, delamination can result in the release of silica-rich glass flakes into a solution contained within the glass container after prolonged exposure to the solution. Consequently, delamination resistance can be characterized by the number of glass particles present in a solution contained within the glass container after exposure to the solution under specific conditions. In order to assess the long-term resistance of the glass container to delamination, an accelerated delamination test is used. The test can be performed in either ion-exchange or non-ion-exchange glass vessels. The test consists of washing the glass container at room temperature for 1 minute and depyrogenating the container at about 320°C for 1 hour. Subsequently, a 20 mM solution of glycine with a pH of 10 in water is placed in the 80 to 90% filled glass vessel, the glass vessel is closed, and the glass vessel is rapidly heated to 100 °C and, then heated from 100°C to 121°C at a ramp rate of 1 degree/min. at a pressure of 2 atmospheres. The glass vessel and solution are held at this temperature for 60 minutes, cooled to room temperature at a rate of 0.5 degrees/min. and the heating and holding cycle are repeated. The glass vessel is then heated to 50°C and held for ten or more days for high temperature conditioning. After heating, the glass container is dropped from a distance of at least 45.72 cm (18 inches) onto a firm surface, such as a laminate tile floor, to dislodge any flakes or particles that are loosely adhered. to the inner surface of the glass container. Drop distance can be graduated appropriately to prevent oversized conceptacles from fracturing under impact.
[0105] Subsequently, the solution contained in the glass container is analyzed to determine the number of glass particles present per liter of solution. Specifically, the solution from the glass vessel is poured directly onto the center of a Millipore Isopore membrane filter (Millipore no. ATTP02500 held in an assembly with parts no. AP1002500 and no. M000025A0) attached to the vacuum suction to pull the solution through the filter within 10 to 15 seconds to 5 ml. Thereafter, another 5 ml of water is used as a rinse to remove buffer residue from the filter medium. The particulate flakes are then counted by differential interference contrast microscopy (DIC) in reflection mode, as described in “Differential interference contrast (DIC) microscopy and modulation contrast microscopy” from Fundamentals of light microscopy and digital imaging; New York: Wiley-Liss, pages 153 to 168. The field of view is set to approximately 1.5 mm X 1.5 mm and particles larger than 50 μm are manually counted. There are 9 such measurements taken at the center of each filter membrane in a 3 X 3 pattern with no overlap between images. If larger areas of the filter medium were analyzed, the results can be normalized to the equivalent area (ie 20.25 mm2). Images collected from the optical microscope are examined with an image analysis program (Media Cybernetic's ImagePro Plus version 6.1) to measure and count the number of glass flakes present. This is accomplished as follows: all features within the image that appeared darker than the background by simple grayscale segmentation are highlighted; the length, width, area and perimeter of all highlighted features that have a length greater than 25 micrometers are then measured; any obviously non-glass particles are then removed from the data; the measurement data is then exported to a spreadsheet. Then, all features greater than 25 micrometers in length and lighter than the background are extracted and measured; the length, width, area and perimeter, and the X-Y aspect ratio of all highlighted features that have a length greater than 25 micrometers are measured; any obviously non-glass particles are removed from the data; and the measurement data is appended to the previously exported data in the spreadsheet. The data within the spreadsheet is then sorted by feature length and boxed according to size. Reported results are for features greater than 50 micrometers in length. Each of these groups is then counted and the counts reported for each of the samples.
[0106] A minimum of 100 ml of solution is tested. As such, the solution from a plurality of small containers can be pooled to bring the total amount of solution up to 100 ml. For containers that have a volume greater than 10 ml, the test is repeated for an assay of 10 containers formed from the same glass composition under the same processing conditions and the particle count result is averaged over the 10 containers to determine an average particle count. Alternatively, in the case of small containers, the test is repeated for a run of 10 conceptacles, each of which is analyzed and the particle count averaged over the multiple runs to determine the average particle count per run. Averaging the particle count over multiple containers explains potential variations in the delamination behavior of individual containers. Table 1 summarizes some non-limiting examples of sample volumes and numbers of test containers: TABLE 1: TEST SPECIMEN TABLE EXAMPLIFIERS

[0107] It should be understood that the aforementioned test is used to identify particles that are loosened from the inner wall(s) of the glass vessel due to delamination and not loose particles present in the vessel from formation processes or particles that precipitate from the solution enclosed in the glass vessel as a result of reactions between the solution and the glass. Specifically, delamination particles can be differentiated from loose glass particles based on the particle aspect ratio (i.e., the ratio of maximum particle length to particle thickness, or a ratio between maximum and minimum dimensions) . Delamination produces particulate flakes or lamellae that are irregularly shaped and typically have a maximum length greater than about 50 μm, but often greater than about 200 μm. The thickness of the flakes is usually greater than about 100 nm and can be as large as about 1 μm. Thus, the minimum flake aspect ratio is typically greater than about 50. The aspect ratio can be greater than about 100 and sometimes greater than about 1000. In contrast, loose glass particles will generally have a low aspect ratio that is less than about 3. Consequently, particles resulting from delamination can be differentiated from loose particles based on aspect ratio during observation with the microscope. Other common non-glass particles include hair, fibers, metal particles, plastic particles and other contaminants and are therefore excluded during inspection. Validation of the results can be performed by evaluating the internal regions of the tested containers. Under observation, evidence of liner corrosion/holes/flake removal as described in “Nondestructive Detection of Glass Vial Inner Surface Morphology with Differential Interference Contrast Microscopy” of Journal of Pharmaceutical Sciences 101(4), 2012, pages 1378 to 1384 , is observed.
[0108] The number of particles present after the accelerated delamination test can be used to establish a delamination factor for the set of tested conceptacles. Tests of glass containers that average less than 10 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test after the accelerated delamination test are considered to have a delamination factor of 10. Tests of glass containers that average less than 9 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test , are considered to have a delamination factor of 9. Tests of glass containers that average less than 8 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, they are considered to have a delamination factor of 8. Tests of glass containers that average less than 7 glass particles with a minimum length of about 50 μm and an aspect ratio m greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 7. Tests of glass containers that average less than 6 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 6. Tests of glass containers that average less than 5 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 5. Tests of glass containers that average less than 4 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 4. Container tests glass that average less than 3 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per run, after the accelerated delamination test, are considered to have a delamination factor of 3 Tests of glass containers that average less than 2 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 2. Testing glass containers that average less than 1 glass particle with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the accelerated delamination test, are considered to have a delamination factor of 1. Tests of glass containers that have 0 glass particles with a minimum length of about 50 μm and an aspect ratio greater than about 50 per test, after the delamination test accelerated inaction, are considered to have a delamination factor of 0. Consequently, it should be understood that the lower the delamination factor, the better the resistance of the glass container to delamination. In some embodiments described herein, at least the inner surface of the body of the glass container has a delamination factor of 10 or less (e.g., a delamination factor of 3, 2, 1 or 0). In some other embodiments, the entire body of the glass container, which includes both the inner and outer surfaces, has a delamination factor of 10 or less (e.g., a delamination factor of 3, 2, 1, or 0) .
[0109] In some embodiments, a glass container having a delamination factor of 10 or less can be obtained by forming the glass container with a barrier coating on the inner surface of the body such that the barrier coating be the inner surface of the body. Referring to Figure 5, by way of example, a glass container 100 with a barrier coating 131 deposited on at least a portion of the inner surface 104 of the body 102 is schematically depicted. The barrier coating 131 does not delaminate or otherwise degrade and prevents the product stored in the internal volume 108 of the glass container 100, such as pharmaceutical compositions, or the like, from contacting the internal surface 104 of the body 102, attenuating, thus, delamination of the glass container. The barrier coating is generally non-permeable to aqueous solutions, is water insoluble and hydrolytically stable.
[0110] In some embodiments described herein, the barrier coating 131 is a tough inorganic coating that is permanently adhered to the inner surface 104 of the glass container 100. The barrier coating 131 may be a metal nitride coating, a coating oxide, a metal sulfide coating, SiO2, diamond-like carbide, graphenes, or a carbide coating. For example, in some embodiments, the tough inorganic coating can be formed from at least one metal oxide, such as Al2O3, TiO2, ZrO2, SnO, SiO2, Ta2O5, NB2O5, Cr2O3, V2O5, ZnO, or HfO2. In some other embodiments, the tough inorganic coating may be formed from a combination of two or more metal oxides, such as Al2O3, TiO2, ZrO2, SnO, SiO2, Ta2O5, NB2O5, Cr2O3, V2O5, ZnO or HfO2. In some other embodiments, barrier coating 131 may comprise a first layer of a first metal oxide deposited on the inner surface of the glass container and a second layer of a second metal oxide deposited on the first layer. In such embodiments, the barrier coating 131 can be deposited using a variety of deposition techniques that include, without limitation, atomic layer deposition, chemical vapor deposition, physical vapor deposition, and the like. Alternatively, the barrier coating can be applied with one or more liquid application techniques, such as dip coating, spray coating or plasma coating. Spray coating techniques can include high volume low pressure (HVLP) and low volume low pressure (LVLP) spray coating, electrostatic spray coating, airless spray coating, ultrasonic atomization with airless spray coating, aerosol jet coating and inkjet coating. Plasma coating techniques can include standard primary and secondary plasma coating, microwave-assisted plasma coating, and atmospheric plasma coating, and the like.
[0111] While embodiments of barrier coating 131 have been described herein as comprising inorganic materials, it should be understood that, in some embodiments, barrier coating 131 may be an organic coating. For example, in embodiments where the barrier coating 131 is an organic coating, the organic coating may comprise polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins that include polytetrafluoroethylenes and other fluor substituted polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenolics, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins including polyethylenes, oxidized polyethylenes, polypropylenes, polyethylene/polyethylene copolymers propylene, polyethylene/vinyl acetate copolymers, polyvinyl chloride, polyacrylates, polymethacrylates, polystyrenes, polyterpenes, polyanhydrides, polymalecanhydrides, polyformaldehydes, polyacetals and copolymers of polyacetals, dimethyl or diphenyl polysiloxanes or methyl/phenyl mixtures, siloxanes perfluorinated and other substituted siloxanes, polyimides, polycarbonates, polyesters, paraffins and waxes, or various combinations thereof. In some embodiments, the organic coating used as a barrier coating 131 may include polysiloxanes of dimethyl, diphenyl, or methyl/phenyl mixtures. Alternatively, the organic coating may be a polycarbonate or polyethylene terephthalate. In some embodiments, barrier coating 131 may be formed from a layered structure comprising one or more of the aforementioned polymers and/or copolymers.
[0112] Barrier coatings can be used in conjunction with glass containers formed from any glass composition. However, barrier coatings are particularly well suited for use with glass containers formed from glass compositions that do not exhibit a resistance to delamination upon formation in a glass container. Such glass compositions may include, without limitation, those glass compositions designated as Type I Class A, Type I Class B and Type II glass compositions in accordance with ASTM E438-92 (2011) entitled “Standard Specification for Glasses in Laboratory Apparatus”. Such glass compositions may have the chemical durability required under the ASTM standard, but do not exhibit resistance to delamination. For example, Table 2 below lists several non-limiting examples of Type I Class B glass compositions that do not exhibit a resistance to delamination. As such, barrier coatings as described herein can be used at least on the inner surfaces of containers formed from these compositions such that the container has a delamination factor of 10 or less.TABLE 2: COMPOSITIONS OF TYPE I GLASS, EXEMPLARY CLASS

[0113] In some alternative embodiments, a glass container that has a delamination factor of 10 or less is achieved by forming the glass container such that the glass container has homogeneous compositional characteristics which, in turn, reduces the susceptibility of the glass container to delamination as described in co-pending patent application no. of U.S. series 13/912,457, filed on June 7, 2013, entitled “Delamination Resistant Glass Containers” and assigned to Corning Incorporated. Specifically, it is believed that the delamination of the glass container may be due, at least in part, to heterogeneities in the glass composition at least on the inside of the glass container, as described above. Minimizing such compositional heterogeneities yields a glass container that has a delamination factor of 10 or less.
[0114] Referring now to Figures 1 and 6, in some embodiments, the glass containers described herein have a homogeneous composition across the thickness of the glass body 102 in each of the wall, heel and base portions, such that so that at least the inner surface 104 of the body has a delamination factor of 10 or less. Specifically, Figure 6 schematically depicts a partial cross-section of a wall portion 110 of the glass container 100. The glass body 102 of the glass container 100 has an internal region 120 that extends from about 10 nm below the inner surface 104 of the glass container 100 (indicated in Figure 6 as DLR1) in the thickness of the wall portion 110 at a depth DLR2 from the inner surface 104 of the glass container. The inner region that extends from about 10 nm below the inner surface 104 is differentiated from the composition at the initial 5 to 10 nm below the surface due to experimental artifacts. At the start of a dynamic secondary ion mass spectroscopy (DSIMS) analysis to determine the composition of the glass, the initial 5 to 10 nm is not included in the analysis due to three concerns: variable ion bombardment rate of ions from the surface as result of accidental carbon, establishment of a steady-state charge in part due to variable ion bombardment rate and species mixing while establishing a steady-state ion bombardment condition. As a result, the first two data points of the analysis are excluded. Accordingly, it should be understood that the inner region 120 has a TLR thickness that is equal to DLR2-DLR1. The glass composition within the inner region has a persistent layer homogeneity which, together with the TLR thickness of the inner region, is sufficient to prevent delamination of the glass body after long-term exposure to a solution contained in the inner volume of the glass. glass container. In some embodiments, the TLR thickness is at least about 100 nm. In some embodiments, the TLR thickness is at least about 150 nm. In some other embodiments, the TLR thickness is at least about 200 nm or even about 250 nm. In some other embodiments, the TLR thickness is at least about 300 nm or even about 350 nm. In still other embodiments, the TLR thickness is at least about 500 nm. In some embodiments, the inner region 120 may extend to a TLR thickness of at least about 1 µm or up to at least about 2 µm.
[0115] Although the inner region is described herein as extending from 10 nm below the inner surface 104 of the glass container 100 in the thickness of the wall portion 110 to a depth DLR2 from the inner surface 104 of the glass container , it should be understood that other modalities are possible. For example, it is assumed that despite the experimental artifacts noted above, the inner region with persistent layer homogeneity may actually extend from the inner surface 104 of the glass container 100 into the thickness of the wall portion. Consequently, in some embodiments, the TLR thickness may extend from the inner surface 104 to the DLR2 depth. In such embodiments, the TLR thickness may be at least about 100 nm. In some embodiments, the TLR thickness is at least about 150 nm. In some other embodiments, the TLR thickness is at least about 200 nm or even about 250 nm. In some other embodiments, the TLR thickness is at least about 300 nm or even about 350 nm. In still other embodiments, the TLR thickness is at least about 500 nm. In some embodiments, the inner region 120 may extend to a TLR thickness of at least about 1 µm or up to at least about 2 µm.
[0116] In embodiments where the glass container is formed such that the glass container has a persistent layer homogeneity, the phrase “persistent layer homogeneity” means that the concentration of the constituent components (e.g. SiO2, Al2O3, Na2O, etc.) of the glass composition in the inner region does not vary from the concentration of the same constituent components at the midpoint of a thickness of the glass layer containing the inner region by an amount that would result in delamination of the glass body under exposure long-term to a solution contained within the glass container. For example, in embodiments where the glass container is formed from a single glass composition, the glass body contains a single layer of glass and the concentration of constituent components in the inner region is compared to the concentration of the same components in a point along the midpoint line MP which evenly divides the glass body between inner surface 104 and outer surface 106 to determine whether persistent layer homogeneity is present. However, in embodiments where the glass container is formed from laminated glass, in which a protective layer of glass of the laminated glass forms the inner surface of the glass container, the concentration of constituent components in the internal region is compared to the concentration of the same components at a point along the center point line that evenly divides the protective glass layer that forms the inner surface of the glass container. In the embodiments described herein, the persistent layer homogeneity in the inner region of the glass body is such that an extreme value (i.e., the minimum or maximum) of a layer concentration of each of the constituent components of the glass composition glass in the inner region 120 is greater than or equal to about 80% and less than or equal to about 120% of the same constituent component at a midpoint of the glass layer that contains the inner region 120. Persistent layer homogeneity, for use in the present invention, refers to the state of the glass container when the glass container is in an as-formed condition or after one or more surface treatments applied to at least the inner surface of the glass container, such as etching, or the like. In other embodiments, the persistent layer homogeneity in the inner region of the glass body is such that the extreme value of the layer concentration of each of the constituent components of the glass composition in the inner region 120 is greater than or equal to about 90 % and less than or equal to about 110% of the same constituent component at the midpoint of the thickness of the glass layer containing the inner region 120. In still other embodiments, the persistent layer homogeneity in the inner region of the glass body is such such that the extreme value of the layer concentration of each of the constituent components of the glass composition in the inner region 120 is greater than or equal to about 92% and less than or equal to about 108% of the same constituent component at the midpoint of the thickness of the glass layer of the glass containing the inner region 120. In some embodiments, persistent layer homogeneity is unique to constituent components of the glass composition that are are present in an amount less than about 2 mol %.
[0117] The term "as-formed condition", for use in the present invention, refers to the composition of the glass container 100 after the glass container has been formed from the glass stock, but before the container is exposed to any steps of further processing, such as ion exchange reinforcement, coating, ammonium sulfate treatment, or the like. In some embodiments, the term "as-formed condition" includes the composition of the glass container 100 after the glass container has been formed and exposed to an etching treatment to selectively remove all or a portion of at least the inner surface of the glass container. glass. In the embodiments described herein, the layer concentration of the constituent components in the glass composition is determined by taking a sample of the composition across the thickness of the glass body in the area of interest using dynamic secondary ion mass spectroscopy ( DSIMS). In the embodiments described herein, the composition profile is sampled from areas of the inner surface 104 of the glass body 102. The sampled areas have a maximum area of 1 mm 2 . This technique yields a profile of species composition in the glass as a function of depth from the inner surface of the glass body to the sampled area.
[0118] Forming the glass container with a persistent layer homogeneity as described above generally improves the glass container's resistance to delamination. Specifically, providing an inner region that is homogeneous in composition (i.e., the extreme value of the concentration of the constituent components in the inner region is within +/- 20% of the same constituent components at the midpoint of the thickness of the glass layer that contains the inner region) prevents the localized concentration of constituent components of the glass composition, which may be susceptible to leaching which, in turn, attenuates the loss of glass particles from the inner surface of the glass container, in the event that that these constituent components are leached from the glass surface.
[0119] As noted herein, the container with persistent layer homogeneity in as-formed condition is free of coatings, which include inorganic and/or organic coatings applied to the inner surface of the glass body. Accordingly, it should be understood that the body of the glass container is formed from a substantially unitary composition that extends from the inner surface of the body to a depth of at least 250 nm or up to at least 300 nm. The term “unit composition” refers to the fact that the glass from which the portion of the body that extends from the inner surface in the thickness of the body, to a depth of at least 250 nm or up to at least 300 nm, a single material composition is formed compared to a coating material applied to another material of the same or different composition. For example, in some embodiments, the container body may be constructed from a single glass composition. In other embodiments, the container body may be constructed from laminated glass such that the inner surface of the body has a unitary composition that extends from the inner surface to a depth of at least 250 nm or up to at least 300 nm. The glass container may include an inner region that extends from the inner surface or from 10 nm below the inner surface to a depth of at least 100 nm, as noted above. This inner region may have a persistent layer homogeneity.
[0120] Now referring to Figures 1 and 7, in some embodiments, the glass containers described herein may also have a homogeneous surface composition over the inner surface 104 of the body 102 such that at least the inner surface 104 of the body 102, which includes the wall, heel and base portions, has a delamination factor of 10 or less when the glass container is in as-formed condition. Figure 7 schematically represents a partial cross-section of a wall portion 110 of the glass container 100. The glass container 100 has a surface region 130 that extends over the entire inner surface of the glass container. The surface region 130 has a depth DSR that extends from the inner surface 104 of the glass container 100 by a thickness of the glass body towards the outer surface. Accordingly, it should be understood that the surface region 130 has a thickness TSR that is equal to the depth DSR. In some embodiments, the surface region extends to a depth DSR of at least about 10 nm from the inner surface 104 of the glass container 100. In some other embodiments, the surface region 130 may extend to a depth DSR of at least about 50 nm. In some other embodiments, the surface region 130 may extend to a depth DSR from about 10 nm to about 50 nm. Consequently, it should be understood that the surface region 130 extends to a shallower depth than the inner region 120. The surface region's glass composition has a persistent surface homogeneity that, together with the DSR depth of the inner region , is sufficient to prevent delamination of the glass body after long-term exposure to a solution contained in the inner volume of the glass container.
[0121] In the embodiments described herein, the phrase "persistent surface homogeneity" means that the concentration of the constituent components (eg, SiO2, Al2O3, Na2O, etc.) of the glass composition at a discrete point in the surface region does not varies from the concentration of the same constituent components at any second discrete point in the surface region by an amount that would result in delamination of the glass body under long-term exposure to a solution contained within the glass vessel. In the embodiments described herein, the persistent surface homogeneity in the surface region is such that, for a discrete point on the inner surface 104 of the glass container, the extreme value (i.e., the minimum or maximum) of the concentration of surface of each of the constituent components in surface region 130 at a discrete point is greater than or equal to about 70% and less than or equal to about 130% of the same constituent components in surface region 130 at any second discrete point on the surface internal 104 of the glass container 100 when the glass container 100 is in an as-formed condition. For example, Figure 7 depicts three discrete points (A, B and C) on the inner surface 104 of the wall portion 110. Each point is separated from an adjacent point by at least about 3 mm. The extreme value of the surface concentration of each of the constituent components in the surface region 130 at point "A" is greater than or equal to about 70% and less than or equal to about 130% of the same constituent components in the surface region 130 at points “B” and “C”. When referring to the heel portion of the container, discrete points may be approximately centered at the apex of the heel with adjacent points located at least 3 mm from the apex of the heel along the base portion of the container and along the wall portion. of the container, the distance between the points being limited by the radius of the container and the height of the side wall (i.e. the point where the side wall passes over the shoulder of the container).
[0122] In some embodiments, the persistent surface homogeneity in the surface region is such that the extreme value of the surface concentration of each of the constituent components of the glass composition in the surface region 130 for any discrete point on the inner surface 104 of the glass container 100 is greater than or equal to about 75% and less than or equal to about 125% of the same constituent component in the surface region 130 at any second discrete point on the inner surface 104 of the glass container 100. In some other In embodiments, the persistent surface homogeneity in the surface region is such that the extreme value of the surface concentration of each of the constituent components of the glass composition in the surface region 130 for any discrete point on the inner surface 104 of the glass container 100 is greater than or equal to about 80% and less than or equal to about 120% of the same constituent component in the region of surface 130 at any second discrete point on the inner surface 104 of the glass container 100. In still other embodiments, the persistent surface homogeneity in the surface region is such that the extreme value of the surface concentration of each of the constituent components of the glass composition in surface region 130 for any discrete point on inner surface 104 of glass container 100 is greater than or equal to about 85% and less than or equal to about 115% of the same constituent component in surface region 130 at any second discrete point on the inner surface 104 of the glass container 100. In the embodiments described herein, the surface concentration of the constituent components of the glass composition in the surface region is measured by X-ray excited photoelectron spectroscopy. In some embodiments, persistent surface homogeneity in the surface region is unique to const components components of the glass composition that are present in an amount less than about 2 mol%.
[0123] The homogeneity of the surface concentration of the constituent glass components in the surface region 130 is generally an indication of the propensity of the glass composition to delaminate and loosen glass particles from the inner surface 104 of the glass container 100. When the composition glass has persistent surface homogeneity in the surface region 130 (i.e., when the extreme value of the surface concentration of the constituent glass components in the surface region 130 at a discrete point on the inner surface 104 is within +/-30 % of the same constituent components in surface region 130 at any second discrete point on inner surface 104), the glass composition has improved resistance to delamination.
[0124] Glass containers that have persistent layer homogeneity and/or persistent surface homogeneity can be achieved using a variety of techniques. For example, in some embodiments, at least the inner surface 104 of the body 102 of the glass container is etched, which produces a glass container that has persistent layer homogeneity and/or persistent surface homogeneity such that at least unless the inner surface of the glass container has a delamination factor of 10 or less. Specifically, compositional variations in the glass due to volatilization of species from the glass and subsequent redeposition of the volatilized species during container formation, as described above, are believed to be a mechanism leading to delamination. The thin liner of volatilized and redeposited species onto the inner surface of the glass container is heterogeneous in composition and hydrolytically weak, such that alkaline and boron species are rapidly depleted from the liner during exposure to pharmaceutical compositions. This behavior leaves behind a silica-rich layer with a high surface area. Exposure of this silica-rich layer to a pharmaceutical composition causes the layer to swell and ultimately detach (ie, delaminate) from the inner surface of the body. However, etching the inner surface of the glass container body removes that thin liner layer and imparts persistent layer homogeneity and/or persistent surface homogeneity to at least the inner surface of the glass container body.
[0125] In some embodiments described herein, the body of the glass container is etched to remove a layer of glass material from the inner surface of the glass body. The etching is sufficient to remove the thin liner layer of volatilized and redeposited species and thereby provide persistent layer homogeneity and/or persistent surface homogeneity to at least the inner surface of the glass container body, such that that at least the inner surface of the glass body has a delamination factor of 10 or less. For example, in some embodiments, the glass container body is etched to remove glass material from the inner surface of the glass body to a depth of 1 μm or even 1.5 μm. In some other embodiments, the body of the glass container may be etched to remove glass material to a depth greater than 1.5 μm, which includes, without limitation, 2 μm, 3 μm, or even 5 μm. In these embodiments, at least the inner surface of the glass container may be formed from glass compositions that meet the criteria for Type I, Class A (Type IA) or Type I, Class B (Type IB) glass under the standard ASTM E438-92 (2011) titled “Standard Specification for Glasses in Laboratory Apparatus”. Borosilicate glasses meet Type I criteria (A or B) and are commonly used for pharmaceutical packaging. Examples of borosilicate glasses include, without limitation, Corning® Pyrex® 7740, 7800, Wheaton 180, 200 and 400, Schott Duran®, Schott Fiolax®, KIMAX® N-51A, Gerresheimer GX-51 Flint and others.
[0126] In one embodiment, etching can be performed by exposing the inner surface of the glass container to an acidic solution, or a combination of acidic solutions. Acidic solutions may include, without limitation, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid and phosphoric acid. For example, the acidic solution may include a mixture of 1.5M hydrofluoric acid and 0.9M sulfuric acid. These acidic solutions effectively remove the thin liner layer of volatilized and redeposited organic solution without leaving a depleted “leach layer” on the inner surface of the glass vessel. Alternatively, etching can be performed by exposing the inner surface of the glass container to a base solution or a combination of base solutions. Suitable base solutions include, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof. Alternatively, etching can be carried out by sequentially acidic solutions followed by base solutions or vice versa.
[0127] While a specific recording treatment is described in this document, it should be understood that other recording treatments may also be used. For example, the etching treatments disclosed in patent no. U.S. 2,106,744, patent publication no. U.S. 2011/0165393, patent publication no. U.S. 2013/0122306 and patent publication no. U.S. 2012/0282449 can also be used to etch at least the inner surface of the glass container.
[0128] In still other embodiments, the glass containers may be provided with persistent layer homogeneity and/or persistent surface homogeneity by forming the glass containers from glass compositions in which the constituent components of the glass composition form species with relatively low vapor pressures (ie, species with a low volatility) at the temperatures required to reform glass containers from glass stock into the desired container shape. Due to the fact that these constituent components form species with relatively low vapor pressures at reforming temperatures, the constituent components are less likely to volatilize and evaporate from the glass surfaces, thus forming a glass vessel with a homogeneous surface. in terms of composition on the inner surface of the glass container and across the thickness of the glass container.
[0129] Certain constituent components of the glass composition can be sufficiently volatile at the temperatures of glass formation and reforming which, in turn, can lead to compositional heterogeneities and subsequent delamination. The temperatures of forming and reforming the glass composition generally correspond to the temperatures at which the glass composition has a viscosity in the range from about 200 poise to about 100 kilopoise. Consequently, in some embodiments, the glass compositions from which the glass containers are formed are free of constituent components that form species that significantly volatilize (i.e., form gas-phase species with equilibrium partial pressures greater than about 10 -3 atm) at temperatures corresponding to a viscosity in the range from about 200 poise to about 100 kilopoise. In some embodiments, the glass compositions from which the glass containers are formed are free of constituent components that volatilize significantly at temperatures corresponding to a viscosity in the range from about 1 kilopoise to about 50 kilopoise. In some other embodiments, the glass compositions from which the glass containers are formed are free of constituent components that volatilize significantly at temperatures corresponding to a viscosity in the range from about 1 kilopoise to about 20 kilopoise. In some other embodiments, the glass compositions from which the glass containers are formed are free of constituent components that volatilize significantly at temperatures corresponding to a viscosity in the range from about 1 kilopoise to about 10 kilopoise. Without being bound by theory, compounds that significantly volatilize under these conditions include, without limitation, boron and boron compounds, phosphorus and phosphorus compounds, zinc and zinc compounds, fluorine and fluorine compounds, chlorine and chlorine compounds, tin and tin compounds, and sodium and sodium compounds.
[0130] In some embodiments described herein, glass containers are generally formed from aluminosilicate glass compositions, such as alkali aluminosilicate glass compositions or alkaline earth aluminosilicate glass compositions, for example. As noted earlier in that document, boron-containing species in glass are highly volatile at the elevated temperatures used for glass forming and reforming, which leads to delamination of the resulting glass container. Furthermore, boron-containing glass compositions are also susceptible to phase separation. Accordingly, in the embodiments described herein, the concentration of boron in the glass compositions from which the glass containers are formed is limited to attenuate both delamination and phase separation. In some embodiments, the glass compositions from which the glass containers are formed include less than or equal to about 1.0 mol% boron oxides and/or boron-containing compounds, which include, without limitation, B2O3. In some of these embodiments, the concentration of boron oxides and/or boron-containing compounds in the glass composition may be less than or equal to about 0.5 mol%, less than or equal to about 0.4 mol%, or even less. or equal to about 0.3 mol%. In some such embodiments, the concentration of boron oxides and/or boron-containing compounds in the glass composition can be less than or equal to about 0.2 mol% or even less than or equal to about 0.1 mol%. In some other embodiments, the glass compositions are substantially free of boron and boron-containing compounds.
[0131] Phosphorus, similar to boron, generally forms species in the glass composition that are highly volatile at the elevated temperatures used for forming and reforming glass. As such, phosphorus in the glass composition can lead to compositional inhomogeneities in the finished glass container, which in turn can lead to delamination. Accordingly, in the embodiments described herein, the concentration of phosphorus and phosphorus-containing compounds (such as P2O5, or the like) in the glass compositions from which the glass containers are formed is limited to attenuate delamination. In some embodiments, the glass compositions from which the glass containers are produced include less than or equal to about 0.3 mol% phosphorus oxides and/or phosphorus-containing compounds. In some such embodiments, the concentration of phosphorus oxides and/or phosphorus-containing compounds in the glass composition may be less than or equal to about 0.2 mol% or even less than or equal to about 0.1 mol%. In some other embodiments, the glass compositions are substantially free of phosphorus and phosphorus-containing compounds.
[0132] Zinc, similar to boron and phosphorus, generally forms species in the glass composition that are highly volatile at the elevated temperatures used for glass forming and reforming. As such, zinc in the glass composition can lead to compositional inhomogeneities in the finished glass container, which in turn can lead to delamination. Accordingly, in the embodiments described herein, the concentration of zinc and zinc-containing compounds (such as ZnO, or the like) in the glass compositions from which the glass containers are formed is limited to attenuate delamination. In some embodiments, the glass compositions from which the glass containers are produced include less than or equal to about 0.5 mol% zinc oxides and/or zinc-containing compounds. In some other embodiments, the glass compositions from which the glass containers are produced include less than or equal to about 0.3 mol% zinc oxides and/or zinc-containing compounds. In some of these embodiments, the concentration of zinc oxides or zinc-containing compounds in the glass composition can be less than or equal to about 0.2 mol% or even less than or equal to about 0.1 mol%. In some other embodiments, the glass compositions are substantially free of zinc and zinc-containing compounds.
[0133] Lead and bismuth also form species in glass composition that are highly volatile at the elevated temperatures used for glass formation and reforming. Accordingly, in the embodiments described herein, the concentration of lead, bismuth, lead-containing compounds and bismuth-containing compounds in the glass compositions from which the glass containers are formed is limited to attenuate delamination. In some embodiments, the lead oxides, bismuth oxides, lead-containing compounds, and/or bismuth-containing compounds are each present in the glass compositions in concentrations less than or equal to about 0.3 mol%. In some of these embodiments, the lead oxides, bismuth oxides, lead-containing compounds, and/or bismuth-containing compounds are each present in the glass compositions in concentrations less than or equal to about 0.2 mol% or even concentrations less than about 0.1 mol %. In some other embodiments, the glass compositions are substantially free of lead and/or bismuth and compounds that contain lead and/or bismuth.
[0134] Species containing chlorine, fluorine and tin oxides are also highly volatile at the high temperatures used for glass formation and reforming. Accordingly, in the embodiments described herein, chlorine, fluorine and tin oxides and compounds containing tin, chlorine or fluorine are present in the glass compositions in concentrations that do not affect the delamination resistance of the resulting glass. Specifically, chlorine, fluorine and tin oxides and compounds containing tin, chlorine or fluorine, are present in the glass compositions from which the glass containers are formed in concentrations less than or equal to about 0.5 mol% or even less than or equal to about 0.3 mol%. In some embodiments, the glass compositions are substantially free of tin, chlorine and fluorine and compounds containing tin, chlorine or fluorine.
[0135] While some embodiments of the glass container may be free of readily volatilized constituent components as described above, in certain other embodiments, the glass containers may be formed from glass compositions that include such volatile constituents, such as when the glass container includes a barrier layer.
[0136] The glass compositions from which the containers are formed are not separated by are phase. The term "phase-separated" for use in the present invention refers to the separation of the glass composition into separate phases with each phase having different compositional characteristics. For example, alkali borosilicate glasses are generally known to phase separate at elevated temperatures (such as the forming and reforming temperatures) into a boron-rich phase and a silica-rich phase. In some embodiments described herein, the concentration of boron oxides in the glass compositions is low enough (i.e., less than or equal to about 1.0 mol%) such that the glass compositions do not undergo separation. of phase.
[0137] In an exemplary embodiment, the glass containers are formed from a delamination resistant glass composition, such as the alkaline earth aluminosilicate glass compositions described in patent application no. U.S. 13/660,141 filed on October 25, 2012 and entitled “Alkaline Earth Alumino-Silicate Glass Compositions with Improved Chemical and Mechanical Durability” (legal registration number SPl 1-241), the entirety of which is incorporated herein by reference . This first exemplary glass composition generally includes a combination of SiO2 , Al2O3 , at least one alkaline earth oxide and alkaline oxide which includes at least Na2O and K2O. In some embodiments, the glass compositions may also be free of boron and boron-containing compounds. The combination of these components makes possible a glass composition that is resistant to chemical degradation and is also suitable for chemical reinforcement by ion exchange. In some embodiments, the glass compositions may additionally comprise minor amounts of one or more additional oxides, such as, for example, SnO2 , ZrO2 , ZnO, or the like. These components may be added as refining agents and/or to further enhance the chemical durability of the glass composition.
[0138] In embodiments of the first exemplary glass composition, the glass composition generally comprises SiO2 in an amount greater than or equal to about 65 mol% and less than or equal to about 75 mol%. In some embodiments SiO2 is present in the glass composition in an amount greater than or equal to about 67 mol% and less than or equal to about 75 mol%. In some other embodiments, SiO2 is present in the glass composition in an amount greater than or equal to about 67 mol% and less than or equal to about 73 mol%. In each of these embodiments, the amount of SiO2 present in the glass composition can be greater than or equal to about 70 mol% or even greater than or equal to about 72 mol%.
[0139] The first exemplary glass composition also includes Al2O3. Al2O3, together with alkaline oxides present in glass compositions, such as Na2O, or similar, improves the susceptibility of glass to ion exchange reinforcement. Furthermore, additions of Al2O3 to the composition reduce the propensity of alkaline constituents (such as Na and K) to leach out of the glass and, as such, additions of Al2O3 increase the resistance of the composition to hydrolytic degradation. Furthermore, additions of Al2O3 greater than about 12.5 mol % can also increase the softening point of the glass, thus reducing the glass forming ability. Accordingly, the glass compositions described herein generally include Al2O3 in an amount greater than or equal to about 6 mol% and less than or equal to about 12.5 mol%. In some embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 6 mol% and less than or equal to about 10 mol%. In some other embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 7 mol% and less than or equal to about 10 mol%.
[0140] The first exemplary glass composition also includes at least two alkali oxides. Alkaline oxides facilitate the ion exchange capacity of the glass composition and, as such, facilitate the chemical reinforcement of the glass. Alkaline oxides also reduce the softening point of the glass, thus compensating for the increase in the softening point due to the higher concentrations of SiO2 in the glass composition. Alkaline oxides also help to improve the chemical durability of the glass composition. Alkaline oxides are generally present in the glass composition in an amount greater than or equal to about 5 mol% and less than or equal to about 12 mol%. In some of these embodiments, the amount of alkali oxides may be greater than or equal to about 5 mol% and less than or equal to about 10 mol%. In some other embodiments, the amount of alkali oxide can be greater than or equal to about 5 mol% and less than or equal to about 8 mol%. In all glass compositions described herein, the alkali oxides comprise at least Na2O and K2O. In some embodiments, the alkali oxides additionally comprise Li2O.
[0141] The ion exchange capacity of the glass composition is mainly imparted to the glass composition by the amount of alkali oxide Na2O initially present in the glass composition before the ion exchange. Specifically, in order to achieve the desired compression stress and layer depth in the glass composition under ion exchange reinforcement, the glass compositions include Na2O in an amount greater than or equal to about 2.5 mol % and less than or equal to about 10 mol % based on the molecular weight of the glass composition. In some embodiments, the glass composition may include Na2O in an amount greater than or equal to about 3.5 mol% and less than or equal to about 8 mol%. In some of these embodiments, the glass composition may include Na2O in an amount greater than or equal to about 6 mol% and less than or equal to about 8 mol%.
[0142] As noted above, the salt oxides in the glass composition also include K2O. The amount of K2O present in the glass composition also refers to the ion exchange capacity of the glass composition. Specifically, as the amount of K2O present in the glass composition increases, the compressive stress obtainable through ion exchange decreases. Consequently, it is desirable to limit the amount of K2O present in the glass composition. In some embodiments, the amount of K2O is greater than 0 mol% and less than or equal to about 2.5 mol% by molecular weight of the glass composition. In some of these embodiments, the amount of K 2 O present in the glass composition is less than or equal to about 0.5 mol% by molecular weight of the glass composition.
[0143] In some embodiments, the alkali oxide in the first exemplary glass composition additionally comprises Li2O. The inclusion of Li2O in the glass composition additionally lowers the softening point of the glass. In embodiments where the alkali oxide includes Li2O, the Li2O may be present in an amount greater than or equal to about 1 mol% and less than or equal to about 3 mol%. In some embodiments, Li2O may be present in the glass composition in an amount that is greater than about 2 mol% and less than or equal to about 3 mol%. However, in some other embodiments, the glass composition may be substantially free of lithium and lithium-containing compounds.
[0144] The alkaline earth oxides in the first exemplary glass composition enhance the meltability of batch glass materials and increase the chemical durability of the glass composition. The presence of alkaline earth oxides in the glass composition also reduces the susceptibility of glass to delamination. In the glass compositions described herein, the glass compositions generally include at least one alkaline earth oxide in a concentration greater than or equal to about 8 mol % or up to 8.5 mol % and less than or equal to about 15 mol %. . In some embodiments, the glass composition may comprise from about 9 mol% to about 15 mol% alkaline earth oxide. In some of these embodiments, the amount of alkaline earth oxide in the glass composition can be from about 10 mol% to about 14 mol%.
[0145] The alkaline earth oxide in the first exemplary glass composition may include MgO, CaO, SrO, BaO or combinations thereof. For example, in the embodiments described herein, the alkaline earth oxide may include MgO. In some embodiments, MgO may be present in the glass composition in an amount that is greater than or equal to about 2 mol% and less than or equal to about 7 mol% by molecular weight of the glass composition, or even greater than or equal to about 7 mol% by molecular weight of the glass composition. of 3 mol % and less than or equal to about 5 mol % by molecular weight of the glass composition.
[0146] In some embodiments, the alkaline earth oxide in the first exemplary glass composition also includes CaO. In such embodiments, CaO is present in the glass composition in an amount from about 2 mol% to less than or equal to 7 mol% by molecular weight of the glass composition. In some embodiments, CaO is present in the glass composition in an amount from about 3 mol% to less than or equal to 7 mol% by molecular weight of the glass composition. In some of these embodiments, CaO may be present in the glass composition in an amount greater than or equal to about 4 mol% and less than or equal to about 7 mol%. In some other embodiments, CaO may be present in the glass composition in an amount greater than or equal to about 5 mol% and less than or equal to about 6 mol%, such as when CaO is used in place of MgO in the alkaline earth oxide. to decrease the liquidus temperature and increase the liquidus viscosity. In still other embodiments, CaO may be present in the glass in an amount greater than or equal to about 2 mol % and less than or equal to about 5 mol %, such as when SrO is used in place of MgO in alkaline earth oxide to decrease the liquidus temperature and increase the liquidus viscosity.
[0147] In some embodiments described herein, the alkaline earth oxide additionally comprises at least one of SrO or BaO. The inclusion of SrO reduces the liquidus temperature of the glass composition and, as a result, improves the formability of the glass composition. In some embodiments, the glass composition may include SrO in an amount greater than 0 mol% and less than or equal to about 6.0 mol%. In some other embodiments, the glass composition may include SrO in an amount greater than about 0 mol% and less than or equal to about 5 mol%. In some of these embodiments, the glass composition may include greater than or equal to about 2 mol% and less than or equal to about 4 mol% SrO, such as when CaO is used in place of MgO in the alkaline earth oxide to lower the temperature. liquidus and increase the liquidus viscosity. In some other embodiments, the glass composition may include from about 1 mol% to about 2 mol% SrO. In still other embodiments, SrO may be present in the glass composition in an amount greater than or equal to about 3 mol% and less than or equal to about 6 mol%, such as when SrO is used in place of MgO in alkaline earth oxide. to decrease the liquidus temperature and increase the liquidus viscosity.
[0148] In embodiments where the glass composition includes BaO, the BaO may be present in an amount greater than about 0 mol % and less than about 2 mol %. In some of these embodiments, BaO may be present in the glass composition in an amount less than or equal to about 1.5 mol% or even less than or equal to about 0.5 mol%. However, in some other embodiments, the glass composition is substantially free of barium and barium compounds.
[0149] In the embodiments of the glass compositions described herein, the glass compositions generally contain less than about 1 mol% boron or boron oxides, such as B2O3. For example, in some embodiments, the glass compositions may comprise greater than or equal to about 0 mol% B2O3 and less than or equal to 1 mol% B2O3. In some other embodiments, the glass compositions may comprise greater than or equal to about 0 mol% B2O3 and less than or equal to 0.6 mol% B2O3. In still other embodiments, the glass compositions are substantially free of boron and boron compounds, such as B2O3. Specifically, it has been found that forming the glass composition with a relatively low amount of boron or boron compounds (i.e., less than or equal to 1 mol%) or without boron or boron compounds significantly increases the chemical durability of the glass composition. glass. In addition, it has also been determined that forming the glass composition with a relatively low amount of boron or boron compounds or without boron or boron compounds improves the ion exchange capacity of the glass compositions by reducing the process time. and/or temperature required to achieve a specific value of compression stress and/or layer depth.
[0150] In some embodiments of the glass compositions described herein, the glass compositions are substantially free of phosphorus and phosphorus-containing compounds that include, without limitation, P2O5. Specifically, it has been determined that the formulation of the glass composition without phosphorus or phosphorus compounds increases the chemical durability of the glass composition.
[0151] In addition to SiO2, Al2O3, alkali oxides and alkaline earth oxides, the first exemplary glass compositions described herein may optionally further comprise one or more refining agents, such as, for example, SnO2, As2O3 and/or CI- (from NaCl, or similar). When a refining agent is present in the glass composition, the refining agent may be present in an amount less than or equal to about 1 mol% or even less than or equal to about 0.5 mol%. For example, in some embodiments, the glass composition may include SnO2 as a refining agent. In these embodiments, SnO2 may be present in the glass composition in an amount greater than about 0 mol % and less than or equal to about 0.30 mol %.
[0152] Furthermore, the glass compositions described herein may comprise one or more additional metal oxides to further enhance the chemical durability of the glass composition. For example, the glass composition may additionally include ZnO or ZrO2, each of which further improves the resistance of the glass composition to chemical attack. In such embodiments, the additional metal oxide may be present in an amount that is greater than or equal to about 0 mol% and less than or equal to about 2.0 mol%. For example, when the additional metal oxide is ZrO2, the ZrO2 may be present in an amount less than or equal to about 1.5 mol%. Alternatively or additionally, the additional metal oxide may include ZnO in an amount less than or equal to about 2.0 mol%. In some embodiments, ZnO may be included as a substitute for one or more of the alkaline earth oxides. For example, in embodiments where the glass composition includes the alkaline earth oxides MgO, CaO and SrO, the amount of MgO can be reduced to lower the liquidus temperature and increase the liquidus viscosity, as described above. In these embodiments, ZnO may be added to the glass composition as a partial replacement for MgO, in addition to or in place of at least one of CaO or SrO.
[0153] Based on the foregoing, it should be understood that, in one embodiment, the first exemplary glass composition may include from about 65 mol% to about 75 mol% SiO2; from about 6 mol% to about 12.5 mol% Al2O3; and from about 5 mol% to about 12 mol% alkali oxide, wherein the alkali oxide comprises Na2O and K2O. K2O may be present in an amount less than or equal to 0.5 mol %. The glass composition can also include from about 8.0 mol% to about 15 mol% alkaline earth oxide. The glass composition may be susceptible to ion exchange reinforcement.
[0154] In another embodiment of the first exemplary glass composition, the glass composition includes from about 67 mol% to about 75 mol% SiO2; from about 6 mol% to about 10 mol% Al2O3; from about 5 mol% to about 12 mol% alkali oxide; and from about 9 mol% to about 15 mol% alkaline earth oxide. The alkaline oxide comprises at least Na2O and K2O. The glass composition is free of boron and boron compounds and is susceptible to ion exchange, thus facilitating chemical reinforcement of the glass to improve mechanical durability.
[0155] In yet another embodiment of the first exemplary glass composition, the glass composition can include from about 67 mol% to about 75 mol% SiO2; from about 6 mol% to about 10 mol% Al2O3; from about 5 mol% to about 12 mol% alkali oxide; and from about 9 mol% to about 15 mol% alkaline earth oxide. The alkaline earth oxide comprises at least one of SrO and BaO. The glass composition is free of boron and boron compounds and is susceptible to ion exchange, thus facilitating chemical reinforcement of the glass to improve mechanical durability.
[0156] In some embodiments described in this document, glass containers with persistent surface homogeneity and/or persistent layer homogeneity can be obtained using forming processes that provide a uniform temperature history for at least the inner surface of the body of the glass container. For example, in one embodiment, the glass container body can be formed at formation temperatures and/or formation rates that attenuate the volatilization of chemical species from the glass composition from which the body is formed. Specifically, forming a flow of glass into a desired shape requires controlling both the viscosity of the glass and the rate of formation. Higher viscosities require slower formation rates, while lower viscosities enable faster formation rates. The volume composition of the glass and temperature are the biggest drivers to affect viscosity. It is possible to use the same forming process for different glasses by adapting the viscosities at each stage in the forming process by adjusting the temperature. Consequently, one approach to reducing volatilization from a glass melt is to operate the process at a lower temperature (higher viscosity). This approach is disadvantageous due to the fact that it requires reducing the throughput speed and capacity of the training equipment, ultimately leading to increased cost. Figure 16 shows that temperature is a major driver for volatilization in two exemplary compositions, and that in all cases reducing temperature (and therefore speed) reduces the driving force for loss of volatilization. The viscosity associated with tube-to-conceptacle conversion processes ranges from 200 P (higher temperature, in cutting and drilling operations) to 20,000 P (lower temperature, in tube forming and finishing stages). For typical expansion borosilicates, these viscosities are approximately 1100 to 1650°C. Since volatilization is significantly reduced at lower temperatures, the primary temperature range of interest lies between 1350 to 1650 °C.
[0157] In another embodiment, glass containers with persistent surface homogeneity and/or persistent layer homogeneity can be obtained by molding the body. There are several methods to form a glass melt into a container shape using molds. All rely on introducing a uniformly hot “portion” of molten glass to a forming machine. In blow and blow molding, the portion is first blown using pressurized air through an orifice (which forms the edge/finish) to create a preform (smaller than the final product). The preform (or parison) is then placed in a second mold where it is additionally blown into contact with the mold surface and defines the final shape of the container. In press blow molding, the portion is held by a ring defining the recall/finish and a plunger is pressed through the portion to form the preform. The preform is then placed in the second mold and blown into contact with the mold surface, forming the final container shape. The mold forming process generally imparts a uniform temperature history to the body during forming, which in turn may impart persistent surface homogeneity and/or persistent layer homogeneity to at least the inner surface of the body. of glass, thus decreasing the susceptibility of the glass body to delamination. For example, molten glass can be formed into a container shape and the temperature of the glass controlled during cooling such that the glass body is monotonically cooled from the glass melt. Monotonic cooling occurs when the temperature of the glass body is lowered from melting to solidification without any intermediate increase in temperature. This results in less volatilization compared to processes that convert tubes to conceptacles. This type of cooling can be facilitated with the use of mold forming processes such as blow molding, press and blow molding, blow molding and blow molding. In some embodiments, these techniques can be used to form a glass container with a delamination factor of 10 or less from Type I Class B glass compositions.
[0158] The glass compositions described herein are formed by mixing a batch of glass raw materials (e.g. SiO2 powders, Al2O3, alkali oxides, alkaline earth oxides and the like) in such a way that the batch of materials glass raw materials have the desired composition. Thereafter, the batch of glass raw materials is heated to form a molten glass composition which is subsequently cooled and solidified to form the glass composition. During solidification (i.e., when the glass composition is plastically deformable), the glass composition can be formed using standard forming techniques to shape the glass composition into a desired final shape. Alternatively, the glass composition may be formed into a stock form, such as a slide, tube, or the like, and subsequently reheated and formed in the glass container 100.
[0159] The glass compositions described herein can be formed into various shapes, such as, for example, sheets, tubes, or the like. Chemically durable glass compositions are particularly well suited for use in forming pharmaceutical packages to contain a pharmaceutical formulation, such as liquids, powders, and the like. For example, the glass compositions described herein can be used to form glass containers, such as vials, ampoules, cartridges, syringe bodies, and/or any other glass container for storing pharmaceutical formulations. Furthermore, the ability to chemically strengthen glass compositions through ion exchange can be used to improve the mechanical durability of such pharmaceutical packaging. Accordingly, it should be understood that, in at least one embodiment, glass compositions are incorporated into a pharmaceutical package in order to improve the chemical durability and/or mechanical durability of the pharmaceutical package.
[0160] Additionally, in some embodiments, glass containers may be formed from glass compositions that are chemically durable and resistant to degradation, as determined by DIN 12116, ISO 695 standard, ISO 719 standard, ISO 720 standard, test USP <660> and/or the European Pharmacopeia test 3.2.1.
[0161] Specifically, the DIN 12116 standard is a measure of the resistance of glass to decomposition when placed in acidic solution. The DIN 12116 standard is divided into individual classes. Class SI indicates weight losses of up to 0.7 mg/dm2; Class S2 indicates weight loss from 0.7 mg/dm2 to 1.5 mg/dm2; Class S3 indicates weight loss from 1.5 mg/dm 2 to 15 mg/dm 2 ; and Class S4 indicates weight loss of more than 15 mg/dm2. The glass compositions described herein have an acid resistance of class S3 or better in accordance with DIN 12116, with some embodiments having an acid resistance of at least class S2 or better or up to class SI. It should be understood that lower grade ratings have improved acid resistance performance. Consequently, a composition rated at SI has better acid resistance than a composition rated at class S2.
[0162] The ISO 695 standard is a measure of the resistance of glass to decomposition when placed in a basic solution. The ISO 695 standard is divided into individual classes. Class Al indicates weight losses of up to 75 mg/dm2; Class A2 indicates weight loss from 75 mg/dm2 to 175 mg/dm2; and Class A3 indicates weight loss of more than 175 mg/dm2. The glass compositions described herein have a base strength in accordance with the ISO 695 standard of class A2 or better, with some embodiments having a base strength of class Al. It should be understood that lower grade ratings have improved base strength performance. Consequently, a composition rated Al has better base strength than a composition rated A2.
[0163] The glass compositions from which glass containers are formed are chemically durable and resistant to degradation as determined by the ISO 720 standard. The ISO 720 standard is a measure of the resistance of glass to degradation in distilled water (ie , the hydrolytic resistance of glass). Ion-exchanged glass samples are evaluated according to the ISO 720 protocol. Ion-exchanged glass samples are evaluated with a modified ISO 720 protocol in which the glass is ground to the required grain size in the ISO 720 standard, subjected to ion exchange in a molten salt bath of 100% KNO3 at a temperature of 450 °C for at least 5 hours to induce a layer of compression stress in the individual glass grains and then tested according to the ISO 720 standard. The ISO 720 standard is divided into individual types. Type HGAl is indicative of up to 62 μg of extracted Na2O equivalent; Type HGA2 is indicative of more than 62 μg and up to 527 μg of extracted Na2O equivalent; and Type HGA3 is indicative of more than 527 μg and up to 930 μg of extracted Na2O equivalent. The glass compositions described herein have an ISO 720 hydrolytic strength of HGA2 type or better, with some embodiments having a hydrolytic strength of HGA1 type or better. It should be understood that lower grade ratings have improved hydrolytic strength performance. Consequently, a composition rated HGAl has better hydrolytic resistance than a composition rated HGA2.
[0164] The glass compositions from which glass containers are formed are also chemically durable and resistant to degradation, as determined by the ISO 719 standard. The ISO 719 standard is a measure of the resistance of glass to degradation in distilled water (ie i.e. the hydrolytic resistance of glass). Ion-exchanged glass samples are evaluated according to the ISO 719 standard. Ion-exchanged glass samples are evaluated to a modified ISO 719 standard in which the glass is ground to the required grain size in the ISO 719 standard, subjected to ion exchange in a molten salt bath of 100% KNO3 at a temperature of 450 °C for at least 5 hours to induce a layer of compression stress on the individual glass grains and then tested to the standard ISO 719. The ISO 719 standard is divided into individual types. Type HGB1 is indicative of up to 31 μg of extracted Na2O equivalent; Type HGB2 is indicative of more than 31 μg and up to 62 μg of extracted Na2O equivalent; Type HGB3 is indicative of more than 62 μg and up to 264 μg of extracted Na2O equivalent; Type HGB4 is indicative of more than 264 μg and up to 620 μg of extracted Na2O equivalent; and Type HGB5 is indicative of more than 620 μg and up to 1085 μg of extracted Na2O equivalent. The glass compositions described herein have an ISO 719 hydrolytic strength of the HGB2 type or better, with some embodiments having a hydrolytic strength of the HGB1 type. It should be understood that lower grade ratings have improved hydrolytic resistance performance. Consequently, a composition rated HGB1 has better hydrolytic resistance than a composition rated HGB2.
[0165] Regarding the USP <660> test and/or the European Pharmacopeia 3.2.1 test, the glass containers described in this document have a Type 1 chemical durability. As noted above, the USP <660> and European tests Pharmacopeia 3.2.1 are performed in intact glass containers rather than crushed glass grains and as such the USP <660> and European Pharmacopeia 3.2.1 tests can be used to directly assess the chemical durability of the inner surface of the containers of glass.
[0166] It should be understood that, when referring to the above-mentioned classifications in accordance with ISO 719, ISO 720, ISO 695 and DIN 12116, a glass composition or glass article having a specified classification of “or better” means that the Glass composition performance is as good or better as the specified rating. For example, a glass article that has an ISO 719 hydrolytic resistance of “HGB2” or better may have an ISO 719 rating of HGB2 or HGB1. DAMAGE RESISTANCE
[0167] As noted in the present document above, glass containers can be subjected to damage, such as impact damage, scratches and/or abrasions, as the containers are processed and filled. Such damage is often caused by contact between individual glass containers or contact between glass containers and manufacturing equipment. This damage often decreases the mechanical strength of the container and can lead to through-cracks that can compromise the integrity of the container's contents. Accordingly, in some embodiments described herein, the glass containers 100 additionally include a lubricious coating 160 positioned around at least a portion of the outer surface 106 of the body 102, as shown in Figure 8. In some embodiments, the lubricious coating 160 may be positioned on at least the outer surface 106 of the body 102 of the glass container, while in other embodiments, one or more intermediate coatings may be positioned between the lubricious coating and the outer surface 106 of the body 102, such as such as when an inorganic coating is used to compressively stress the surface of the body 102. The lubricious coating decreases the coefficient of friction of the portion of the body 102 with the coating and, as such, decreases the occurrence of abrasions and surface damage on the outer surface. 106 of the glass body 102. Essentially, the coating allows the container to "slide" relative to another object (or container) thus reducing the possibility of surface damage to the glass. Furthermore, the lubricious coating 160 also dampens the body 102 of the glass container 100, thus lessening the effect of blunt impact damage to the glass container.
[0168] The term lubricious, for use in the present invention, means that the coating applied to the outer surface of the glass container has a lower coefficient of friction than the uncoated glass container, thus providing the glass container with improved resistance to wear. damage such as scratches, abrasions or the like.
[0169] Various properties of coated glass containers (i.e., coefficient of friction, horizontal compression force, 4-point bending force, transparency, colorlessness, and the like) can be measured when coated glass containers are in a as coated condition (i.e. after application of the coating without any further treatment) or after one or more processing treatments, such as those similar or identical to treatments performed in a pharmaceutical filling line, which includes, without limitation, washing, lyophilization, depyrogenization, autoclaving, or the like.
[0170] Depyrogenization is a process in which chepyrogens are removed from a substance. Depyrogenization of glass articles, such as pharmaceutical packaging, can be accomplished by a heat treatment applied to a sample, whereby the sample is heated to an elevated temperature for a period of time. For example, depyrogenization can include heating a glass vessel to a temperature between about 250°C and about 380°C for a period of time from about 30 seconds to about 72 hours, which includes, without limitation, 20 minutes, 30 minutes 40 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, 48 hours and 72 hours. After heat treatment, the glass vessel is cooled to room temperature. A conventional depyrogenization condition commonly employed in the pharmaceutical industry is heat treatment at a temperature of about 250 °C for about 30 minutes. However, it is contemplated that the heat treatment time may be reduced if higher temperatures are used. Coated glass containers as described herein may be exposed to elevated temperatures for a period of time. The elevated temperatures and heating time periods described herein may or may not be sufficient to depyrogen a glass vessel. However, it should be understood that certain temperatures and heating times described herein are sufficient to dehydrogenate a coated glass container, such as the coated glass containers described herein. For example, as described herein, coated glass containers can be exposed to temperatures of about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380°C, about 390°C, or about 400°C, for a period of 30 minutes.
[0171] For use in the present invention, freeze-drying conditions (i.e. freeze-drying) refer to a process in which the sample is filled with a liquid containing protein and then frozen at -100°C, followed by water sublimation for 20 hours at -15°C under vacuum.
[0172] For use in the present invention, autoclave conditions refer to the steam purging of a sample for 10 minutes at 100 °C, followed by a dwell period of 20 minutes, in which the sample is exposed to an environment of 121 °C, followed by 30 minutes of heat treatment at 121 °C.
[0173] The coefficient of friction (μ) of the portion of the glass container coated with the lubricious coating may have a lower coefficient of friction than a surface of an uncoated glass container formed from the same glass composition. A coefficient of friction (μ) is a quantitative measurement of the friction between two surfaces and is a function of the mechanical and chemical properties of the first and second surfaces, which include surface roughness as well as environmental conditions such as, but not limited to, temperature. and humidity. For use in the present invention, a coefficient of friction measurement for a coated glass container 100 is reported as the coefficient of friction between the outer surface of a first glass container (which has an outside diameter between about 16.00 mm and about 17.00 mm) and the outer surface of the second glass container, which is identical to the first glass container, wherein the first and second glass containers have the same body composition and the same coating composition ( when applied) and has been exposed to the same environments before manufacture, during manufacture and after manufacture. Except where otherwise stated herein, the coefficient of friction refers to the maximum coefficient of friction measured with a normal load of 30 N measured on a conceptcar-on-conceptacle test jig as described herein. However, it should be understood that a coated glass vessel that exhibits a maximum coefficient of friction at a specific applied load will also exhibit the same or better (ie lesser) maximum coefficient of friction at a lower load. For example, if a coated glass container exhibits a maximum coefficient of friction of 0.5 or less under an applied load of 50 N, the coated glass container will also exhibit a maximum coefficient of friction of 0.5 or less under an applied load of 50 N. applied load of 25 N.
[0174] In the embodiments described herein, the coefficient of friction of glass containers (both coated and uncoated) is measured with a concept-on-concept test template. Test template 300 is shown schematically in Figure 9. The same apparatus can also be used to measure the frictional force between two glass containers positioned on the template. The concept-on-concept test template 300 comprises a first jaw 312 and a second jaw 322 arranged in a transverse configuration. The first clamp 312 comprises a first clamp arm 314 secured to a first base 316. The first clamp arm 314 attaches to the first glass container 310 and holds the first glass container 310 stationary with respect to the first clamp 312. Similarly, the second clamp 322 comprises a second clamp arm 324 attached to a second base 326. The second clamp arm 324 attaches to the second glass container 320 and holds it stationary with respect to the second clamp 322. The first glass container 310 is positioned on the first jaw 312 and the second glass container 320 is positioned on the second jaw 322 such that the longitudinal axis of the first glass container 310 and the longitudinal axis of the second glass container 320 are positioned at about a angle of 90° with respect to the other and in a horizontal plane defined by the geometric axis xy.
[0175] A first glass container 310 is positioned in contact with the second glass container 320 at a point of contact 330. A perpendicular force is applied in a direction orthogonal to the horizontal plane defined by the geometric x-y axis. The perpendicular force may be applied by a static weight or other force applied to the second jaw 322 under a stationary first jaw 312. For example, a weight may be positioned on the second base 326 and the first base 316 may be placed on a stable surface, inducing, a measurable force between the first glass container 310 and the second glass container 320 at the point of contact 330. Alternatively, the force can be applied with a mechanical device, such as a UMT (universal mechanical tester) machine.
[0176] The first jaw 312 or second jaw 322 can be moved relative to each other in a direction that is at a 45° angle with the longitudinal axis of the first glass container 310 and the second glass container 320. For example, the first jaw 312 can be held stationary and the second jaw 322 can be moved such that the second glass container 320 moves through the first glass container 310 in the direction of the x axis. A similar configuration is described by RL De Rosa et al., in “Scratch Resistant Polyimide Coatings for Aluminum Silicate Glass surfaces” in The Journal of Adhesion, 78: 113 to 127, 2002. To measure the coefficient of friction, the force required to moving the second claw 322 and the perpendicular force applied to the first and second glass containers 310, 320 are measured with load cells and the coefficient of friction is calculated as the quotient of the friction force and the perpendicular force. The jig is operated in an environment of 25 °C and 50% relative humidity.
[0177] In the embodiments described herein, the portion of the glass container coated with the lubricious coating has a coefficient of friction less than or equal to about 0.7 relative to a similar coated glass container, as determined with the conceptacle upon conceptacle described above. In other embodiments, the coefficient of friction can be less than or equal to about 0.6, or even less than or equal to about 0.5. In some embodiments, the portion of the glass container coated with the lubricious coating has a coefficient of friction less than or equal to about 0.4 or even less than or equal to about 0.3. Coated glass containers with coefficients of friction less than or equal to about 0.7 generally exhibit improved resistance to frictional damage and, as a result, have improved mechanical properties. For example, conventional glass containers (without a lubricious coating) can have a coefficient of friction greater than 0.7.
[0178] In some embodiments described herein, the coefficient of friction of the portion of the glass container coated with the lubricious coating is at least 20% less than a coefficient of friction of a surface of an uncoated glass container formed from the same glass composition. For example, the coefficient of friction of the portion of the glass container coated with the lubricious coating may be at least 20% lower, at least 25% lower, at least 30% lower, at least 40% lower, or even at least 50% lower. that a coefficient of friction of a surface of an uncoated glass container formed from the same glass composition.
[0179] In some embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7 after exposure to a temperature of about 250°C, about 260°C , about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C, or about 400 °C, for a period of time of 30 minutes (i.e., depyrogenation conditions ). In other embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7, (i.e., less than or equal to about 0.6, less than or equal to about 0.6). of 0.5, less than or equal to about 0.4, or even less than or equal to about 0.3) after exposure to a temperature of about 250 °C, about 260 °C, about 270 °C , about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about of 360°C, about 370°C, about 380°C, about 390°C or about 400°C, for a period of time of 30 minutes. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% after exposure to a temperature of about 260°C for 30 minutes. In other embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to a temperature of about 250 °C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C or about 400°C for a period of 30 minutes. In other embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 0.5 (i.e., about 0.45, about 0.4, about 0, 35, about 0.3, about 0.25, about 0.2, about 0.15, about 0.1 or even about 0.5) after exposure to a temperature of about 250° C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C or about 400 °C, for a period of time of 30 minutes . In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase at all after exposure to a temperature of about 250°C, about 260°C, about 270°C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360°C, about 370°C, about 380°C, about 390°C or about 400°C, for a period of time of 30 minutes.
[0180] In some embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7 after being submerged in a water bath at a temperature of about 70 °C for 10 minutes. In other embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7, (i.e., less than or equal to about 0.6, less than or equal to about 0.6). of 0.5, less than or equal to about 0.4 or even less than or equal to about 0.3) after being submerged in a water bath at a temperature of about 70 °C for 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or even 1 hour. In some embodiments, the coefficient of friction of the portion of the glass vessel coated with the lubricious coating may not increase by more than about 30% after being submerged in a water bath at a temperature of about 70°C for 10 minutes. In other embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after being submerged in a water bath at a temperature of about 70 °C for 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or up to 1 hour. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase at all after being submerged in a water bath at a temperature of about 70°C for 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or up to 1 hour.
[0181] In some embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7 after exposure to lyophilization conditions. In other embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7, (i.e., less than or equal to about 0.6, less than or equal to about 0.6). of 0.5, less than or equal to about 0.4, or even less than or equal to about 0.3) after exposure to lyophilization conditions. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% after exposure to lyophilization conditions. In other embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to lyophilization conditions. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase at all after exposure to lyophilization conditions.
[0182] In some embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7 after exposure to autoclave conditions. In other embodiments, the portion of the glass container coated with the lubricious coating may have a coefficient of friction less than or equal to about 0.7, (i.e., less than or equal to about 0.6, less than or equal to about 0.6). of 0.5, less than or equal to about 0.4, or even less than or equal to about 0.3) after exposure to autoclave conditions. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% after exposure to autoclave conditions. In other embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to autoclave conditions. In some embodiments, the coefficient of friction of the portion of the glass container coated with the lubricious coating may not increase at all after exposure to autoclave conditions.
[0183] In some embodiments, after the glass container 100 with the lubricious coating 160 is ground by an identical glass container with a normal force of 30 N, the coefficient of friction of the ground area of the glass container 100 does not increase by more than about 20% following another abrasion by an identical glass vessel with a normal force of 30 N in the same place. In other embodiments, after the glass container 100 with the lubricious coating 160 is ground by an identical glass container with a normal force of 30 N, the coefficient of friction of the ground area of the glass container 100 does not increase by more than about 15% or even 10% following another abrasion by an identical glass vessel with a normal force of 30 N in the same place. However, it is not necessary that all embodiments of the glass container 100 with the lubricious coating 160 exhibit such properties.
[0184] The coated glass containers described herein have a horizontal compressive force. The horizontal compression force, as described herein, is measured by a horizontal compression apparatus 500, which is schematically depicted in Figure 4. The coated glass container 100 is tested by positioning the container horizontally between two upper plates 502a, 502b which are oriented parallel to the long axis of the glass container, as shown in Figure 4. A mechanical load 504 is then applied to the coated glass container 100 with the upper plates 502a, 502b in the direction perpendicular to the long axis of the glass container. The load rate for conceptacle compression is 1.27 cm/min (0.5 inch/min), which means that the top plates move towards each other at a rate of 1.27 cm/min (0 .5 inch/min). The horizontal compressive strength is measured at 25 °C and 50% relative humidity. A measurement of horizontal compressive strength can be given as a probability of failure at a selected normal compressive load. As used herein, failure occurs when the glass vessel breaks under horizontal compression in at least 50% of samples. In some embodiments, a coated glass container may have a horizontal compressive force at least 10%, 20% or 30% greater than an uncoated conceptacle.
[0185] Referring now to Figures 8 and 9, the measurement of horizontal compressive force can also be performed in a ground glass container. Specifically, operation of the test jig 300 can create damage to the coated glass container's outer surface, such as a surface scratch or abrasion that weakens the strength of the coated glass container 100. The glass container is then subjected to the procedure of horizontal compression described above, wherein the container is placed between two upper plates where the streak points out parallel to the upper plates. The scratch can be characterized by the normal pressure selected by a conceptacle on conceptacle jig and the scratch length. Unless otherwise noted, scratches for ground glass containers for the horizontal compression procedure are characterized by a scratch length of 20 mm created by a normal load of 30 N.
[0186] Coated glass containers can be evaluated for horizontal compressive strength following a heat treatment. Heat treatment can be exposure to a temperature of about 250 °C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C or about 400 °C, for a period of time of 30 minutes. In some embodiments, the horizontal compressive strength of the coated glass container is not reduced by more than about 20%, 30%, or even 40% after being exposed to a heat treatment, such as those described above, and then being ground, as described above. In one embodiment, the horizontal compressive strength of the coated glass container is not reduced by more than about 20% after being exposed to heat treatment of about 250°C, about 260°C, about 270°C, about 280 °C, about 290 °C, about 300 °C, about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C or about 400 °C, for a period of time of 30 minutes, and then being ground.
[0187] In other embodiments, the glass container 100 with the lubricious coating 160 can be thermally stable at elevated temperatures. The phrase "thermally stable", as used herein, means that the lubricious coating 160 applied to the glass container remains substantially intact on the surface of the glass container after exposure to elevated temperatures so that, upon exposure, the mechanical properties of the coated glass container, specifically the coefficient of friction and horizontal compressive force, are only minimally affected, if at all. This indicates that the lubricious coating remains adhered to the glass surface following exposure to an elevated temperature and continues to protect the container from mechanical insults such as abrasions, impacts, and the like. The glass containers with lubricious coatings described herein may be thermally stable after heating to a temperature of at least about 250°C or even about 260°C for a period time period of 30 minutes.
[0188] In the embodiments described herein, a glass container with a lubricious coating (i.e., the coated glass container) is considered to be thermally stable if the coated glass container satisfies both a coefficient of friction standard and a standard of friction. horizontal compressive force after heating to the specified temperature and remaining at that temperature for the specified time. To determine whether the coefficient of friction pattern is satisfied, the coefficient of friction of a first coated glass container is determined in condition received in this manner (i.e. before any thermal exposure) using the test template depicted in Figure 9. and an applied force of 30 N. A second coated glass container (i.e., a glass container that has the same glass composition and the same coating composition as the first coated glass container) is thermally exposed under the prescribed conditions and cooled to room temperature. Then, the coefficient of friction of the second glass vessel is determined using the test jig pictured in Figure 9 to grind the coated glass vessel with an applied load of 30 N which results in a ground (i.e., a "risk of ") which has a length of approximately 20 mm. If the coefficient of friction of the second coated glass container is less than 0.7 and the glass surface of the second glass container in the ground area does not have any observable damage, then the standard coefficient of friction is satisfied for the purposes of determine the thermal stability of the lubricious coating. The term "observable damage" as used herein means that the glass surface in the ground area of the glass vessel has less than six glass cracks per 0.5 cm length of ground area when viewed with a spectroscopy microscope. or Nomarski Interference Contrast (DIC) at 100X magnification with LED or halogen light sources. A standard definition of a glass crack or glass crack is described in GD Quinn, "NIST Recommended Practice Guide: Fractography of Ceramics and Glasses”, NIST special publication 960-17 (2006).
[0189] To determine if the standard horizontal compressive force is satisfied, a first coated glass container is ground on the test jig pictured in Figure 9 under a 30 N load to form a 20 mm scratch. The first coated glass container is then subjected to a horizontal compression test, as described herein, and the retained force of the first coated glass container is determined. A second coated glass container (i.e., a glass container that has the same glass composition and the same coating composition as the first coated glass container) is thermally exposed under the prescribed conditions and cooled to room temperature. Next, the second coated glass container is ground in the test jig depicted in Figure 9 under a load of 30 N. The second coated glass container is then subjected to a horizontal compression test as described herein. and the retained force of the second coated glass container is determined. If the retained force of the second coated glass container does not decrease by more than about 20% relative to the first coated glass container then the standard horizontal compression force is satisfied for the purposes of determining the thermal stability of the lubricious coating.
[0190] In the embodiments described herein, coated glass containers are considered to be thermally stable if the friction coefficient pattern and horizontal compressive force pattern are satisfied after exposing the coated glass containers to a temperature of at least about 250 °C or even about 260 °C for a time period of about 30 minutes (i.e. coated glass containers are thermally stable at a temperature of at least about 250 °C or even about 260 °C per time period of about 30 minutes). Thermal stability can also be evaluated at temperatures from about 250°C to about 400°C. For example, in some embodiments, coated glass containers will be considered to be thermally stable if standards are met at a temperature of at least about 270°C or even about 280°C for a time period of about 30 minutes. In still other embodiments, the coated glass containers will be considered to be thermally stable if the standards are met at a temperature of at least about 290°C or even about 300°C for a time period of about 30 minutes. In additional embodiments, the coated glass containers will be considered to be thermally stable if the standards are met at a temperature of at least about 310°C or even about 320°C for a time period of about 30 minutes. In still other embodiments, the coated glass containers will be considered to be thermally stable if the standards are met at a temperature of at least about 330°C or even about 340°C for a time period of about 30 minutes. In still other embodiments, the coated glass containers will be considered to be thermally stable if the standards are met at a temperature of at least about 350°C or even about 360°C for a period of time of about 30 minutes. In other embodiments, coated glass containers will be considered to be thermally stable if standards are met at a temperature of at least about 370°C or even about 380°C for a time period of about 30 minutes. In still other embodiments, the coated glass containers will be considered to be thermally stable if the standards are met at a temperature of at least about 390°C or even about 400°C for a time period of about 30 minutes.
[0191] The coated glass containers disclosed herein may also be thermally stable over a range of temperatures, which means that the coated glass containers are thermally stable by satisfying the standard coefficient of friction and standard horizontal compression force in each temperature in the range. For example, in the embodiments described herein, coated glass containers can be thermally stable from at least about 250°C or even about 260°C at a temperature less than or equal to about 400°C. In some embodiments, the coated glass containers may be thermally stable over a range of at least about 250°C or even about 260°C to about 350°C. In other embodiments, the coated glass containers may be thermally stable from at least about 280°C to a temperature less than or equal to about 350°C. In still other embodiments, the coated glass containers may be thermally stable from at least about 290°C to about 340°C. In another embodiment, the coated glass container may be thermally stable over a temperature range of about 300°C to about 380°C. In another embodiment, the coated glass container may be thermally stable over a temperature range of about 320°C to about 360°C.
[0192] Mass loss refers to a measurable property of the coated glass container that refers to the amount of volatiles released from the coated glass container when the coated glass container is exposed to a selected elevated temperature for a selected period of time. Mass loss is generally indicative of mechanical degradation of the coating due to thermal exposure. Since the glass body of the coated glass vessel exhibits no measurable mass loss at the measured temperatures, the mass loss test, as described in detail herein, generates mass loss data for only the lubricious coating that is applied. in the glass container. Multiple factors can affect mass loss. For example, the amount of organic material that can be removed from the coating can affect mass loss. The breaking of carbon structures and chains in a polymer will result in a theoretical 100% removal of the coating. Organometallic polymer materials typically lose all of their organic components, however, the inorganic component remains. Therefore, mass loss results are normalized based on how much of the coating is organic and inorganic (eg, % silica in the coating) upon theoretical complete oxidation.
[0193] To determine mass loss, a coated sample, such as a coated glass vessel, is initially heated to 150 °C and held at that temperature for 30 minutes to dry the coating, effectively driving H2O away from the coating. the sample is then heated to 150 °C to 350 °C at a ramp rate of 10 °C/min in an oxidizing environment such as air. For the purposes of mass loss determination, only data collected from 150 °C to 350 °C are considered. In some embodiments, the lubricious coating has a mass loss of less than about 5% of its mass when heated from a temperature of 150°C to 350°C at a ramp rate of about 10°C/minute. In other embodiments, the lubricious coating has a mass loss of less than about 3% or even less than about 2% when heated from a temperature of 150°C to 350°C at a ramp rate of about 10 °C/minute. In other embodiments, the lubricious coating has a mass loss of less than about 1.5% when heated from a temperature of 150°C to 350°C at a ramp rate of about 10°C/minute. In other embodiments, the lubricious coating has a mass loss of less than about 0.75% when heated from a temperature of 150°C to 350°C at a ramp rate of about 10°C/minute. In other embodiments, the lubricious coating loses substantially none of its mass when heated from a temperature of 150°C to 350°C at a ramp rate of about 10°C/minute.
[0194] The mass loss results are based on a procedure in which the weight of a coated glass container is compared before and after a heat treatment, such as a temperature increasing by 10°/minute from 150°C to 350° C, as described herein. The difference in weight between the pre-heat treatment concept and the post-heat treatment concept is the coating weight loss, which can be standardized as a percentage of coating weight loss so that the preheat weight -coating heat treatment (weight not including the glass body of the vessel and following the preliminary heating step) is known by comparing the weight in an uncoated glass vessel with a pre-treatment coated glass vessel . Alternatively, the total coating mass can be determined by a total organic carbon test or other similar means.
[0195] Referring now to Figure 10, degassing refers to a measurable property of the coated glass container 100 that refers to the amount of volatiles released from the coated glass container 100 when the coated glass container is exposed to an elevated temperature selected for a selected period of time. Outgassing measurements are reported herein as a weight amount of volatiles released per surface area of the glass vessel that has the coating upon exposure to elevated temperature for a period of time. Since the glass body of the coated glass vessel does not exhibit measurable outgassing at the temperatures reported for outgassing, the outgassing test, as described in detail above, generates outgassing data for substantially only the lubricious coating that is applied to the glass vessel. Degassing results are based on a procedure in which a coated glass vessel 100 is placed in a video sample chamber 402 of apparatus 400 pictured in Figure 10. A bottom sample from the empty sample chamber is collected prior to each run. sample. The sample chamber is maintained under a constant 100ml/min air purge as measured by rotameter 406 when the oven 404 is heated to 350°C and held at that temperature for 1 hour to collect the chamber bottom sample. Next, the coated glass vessel 100 is positioned in the sample chamber 402 and the sample chamber is maintained at a constant 100ml/min air purge and heated to an elevated temperature and maintained at temperature for a period of time to collect a sample from a coated glass vessel 100. The glass sample chamber 402 is made of Pyrex, limiting the maximum analysis temperature to 600°C. An adsorbent trap 408 Carbotrap 300 is mounted in the exhaust port of the sample chamber to absorb the resulting volatile species as they are released from the sample and are swept onto the adsorbent resin air purge gas 410 where the volatile species are absorbed. The adsorbent resin is then placed directly into a Gerstel Thermal Desorption unit coupled directly to a Hewlett Packard 5890 Series II gas chromatograph / Hewlett Packard 5989 MS engine. The degassing species are thermally desorbed at 350 °C from the adsorbent resin and cryogenically focused into the head of a non-polar gas chromatographic column (DB-5MS). The temperature in the gas chromatograph is increased at a rate of 10 °C/min to a final temperature of 325 °C in order to provide for the separation and purification of volatile and semi-volatile species. The separation mechanism has been shown to be based on the heats of vaporization of different organic species which essentially result in a boiling point or distillation chromatogram. Following separation, purified species are analyzed by electron impact ionization mass spectrometry protocols. Operating under standardized conditions, the resulting mass spectra can be compared with existing mass spectra libraries.
[0196] In some embodiments, the coated glass containers described herein exhibit outgassing less than or equal to about 54.6 ng/cm2, less than or equal to about 27.3 ng/cm2 or even less than or equal to about 5.5 ng/cm2 during exposure to an elevated temperature of about 250 °C, about 275 °C, about 300 °C, about 320 °C, about 360 °C, or even about 300 °C. 400°C for time periods of about 15 minutes, about 30 minutes, about 45 minutes or about 1 hour. Additionally, coated glass vessels can be thermally stable over a specified range of temperatures, which means that the coated vessels exhibit some outgassing, as described above, at each temperature within the specified range. Prior to degassing measurements, coated glass vessels may be in a coated condition (i.e., immediately following application of the lubricious coating) or following any one of depyrogenization, lyophilization, or autoclave. In some embodiments, coated glass container 100 may exhibit substantially no outgassing.
[0197] In some embodiments, degassing data can be used to determine mass loss of the lubricious coating. A pre-heat treatment coating mass can be determined by the coating thickness (determined by SEM imaging or otherwise), the density of the lubricious coating, and the surface area of the lubricious coating. Thereafter, the coated glass vessel can be subjected to the degassing procedure, and the mass loss can be determined by finding the ratio of mass expelled in degassing in the preheating mass.
[0198] The coated glass containers described herein have a four point bending force. To measure the four-point bending force of a glass vessel, a glass tube which is the precursor to the coated glass vessel 100 is used for the measurement. The glass tube has a diameter that is the same as the glass container, but does not include a glass container base or a glass container mouth (i.e., prior to forming the tube into a glass container). The glass tube is then subjected to a four-point bending stress test to induce mechanical failure. The test is performed at 50% relative humidity with outer contact members 22.86 cm (9 inches) apart and inner contact members 7.62 cm (3 inches) apart at a loading rate of 10 mm/min .
[0199] Four-point bending stress measurement can also be performed on a coated and ground pipe. Operation of the test jig 300 can create an abrasion on the pipe surface such as a surface scratch that weakens the strength of the pipe, as described in measuring the horizontal compression force of a ground conceptacle. The glass tube is then subjected to a four-point bending stress test to induce mechanical failure. Testing is performed at 25°C and 50% relative humidity using external probes 22.86 cm (9 inches) apart and internal contact members 7.62 cm (3 inches) apart at a loading rate of 10 mm/min, while the tube is positioned so that the risk is placed under tension during the test.
[0200] In some embodiments, the four-point bending force of a glass tube with a lubricious coating after abrasion shows, on average, at least 10%, 20% or even 50% mechanical strength greater than that for a glass tube. ground uncoated glass under the same conditions.
[0201] Referring to Figure 11 the transparency and color of the coated container can be evaluated by measuring the light transmission of the container within a range of wavelengths between 400 to 700 nm using a spectrophotometer. Measurements are performed by directing a beam of light over the normal container to the container wall so that the beam passes through the lubricious coating twice, first as it enters the container and then as it leaves it. In some embodiments, the light transmission through the coated glass container may be greater than or equal to about 55% of a light transmission through the uncoated glass container for wavelengths from about 400 nm to about 400 nm. 700 nm. As described herein, a light transmission can be measured before a heat treatment or after a heat treatment, such as the heat treatments described herein. For example, for each wavelength from about 400 nm to about 700 nm, the light transmission can be greater than or equal to about 55% of the light transmission through an uncoated glass container. In other embodiments, the light transmission through the coated glass container is greater than or equal to about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or even about 90% of light transmission through an uncoated glass container for wavelengths from about 400 nm to about 700 nm.
[0202] As described herein, a light transmission can be measured before an environmental treatment, such as a heat treatment described herein, or after an environmental treatment. For example, following a heat treatment of about 250 °C, about 260 °C, about 270 °C, about 280 °C, about 290 °C, about 300 °C, about 310 °C , about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C or about temperature of 400 °C, for a period of time of 30 minutes, or after exposure to lyophilization conditions, or after exposure to autoclave conditions, the light transmission through the coated glass container is greater than or equal to about 55% , about 60%, about 65%, about 70%, about 75%, about 80% or even about 90% of a light transmission through an uncoated glass container for wavelengths of about from 400 nm to about 700 nm
[0203] In some embodiments, coated glass container 100 may be perceived as colorless and transparent to the naked human eye when viewed from any angle. In other embodiments, the lubricious coating 160 may have a noticeable slope, such as when the lubricious coating 160 comprises a polyimide formed from poly(pyromellitic dianhydride-co-4,4'-oxydianililine) amic acid commercially available from Aldrich.
[0204] In some embodiments, the glass container 100 with the lubricious coating 160 may have an outer surface that is capable of receiving an adhesive label. That is, even though the lubricious coating 160 has a low coefficient of friction, the coating can still receive an adhesive label so that the adhesive label is securely affixed. However, the ability to attach an adhesive label is not a requirement for all embodiments of the glass container 100 with the lubricious coating 160 described herein.
[0205] Referring again to Figure 8, in some embodiments, the lubricious coating 160 may be a transient coating. The phrase "transient coating", as used herein, means that the coating is not permanently adhered to the glass container 100 and can be removed from the glass container 100, such as by washing, heating (i.e., pyrolyzing) or the like. For example, in embodiments where the lubricious coating 160 is a transient coating that can be removed by pyrolysis, the coating may pyrolyze at temperatures less than or equal to about 300° C. Alternatively, the lubricious coating 160 may be a coating. transient that can be removed by washing the glass container with a solution of detergent and water.
[0206] In the embodiments described herein, the glass container may be coated with inorganic coatings, transient organic coatings and/or tough organic coatings in order to achieve low coefficient of friction and damage resistance. INORGANIC COATING
[0207] Still referring to Figure 8, in some embodiments described herein, the lubricious coating 160 is an inorganic coating. The inorganic coating can be a tough inorganic coating that is permanently adhered to the outer surface 106 of the body 102 of the glass container. The properties of the tough inorganic coating are not degraded by exposure to high temperatures and as such the coefficient of friction and horizontal compressive force of the glass container with the tough inorganic coating are substantially the same before and after exposure to high temperatures. which include, without limitation, temperatures in the range of about 250°C to about 400°C. The tough inorganic coating is a continuous coating applied to at least a portion of the outer surface of the body and is generally insoluble in water and/or organic solvents. For example, in some embodiments, the tough inorganic coating may comprise a metal nitride coating, a metal sulfide coating, a metal oxide coating, SiO 2 , diamond-like carbon, or a carbide coating. For example, the tough inorganic coating may include at least one of TiN, BN, hBN, TiO2, Ta2O5, HfO2, NB2O5, V2O5, SnO, SnO2, ZrO2, Al2O3, SiO2, ZnO, MoS2, BC, SiC, or metal, metal nitride and similar carbide coatings which exhibit a relatively low coefficient of friction relative to a similarly coated glass container as well as having relatively high thermal stabilities. In such embodiments, the coatings may be applied to the outer surface of the glass vessel by physical vapor deposition methods such as evaporation, electron beam evaporation, dc magnetron sputtering, unbalanced dc magnetron sputtering, sputtering by ac magnetron and unbalanced ac magnetron sputtering. Alternatively, the coatings can be applied by powder coating. Chemical Vapor Deposition (CVD) Procedure Kits can also be used to apply coatings that include Ultra High Vacuum CVD, Low Pressure CVD, Atmospheric Pressure CVD, Metal Organic CVD, Laser CVD, Photochemical CVD , aerosol-assisted CVD, microwave plasma CVD, plasma-enhanced CVD, direct liquid injection CVD, atomic layer CVD, combustion CVD, hot wire CVD, fast thermal CVD, chemical vapor infiltration and epitaxy by chemical beam.
[0208] In a particular embodiment, the tough inorganic coating is diamond-like carbon. Films or coatings formed from diamond-like carbon generally exhibit a low coefficient of friction and high hardness. Specifically, a significant amount of the carbon in DLC coatings is SP3 hybridized carbon. This material imparts some diamond-like properties to those coatings, such as high hardness and superior wear resistance. The hardness of DLC coatings is directly proportional to the hybridized content in SP3. DLC coatings can be deposited onto the outer surface of the glass vessel by ion beam deposition, arc sputtering, pulsed laser ablation, argon ion sputtering, and plasma-enhanced chemical vapor deposition. Depending on the thickness of the deposited DLC coating, the specific method of deposition and the coating composition, the color of the deposited layer may vary from optically clear yellow (i.e. a 0.1 μm thick film of DLC may be optically clear with a slightly yellow casting) to amber and black.
[0209] Alternatively, the lubricious coating 160 may be an inorganic coating that is temporarily affixed to the outer surface of the glass container, such as a transient coating. In such embodiments, the transient coating may include an inorganic salt such as MgSO4, CaSO4, Ca3(PO4)2, Mg3(PO4)2, KNO3, K3PO4 or the like. ORGANIC COATINGS
[0210] In some alternative embodiments, the lubricious coating 160 may be an organic coating, such as a transient coating temporarily affixed to the outer surface of the glass vessel, or a tough organic coating that is permanently affixed to the outer surface of the glass vessel.
[0211] Regarding transient organic coatings, it is desirable to protect the surfaces of glass articles (such as glass containers or the like) from damage during manufacture in order to mitigate the reduction in the mechanical strength of the glass due to surface flaws caused by contact with the glass. This is generally achieved by applying a coating that has a low coefficient of friction as described above. However, due to the fact that the glass vessel can undergo further processing, the coating does not need to be permanently adhered to the outer surface of the glass vessel and instead can be removed in downstream processing steps after coating. it served its purpose of protecting the glassware. For example, the transient coating can be removed by pyrolysis. In the embodiments described herein, the transient coating can be pyrolyzed at temperatures less than or equal to 300°C in a period of time less than or equal to 1 hour. Alternatively, the transient coating can be pyrolyzed at temperatures of 265°C for 2.5 hours or even at 360°C for 10 minutes or less.
[0212] Various organic materials can be used to form the transitional coating. For example, in some embodiments, the transient coating may comprise, for example, a mixture of polyoxyethylene glycol, methacrylate resin, melamine formaldehyde resin, and polyvinyl alcohol as disclosed in US Patent No. 3,577,256. Such a coating can be applied to the outer surface of the glass vessel after forming and can be pyrolyzed from the glass surface in the annealing lehr.
[0213] In another embodiment, the transient organic coating may comprise one or more polysaccharides, as disclosed in US Patent No. 6,715,316B2 which describes removable protective coatings. Such coatings can be removed from the glass surface using a mild water-based detergent, such as, for example, 2% Semiclean KG in water.
[0214] In another embodiment, the transient organic coating may be a "cold end" coating as described in US Patent 4,055,441 or similar coatings. Such coatings may be formed from at least one of poly(ethylene oxides), poly(propylene oxides), ethylene oxide-propylene oxide copolymers, polyvinyl pyrrolidinones, polyethyleneimines, poly(methyl vinyl ethers), polyacrylamides, polymethacrylamides, polyurethanes, poly(vinylacetates), polyvinyl formal, polyformaldehydes including polyacetals and acetal copolymers, poly(alkyl methacrylates), methyl celluloses, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl celluloses, sodium carboxymethyl celluloses, methyl hydroxypropyl celluloses , poly(acrylic acids) and salts thereof, poly(methacrylic acids) and salts thereof, ethylene-maleic anhydride copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, vinyl acetate-vinyl alcohol copolymers , methyl vinyl ether-maleic anhydride copolymers, emulsifiable polyurethanes, polyoxyethylene stearates and polyolefins including polyethylenes, polypropylene oprylenes and copolymers thereof, modified starches and starches, hydrocolloids, polyacrylamide, vegetable and animal fats, wax, tallow, soap, stearin-paraffin emulsions, dimethyl or diphenyl polysiloxanes or methyl/phenyl mixtures, perfluorinated siloxanes and other substituted siloxanes , alkyl silanes, aromatic silanes and oxidized polyethylene, combinations thereof, or similar coatings.
[0215] Transient organic coatings can be applied by placing such a coating directly in contact with the glass container. For example, the coating may be applied by a dipping process, or alternatively, by spraying or other suitable means. The coating can then be dried, and optionally cured at high temperatures.
[0216] Referring now to Figures 8 and 12A, in some embodiments, the lubricious coating 160 is a tough organic coating adhered to at least a portion of the outer surface 106 of the glass body 102. The tough organic coating has a coefficient of friction low and is also thermally stable at elevated temperatures as described above. Lubricious coating 160 has an outer surface 162 and a glass-contacting surface 164. In embodiments where the lubricious coating 160 is a tough organic coating, the lubricious coating 160 may comprise a coupling agent layer 180 that is in direct contact. with the outer surface 106 of the glass body 102 and a polymer layer 170 is in direct contact with the coupling agent layer 180. However, it should be understood that, in some embodiments, the lubricious coating 160 may not include a coupling agent layer 180 and polymer layer 170 may be in direct contact with the outer surface 106 of the glass body 102. In some embodiments, the lubricious coating 160 is a coating layer as described in US Interim Application 13/ 780,754 filed February 28, 2013 entitled "Glass Articles with Low Friction Coatings", the entirety of which is incorporated herein by way of reference.
[0217] Now referring to Figures 8 and 12A, in one embodiment, the lubricious coating 160 comprises a double layer structure. Figure 12A shows a cross-section of a portion of a coated glass container in which the lubricious coating 160 comprises a polymer layer 170 and a coupling agent layer 180. A polymer chemical composition may be contained in the polymer layer 170. and a coupling agent may be contained in a coupling agent layer 180. The coupling agent layer 180 may be in direct contact with the outer surface 106 of the glass body 102. The polymer layer 170 may be in direct contact with the coupling agent layer 180 and may form the outer surface 162 of the lubricious coating 160. In some embodiments the coupling agent layer 180 is bonded to the outer surface 106 of the glass body 102 and the polymer layer 170 is bonded to the coupling agent layer 180 at an interface 174. However, it should be understood that, in some embodiments, the lubricious coating 160 may not include a coupling agent, and the polymer chemical composition may be disposed in a polymer layer 170 in direct contact with the outer surface 106 of the glass body 102. In another embodiment, the polymer chemical composition and coupling agent may be substantially blended into a single layer. . In other embodiments, the polymer layer 170 may be positioned over the coupling agent layer 180, which means that the polymer layer 170 is on an outer layer with respect to the coupling agent layer 180, and the outer surface 106 of the glass body 102. As used herein, a first layer positioned "over" a second layer means that the first layer may be in direct contact with the second layer or separate from the second layer, such as with a third layer disposed between the first and second layers.
[0218] Referring now to Figure 12B, in one embodiment, the lubricious coating 160 may further comprise an interface layer 190 positioned between the coupling agent layer 180 and the polymer layer 170. The interface layer 190 may comprise a or more chemical compositions of the polymer layer 170 bonded to one or more of the chemical compositions of the coupling agent layer 180. In this embodiment, the interface of the coupling agent layer 180 and polymer layer 170 forms an interface layer 190 wherein binding occurs between the polymer chemical composition and the coupling agent. However, it should be understood that in some embodiments, there may be no appreciable layer at the interface of the coupling agent layer 180 and the polymer layer 170 where the polymer and coupling agent are chemically bonded together as described above with reference to to Figure 12A.
[0219] In another embodiment, the polymer chemical composition and the coupling agent can be substantially mixed in a single layer, forming a homogeneous layer of lubricious coating. Such a single blended layer can be in direct contact with the outer surface 106 of the glass body 102. As described herein, the materials of polymer layer 170 and coupling agent layer 180 (i.e., at least one polymer and at least one coupling agent, respectively) may be mixed to form at least one layer of a lubricious coating 160. The mixed layer lubricious coating 160 may additionally comprise materials other than a polymer chemical composition and a coupling agent. . To form the mixed layer lubricious coating 160, the various materials of such layer may be mixed together in solution prior to application of the lubricious coating 160 to the glass container 100. In other embodiments, the mixed layers may be unmixed top or bottom layers. , such as, for example, a mixed layer of polymer and coupling agent under a layer of substantially only polymer material. In other embodiments, the lubricious coating may comprise more than two layers, such as three or four layers.
[0220] The lubricious coating 160 applied to the outer surface 106 of the glass body 102 may have a thickness of less than about 100 µm or even less than or equal to about 1 µm. In some embodiments, the thickness of the lubricious coating 160 can be less than or equal to about 100 nm in thickness. In other embodiments, the lubricious coating 160 may be less than about 90 nm thick, less than about 80 nm thick, less than about 70 nm thick, less than about 60 nm thick, less than about 60 nm thick. 50 nm, or even less than about 25 nm thick. In some embodiments, the lubricious coating 160 may not be of uniform thickness over the entire glass body 102. For example, the coated glass container 100 may have a thicker lubricious coating 160 in some areas, due to the process of laying the surface. 106 of the glass body 102 in contact with one or more coating solutions that form the lubricious coating 160. In some embodiments, the lubricious coating 160 may have a non-uniform thickness. For example, the coating thickness can be varied in different regions of a coated glass container 100, which can provide protection in a selected region. In another embodiment, only selected portions of the outer surface 106 of the glass body are coated with a lubricious coating 160.
[0221] In embodiments that include at least two layers, such as a polymer layer 170, an interface layer 190, and/or a coupling agent layer 180, each layer may have a thickness of less than about 100 µm or even less. than or equal to about 1 μm. In some embodiments, the thickness of each layer may be less than or equal to about 100 nm. In other embodiments, each layer may be less than about 90 nm thick, less than about 80 nm thick, less than about 70 nm thick, less than about 60 nm thick, less than about 50 nm thick or even less than about 25 nm thick.
[0222] As noted herein, in some embodiments, the lubricious coating 160 comprises a coupling agent. The coupling agent can enhance the adhesion or bonding of the polymer chemical composition to the outer surface 106 of the glass body 102 and is generally disposed between the glass body 102 and the polymer chemical composition in a polymer chemical composition. layer 170 or mixed with the polymer chemical composition. Adhesion, as used herein, refers to the strength of adhesion or bonding of the polymer layer before and after a treatment applied to the coated glass container, such as a heat treatment. Heat treatments include, without limitation, autoclave, depyrogenization, lyophilization or the like.
[0223] In one embodiment, the decoupling agent may comprise at least one silane chemical composition. As used herein, a "silane" chemical composition is any chemical composition that comprises a silane chemical moiety, including functional organosilanes as well as silanols formed from silanes in aqueous solutions. The silane chemical compositions of the coupling agent can be aromatic or aliphatic. In some embodiments, the at least one silane chemical composition may comprise an amine chemical moiety, such as a primary amine chemical moiety or a secondary amine chemical moiety. Additionally, the coupling agent may comprise hydrolysates and/or oligomers of such silanes, such as one or more silsesquioxane chemical compositions that are formed from one or more silane chemical compositions. Silsesquioxane chemical compositions can comprise a full cage structure, a partial cage structure or no cage structure at all.
[0224] The coupling agent may comprise any number of different chemical compositions, such as one chemical composition, two different chemical compositions or more than two different chemical compositions including oligomers formed from more than one monomeric chemical composition. In one embodiment, the coupling agent may comprise at least one of (1) a first chemical composition of silane, hydrolyzate thereof, or oligomer thereof, and (2) a chemical composition formed from the oligomerization of at least the first chemical composition. silane and a second silane chemical composition. In another embodiment, the coupling agent comprises a first and a second silane. As used herein, a "first" silane chemical composition and a "second" silane chemical composition are silanes that have different chemical compositions. The first silane chemical composition may be an aromatic chemical composition or an aliphatic chemical composition, may optionally comprise an amine chemical moiety, and may optionally be an alkoxysilane. Similarly, the second silane chemical composition may be an aromatic chemical composition or an aliphatic chemical composition, may optionally comprise an amine chemical moiety, and may optionally be an alkoxysilane.
[0225] For example, in one embodiment, only a silane chemical composition is applied as the coupling agent; in such an embodiment, the coupling agent may comprise a silane chemical composition, hydrolyzate thereof, or oligomer thereof.
[0226] In another embodiment, multiple silane chemical compositions can be applied as the coupling agent. In such an embodiment, the coupling agent may comprise at least one of (1) a mixture of the first silane chemical composition and a second silane chemical composition, and (2) a chemical composition formed from the oligomerization of at least the first silane chemical composition and the second silane chemical composition.
[0227] Referring to the modalities described above, the first silane chemical composition, the second silane chemical composition or both may be aromatic chemical compositions. As used herein, an aromatic chemical composition contains one or more characteristic six-carbon rings of the benzene series and related organic chemical moieties. The aromatic silane chemical composition may be an alkoxysilane such as, but not limited to, a dialkoxysilane chemical composition, hydrolyzate thereof, or oligomer thereof, or a trialkoxysilane chemical composition, hydrolyzate thereof, or oligomer thereof. In some embodiments, the aromatic silane may comprise an amine chemical moiety, and may be an alkoxysilane comprising an amine chemical moiety. In another embodiment, the aromatic silane chemical composition can be an aromatic trialkoxysilane chemical composition, an aromatic acyloxysilane chemical composition, an aromatic halogen silane chemical composition, or an aromatic aminosilane chemical composition. In another embodiment, the aromatic silane chemical composition can be selected from the group consisting of aminophenyl, 3-(m-aminophenoxy)propyl, N-phenylaminopropyl, or substituted alkoxy (chloromethyl)phenyl, acyloxy, halogen or aminosilanes. For example, the aromatic alkoxysilane may, but are not limited to, aminophenyltrimethoxy silane (sometimes referred to herein as "APhTMS"), aminophenyldimethoxy silane, aminophenyltriethoxy silane, aminophenyldiethoxy silane, 3-(m-aminophenoxy silane ) propyltrimethoxy, 3-(m-aminophenoxy)propyldimethoxy silane, 3-(m-aminophenoxy)propyltriethoxy silane, 3-(m-aminophenoxy)propyldiethoxy silane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyldimethoxysilane, N-phenylaminopropyltriethoxysilane, N- phenylaminopropyldiethoxysilane, hydrolysates thereof or an oligomerized chemical composition thereof. In an exemplary embodiment, the aromatic silane chemical composition may be aminophenyltrimethoxy silane.
[0228] Referring again to the modalities described above, the first silane chemical composition, the second silane chemical composition or both may be aliphatic chemical compositions. As used herein, an aliphatic chemical composition is non-aromatic, such as a chemical composition that has an open-chain structure, such as, but not limited to, alkanes, alkenes, and alkynes. For example, in some embodiments, the coupling agent may comprise a chemical composition which is an alkoxysilane and may be an aliphatic alkoxysilane, such as, but not limited to, a dialkoxysilane chemical composition, a hydrolyzate thereof, or an oligomer thereof. , or a chemical composition of trialkoxysilane, a hydrolyzate thereof, or an oligomer thereof. In some embodiments, the aliphatic silane may comprise an amine chemical moiety and may be an alkoxysilane which comprises an amine chemical moiety, such as an aminoalkyltrialkoxysilane. In one embodiment, an aliphatic silane chemical composition may be selected from the group consisting of 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, vinyl, methyl, N-phenylaminopropyl, (N-phenylamino)methyl , substituted alkoxy of N-(2-vinylbenzylaminoethyl)-3-aminopropyl, acyloxy, halogen or aminosilanes, hydrolysates thereof or oligomers thereof. and aminoalkyltrialkoxysilanes, include, but are not limited to, 3-aminopropyltrimethoxy silane (sometimes referred to herein as "GAPS"), 3-aminopropyldimethoxy silane, 3-aminopropyltriethoxy silane, 3-aminopropyldiethoxy silane, N-(2 -aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldiethoxysilane, hydrolysates thereof and a composition thereof oligomerized chemistry thereof. In other embodiments, the aliphatic trialkoxysilane chemical composition may not contain an amine chemical moiety, such as an alkyltrialkoxysilane or alkylbialkoxysilane. Such alkyltrialkoxysilanes or alkylbialkoxysilanes include, but are not limited to, vinyltrimethoxy silane, vinyldimethoxy silane, vinyltriethoxy silane, vinyldiethoxy silane, methyltrimethoxysilane, methyldimethoxysilane, methyltriethoxysilane, methyldiethoxysilane, hydrolysates thereof, or an oligomerized chemical composition thereof including silsesquiomers oligomers amino acids such as, but not limited to, WSA-7011, WSA-9911, WSA-7021, WSAV-6511 manufactured by Gelest. In an exemplary embodiment, the chemical composition of the aliphatic silane is 3-aminopropyltrimethoxy silane.
[0229] In another embodiment, the coupling agent layer 180 may comprise chemical species that are hydrolyzed analogs of aminoalkoxysilanes such as, but not limited to, (3-aminopropyl)silanetriol, N-(2-aminoethyl)-3-aminopropyl- silanetriol and/or mixtures thereof.
[0230] In another embodiment, the decoupling agent layer 180 may comprise a chemical species which is an aminoalkylsilsesquioxane. In one embodiment the coupling agent layer 180 comprises aminopropylsilsesquioxane (APS) oligomer (commercially available as an aqueous solution from Gelest).
[0231] In another embodiment, the coupling agent layer 180 may be an inorganic material, such as metal film and/or ceramic. Non-limiting examples of inorganic materials used as the coupling agent layer 180 include tin, titanium and/or oxides thereof.
[0232] It has been observed that forming the coupling agent from combinations of different chemical compositions, particularly combinations of silane chemical compositions, can improve the thermal stability of the lubricious coating 160. For example, it has been observed that combinations of aromatic silanes and silanes aliphatics, such as those described above, improve the thermal stability of the lubricious coating, thereby producing a coating that retains its mechanical properties, such as coefficient of friction and adhesion performance following heat treatment at elevated temperatures. Accordingly, in one embodiment the coupling agent comprises a combination of aromatic and aliphatic silanes. In such embodiments, the ratio of aliphatic silanes to aromatic silanes (aliphatic:aromatic) can be from about 1:3 to about 1:0.2. If the coupling agent comprises two or more chemical compositions, such as at least an aliphatic silane and an aromatic silane, the weight ratio of the two chemical compositions can be any ratio, such as a weight ratio of a first silane chemical composition. for a second silane chemical composition (first silane: second silane) from about 0.1:1 to about 10:1. For example, in some embodiments the ratio may be from 0.5:1 to about 2:1, such as 2:1, 1:1, 0.5:1. In some embodiments, the coupling agent may comprise combinations of multiple aliphatic silanes and/or multiple aromatic silanes, which could be applied to the glass vessel in one or multiple steps with or without organic or inorganic fillers. In some embodiments, the coupling agent comprises oligomers, such as silsesquioxanes, formed from either aliphatic or aromatic silanes.
[0233] In an exemplary embodiment, the first silane chemical composition is an aromatic silane chemical composition and the second silane chemical composition is an aliphatic silane chemical composition. In an exemplary embodiment, the first silane chemical composition is an aromatic trialkoxysilane chemical composition comprising at least an amine chemical moiety and the second silane chemical composition is an aliphatic trialkoxysilane chemical composition comprising at least an amine chemical moiety. . In another exemplary embodiment, the coupling agent comprises an oligomer of one or more silane chemical compositions, wherein the oligomer is a silsesquioxane chemical composition and at least one of the silane chemical compositions comprises at least one aromatic chemical moiety and at least an amine chemical moiety. In a particular exemplary embodiment, the first silane chemical composition is aminophenyltrimethoxy silane and the second silane chemical composition is 3-aminopropyltrimethoxy silane. The ratio of aromatic silane to aliphatic silane can be about 1:1. In another particular exemplary embodiment, the coupling agent comprises an oligomer formed from aminophenyltrimethoxy and 3-aminopropyltrimethoxy. In another embodiment, the coupling agent may comprise either a mixture of aminophenyltrimethoxy and 3-aminopropyltrimethoxy or oligomers formed from the two.
[0234] In one embodiment, the coupling agent is applied to the outer surface 106 of the glass body 102 by bringing the surface into contact with the diluted coupling agent through a submersion process. The coupling agent may be mixed in a solvent when applied to the glass body 102. In another embodiment, the coupling agent may be applied to the glass body 102 by spraying or other suitable means. The glass body 102 with coupling agent can then be dried at about 120°C for about 15 minutes or any time and temperature sufficient to properly release the water and/or other organic solvents present on the outer surface 106 of the glass. wall portion 110.
[0235] Referring to Figure 12A, in one embodiment, the coupling agent is positioned over the glass container as a layer of coupling agent 180 and is applied as a solution comprising about 0.5% by weight of a first silane and about 0.5% by weight of a second silane (total 1% by weight of silane) mixed with at least one of water and an organic solvent such as, but not limited to, methanol. However, it should be understood that the total concentration of silane in the solution can be more or less than about 1% by weight, such as from about 0.1% by weight to about 10% by weight, from about 0.3% by weight to about 5.0% by weight, or from about 0.5% by weight to about 2.0% by weight. For example, in one embodiment, the weight ratio of organic solvent to water (organic solvent:water) can be from about 90:10 to about 10:90, and, in one embodiment, can be from about 75:25 . The weight ratio of silane to solvent can affect the thickness of the coupling agent layer, whereby increasing percentages of silane chemical composition in the coupling agent solution can increase the thickness of the coupling agent layer 180. However, it should be It is understood that other variables can affect the thickness of the coupling agent layer 180 such as, but are not limited to, the specifics of the dip coating process, such as the rate of removal from the bath. For example, a faster withdrawal rate can form a thicker coupling agent layer 180.
[0236] In one embodiment, the decoupling agent layer 180 is applied as a solution comprising a first silane chemical species and a second silane chemical species, which can enhance the thermal stability and/or mechanical properties of the lubricious coating 160 For example, the first silane chemical species can be an aliphatic silane, such as GAPS, and the second silane chemical species can be an aromatic silane, such as APhTMS. In this example, the ratio of aliphatic silanes to aromatic silanes (aliphatic:aromatic) might be about 1:1. However, it should be understood that other ratios are possible, including from about 1:3 to about 1:0.2, as described above. The aromatic silane chemical species and the aliphatic silane chemical species may be mixed with at least one of water and an organic solvent, such as, but not limited to, methanol. This solution is then coated onto the outer surface 106 of the glass body 102 and cured to form the coupling agent layer 180.
[0237] In another embodiment, the coupling agent layer 180 is applied as a solution comprising 0.1% by volume of a commercially available aminopropylsilsesquioxane oligomer. Coupling agent layer solutions of other concentrations may be used, including, but not limited to, 0.01 to 10.0% by volume of aminopropylsilsesquioxane oligomer solutions.
[0238] In some embodiments, the coupling agent layer 180 is sufficient and thermally stable so that the coupling agent layer 180 can, by itself, act as the lubricious coating 160 without any additional coating, such as a chemical composition. polymer layer 170 or the like. Accordingly, it should be understood that, in such embodiments, the lubricious coating 160 includes a single composition, specifically the coupling agent.
[0239] As noted herein, when the lubricious coating 160 is a tough organic coating, the coating may also include a polymer chemical composition as well as a layer 170 polymer chemical composition. The polymer chemical composition may be a thermally stable polymer. or mixture of polymers, such as, but not limited to, polyimides, polybenzimidazoles, polysulfones, polyetheretheketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, heterocyclic and polyaromatic polymers with and without organic or inorganic fillers. The polymer chemical composition can be formed from other thermally stable polymers, such as polymers that do not degrade at temperatures in the range of 200°C to 400°C, including 250°C, 300°C and 350°C. These polymers can be applied with or without a coupling agent.
[0240] In one embodiment, the polymer chemical composition is a polyimide chemical composition. If the lubricious coating 160 comprises a polyimide, the polyimide composition may be derived from a polyamic acid, which is formed in solution by the polymerization of monomers. Such polyamic acid is Novastrat® 800 (commercially available from NeXolve). A curing step imidizes the polyamic acid to form the polyimide. Polyamic acid can be formed from the reaction of a diamine monomer, such as a diamine, and an anhydride monomer, such as a dianhydride. As used herein, polyimide monomers are described as diamine monomers and dianhydride monomers. However, it should be understood that although a diamine monomer comprises two amine chemical moieties, in the description that follows, any monomer comprising at least two amine chemical moieties may be suitable as a diamine monomer. Similarly, it should be understood that although a dianhydride monomer comprises two anhydride chemical moieties, in the description that follows any monomer comprising at least two anhydride chemical moieties may be suitable as a dianhydride monomer. The reaction between the anhydride chemical moieties of the anhydride monomer and the amine chemical moieties of the diamine monomer forms polyamic acid. Therefore, as used herein, a chemical polyimide composition that is formed from the polymerization of specified monomers refers to the polyimide that is formed following the imidization of a polyamic acid that is formed from those specified monomers. In general, the molar ratio of anhydride monomers to total diamine monomers can be about 1:1. Although the polyimide can be formed from two distinct chemical compositions (an anhydride monomer and a diamine monomer), at least one anhydride monomer can be polymerized and at least one diamine monomer can be polymerized to form the polyimide. For example, an anhydride monomer can be polymerized with two different diamine monomers. Any number of combinations of monomer species may be used. Additionally, the ratio of one anhydride monomer to a different anhydride monomer, or one or more diamine monomers to a different diamine monomer can be any ratio, such as between about 1:0.1 to 0.1:1 , such as about 1:9, 1:4, 3:7, 2:3:, 1:1, 3:2, 7:3, 4:1 or 9:1.
[0241] The anhydride monomer from which, together with the diamine monomer, the polyimide is formed may comprise any anhydride monomer. In one embodiment, the anhydride monomer comprises a benzophenone backbone. In an exemplary embodiment, benzophenone-3,3',4,4'-tetracarboxylic dianhydride can be at least one of the anhydride monomers from which the polyimide is formed. In other embodiments, the diamine monomer may have an anthracene structure, a phenanthrene structure, a pyrene structure, or a pentacene structure, which includes substituted versions of the aforementioned dianhydrides.
[0242] The diamine monomer from which, together with the anhydride monomer, the polyimide is formed may comprise any diamine monomer. In one embodiment, the diamine monomer comprises at least one aromatic ring chemical moiety. Figures 13 and 14 show examples of diamine monomers which, together with one or more selected anhydride monomers, can form the polyimide comprising the polymer chemical composition. The diamine monomer may have one or more carbon molecules that connect two aromatic ring chemical moieties together, as shown in Figure 13, where R of Figure 13 corresponds to an alkyl chemical moiety comprising one or more carbon atoms. Alternatively, the diamine monomer may have two aromatic ring chemical moieties that are directly connected and not separated by at least one carbon molecule, as shown in Figure 14. The diamine monomer may have one or more alkyl chemical moieties, as shown in Figure 14. represented by R' and R" in Figures 13 and 14. For example, in Figures 13 and 14, R' and R" may represent an alkyl chemical moiety such as a methyl, ethyl, propyl or butyl chemical moiety, connected to a or more aromatic ring chemical moieties. For example, the diamine monomer may have two aromatic ring chemical moieties wherein each aromatic ring chemical moiety has an alkyl chemical moiety connected thereto and adjacent to an amine chemical moiety connected to the aromatic ring chemical moiety. It should be understood that R' and R", in both Figures 13 and 14, may be the same chemical moiety or they may be different chemical moieties. Alternatively, R' and/or R", in both Figures 13 and 14, can represent no atom.
[0243] Two different chemical compositions diamine demonomers can form the polyimide. In one embodiment, a first diamine monomer comprises two aromatic ring chemical moieties that are directly connected and not separated by a bonding carbon molecule, and a second diamine monomer comprises two aromatic ring chemical moieties that are connected to at least a carbon molecule that connects the two chemical portions of an aromatic ring. In an exemplary embodiment, the first diamine monomer, the second diamine monomer, and the anhydride monomer have a molar ratio (first diamine monomer:second diamine monomer:anhydride monomer) of about 0.465:0.035:0.5 . However, the ratio of the first diamine monomer and the second diamine monomer can vary in a range from about 0.01:0.49 to about 0.40:0.10, while the anhydride monomer ratio remains by about 0.5.
[0244] In one embodiment, the polyimide composition is formed from the polymerization of at least a first diamine monomer, a second diamine monomer, and an anhydride monomer, wherein the first and second diamine monomers are different chemical compositions. . In one embodiment, the anhydride monomer is a benzophenone, the first diamine monomer comprises two aromatic rings directly linked together, and the second diamine monomer comprises two aromatic rings linked together by at least one carbon molecule connecting the first and the second. second aromatic rings. The first diamine monomer, second diamine monomer and anhydride monomer can have a molar ratio (first diamine monomer:second diamine monomer:anhydride monomer) of about 0.465:0.035:0.5.
[0245] In an exemplary embodiment, the first diamine monomer is ortho-Tolidine, the second diamine monomer is 4,4'-methylene-bis(2-methylaniline), and the anhydride monomer is benzophenone-3,3' dianhydride ,4,4'-tetracarboxylic acid. The first diamine monomer, second diamine monomer and anhydride monomer can have a molar ratio (first diamine monomer:second diamine monomer:anhydride monomer) of about 0.465:0.035:0.5.
[0246] In some embodiments, the polyimide may be formed from the polymerization of one or more of: bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 1,2;3,4-cyclopentane dianhydride - 1,2,3,4-tetracarboxylic, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,3:6,7-4arH,8acH)-decahydro-1t,4t dianhydride: 5c,8c-dimethananephthalene-2t,3t,6c,7c-tetracarboxylic acid, 2,3:6,7-dianhydride 2c,3c,6c,7c-tetracarboxylic acid, 2,3:5,5-dianhydride 5-endo-carboxymethylbicyclo acid [2.2.1]-heptane-2-exo,3-exo,5-exo-tricarboxylic anhydride 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , isomers of bis(aminomethyl)bicyclo[2.2.1]heptane, or 4,4'-methylenebis(2-methylcyclohexylamine), pyromellitic dianhydride (PMDA) 3,3',4,4'-biphenyl dianhydride (4,4 '-BPDA), 3,3',4,4'-benzophenone dianhydride (4,4'-BTDA), 3,3',4,4'-oxydiphthalic anhydride (4,4'-ODPA), 1,4-bis(3,4-dicarboxyl-phenoxy)benzene (4,4'-HQDPA), 1,3-bis(2,3-dicarboxyl-phenoxy)benzene dianhydride no (3,3'-HQDPA), 4,4'-bis(3,4-dicarboxylphenoxyphenyl)-isoproprylidene dianhydride (4,4'-BPADA), 4,4'-(2,2,2,diphthalic dianhydride) 2-trifluoro-1-pentafluorophenylethylidene) (3FDA), 4,4'-oxydianilline (ODA), m-phenylenediamine (MPD), p-phenylenediamine (PPD), m-toluenediamine (TDA), 1,4-bis(4) - aminophenoxy)benzene (1,4,4-APB), 3,3'-(m-phenylenebis(oxy))dianilline (APB), 4,4'-diamino-3,3'-dimethyldiphenylmethane (DMMDA), 2 ,2'-bis(4-(4-aminophenoxy)phenyl)propane (BAPP), 1,4-cyclohexanediamine 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoroisoproprylidene (4-BDAF), 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan (DAPI), maleic anhydride (MA), citraconic anhydride (CA), nadic anhydride (NA), 4-(phenylethynyl) acid anhydride -1,2-benzenedicarboxylic acid (PEPA), 4,4'-diaminobenzanilide (DABA), 4,4'-(hexafluoroisopropylidene)diphthalicanhydride (6-FDA), pyromellitic dianhydride, benzophenone-3,3',4 dianhydride, 4'-tetracarboxylic, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisop roprilidene)diphthalic, perylene-3,4,9,10-tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4'-isoproprylidenediphenoxy)bis (phthalic anhydride), 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, as well as those materials described in US Patent 7,619,042, US Patent 8,053,492, US Patent 8,053,492 in US 4,880,895, in US Patent 6,232,428, in US Patent 4,595,548, in WO Publication 2007/016516, in US Patent Publication 2008/0214777, in US Patent 6/444/783, in US Patent No. 6,277,950 and in US Patent No. 4,680,373. Figure 15 depicts the chemical structure of some suitable monomers that can be used to form a polyimide coating applied to the glass body 102. In another embodiment, the polyamic acid solution from which the polyimide is formed may comprise poly( (commercially available from Aldrich) pyromellitic-co-4,4'-oxydianilline) dianhydride.
[0247] In another embodiment, the polymer chemical composition may comprise a fluoropolymer. The fluoropolymer may be a copolymer in which both monomers are highly fluorinated. Some of the fluoropolymer monomers may be fluoroethylene. In one embodiment, the polymer chemical composition comprises an amorphous fluoropolymer, such as, but not limited to, Teflon AF (commercially available from DuPont). In another embodiment, the polymer chemical composition comprises perfluoroalkoxy resin (PFA) particles, such as, but not limited to, Teflon PFA TE-7224 (commercially available from DuPont).
[0248] In another embodiment, the polymer chemical composition may comprise a silicone resin. The silicone resin can be a highly branched three-dimensional polymer that is formed from branched, cage-like oligosiloxanes with the general formula RnSi(X)mOy, where R is a non-reactive substituent, usually methyl or phenyl, and X is OH or H. While not wishing to be bound by theory, it is believed that resin curing occurs through a condensation reaction of chemical moieties of Si-OH with a formation of Si-O-Si bonds. The silicone resin can have at least one of four possible functional siloxane monomeric units, which include M-resins, D-resins, T-resins and Q-resins, where M-resins refer to resins with the general formula R3SiO , D-resins refer to resins with the general formula R2SiO2, T-resins refer to resins with the general formula RSiO3 and Q-resins refer to resins with the general formula SiO4 (a fused quartz). In some embodiments resins are composed of D and T units (DT resins) or M and Q units (MQ resins). In other modalities, other combinations (MDT, MTQ, QDT) are also used.
[0249] In one embodiment, the polymer chemical composition comprises phenylmethyl silicone resins due to their higher thermal stability compared to methyl or phenyl silicone resins. The ratio of phenyl to methyl chemical moieties in silicone resins can be varied in polymer chemical composition. In one embodiment, the ratio of phenyl to methyl is about 1.2. In another embodiment, the ratio of phenyl to methyl is about 0.84. In other embodiments, the chemical moiety ratio of phenyl to methyl can be about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.3, 1 .4 or 1.5. In one embodiment, the silicone resin is DC 255 (commercially available from Dow Corning). In another embodiment, the silicone resin is DC806A (commercially available from Dow Corning). In other embodiments, the polymer chemical composition may comprise any of the DC series resins (commercially available from Dow Corning) and/or Hardsil series AP and AR resins (commercially available from Gelest). Silicone resins can be used without a coupling agent or with a coupling agent.
[0250] In another embodiment, the polymer chemical composition may comprise silsesquioxane-based polymers such as, but not limited to, T-214 (commercially available from Honeywell), SST-3M01 (commercially available from Gelest), POSS Imiclear ( commercially available from Hybrid Plastics) and FOX-25 (commercially available from Dow Corning). In one embodiment, the polymer chemical composition may comprise a silanol chemical moiety.
[0251] Referring again to Figures 8 and 12A, the lubricious coating 160 can be applied in a multi-stage process where the glass body 102 is brought into contact with the coupling agent solution to form the layer of coupling agent 180 (as described above), and dried, and then contacted with a solution of polymer chemical composition, such as a solution of polymer or polymer precursor, such as through a submersion process, or alternatively , the polymer layer 170 can be applied by spraying or other suitable means, and dried, and then cured at high temperatures. Alternatively, if a coupling agent layer 180 is not used, the polymer chemical composition of the polymer layer 170 can be directly applied to the outer surface 106 of the glass body 102. In another embodiment, the polymer chemical composition and agent Coating agents can be mixed into the lubricious coating 160, and a solution comprising the polymer chemical composition and the coupling agent can be applied to the glass body 102 in a single coating step.
[0252] In one embodiment, the polymer chemical composition comprises a polyimide in which a polyamic acid solution is applied over the coupling agent layer 180. In other embodiments, a polyamic acid derivative may be used, such as, for example, a polyamic acid salt, a polyamic acid ester or the like. For example, suitable polyamic acid salts may include polyamic acid salt formed from triethylamine. Other suitable salts may include those salts formed by the deprotonation of the carboxylic acid groups of polyamic acids by basic additives which leads to an ionic interaction of the resulting carboxylate group with its conjugate acid. Basic additives may include organic, inorganic or organometallic species or combinations thereof. Inorganic species may include chemical moieties such as alkali, alkaline earth or metal bases. Organic bases (proton acceptors) can include aliphatic amines, aromatic amines or other organic bases. Aliphatic amines include primary amines such as, but not limited to, ethylamine, secondary amines such as, but not limited to, diethylamines, and tertiary amines such as triethylamines. Aromatic amines include anilines, pyridines and imidazoles. Organometallic bases may include 2,2-dimethylpropylmagnesium chlorides or others. In one embodiment, the polyamic acid solution may comprise a mixture of 1% by volume of polyamic acid and 99% by volume of organic solvent. The organic solvent may comprise a mixture of toluene and at least one of the solvents N,N-Dimethylacetamide (DMAc), N,N-Dimethylformamide (DMF), and 1-Methyl-2-pyrrolidinone (NMP), or a mixture of the same. In one embodiment the organic solvent solution comprises about 85% by volume of at least one of DMAc, DMF and NMP, and about 15% by volume of toluene. However, other suitable organic solvents can be used. The coated glass container 100 can then be dried at about 150°C for about 20 minutes, or any time and temperature sufficient to adequately release the organic solvent present in the lubricious coating 160.
[0253] In the layer transient organic lubricous coating mode, after the glass body 102 is brought into contact with the coupling agent to form the coupling agent layer 180 and the polyamic acid solution to form the polymer layer 170, coated glass container 100 can be cured at high temperatures. Coated glass container 100 can be cured at 300 °C for about 30 minutes or less or can be cured at a temperature higher than 300 °C, such as at least 320 °C, 340 °C, 360 °C, 380 °C or 400 °C for a shorter time. It is believed that, without being bound by theory, the curing step imidizes the polyamic acid to form the polymer layer 170 by reacting chemical carboxylic acid moieties and chemical amide moieties to create a polymer layer 170 that comprises a polyimide. Curing can also promote bonds between the polyimide and the coupling agent. The coated glass vessel 100 is then cooled to room temperature.
[0254] Additionally, without being bound by limitations, curing the coupling agent, the polymer chemical composition, or both, is believed to drive away volatile materials such as water and other organic molecules. As such, those volatile materials that are released during curing are not present when the article, if used as a container, is heat treated (such as for depyrogenation) or comes into contact with material in which it is a packaging, such as like a pharmaceutical package. It should be understood that the curing processes described herein are separate heating treatments than other heating treatments described herein, such as those heating treatments similar or identical to processes in the pharmaceutical packaging industry, such as depyrogenation or heating treatments used to define thermal stability as described herein.
[0255] In one embodiment, the coupling agent comprises a silane chemical composition, such as an alkoxysilane, which can enhance the adhesion of the polymer chemical composition to the glass body. Without being bound by theory, it is believed that alkoxysilane molecules rapidly hydrolyze into isolated monomers formed in water, large intramolecular cyclic and cyclic oligomers. In various modalities, control over which species predominates can be determined by silane type, concentration, pH, temperature, storage condition, and time. For example, at low concentrations in aqueous solution, aminopropyltrialkoxysilane (APS) can be stable and form very low molecular weight oligomeric trisilanol and cyclic monomers.
[0256] It is believed, without being bound to theory, that the reaction of one or more chemical compositions of silanes to the glass body may involve several steps. As shown in Figure 17, in some embodiments, following hydrolysis of the silane chemical composition, a reactive silanol chemical moiety can be formed which can condense with other silanol chemical moieties, for example those on the surface of a substrate such as like a glass body. After the first and second hydrolyzable chemical moieties are hydrolyzed, a condensation reaction can be initiated. In some embodiments, the tendency toward self-condensation can be controlled using fresh solutions, alcoholic solvents, dilution, and through careful selection of pH ranges. For example, silanetriols are nearly stable at pH 3 to 6, however, they condense rapidly at pH 7 to 9.3, and partial condensation of silanol monomers can produce silsesquioxanes. As shown in Figure 17, the chemical silanol moieties of the species formed can form hydrogen bonds with chemical silanol moieties on the substrate, and during drying or curing a covalent bond can be formed with the substrate with the elimination of water. For example, a moderate cure cycle (110°C for 15 minutes) can leave chemical moieties of silanol remaining in free form and, along with any silane organofunctionality, can bond to the subsequent finish, providing improved adhesion.
[0257] In some embodiments, the one or more silane chemical compositions of the coupling agent may comprise an amine chemical moiety. Still without being bound by theory, it is believed that this amine chemical moiety can act as a base catalyst in hydrolysis and co-condensation polymerization and improves the adsorption rate of silanes that have an amine chemical moiety on a surface of glass. A high pH (9.0 to 10.0) can also be created in the aqueous solution which conditions the glass surface and increases the density of chemical moieties of silanol on the surface. The strong interaction with water and protic solvents maintains the solubility and stability of a silane that has an amine chemical moiety, such as APS.
[0258] In an exemplary embodiment, the glass body 102 may comprise ion-exchanged glass and the coupling agent may be a silane. In some embodiments, the adhesion of the lubricious coating to a glass with ion exchange may be stronger than the adhesion of the lubricious coating to a glass without ion exchange. It is believed, without being bound by theory, that any of the various aspects of ion-exchanged glass can promote bonding and/or adhesion, compared to non-ion-exchanged glass. First, ion-exchanged glass may have improved chemical/hydrolytic stability which may affect the stability of the coupling agent and/or its adhesion to the glass surface. Glass without ion exchange typically has lower hydrolytic stability and under humid conditions and/or elevated temperature conditions, alkali metals can migrate out of the glass body to the interface of the glass surface and the coupling agent layer (if the is present), or even migrate to the coupling agent layer, if it is present. If alkali metals migrate, as described above, and there is a change in pH, hydrolysis of Si-O-Si bonds at the glass/coupling agent layer interface or in the coupling agent layer itself may weaken or the mechanical properties of coupling agent or its adhesion to the glass. Second, when ion-exchanged glasses are exposed to strong oxidizing baths, such as potassium nitride baths, at elevated temperatures, such as 400 °C to 450 °C, and organic chemical compositions removed on the surface of the glass are removed, making it particularly well suited for silane coupling agents without additional cleaning. For example, glass without ion exchange may have to be exposed to an additional surface cleaning treatment, adding time and cost to the process.
[0259] In an exemplary embodiment, the coupling agent may comprise at least one silane that comprises an amine chemical moiety, and the polymer chemical composition may comprise a chemical polyimide composition. Now referring to Figure 18, without being bound by theory, it is believed that the interaction between this interaction of the chemical amine moiety and the polyamic acid precursor of the polyimide follows a stepwise process. As shown in Figure 18, the first step is the formation of a polyamic acid salt between a carboxyl chemical moiety of the polyamic acid and the chemical amine moiety. The second step is thermal conversion of the salt to a chemical amide moiety. The third step is further conversion of the amide chemical moiety to an imide chemical moiety by cleaving the polymer amide bonds. The result is a covalent imide attachment of a shortened polymer chain (polyimide chain) to an amine chemical moiety of the coupling agent, as shown in Figure 18.EXAMPLES
[0260] The various embodiments of glass containers with enhanced attributes will be further clarified by the following examples. The examples are illustrated in nature and are not intended to limit the subject matter of the present disclosure.EXAMPLE 1
[0261] Glass concepts were formed from Type B glass which has the same composition as Example 2 of Table 2 above and the glass composition identified as "Example E" of Table 1 of Patent Application Serial Number 13 /660,394 filed October 25, 2012 entitled "Glass Compositions with Improved Chemical and Mechanical Durability" assigned to Corning, Incorporated (hereinafter "the Reference Glass Composition"). Conceptacles were washed with deionized water, blow-dried with nitrogen and immersion coated with a 0.1% APS (aminopropylsilsesquioxane) solution. The APS coating was dried at 100 °C in a convection oven for 15 minutes. The conceptacles were then immersed in a solution of 0.1% Novastrat® 800 polyamic acid in a 15/85 solution of toluene/DMF (dimethylformamide) or in a solution of 0.1% to 1% amic acid. PMDA-ODA (poly(4,4'-oxydiphenylene-pyromelithimide) from poly(pyromellitic dianhydride-co-4,4'-oxydianililine) in N-methyl-2-pyrrolidone (NMP).The coated conceptacles were heated to 150° C and held for 20 minutes to evaporate the solvents. Next, the coatings were cured by placing the coated conceptacles in a preheated oven at 300 °C for 30 minutes. After curing, the coated conceptacles with the 0 .1% of Novastrat® 800 had no visible color. However, conceptculae coated with the poly(pyromellitic dianhydride-co-4,4'oxydianililine) solution were visibly yellow in color due to the thickness of the coating. Both coatings exhibited a low coefficient of friction in conceptacle-to-conceptacle contact tests.EXAMPLE 2
[0262] Glass conceptacles formed from Type B glass concepts formed from the same composition as Example 2 of Table 2 above (as received/uncoated) and conceptacles coated with a lubricious coating were compared to assess strength loss mechanics due to abrasion. The coated conceptacles were primarily produced by ion exchange reinforced glass conceptacles produced from the Reference Glass Composition. Ion exchange reinforcement was performed in a bath of 100% KNO3 at 450 °C for 8 hours. Then, the conceptacles were washed with deionized water, blow-dried with nitrogen and coated by immersion with a solution of 0.1% APS (aminopropylsilsesquioxane) in water. The APS coating was dried at 100 °C in a convection oven for 15 minutes. The conceptacles were then immersed in a 0.1% solution of Novastrat® 800 polyamic acid in a 15/85 toluene/DMF solution. The coated conceptacles were heated to 150 °C and held for 20 minutes to evaporate the solvents. Next, the coatings were cured by placing the coated conceptacles in an oven preheated to 300 °C for 30 minutes. The coated conceptacles were then soaked in deionized water at 70 °C for 1 hour and heated in open air at 320 °C for 2 hours to simulate real processing conditions.
[0263] Unground conceptacles formed from Type B glass formed from the same composition as Example 2 of Table 2 above and unground conceptacles formed from the ion exchange reinforced and coated Reference Glass Composition were tested for failure in a horizontal compression test (i.e. a plate was placed over the top of the conceptacle and a plate was placed under the bottom of the conceptacle and the plates were pressed together and the load applied to the failure was determined with a load cell). Figure 19 graphically depicts the probability of failure as a function of applied load in a horizontal compression test for conceptacles formed from a Reference Glass Composition, the vials formed from a Reference Glass Composition in a coated condition. and ground, the weak formed from Type B glass and the weak formed from Type B glass in a ground condition. The failure loads of the unground conceptacles are graphically depicted in the Weibull plots. Sample vials formed from Type B glass and unground conceptacles formed from coated ion exchange reinforced glass were then placed in the conceptacle-on-conceptacle template of Figure 9 to grind the conceptacles and determine the coefficient of friction between the conceptacles as they are rubbed together. The load on the concepts during the test was applied with a UMT machine and was varied between 24 N and 44 N. The applied loads and the corresponding maximum coefficient of friction are reported in the Table contained in Figure 20. For uncoated concepts, the maximum coefficient of friction ranged from 0.54 to 0.71 (shown in Figure 20 as samples of the "3&4" and "7&8" concept, respectively) and while for coated concepts the maximum coefficient of friction ranged from 0.19 to 0 .41 (shown in Figure 20 as the "15&16" and "12&14" concept samples, respectively). Next, the scratched conceptacles were tested in the horizontal compression test to assess the loss of mechanical strength relative to the unground conceptacles. The failure loads applied to the unground conceptacles are graphically depicted in the Weibull plots of Figure 19.
[0264] As shown in Figure 19, uncoated concepts had a significant increase in strength after abrasion while coated concepts had a relatively minor decrease in strength after abrasion. Based on these results, it is believed that the coefficient of friction between the conceptacles should be less than 0.7 or 0.5, or even less than 0.45 in order to mitigate the loss of strength following conceptacle-on-conceptacle abrasion. .EXAMPLE 3
[0265] In this example, multiple sets of glass tubes were tested in four-point bending to assess their respective strengths. A first set of tubes formed from the Reference Glass Composition was tested in four-point bending in condition received this way (uncoated, unreinforced by ion exchange). A second set of tubes formed from the Reference Glass Composition was tested in four-point bending after being reinforced by ion exchange in a bath of 100% KNO3 at 450 °C for 8 hours. A third set of tubes formed from the Reference Glass Composition was tested in four-point bending after being reinforced by ion exchange in a bath of 100% KNO3 at 450 °C for 8 hours and coated with 0.1% of APS/0.1% Novastrat® 800 as described in Example 2. The coated tubes were also soaked in deionized water at 70°C for 1 hour and heated in air at 320°C for 2 hours to simulate actual processing conditions . These coated tubes were also ground in the concept-on-concept jig shown in Figure 9 under a load of 30 N before bending test. A fourth set of tubes formed from the Reference Glass Composition was tested in four-point bending after being reinforced by ion exchange in a bath of 100% KNO3 at 450 °C for 1 hour. These uncoated, ion exchange reinforced tubes were also ground in the conceptacle-on-conceptacle jig shown in Figure 9 under a load of 30 N prior to the bending test. A fifth set of tubes formed from Type B glass was tested in four-point bending in condition received this way (uncoated, unreinforced by ion exchange). A sixth set of tubes formed from Type B glass was tested in four-point bending after being reinforced by ion exchange in a bath of 100% KNO3 at 450 °C for 1 hour. The test results are graphically depicted in the Weibull plots shown in Figure 21.
[0266] Referring to Figure 21, the second set of tubes that were unground and formed from the Reference Glass Composition and reinforced by ion exchange withstood the highest stress before breaking. The third set of tubes that were coated with 0.1% APS/0.1% Novastrat® 800 prior to abrasion showed a slight reduction in strength over their uncoated, unground equivalents (i.e., the second tube set). However, the reduction in strength was relatively minor despite being subjected to abrasion after coating.EXAMPLE 4
[0267] Two sets of concepts were prepared and subjected to a pharmaceutical fill line. A pressure sensitive tape (commercially available from Fujifilm) was inserted between the concepts to measure impact/contact forces between the concepts and between the concepts and the equipment. The first set of concepts was formed from Type B glass and was uncoated. The second set of concepts was formed from the Reference Glass Composition and was coated with a low friction polyimide based coating which has a coefficient of friction of about 0.25 as described above. The pressure sensitive tapes were analyzed after the conceptacles were subjected to the pharmaceutical fill line and demonstrated that the coated conceptacles from the second set exhibited a two to threefold reduction in tension compared to the uncoated conceptacles from the first set.EXAMPLE 5
[0268] Three sets of four concepts each were prepared. All concepts were formed from the Reference Glass Composition. The first set of concepts were coated with the APS/Novastrat® 800 coating as described in Example 2. The second set of concepts were dip coated with 0.1% DC806A in toluene. The solvent was evaporated at 50 °C and the coating was cured at 300 °C for 30 minutes. Each set of conceptacles was placed in a tube and heated to 320 °C for 2.5 hours under an air purge to remove trace contaminants adsorbed on the conceptacles in the laboratory environment. Each set of samples was then heated in the tube for another 30 minutes and the degassed volatiles were captured on an activated carbon sorbent trap. The capturer was heated at 350 °C for 30 minutes to desorb any captured material that was fed into a gas chromatography-mass spectrometer. Figure 22 depicts gas chromatography-mass spectrometer output data for the APS/Novastrat® 800 coating. Figure 23 depicts gas chromatography-mass spectrometer output data for the DC806A coating. No outgassing was detected in the 0.1% APS/0.1% Novastrat® 800 coating or the DC806A coating.
[0269] A set of four conceptacles was coated with a coextrusion adhesive using a 0.5%/0.5% solution of GAPS/APhTMS (3-aminopropyltrimethoxysilane/aminophenyltrimethoxysilane) in methanol/water mixture. Each conceptacle had a coated surface area of about 18.3 cm. The solvent was allowed to evaporate at 120 °C for 15 minutes from the coated conceptacles. Then a 0.5% solution of Novastrat® 800 in dimethylacetamide was applied to the samples. The solvent was evaporated at 150 °C for 20 minutes. These uncured conceptacles were subjected to a degassing test described. The conceptacles were heated to 320 °C in an air stream (100 ml/min) and upon reaching 320 °C the degassed volatiles were captured in activated carbon sorbent traps every 15 minutes. The scavengers were then heated at 350 °C for 30 minutes to desorb any captured material that was fed into a gas chromatography-mass spectrometer. Table 3 shows the amount of materials in the time segments where the samples were held at 320°C. Time zero corresponds to the time when the sample first reached a temperature of 320 °C. As seen in Table 3, after 30 minutes of heating, the amount of volatiles decreases below the instrument's detection limit of 100 ng. Table 3 also reports the volatiles lost per square cm of coated surface.
TABLE 3. VOLATILE BY CONCEPTACLE AND BY COATED AREA.EXAMPLE 6
[0270] A plurality of conceptacles were prepared with various coatings based on silicon resin or polyimides with and without coupling agents. When coupling agents were used, the coupling agents included APS and GAPS, which is a precursor to APS. The outer coating layer was prepared from Novastrat® 800, the poly(pyromellitic dianhydride-co-4,4'oxydianilline) described above, or silicone resins such as DC806A and DC255. The APS/poly(4,4'-oxydiphenylene-pyromelithimide) coatings were prepared using a 0.1% solution of APS (aminopropylsilsesquioxane) and a 0.1% solution, a 0.5% solution or 1.0% solutions of PMDA-ODA poly(4,4'-oxydiphenylene-pyromelithimide)) amic acid) of poly(pyromellitic dianhydride-co-4,4'-oxydianilline) in N-methyl-2-pyrrolidone (NMP) . The poly(4,4'-oxydiphenylene-pyromellitimide) coatings were also applied without a coupling agent using a 1.0% solution of poly(pyromellitic dianhydride-co-4,4'oxydianililine) in NMP. The APS/Novastrat® 800 coatings were prepared using a 0.1% solution of APS and a 0.1% solution of Novastrat® 800 polyamic acid in a 15/85 solution of toluene/DMF. DC255 coatings were applied directly to glass without a coupling agent using a 1.0% solution of DC255 in Toluene. APS/DC806A coatings were prepared by first applying a 0.1% solution of APS in water and then either a 0.1% solution or a 0.5% solution of DC806A in Toluene. The GAPS/DC806A coatings were applied using a 1.0% solution of GAPS in 95% by weight ethanol in water as a coupling agent and then a 1.0% solution of DC806A in Toluene. The coupling agents and coatings were applied using dip coating methods as described herein wherein the coupling agents are heat treated after application and the silicon resin and polyimide coatings are dried and cured after application. application. Coating thicknesses were estimated based on the concentrations of the solutions used. The Table contained in Figure 24 lists the various coating compositions, estimated coating thicknesses and test conditions.
[0271] Next, some of the conceptacles were polished to simulate damage to the coating and others were subjected to abrasion under loads of 30 N and 50 N in the concepta-on-concept jig pictured in Figure 9. Next, all the conceptacles were subjected to a lyophilization (freeze-drying process) in which conceptacles were filled with 0.5 ml of sodium chloride solution and then frozen at -100 °C. Lyophilization was then carried out for 20 hours at -15 °C under vacuum. The conceptacles were inspected with quality-assured optical equipment and under a microscope. No damage to the coatings was observed due to lyophilization.EXAMPLE 7
[0272] Three sets of six concepts were prepared to evaluate the effect of increasing load on the coefficient of friction for uncoated concepts and concepts coated with Dow Corning's DC 255 silicone resin. A first set of concepts were formed from Type B glass and left uncoated. The second set of concepts were formed from the Reference Glass Composition and coated with a 1% solution of DC255 in Toluene and cured at 300°C for 30 minutes. The third set of concepts was formed from Type B glass and coated with a 1% solution of DC255 in Toluene. The conceptacles from each set were placed on the concepta-on-concept template pictured in Figure 9 and the coefficient of friction relative to a similarly coated conceptacle was measured during abrasion under static loads of 10 N, 30 N and 50 N. The results are graphically reported in Figure 25. As shown in Figure 25, coated conceptacles showed appreciably lower coefficients of friction compared to uncoated conceptacles when ground under the same conditions regardless of glass composition.EXAMPLE 8
[0273] Three sets of two glass conceptacles were prepared with an APS/poly(4,4'-oxydiphenylene-pyromellitimide) coating. First, each conceptacle was coated by immersion in a 0.1% APS (aminopropylsilsesquioxane) solution. The APS coating was dried at 100 °C in a convection oven for 15 minutes. The conceptacles were then immersed in a solution of 0.1% amic acid (PMDA-ODA (poly(4,4'-oxydiphenylene-pyromellithimide)) and poly(pyromellitic dianhydride-co-4,4'-oxydianiline) in N-methyl-2-pyrrolidone (NMP) The coatings were then cured by placing the coated conceptacles in an oven preheated to 300 °C for 30 minutes.
[0274] Two conceptacles were placed on the concepta-on-conceptacle jig pictured in Figure 9 and ground under a load of 10 N. The abrasion procedure was repeated 4 more times over the same area and the coefficient of friction was determined for each abrasion. The conceptacles were cleaned between abrasions and the starting point of each abrasion was positioned in a previously unground area. However, each abrasion traveled the same "track". The same procedure was repeated for loads of 30 N and 50 N. The coefficients of friction for each abrasion (ie, A1 to A5) are graphically depicted in Figure 26 for each load. As shown in Figure 26, the coefficient of friction of the APS/poly(4,4'-oxydiphenylene-pyromellimide) coated conceptacles was generally less than 0.30 for all abrasions at all loads. Examples demonstrated improved abrasion resistance for polyimide coating when applied to a glass surface treated with a coupling agent.EXAMPLE 9
[0275] Three sets of two glass concepts were prepared with an APS coating. Each of the conceptacles was coated by immersion in a 0.1% APS (aminopropylsilsesquioxane) solution and heated at 100 °C in a convection oven for 15 minutes. Two conceptacles were placed on the concepta-on-conceptacle jig pictured in Figure 9 and ground under a load of 10 N. The abrasion procedure was repeated 4 more times over the same area and the coefficient of friction was determined for each abrasion. The conceptacles were cleaned between abrasions and the starting point of each abrasion was positioned in a previously unground area. However, each abrasion traveled the same "track". The same procedure was repeated for loads of 30 N and 50 N. The coefficients of friction for each abrasion (ie A1 to A5) are graphically depicted in Figure 27 for each load. As shown in Figure 27, the coefficient of friction of APS-only conceptacles is generally higher than 0.3 and often reaches 0.6 or even higher EXAMPLE 10
[0276] Three sets of two glass conceptacles were prepared with an APS/poly(4,4'-oxydiphenylene-pyromellitimide) coating. Each conceptacle was coated by immersion in a 0.1% APS (aminopropylsilsesquioxane) solution. The APS coating was heated to 100 °C in a convection oven for 15 minutes. The conceptacles were then immersed in a solution of 0.1% amic acid (PMDA-ODA (poly(4,4'-oxydiphenylene-pyromellithimide)) and poly(pyromellitic dianhydride-co-4,4'-oxydianiline) in N-methyl-2-pyrrolidone (NMP). Next, the coatings were cured by placing the coated conceptacles in a preheated oven at 300 °C for 30 minutes. The coated conceptacles were then depyrogenized (heated) at 300 °C for 12 hours.
[0277] Two conceptacles were placed on the concepta-on-conceptacle jig pictured in Figure 9 and ground under a load of 10 N. The abrasion procedure was repeated 4 more times over the same area and the coefficient of friction was determined for each abrasion. The conceptacles were cleaned between abrasions and the starting point of each abrasion was positioned on a previously ground area and each abrasion was performed on the same "track". The same procedure was repeated for loads of 30 N and 50 N. The coefficients of friction for each abrasion (ie, A1 to A5) are graphically depicted in Figure 28 for each load. As shown in Figure 28, the friction coefficients of the APS/poly(4,4'-oxydiphenylene-pyromellitimide) coated conceptacles were generally uniform and approximately 0.20 or less for abrasions introduced at loads of 10 N and 30 N. However, when the applied load was increased to 50 N, the coefficient of friction increased for each successive abrasion, with the fifth abrasion having a coefficient of friction slightly less than 0.40.EXAMPLE 11
[0278] Three sets of two glass conceptacles were prepared with an APS (aminopropylsilsesquioxane) coating. Each of the conceptacles was coated by immersion in a 0.1% APS solution and heated to 100 °C in a convection oven for 15 minutes. The coated conceptacles were then depyrogenized (heated) at 300 °C for 12 hours. Two conceptacles were placed on the concepta-on-conceptacle jig pictured in Figure 9 and ground under a load of 10 N. The abrasion procedure was repeated 4 more times over the same area and the coefficient of friction was determined for each abrasion. The conceptacles were cleaned between abrasions and the starting point of each abrasion was positioned in a previously ground area and each abrasion traveled the same "track". The same procedure was repeated for loads of 30 N and 50 N. The friction coefficients of each abrasion (i.e., A1 to A5) are graphically depicted in Figure 29 for each load. As shown in Figure 29, the friction coefficients of the APS coated conceptacles depyrogenized for 12 hours were significantly higher than the APS coated conceptacles shown in Figure 27 and were similar to the coefficients of friction exhibited by uncoated glass conceptacles, indicating that conceptacles may have experienced a significant loss of mechanical strength due to abrasions.EXAMPLE 12
[0279] Three sets of two glass conceptacles formed from Type B glass were prepared with a coating of poly(4,4'-oxydiphenylene-pyromellithimide). The conceptacles were immersed in a solution of 0.1% amic acid (PMDA-ODA (poly(4,4'-oxydiphenylene-pyromellithimide)) of poly(pyromellitic dianhydride-co-4,4'-oxidianilline) in N- Methyl-2-pyrrolidone (NMP) The coatings were then dried at 150 °C for 20 minutes and then cured by placing the coated conceptacles in an oven preheated to 300 °C for 30 minutes.
[0280] Two conceptacles were placed on the concepta-on-conceptacle jig pictured in Figure 9 and ground under a load of 10 N. The abrasion procedure was repeated 4 more times over the same area and the coefficient of friction was determined for each abrasion. The conceptacles were cleaned between abrasions and the starting point of each abrasion was positioned in a previously unground area. However, each abrasion traveled the same “track.” The same procedure was repeated for loads of 30 N and 50 N. The coefficients of friction for each abrasion (ie A1 to A5) are graphically depicted in Figure 30 for each load. As shown in Figure 30, the coefficients of friction of poly(4,4'-oxydiphenylene-pyromellimide) coated conceptculae, in general, increased after the first abrasion demonstrating poor abrasion resistance of a polyimide coating applied to a glass without a coupling agent.EXAMPLE 13
[0281] The APS/Novastrat® 800 coated concepts of Example 6 were tested for their coefficient of friction after freeze-drying using a concepta-on-conceptacle jig shown in Figure 9 with a load of 30 N. No increase in coefficient of friction was observed. detected after lyophilization. Figure 31 contains Tables showing the coefficient of friction for APS/Novastrat® 800 coated conceptculae before and after lyophilization.EXAMPLE 14
[0282] The Reference Glass Composition conceptacles were subjected to ion exchange and coated as described in Example 2. The coated conceptacles were autoclaved using the following protocol: 10 minute current purge at 100 °C, followed by a period residence time of 20 minutes in which the coated glass vessel 100 is exposed to an environment at 121°C, followed by 30 minutes of treatment at 121°C. The coefficient of friction for autoclaved and non-autoclaved concepts was measured using a concept car-on-concepta jig shown in Figure 9 with a load of 30 N. Figure 32 shows the coefficient of friction for concepts coated with APS/Novastrat® 800 before and after the autoclave. No increase in coefficient of friction was detected after autoclave.EXAMPLE 15
[0283] Three sets of conceptacles were coated with an APS/APhTMS coextrusion adhesive (1:8 ratio) and the outer layer consisting of Novastrat® 800 polyimide applied as a solution of polyamic acid in dimethylacetamide and imidized at 300°C. One set was depyrogenized for 12 hours at 320 °C. The second set was depyrogenized for 12 hours at 320 °C and then autoclaved for 1 hour at 121 °C. A third set of concepts were left uncoated. Each conceptacle set was then subjected to a conceptacle-on-conceptacle test under a load of 30 N. The coefficient of friction for each conceptacle set is reported in Figure 33. Photographs of the conceptacle surface showing damage (or lack of damage) experienced by each conceptacle are also depicted in Figure 33. As shown in Figure 33, the uncoated conceptacles generally had a coefficient of friction greater than about 0.7. Uncoated concept cars also incurred visually noticeable damage as a result of the test. However, the coated concepts had a coefficient of friction of less than 0.45 without any visually noticeable surface damage.
[0284] The coated conceptacles were also subjected to depyrogenization as described above, autoclave conditions, or both. Figure 34 graphically depicts the probability of failure as a function of applied load in a horizontal compression test for the conceptacles. There was no statistical difference between depyrogenized and autoclaved and depyrogenized conceptacles.EXAMPLE 16
[0285] Fractures formed from Type B glass with ion exchange were prepared with lubricious coatings that have varying ratios of silanes. Referring now to Figure 35, the concepts were prepared with three different coating compositions to evaluate the effect of different ratios of silanes on the coefficient of friction of the applied coating. The first coating composition included a coupling agent layer that has a 1:1 ratio of GAPS to aminophenyltrimethyloxysilane (APhTMS) and an outer coating layer that consisted of 1.0% Novastrat® 800 polyamide. The second coating composition included a coupling agent layer that has a 1:0.5 ratio of GAPS to APhTMS and an outer coating layer that consisted of .0% Novastrat® 800 polyimide. The third coating composition included a coupling agent layer which has a 1:0.2 ratio of GAPS to APhTMS and an outer coating layer consisting of 1.0% Novastrat® 800 polyimide. All conceptacles were depyrogenized for 12 hours at 320°C. The concepts were then subjected to a conceptcar on conceptcar friction test under loads of 20 N and 30 N. The average applied normal force, the average coefficient of friction and the average maximum friction force (Fx) for each conceptacle were reported in Figure 35. As shown in Figure 35, decreasing the amount of aromatic silane (ie, aminophenyltrimethyloxysilane) increases the coefficient of friction between the conceptacles as well as the frictional force experienced by the conceptacles.EXAMPLE 17
[0286] Fractures formed from ion-exchanged Type B glass were prepared with lubricious coatings that have varying ratios of silanes.
[0287] Samples were prepared with a composition that included a coupling agent layer formed from 0.125% APS and 1.0% aminophenyltrimethyloxysilane (APhTMS), which has an APS/APhTMS ratio of 1:8, and an outer coating layer formed from 0.1% Novastrat® 800 polyimide. The thermal stability of the applied coating was evaluated by determining the coefficient of friction and the friction force of conceptacles before and after depyrogenization. Specifically, the coated conceptacles were subjected to a concepta-to-conceptacle friction test under a load of 30 N. The friction coefficient and friction force were measured and are plotted in Figure 36 as a function of time. A second set of conceptacles were depyrogenized for 12 hours at 320°C and subjected to the same concepta-to-conceptacle friction test under a load of 30N. The coefficient of friction remained the same both before and after depyrogenation indicating that the coatings were thermally stable and protected the glass surface from friction damage. A photograph of the contact area of the glass is also shown.
[0288] Samples were prepared with a composition that included a coupling agent layer formed from 0.0625% APS and 0.5% APhTMS, which has an APS/APhTMS ratio of 1:8 and a layer of external coating formed from 0.05% Novastrat® 800 polyimide. The thermal stability of the applied coating was evaluated by determining the coefficient of friction and the friction force of conceptacles before and after depyrogenization. Specifically, the coated conceptacles were subjected to a conceptcar-on-conceptacle friction test under a load of 30 N. The friction coefficient and friction force were measured and are plotted in Figure 37 as a function of time/distance. A second set of conceptacles were depyrogenized for 12 hours at 320°C and subjected to the same concepta-to-conceptacle friction test under a load of 30N. The coefficient of friction remained the same both before and after depyrogenation indicating that the coatings were thermally stable. A photograph of the contact area of the glass is also shown.
[0289] Figure 38 graphically depicts the probability of failure as a function of applied load in a horizontal compression test for conceptacles with lubricious coatings formed from 0.125% APS and 1.0% APhTMS, and a layer of outer coating formed from 0.1% Novastrat® 800 polyimide (shown as "260" in Figure 38), and formed from 0.0625% APS and 0.5% APhTMS and an outer coating layer formed from 0.05% Novastrat® 800 polyimide (shown as "280" in Figure 38). The data shows that the failure load remains unchanged from un-scratched uncoated samples to scratched, depyrogenized and coated samples that demonstrate protection of glass by the coating from damage.
[0290] The concepts were prepared with lubricious coatings using GAPS hydrolyzate. The samples were prepared with a composition that included a coupling agent layer formed from 0.5% Dynasylan® Hydrosil 1151 (3-aminopropylsilane hydrolyzate) and 0.5% aminophenyltrimethyloxysilane (APhTMS), which has a ratio of 1:1, and an outer coating layer formed from 0.05% Novastrat® 800 polyimide. Coating performance was evaluated by determining the coefficient of friction and frictional force of conceptacles before and after depyrogenization. . Specifically, Type 1B concepts that were reinforced by ion exchange (100% KNO3 at 450°C, 8 hours) were subjected to a conceptcar-to-conceptacle friction test under a load of 30N. friction force were measured and are plotted in Figure 39 as a function of time/distance. A second set of conceptacles were depyrogenized for 12 hours at 320°C and subjected to the same concepta-to-conceptacle friction test under a load of 30N. The coefficient of friction remained the same both before and after depyrogenation indicating that the coatings were thermally stable. A photograph of the contact area of the glass is also shown. This suggests that aminosilanes hydrolyzates are useful in coating formulations as well.
[0291] The thermal stability of the applied coating was also evaluated for a number of depyrogenation conditions. Specifically, Type B glass with conceptacle ion exchange was prepared with a composition that included a coupling agent layer that has a 1:1 ratio of GAPS (0.5%) to aminophenyltrimethyloxysilane (APhTMS) (0.5% ) and an outer coating layer that consisted of 0.5% Novastrat® 800 polyimide. The concepts were dip-coated in the solution using an automated dip-coating device with a take-off rate of 2 mm/sec. The sample conceptculae were subjected to the following depyrogenization cycles: 12 hours at 320 °C; 24 hours at 320°C; 12 hours at 360°C; or 24 hours at 360°C. The friction coefficient and friction force were then measured using a conceptacle over conceptacle friction test and plotted as a function of time for each depyrogenation condition, as shown in Figure 40. As shown in Figure 40, the The conceptacles' friction coefficient did not vary with the depyrogenization conditions, which indicates that the coating was thermally stable. Figure 41 graphically depicts the coefficient of friction after varying heat treatment times at 360 °C and 320 °C.EXAMPLE 18
[0292] Conceptacles were coated as described in Example 2 with an APS/Novastrat 800 coating. The light transmission of coated concepts, as well as uncoated concepts, was measured over a wavelength range between 400 to 700 nm using a spectrometer. Measurements are carried out in such a way that a beam of light is directed normally towards the wall of the vessel so that the bead passes through the lubricious coating twice, first when entering the vessel and then when leaving it. Figure 11 graphically depicts light transmittance data for coated and uncoated conceptacles measured in the visible light spectrum from 400 to 700 nm. Line 440 shows an uncoated glass container and line 442 shows a coated glass container.EXAMPLE 19
[0293] Conceptacles were coated with a coupling agent of 0.25% GAPS/0.25% APhTMS and 1.0% Novastrat® 800 polyimide and were tested for light transmission before and after depyrogenation at 320°C by 12 hours. An uncoated concept was also tested. The results are shown in Figure 42.EXAMPLE 20
[0294] To improve the uniformity of polyimide coating, Novastrat® 800 polyamic acid was converted into polyamic acid salt and dissolved in methanol, a solvent that evaporates significantly faster compared to dimethylacetamide, by adding 4 g of triethylamine to 1 liter of methanol and then adding Novastrat® 800 polyamic acid to form 0.1% solution. The methanol-soluble amic acid salt of poly(pyromellitic dianhydride-co-4,4'-oxydianilline) can be produced.
[0295] Coating on Type 1B vials with ion exchange formed from 1.0% GAPS/1.0% APhTMS in methanol/water mixture and 0.1% Novastrat® 800 polyamic acid salt in methanol . The coated conceptacles were depyrogenized for 12 hours at 360 °C and samples coated and depyrogenized in this way were ground in conceptacle jig on conceptacle at normal loads of 10 N, 20 N and 30 N. No damage to the glass was observed at normal forces of 10 N, 20 N and 30 N. Figure 43 shows the coefficient of friction, applied force and friction force for the samples after a heat treatment at 360 °C for 12 hours. Figure 44 graphically depicts the probability of failure as a function of applied load in a horizontal compression test for the samples. Statistically, the sample series at 10 N, 20 N and 30 N were indistinguishable from each other. Low load fault samples broke from sources located far from the hazard.
[0296] The thickness of the coating layers that was estimated using ellipsometry and scanning electric microscopy (SEM) is shown in Figures 45 to 47, respectively. Samples for coating thickness measurements were produced using silicon wafer (ellipsometry) and glass slides (SEM). The methods show thicknesses ranging from 55 to 180 nm for the coextrusion adhesive and 35 nm for the Novastrat® 800 polyamic acid salt.EXAMPLE 21
[0297] Plasma-cleaned Si wafer pieces were immersion coated using a 0.5% GAPS/0.5% APhTMS solution in a 75/25 methanol/water mixture by volume. The coating was exposed to 120 °C for 15 minutes. The coating thickness was determined using ellipsometry. Three samples were prepared and had thicknesses of 92.1 nm, 151.7 nm and 110.2 nm, respectively, with a standard deviation of 30.6 nm.
[0298] The glass slides were dip coated and examined with a scanning electron microscope. Figure 45 shows an SEM image of a glass slide coated in a coating solution of 1.0% GAPS, 1.0% APhTMS and 0.3% NMP in a 75/25 methanol/water mixture. with a withdrawal of 8 mm/s followed by curing at 150 °C for 15 minutes. The coating appears to be about 93 nm thick. Figure 46 shows an SEM image of a glass slide coated in a coating solution of 1.0% GAPS, 1.0% APhTMS and 0.3% NMP in a mixture of 75/25 methanol/ water with a withdrawal rate of 4 mm/s followed by curing at 150 °C for 15 minutes. The coating appears to be about 55 nm thick. Figure 47 shows an SEM image of a glass slide coated in a coating solution of 0.5% Novastrat® 800 solution with a withdrawal rate of 2 mm/s followed by curing at 150 °C for 15 min. and heat treatment at 320 °C for 30 minutes. The coating appears to be about 35 nm thick.COMPARATIVE EXAMPLE TO
[0299] Glass conceptacles formed from a Type B glass were coated with a diluted coating of Bayer Silicone aqueous emulsion of Baysilone M having a solids content of about 1 to 2%. The conceptacles were treated at 150°C for 2 hours to drive water away from the surface leaving a polydimethylsiloxane coating on the outer surface of the glass. The nominal thickness of the coating was about 200 nm. A first set of conceptacles were kept in untreated condition (i.e. the "conceptacles clad in this way"). A second set of conceptacles were treated at 280°C for 30 minutes (i.e. the "treated concepts"). Some of the concepts in each set were first mechanically tested by applying a scratch with a linearly increasing load from 0 to 48N and a length of approximately 20 mm using a UMT-2 tribometer and a test template from concept to concept. Scratches were evaluated for coefficient of friction and morphology to determine whether the scratching procedure damaged the glass or whether the coating protected the glass from damage due to scratch formation.
[0300] Figure 48 is a graph showing the coefficient of friction, scratch penetration, applied normal force, and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for conceptculae coated in this manner. As graphically depicted in Figure 48, conceptculae coated in this way exhibited a coefficient of friction of approximately 0.03 up to loads of about 30 N. The data show that below approximately 30 N the COF is always below 0.1. However, at normal forces greater than 30 N, the coating began to fail, as indicated by the presence of glass cracking along the scratch length. Glass cracking is indicative of damage to the glass surface and an increased propensity of glass to fail as a result of the damage.
[0301] Figure 49 is a graph showing the coefficient of friction, scratch penetration, applied normal force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the treated conceptacles. For the treated concepts, the coefficient of friction remained low until the applied load reached a value of approximately 5 N. At that point the coating began to fail and the glass surface was severely damaged as evident by the increased amount of glass cracking that occurred. with increased load. The coefficient of friction of the treated concepts increased to about 0.5. However, the coating failed to protect the glass surface at loads of 30 N following thermal exposure, indicating that the coating was not thermally stable.
[0302] The concepts were then tested by applying static loads of 30 N along the entire length of the 20 mm risk. Ten samples of conceptacles coated in this way and ten samples of treated conceptacles were tested in horizontal compression by applying a static load of 30 N along the entire length of the 20 mm scratch. None of the samples coated in this way failed the scratch while 6 of the 10 treated conceptacles failed the scratch, indicating that the treated conceptacles had lower retained strength.COMPARATIVE EXAMPLE B
[0303] A solution of Wacker Silres MP50 (part#60078465 lot #EB21192) was diluted to 2% and applied to vials formed from the Reference Glass Composition. The concepts were first cleaned by applying plasma for 10 seconds before coating. The conceptacles were dried at 315 °C for 15 minutes to remove water from the coating. A first set of conceptacles were kept in “coated this way” condition. A second set of conceptacles were treated for 30 minutes at temperatures in the range of 250°C to 320°C (i.e. "treated concepts"). Some of the concepts in each set were first mechanically tested by applying a scratch with a linearly increasing load from 0 to 48N and a length of approximately 20 mm using a UMT-2 tribometer. Scratches were evaluated for coefficient of friction and morphology to determine whether the scratching procedure damaged the glass or whether the coating protected the glass from damage due to scratch formation.
[0304] Figure 50 is a graph showing the coefficient of friction, scratch penetration, applied normal force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the conceptacles as coated.
[0305] Figure 51 is a graph showing the coefficient of friction, scratch penetration, applied normal force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the conceptacles treated at 280 °C . The treated conceptacles exhibited significant glass surface damage at loads greater than about 20N. It was also determined that the threshold load value for glass damage decreased with increasing thermal exposure temperatures, indicating that the coatings degraded with increasing temperature (i.e., the coating is not thermally stable). Samples treated at temperatures below 280 °C showed damage to glass at loads above 30N. COMPARATIVE EXAMPLE C
[0306] Fractures formed from the Reference Glass Composition were treated with Evonik Silikophen P 40/W diluted to 2% solids in water. The samples were then dried at 150 °C for 15 minutes and subsequently cured at 315 °C for 15 minutes. A first set of conceptacles were kept in “coated this way” condition. A second set of conceptacles were treated for 30 minutes at a temperature of 260 °C (i.e. "the conceptacles treated at 260 °C"). A third set of conceptacles were treated for 30 minutes at a temperature of 280 °C (i.e. "the conceptacles treated at 280 °C"). The conceptacles were scratched with a static load of 30 N using the test template depicted in Figure 9. The conceptacles were then tested in horizontal compression. The concepts treated at 260°C and the concepts treated at 280°C failed in compression while 2 out of 16 of the as-coated concepts failed to scratch. This indicates that the coating degraded upon exposure to elevated temperatures and, as a result, the coating did not adequately protect the surface of the 30 N load.EXAMPLE 22
[0307] Flasks formed from the Reference Glass Composition were coated with a solution of 1.0%/1.0% GAPS/m-APhTMS in methanol/water at a concentration of 75/25. The conceptacles were dip coated in the solution with a withdrawal rate of 2 mm/s. The coating was cured at 150 °C for 15 minutes. A first set of conceptacles were kept in untreated condition (i.e. the "conceptacles clad in this way"). A second set of conceptacles were depyrogenized at 300 °C for 12 hours (ie, the "treated concepts"). Some of the concept cars in each set were mechanically tested by applying a scratch with a load of 10 N from the concept car's shoulder to the concept's heel using a UMT-2 tribometer and a concept-on-concept test jig. Additional concepts from each set were mechanically tested by applying a risk with a load of 30 N from the concept car's shoulder to the concept's heel using a UMT-2 tribometer and a concept-to-concept test jig. Scratches were evaluated for coefficient of friction and morphology to determine whether the scratching procedure damaged the glass or if the coating protected the glass from damage due to scratch formation.
[0308] Figures 52 and 53 are graphs showing the coefficient of friction, scratch penetration, applied normal force and friction force (y-ordinate) as a function of the applied scratch length (x-ordinate) for the conceptacles as coated. As graphically depicted in Figures 52 and 53, conceptculae coated in this manner exhibited some rubbing wear and damage to the glass following testing. However, the coefficient of friction was approximately 0.4 to 0.5 during the test. Figures 54 and 55 depict the results of similar testing performed on the treated concepts. Following testing, the treated concepts exhibited some abrasion of the coating surface as well as some damage to the glass. The coefficient of friction was approximately 0.7 to 0.8 during the test.EXAMPLE 23
[0309] Flasks formed from the Reference Glass Composition were coated with a solution of 1.0%/1.0% GAPS/m-APhTMS in methanol/water at a concentration of 75/25. The concepts were dip coated in the solution and stripped at stripping rates in the range of 0.5 mm/s to 4 mm/s to vary the coating thickness on respective concepts. The coating was cured at 150 °C for 15 minutes. A first set of conceptacles were kept in untreated condition (i.e. the "conceptacles clad in this way"). A second set of conceptacles were depyrogenized at 300 °C for 12 hours (ie, the "treated concepts"). Some of the concepts in each set were mechanically tested by applying a scratch with a load of 10 N from the conceptacle's shoulder to the concepta's heel using a UMT-2 tribometer. Additional concepts from each set were mechanically tested by applying a scratch with a load of 30 N from the conceptacle's shoulder to the concepta's heel using a UMT-2 tribometer. The concepts were then tested in horizontal compression. The results of the horizontal compression tests are reported in Figures 56 and 57. Conceptculae scratched under a load of 10 N showed only minimal difference in mechanical strength despite variation in coating thickness. Conceptcars scratched under a load of 30N and having a thinner coating (i.e., a coating that corresponds to a 0.5 mm/sec pull-off) exhibited a greater propensity to fail in horizontal compression relative to concepts that have a relatively thicker coating.
[0310] It should now be understood that the glass containers described in this document have at least two performance attributes selected from delamination resistance, enhanced strength and increased damage resistance. For example, glass containers can have a combination of delamination resistance and improved strength; improved strength and increased damage resistance; or increased delamination resistance and damage resistance. The glass containers described herein can be understood in terms of several aspects.
[0311] In a first aspect, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A tough inorganic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tough inorganic coating may have a coefficient of friction less than or equal to 0.7.
[0312] In a second aspect, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor of less than or equal to 10. A transient coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the transient coating may have a coefficient of friction less than or equal to 0.7.
[0313] In a third aspect, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends between the outer surface and the inner surface. At least the inner surface of the body has a delamination factor of less than or equal to 10. A tough organic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tenacious organic coating may have a coefficient of friction less than or equal to 0.7.
[0314] In a fourth aspect, a glass container may include a body that has an inner surface, an outer surface, and a wall thickness that extends between the outer surface and the inner surface. The body may be formed from a Type I, Class B glass in accordance with ASTM standard E438-92. A barrier coating may be positioned on the inner surface of the body so that a composition contained in the glass container does not come into contact with the inner surface of the body. A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0315] In a fifth aspect, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends from the outer surface to the inner surface. The body may have a hydrolytic resistance of at least HgB2 or better in accordance with the ISO 719 standard. The body may be formed from a glass composition that is free of constituent components that form species that volatilize significantly at temperatures corresponding to a viscosity in the range of about 20 Pa 2 s (200 poise) to about 1000 Pa 2 s (100 kilopoise). A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0316] In a sixth aspect, a glass container may include a body having an inner surface, an outer surface and a wall thickness that extends between the outer surface and the inner surface. The body may be formed from a Type I, Class B glass in accordance with ASTM standard E438-92. The body can be formed under processing conditions that mitigate the vaporization of volatile species in the glass composition. A lubricious coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the lubricious coating may have a coefficient of friction less than or equal to 0.7.
[0317] A seventh aspect includes the glass vessel of any of the first and third to sixth aspects, wherein the coating is thermally stable at a temperature of at least about 250°C for 30 minutes.
[0318] An eighth aspect includes the glass vessel of any of the first and third to seventh aspects, wherein the tough inorganic coating is thermally stable at a temperature of at least about 280°C for 30 minutes.
[0319] A ninth aspect includes the glass container of the first aspect, wherein the tough inorganic coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO2, diamond-like carbon, graphenes or a carbide coating.
[0320] A tenth aspect includes the glass container of the first aspect, wherein the tough inorganic coating comprises at least one of TiN, BN, HBN, TiO2, Ta2O5, HfO2, NB2O5, V2O5, SiO2, MoS2, SiC, SnO, SnO2 , ZrO2, Al2O3, BN, ZnO and BC.
[0321] An eleventh aspect includes the glass container of any one of the first through tenth aspects, wherein the body has an interior region that extends between the inner surface of the body and the outer surface of the body, the interior region being has a persistent layer homogeneity.
[0322] A twelfth aspect includes the glass container of the eleventh aspect, wherein the interior region has a thickness of at least 100 nm.
[0323] A thirteenth aspect includes the glass vessel of any one of the first through the twelfth aspects, wherein the inner surface of the body has a persistent surface homogeneity.
[0324] A fourteenth aspect includes the thirteenth aspect glass container, wherein a persistent surface homogeneity extends in the wall thickness of the body to a DSR depth of at least 10 nm from the inner surface of the body.
[0325] A fifteenth aspect includes the glass vessel of any of the first through fourteenth aspects, wherein the inner surface of the body is marked.
[0326] A sixteenth aspect includes the glass vessel of any one of the first through fifteenth aspects, wherein the inner surface of the body is marked with acid.
[0327] A seventeenth aspect includes the glass container of any one of the first through sixteenth aspects, wherein the inner surface of the glass body is a barrier coating and the barrier coating has a delamination factor less than or equal to 10.
[0328] An eighteenth aspect includes the seventeenth aspect glass vessel, wherein the barrier coating is an inorganic coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO2, diamond-like carbon, graphene or a carbide coating.
[0329] A tenth new aspect includes the seventeenth aspect glass container, wherein the barrier coating comprises at least one of Al2O3, TiO2, ZrO2, SnO, SnO2, SiO2, Ta2O5, NB2O5, Cr2O3, V2O5, ZnO or HfO2, or combinations thereof.
[0330] A twentieth aspect includes the seventeenth aspect glass container, wherein the barrier coating comprises at least one of polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfites, polysulfones, polycyanurates, parylenes, fluorinated polyolefins which include polytetrafluoroethylenes and other fluoro-substituted polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenols, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins including polyethylenes, oxidized polyethylenes, polypropylenes , polyethylene/propylene copolymers, polyethylene/vinyl acetate copolymers, polyvinylchloride, polyacrylates, polymethacrylates, polystyrenes, polyterpenes, polyanhydrides, polymaleicanhydrides, polyformaldehydes, polyacetals and copolymers of polyacetals, dimethyl or diphenyl polysiloxanes or mixtures of methyl/phenyl, silox perfluorinated and other substituted siloxanes, polyimides, polycarbonates, polyesters, paraffins and waxes, or various combinations thereof.
[0331] A twenty-first aspect includes the glass container of any one of the first to the twentieth aspects, wherein the body has at least an acid resistance of class S3 or better in accordance with DIN 12116.
[0332] A twenty-second aspect includes the glass container of any one of the first to the twenty-first aspects, wherein the body has at least a base strength of class A2 or better in accordance with ISO 695.
[0333] A twenty-third aspect includes the glass container of any one of the first to the twenty-second aspects, wherein the body has at least a hydrolytic resistance of type HgB2 or better in accordance with ISO 719.
[0334] A twenty-fourth aspect includes the glass container of any one of the first to the twenty-third aspects, wherein the body has at least a hydrolytic resistance of type HgA2 or better in accordance with ISO 720.
[0335] A twenty-fifth aspect includes the glass vessel of any one of the first to the twenty-fourth aspects, wherein the body has a Type 1 chemical durability in accordance with USP <660>.
[0336] A twenty-sixth aspect includes the glass vessel of any one of the first to the twenty-fifth aspects, wherein the body is a mold-formed body.
[0337] A twenty-seventh aspect includes the glass vessel of any one of the first to the twenty-sixth aspects, wherein the body is formed by a glass-forming process in which the body is mono-monotonically cooled from a melt. of glass.
[0338] A twenty-eighth aspect includes the glass vessel of any one of the first to the twenty-seventh aspects, wherein the body is formed from an aluminosilicate glass composition.
[0339] A twenty-ninth aspect includes the glass container of any one of the first to the twenty-eighth aspects, wherein the body is formed from an alkali aluminosilicate glass composition.
[0340] A thirtieth aspect includes the glass container of the twenty-ninth aspect, wherein the alkali aluminosilicate glass composition is substantially free of boron and boron-containing compounds.
[0341] A thirty-first aspect includes the glass container of any of the twenty-ninth and thirtieth aspects, wherein the alkali aluminosilicate glass composition is substantially free of zinc and zinc-containing compounds.
[0342] A thirty-second aspect includes the glass container of any of the twenty-ninth to thirty-first aspects, wherein the alkali aluminosilicate glass composition is substantially free of phosphorus and phosphorus-containing compounds.
[0343] A thirty-third aspect includes the glass container of any one of the first to the thirty-second aspects, wherein the body is formed from a glass composition comprising: from about 67% by mol to about 75% by mol of SiO2; from about 6 mol% to about 10 mol% Al2O3; from about 5 mol% to about 12 mol% alkali oxide, wherein the alkali oxide comprises from about 2.5 mol% to about 10 mol% Na2O and greater than about 0 mol% at about 2.5% by mol K2O; from about 9 mol% to about 15 mol% alkaline earth oxide; and from about 0 mol% to about 0.5 mol% SnO 2 .
[0344] A thirty-fourth aspect includes the glass container of the thirty-third aspect, wherein the glass composition is substantially free of boron and boron-containing compounds.
[0345] A thirty-fifth aspect includes the glass container of the thirty-third and thirty-fourth aspects, wherein the glass composition is substantially free of zinc and zinc-containing compounds.
[0346] A thirty-sixth aspect includes the glass container of the thirty-third to thirty-fourth aspects, wherein the glass composition is substantially free of phosphorus and phosphorus-containing compounds.
[0347] A Thirty-seventh Aspect includes the first through third and fifth aspects of glass, wherein the body is formed from a Type I, Class B glass in accordance with ASTM standard E438-92.
[0348] A thirty-eighth aspect includes the thirty-seventh aspect glass container, wherein the Type I, Class B glass in accordance with ASTM standard E438-92 is substantially free of zinc and zinc-containing compounds.
[0349] A thirty-ninth aspect includes the glass vessel of the second aspect, wherein the transient coating pyrolyzes at temperatures less than or equal to 300°C in less than or in 1 hour.
[0350] A fortieth aspect includes the glass container of any of the second and thirty-ninth aspects, wherein the transient coating comprises a mixture of polyoxyethylene glycol, methacrylate resin, melamine formaldehyde resin and polyvinyl alcohol.
[0351] A forty-first aspect includes the glass container of any of the second and the new thirty to fortieth aspects, wherein the transient coating comprises one or more polysaccharides.
[0352] A forty-second aspect includes the glass container of any of the second and the thirty-new to the forty-first aspects, wherein the transient coating comprises polyacrylic acid or a polyacrylic acid derivative.
[0353] A forty-third aspect includes the glass vessel of any of the second and the thirty new to the forty-second aspects, wherein the transient coating comprises an inorganic salt.
[0354] A forty-fourth aspect includes the glass container of any of the second and the thirty-new to the forty-fourth aspects, wherein the transient coating comprises at least one of: poly(ethylene oxides), poly(propylene oxides), copolymers of ethylene oxide-propylene oxide, polyvinyl pyrrolidinones, polyethyleneimines, poly(methyl vinyl ethers), polyacrylamides, polymethacrylamides, polyurethanes, poly(vinylacetates), polyvinyl formal, polyformaldehydes including polyacetals and acetal copolymers, poly(methacrylates of alkyl), methyl celluloses, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl celluloses, sodium carboxymethyl celluloses, methyl hydroxypropyl celluloses, poly(acrylic acids) and salts thereof, poly(methacrylic acids) and salts thereof, ethylene-maleic anhydride copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, vinyl acetate-vinyl alcohol copolymers, ether copolymers of methyl vinyl maleic anhydride, emulsifiable polyurethanes, polyoxyethylene stearates and polyolefins including polyethylenes, polypropylenes and copolymers thereof, starches and modified starches, hydrocolloids, polyacryloamide, vegetable and animal fats, wax, tallow, soap, stearin-paraffin emulsions, dimethyl or diphenyl polysiloxanes or methyl/phenyl mixtures, perfluorinated and other substituted siloxanes, alkyl silanes, aromatic silanes and oxidized polyethylene.
[0355] A forty-fifth aspect includes the glass container of any one of the first to the forty-fourth aspects, wherein the glass container is formed from a glass composition comprising greater than about 75 mol% SiO2 and is substantially free of boron and alkali oxides.
[0356] A forty-sixth aspect includes the glass vessel of any of the third to sixth aspects, wherein the coating has a mass loss of less than about 5% of its mass when heated from a temperature of 150°C to 350°C. °C at a ramp rate of about 10 °C/minute.
[0357] A forty-seventh aspect includes the glass container of any of the third to sixth aspects, wherein the tough organic coating comprises a polymer chemical composition.
[0358] A forty-eighth aspect includes the glass container of any of the third through the sixth and forty-seventh aspects, wherein the tough organic coating further comprises a coupling agent.
[0359] A forty-ninth aspect includes the glass vessel of any of the fifth or sixth aspects, wherein at least the inner surface of the body has a delamination factor of less than or equal to 10.
[0360] A fiftieth aspect includes the glass container of any one of the first to the forty-ninth aspects, wherein a light transmission through the glass container is greater than or equal to about 55% of a light transmission through an article of uncoated glass for wavelengths from about 400 nm to about 700 nm.
[0361] A fifty-first aspect includes the glass container of any one of the first to the fiftieth aspects, wherein the glass container is a pharmaceutical package.
[0362] It will be apparent to those skilled in the art that various modifications and variations may be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, the specification is intended to cover modifications and variations of the various embodiments described herein so long as such modifications and variations fall within the scope of the appended claims and their equivalents.

权利要求:
Claims (15)
[0001]
1. A glass container (100), comprising: a body (102) having an inner surface (104), an outer surface (106) and a wall thickness extending between the outer surface (106) and the inner surface (104), wherein at least the inner surface (104) of the body (102) has a delamination factor of less than or equal to 10; and a coating positioned on at least a portion of the outer surface (106) of the body (102), characterized in that the coating is a tough inorganic coating and the outer surface (106) of the body (102) with the tough inorganic coating has a friction coefficient less than or equal to 0.7.
[0002]
2. A glass container (100), comprising: a body (102) having an inner surface (104), an outer surface (106) and a wall thickness extending between the outer surface (106) and the inner surface (104), wherein at least the inner surface (104) of the body (102) has a delamination factor of less than or equal to 10; and a coating positioned on at least a portion of the outer surface (106) of the body (102), characterized in that the coating is a transient coating and the outer surface (106) of the body (102) with the transient coating has a coefficient friction less than or equal to 0.7.
[0003]
3. A glass container (100) comprising: a body (102) comprising a borosilicate glass having a Type 1 chemical durability in accordance with USP <660>, the body having an inner surface (104), an outer surface (106 ) and a wall thickness extending between the outer surface (106) and the inner surface (104), wherein at least the inner surface (104) of the body (102) has a delamination factor less than or equal to 10 , and wherein the glass container (100) is devoid of a coating on the inner surface (104) of the body (102); and a tough organic coating positioned on at least a portion of the outer surface (106) of the body (102), characterized in that the tough organic coating is thermally stable at a temperature of at least 250°C for 30 minutes, and the outer surface (106) of the body (102) with the tough organic coating has a coefficient of friction less than or equal to 0.7; wherein the tough organic coating comprises a polymer layer (170) and a coupling agent layer (180).
[0004]
4. Glass container (100), according to claim 1 or 2, characterized in that the coating is thermally stable at a temperature of at least 250°C for 30 minutes.
[0005]
5. Glass container (100), according to any one of claims 1 to 3, characterized in that the glass container (100) is a pharmaceutical package.
[0006]
6. Glass container (100) according to any one of claims 1 to 3, characterized in that the body (102) has an interior region (120) that extends between the internal surface (104) of the body (102) and the outer surface (106) of the body (102), the inner region (120) having a persistent layer homogeneity.
[0007]
7. Glass container (100) according to any one of claims 1 to 3, characterized in that the inner surface (104) of the body (102) has a persistent surface homogeneity.
[0008]
8. Glass container (100) according to claim 1 or 2, characterized in that the inner surface (104) of the glass body (102) is a barrier coating (131).
[0009]
9. Glass container (100) according to any one of claims 1 to 3, characterized in that the body (102) has: at least an acid resistance of class S3 or better according to DIN 12116 ( March 2001); at least one base strength of class A2 or better in accordance with ISO 695 (1991); at least one hydrolytic strength of type HgB2 or better in accordance with ISO 719 (1985); and at least one hydrolytic resistance of the HgA2 type or better in accordance with ISO 720 (1985).
[0010]
10. A glass container (100) according to claim 1 or 2, characterized in that the body (102) has a Type 1 chemical durability in accordance with USP <660>.
[0011]
11. A glass container (100) according to claim 1 or 2, characterized in that the body (102) is formed from an aluminosilicate glass composition that is substantially free of boron and boron-containing compounds, zinc and compounds containing zinc and phosphorus and compounds containing phosphorus.
[0012]
12. Glass container (100), according to any one of claims 1 to 3, characterized in that the body (102) is formed from a Type I, Class B glass in accordance with standard E438 -92 from ASTM (2011).
[0013]
13. Glass container (100), according to claim 2, characterized in that the transient coating pyrolyzes at temperatures less than or equal to 300 °C in less than or in 1 hour.
[0014]
14. A glass container (100) according to any one of claims 1 or 3, characterized in that a light transmission through the glass container is greater than or equal to 55% of a light transmission through a glass container. uncoated glass article for wavelengths from 400 nm to 700 nm.
[0015]
15. Glass container (100), according to claim 3, characterized in that the tough organic coating has a mass loss of less than 5% of its mass when heated from a temperature of 150°C to 350°C °C at a ramp rate of 10 °C/minute.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-08-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-02-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261731767P| true| 2012-11-30|2012-11-30|

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US61/731.767|2012-11-30|

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US13/780.754|2013-02-28|

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US14/075.620|2013-11-08|

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