Composite article manufacturing method, device, device manufacturing method, composite and method

专利摘要:
COMPOSITE ARTICLE, COMPOSITE ARTICLE MANUFACTURING METHOD, COMPOSITE ARTICLE USE, DEVICE, DEVICE MANUFACTURING METHOD, COMPOSITE AND METHOD. A structural reinforcement for an article that includes a carrier (10) that includes: (i) a mass of polymeric material (12) having an outer surface; and (ii) at least one composite fibrous insert (14) or overlay (960) that has an outer surface and that includes at least one array of elongated fibers (e.g., having a plurality of ordered fibers). The fibrous insert (14) or overlay (960) is provided to gather the mass of polymeric material at a predetermined location to carry a predetermined load that is subjected to the predetermined location (thereby providing localized reinforcement at that predetermined location). . The fibrous insert (14) or the overlay (960) and the bulk of polymeric material (12) are of compatible materials, structures or both, to allow the fibrous insert or overlay to be joined at least partially to the bulk of the polymeric material. A mass of activatable material (126) may be disposed on at least a portion of the conveyor (10). The fibrous insert (14) or overlay (960) may include a polymeric matrix that includes a thermoplastic epoxy.
公开号:BR112017019276B1
申请号:R112017019276-4
申请日:2016-03-10
公开日:2022-02-01
发明作者:Henry E. Richardson；Sylvain Gleyal
申请人:Zephyros, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention generally relates to composite materials, particularly composites having a thermoplastic epoxy polymeric phase, which can be used in various applications, such as structural reinforcements and/or baffles for use in transport vehicles. BACKGROUND OF THE INVENTION
[002] There is an ongoing effort in many industries to lighten the weight of articles. In many cases, this is achieved by selecting materials that have a lower density, thinner section thicknesses, or both, compared to previous materials or structures. As a result, there is a potential for weakening of structures and the consequent need for reinforcement or additional structural reinforcement.
[003] In the field of automotive vehicle manufacturing, it is common to employ structural reinforcements within cavities of the vehicle body structure. For example, it has become commonplace to employ within a cavity of the vehicle body structure a relatively rigid molded polymer support that supports an activatable material on one or more of its external surfaces. For certain activatable materials, upon activation (eg, by heat from a liner baking oven), the activatable material may expand and bond to a surface defining the cavity.
[004] In order to selectively control the properties of the reinforcing structure of the article, it has been taught to use hybrid reinforcing structures that include a combination of multiple materials for the support. See, for example, US patent document 8430448, expressly incorporated herein by reference for all purposes. See also WO 2010/054194, expressly incorporated herein by reference for all purposes.
[005] In the motor vehicle industry, the use of computer modeling (eg finite element analysis) has been employed to simulate a vehicle crash and to model how a particular section of a vehicle will respond to the accident. This modeling can be used to determine appropriate locations for placement of reinforcing structures.
[006] Notwithstanding the above efforts, there remains a need for alternative transport structures. For example, there continues to be a need for alternative support structures that employ a combination of different materials that, even if they are different, are still generally compatible (e.g. chemically and/or physically compatible) with each other so that they can be joined together in together without the need for an adhesive, a mechanical closure or other means to physically join two or more dissimilar materials. There is also a continuing need for alternative support structures that employ a combination of different materials each containing a substantial polymeric portion (e.g., a non-metallic portion) so that weight reduction can be achieved. There is also a need for polymeric materials that can be combined to increase the overall modulus and flexural strength of a reinforcement so that it exceeds that of either material on its own. There is also a continuing need for alternative support structures that employ a combination of different materials that come together at an interface region that is generally continuous with the support portions defined by the respective different materials. There is also a continuing need for an alternative support which can employ one or more local reinforcement regions through the use of a particular material within the support and which can be achieved in the absence of the need for a structural feature (e.g. a rib) to give additional strength to the localized reinforcement.
[007] Examples of composite structures are illustrated in WO 2007/008569, in patent applications US 2011/0039470 and US 2012/0251863 and in US patent 7581932, all incorporated by reference for all purposes. See also patent documents US 6855652 , US 7125461 and US 7318873 , and patent applications US 2003/0039792 , US 2010/0289242 , US 2011/0278802 and US 2009/0202294 , incorporated by reference for all purposes.
[008] The present application also relates to and incorporates, by reference for all purposes, patent application GB 1318595.4, filed October 21, 2013.
[009] In addition to the above, thermoplastic polymers having at least one epoxy group have been described in US patents 5115075, US 4438254, US 6011111 and in WO 98/14498 (see, for example, pages 3-8) together with illustrative synthesis conditions, all incorporated by reference herein (see also US patent 3317471 and US 4647648, also incorporated herein by reference). Examples of such materials can also be found, without limitation, in paragraphs 15-25 of US patent application 2007/0270515 (Chmielewski et al.), incorporated by reference for all purposes.
[010] The use of such thermoplastic polymers in a composite material has been described from WO 2008/010823 (in situ reaction of an epoxy and an amine after impregnation), incorporated herein by reference. Notwithstanding the foregoing, a need remains for composite materials that are suitable for use in a support for a baffle and/or structural reinforcement for a transport vehicle of a type exemplified in the patent publications discussed above. For example, in cases where it may be desirable to locally change or improve a property of a support material, there continues to be a need for alternative materials suitable for such a purpose. There is also a need for materials that allow recycling, recovery and/or reuse beyond the material's useful life in its intended application. See also US patent application 2009/0298974 (incorporated by reference). SUMMARY OF THE INVENTION
[011] One or more of the above needs are met by the present teachings which contemplate improved structures and methods which can be advantageously employed for sealing, deflecting and/or structural reinforcement of various articles, and particularly for structural reinforcement of transport vehicles such as auto-vehicles. The materials of the present teaching also find application in a number of other applications, as will be seen from the following discussion. That is, the present teachings generally relate to composite materials. As an example, the present teachings relate to fibrous composite materials that employ a distributed phase (e.g., a fibrous phase) and a thermoplastic polymeric material having at least one epoxy group. The material offers the benefit of mechanical properties typically achieved through the use of thermoset polymeric materials (eg, a thermoset epoxy material) as part or all of a matrix phase of a composite. However, the material has a number of physical attributes that make it suitable for post-life handling, processing and/or recovery, recycling and/or reuse.
[012] The teachings referred to herein refer to a composite article. The composite article may be in a form suitable for use as part of a deflector and/or structural reinforcement for a transport vehicle. The composite article may include at least two phases. For example, it may include a distributed phase and a matrix phase within which the distributed phase is distributed. The phase distributed in the composite article may include a plurality of selected segmented forms of fibers, platelets, flakes, chopped fibers or any combination thereof. The polymeric matrix in the composite article in which the distributed phase is distributed may include at least about 25% by weight of the polymeric matrix of a substantially thermoplastic polymer having at least one epoxide functional group. The composite article may be substantially free of a distributed phase.
[013] The teachings contained herein also relate to a method for producing a composite article. In general, a method in accordance with the present teachings may employ a step of contacting a plurality of segmented shapes, provided to define a phase distributed with a thermoplastic epoxy resin, such as a hydroxy-phenoxyether polymer (e.g., a usually thermoplastic reaction of an epoxy and an amine) that is in a softened state (e.g. in a liquid molten state). For example, a method in accordance with the present teachings may employ forming a composite material by extrusion, injection molding, pultrusion, or a combination of such processes. Thus, it is proposed for the teachings described herein that there is a method of manufacturing the composite article which includes contacting an epoxy/amine reaction product material during an extrusion, injection molding, pultrusion step, or any combination thereof. Contact may only be after the reaction has completed between the epoxy and the amine (for example, only after the epoxy and amine reaction). Thus, it is possible that the present method does not involve any chemical reaction between any epoxy and amine reagents that occur within an injection molding machine and/or an extruder. That is, the method may include advancing a thermoplastic polymer with at least one epoxide functional group reaction product along a rotating feed screw into a barrel of a polymeric material molding device.
[014] The composites that are made in accordance with the present teachings may be used as some or all of inserts and/or overlays of consolidated fibrous composite material. The fibrous materials contained herein may include a distributed phase and a matrix phase, wherein the distributed phase includes at least one array of elongated fibers to define a consolidated fibrous insert for a support. The support, the consolidated and/or overlapping fibrous insert, or each separately may have an outer surface. The composite, insert and/or overlay, or each may include at least an array of elongated fibers with a plurality of ordered fibers (e.g., organic and/or inorganic fibers) that may be distributed in a predetermined manner in a matrix of polymeric material. The matrix of polymeric material may include a thermoplastic epoxy resin material as described generally, or as described in any of the particular illustrative materials contained herein. The composites of the present teachings may be employed alone to define a support for the baffles and/or structural reinforcements of the present teachings. The composites of the present teachings may be employed as a fibrous insert adjacent (e.g., to achieve as a continuous outer surface) a mass of polymeric material (e.g., one that includes a polyamide such as Nylon, Nylon 6, Nylon 66 , polybutylene terephthalate, or any combination thereof, optionally including glass fibers) to define such a support. The location, size, shape, or any combination thereof, of the fibrous insert can be selected to help improve one or more properties of the support in the region where the insert is located. The support may support an activatable material on at least a portion of the external surface of the support. For example, the activatable material can be activated by heat (e.g., heat from a paint-baking oven, such as an automotive paint-baking oven, or by induction heating) to foam, expand, adhere, and/or cure. .
[015] The teachings contained herein further provide for composites comprising a mass of polymeric material having an outer surface and including a first polymeric material, at least one overlay of fibrous material having an outer surface and including at least one elongated fiber array having a plurality of ordered fibers, at least one fibrous insert; and a second layer of polymeric material located in between and in direct planar contact with each mass of polymeric material and at least one overlay of fibrous material, wherein the second polymeric material is a hydroxy-phenoxyether polymer, such as a thermoplastic material of polyetheramine, which is a product (e.g. a thermoplastic condensation reaction product) of a reaction of a monofunctional or difunctional species (e.g. monoethanolamine) with an epoxide-containing moiety, such as a diepoxide (e.g. for example, bisphenol A) diglycidyl ether which was reacted under conditions to cause the hydroxyl moieties to react with the epoxy moieties to form a generally linear polymeric backbone with ether linkages.
[016] The composite may include a single mass of polymeric material, which may be a polyethylene material. The composite may include exactly two overlays of fibrous material. The composite may include at least two second polymeric layers. The composite may include at least four second polymeric layers. The composite may include exactly four polymeric layers. The second polymeric layer may be a film. The mass of polymeric material may include a polyethylene material. At least one overlay of fibrous material may include glass fibers.
[017] The teachings contained herein also provide a method comprising forming the composite materials described herein in a heated press.
[018] The teachings contained herein further provide a device comprising a pultruded elongated remouldable thermoplastic epoxy backing, a sealant material located in direct planar contact with a portion of the backing, and one or more portions of remoldable thermoplastic epoxy film layer located in contact glide straight with the support. BRIEF DESCRIPTION OF THE DRAWINGS
[019] Figure 1 is a side sectional view of a portion of an illustrative part in accordance with the present teachings.
[020] Figure 2 is a side sectional view of a portion of another illustrative part in accordance with the present teachings.
[021] Figure 3 is a side sectional view of a portion of yet another illustrative part in accordance with the present teachings.
[022] Figure 4a is a top perspective view of an illustrative vehicle in accordance with the present teachings.
[023] Figure 4b is a lower perspective view of the support of Figure 4a.
[024] Figure 5 is an exploded perspective view of an illustrative arrangement of a fibrous insert of the present teachings.
[025] Figure 6A is a perspective view of an illustrative fibrous insert in accordance with the present teachings.
[026] Figure 6B is a perspective view of an illustrative part that incorporates the fibrous insert of Figure 6A.
[027] Figure 7A is a perspective view of another illustrative fibrous insert in accordance with the present teachings.
[028] Figure 7B is a perspective view of an illustrative part that incorporates the fibrous insert of Figure 6A.
[029] Figure 8 is a schematic illustrating the formation of an illustrative part in accordance with the present teachings.
[030] Figure 9 is an illustrative example of a profile of an elongate article (e.g., a support) having an illustrative overlay in accordance with the present teachings.
[031] Figure 10 is a schematic of a system for making an article in accordance with the present teachings.
[032] Figure 11A is a perspective view of an illustrative article in accordance with the present teachings.
[033] Figure 11B is a rear perspective view of the article in Figure 11A.
[034] Figure 11C is a side profile view of the article in Figure 11A. DETAILED DESCRIPTION
[035] The present teachings meet one or more of the above needs for the improved devices and methods described herein. The explanations and illustrations presented herein are intended to familiarize others skilled in the art with the teachings, their principles, and their practical application. Those skilled in the art can adapt and apply the teachings in their numerous forms, which may be more suited to the requirements of a specific use. Accordingly, the specific embodiments of the present teachings, as set forth, are not to be construed as being exhaustive or limiting of the teachings. The scope of the teachings should therefore be determined not with reference to the above description, but should rather be determined with reference to the appended claims, together with the full range of equivalents to which such claims are entitled. Descriptions of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible, as will be obtained from the following claims, which are also incorporated herein by reference in this disclosed description.
[036] The present application relates to the teachings of PCT/US14/070853, filed December 17, 2014; provisional application US 61/916884, filed December 17, 2013; and application PCT/US14/61531, filed October 21, 2014, the contents of these applications being incorporated by reference for all purposes.
[037] This application claims the benefit of filing dates from provisional US 62/130,832 filed March 10, 2015; provisional application US 62/183380, filed on June 23, 2015; provisional application US 62/294160, filed on February 11, 2016; and provisional application US 62/296374, filed February 17, 2016; all of which are incorporated by reference for all purposes.
[038] As noted, the present teachings generally relate to composite materials. In this regard, there are several composites to which the teachings belong. Composites share the common feature that each employs a fibrous composite material. The fibrous composite material may have a distributed phase (e.g., a fibrous phase) and a polymer thermoplastic material (e.g., a remoldable resin material or thermoplastic reaction product) with at least one epoxy group. The thermoplastic polymeric material having at least one epoxy group can define a matrix material in which the distributed phase resides. The thermoplastic polymeric material having at least one epoxy group may be a hydroxyphenoxyether polymer, such as a polyetheramine thermoplastic material as described herein. For example, such a thermoplastic polymeric material having at least one epoxy group may be a product (e.g., a thermoplastic condensation reaction product) of a reaction of a mono-functional or di-functional species (i.e., respectively, a species with one or two reactive groups, such as an amide-containing species), with an epoxide-containing moiety, such as a diepoxide (i.e., a compound with two epoxide functionalities), which reacts under conditions to react the hydroxyl moieties with the epoxy moieties to form a generally linear polymeric backbone with ether linkages. The remoldable thermoplastic polymeric material may be formed as a sheet or film and may be substantially free of any distributed (e.g., fibrous) phase. In a non-limiting example, the thermoplastic polymeric material can be formed as a film that can be in contact with a fibrous layer. The remoldable thermoplastic polymeric material may be formed into a yarn.
[039] The teachings contemplate the possibility that a structure may be fabricated using a remoldable thermoplastic material in accordance with the present teachings. In particular, the structure may be made from a thermoplastic material in accordance with the present teachings which is reinforced with a reinforcing step. The reinforcing phase may be distributed in a matrix of thermoplastic material (e.g. a polyamide as described and/or a remouldable resin material as described). For example, the reinforcement phase can be at least a large part (by volume) of the total material. It may be greater by about 60% by volume or greater by about 70% by volume. It can be less than about 90% by volume, below about 80% by volume, or below about 70% by volume. Any reinforcement phase may be distributed randomly, generally uniformly, and/or at one or more predetermined locations on an article. The reinforcing phase may comprise the remoldable thermoplastic material.
[040] Fibrous composite materials can be used as a portion of another composite material. For example, it may be employed as an insert (e.g., a fibrous insert) and/or an overlay (e.g., sheet) of a composite that includes one or more other materials.
[041] The teachings here refer to a composite article. The composite article may be in a form suitable for use as part of a deflector and/or structural reinforcement for a transport vehicle. The composite article may be in a form suitable for use as a panel structure. The composite article may be in a form suitable for use as a building construction material, as a furniture material, as a good sporting material (e.g. for skis, snowboards, bicycles, poles, tennis rackets or the like) or as protective material (eg for police shields, armored vehicle panels or similar). The fibrous composite materials of any composite article may include a single phase or may include at least two phases. For example, it may include a distributed phase and a matrix phase within which the distributed phase is distributed. The phase distributed in the composite article may include a plurality of elongated segmented shapes (e.g., in a ratio of at least 2:1 between a major and minor dimension of the shape) selected from fibers, platelets, flakes, chopped fibers, or any combination of these. For the fibers used herein, the fibers may be employed in the distributed phase in the form of a random distribution, a fabric, a non-woven batt, a plurality of generally axially aligned fibers (e.g. a bundle), a plurality of axially intertwined fibers (for example, a thread) or any combination of them. A plurality of individual fibers can therefore be in a generally ordered relationship (e.g. according to a predetermined pattern) with respect to one another.
[042] The material composition of the distributed phase can be the same or different from the polymer matrix composition. For example, it is possible that the material of the distributed phase may be a thermoplastic polymer having at least one epoxide functional group as described generally or specifically within the present teachings. The polymeric matrix material may also be or include a thermoplastic polymer having at least one epoxide functional group as described generally or specifically within the present teachings.
[043] The weight ratio of polymer matrix to the distributed phase can range from about 1:10 to about 100:1 (for example, it can range from about 1:5 to about 10:1, about 1 :3 to about 5:1, about 1:2 to about 2:1).
[044] The polymer matrix in the fibrous composite material in which the distributed phase is distributed may include at least about 25%, 33%, 50%, 67%, 85% by weight of the polymer matrix of a substantially thermoplastic polymer having at least an epoxide functional group. The polymer matrix of the substantially thermoplastic polymer having at least one epoxide functional group may have less than about 5%, 3% or even 1% by weight of a polymeric ingredient other than the thermoplastic polymer having at least one epoxide functional group (e.g. , the polymer matrix essentially consists of the thermoplastic polymer with at least one epoxide functional group).
[045] The balance of the fibrous composite material can be the distributed phase. The composite material balance may include the phase distributed in addition to another phase and/or material.
[046] The distributed phase may include one, two or more different materials. For example, it may include a single shape (e.g., a single elongate segment shape), or a plurality of different shapes (e.g., a plurality of elongate segment shapes). At least about 25%, 33%, 50%, 67%, 85% by weight of the distributed phase may be fibers. The distributed phase can be less than about 5%, 3% or even 1% by weight of a form other than a fiber.
[047] The fibrous material, which may be formed as a distributed phase, may include an organic material, an inorganic material, or a combination of each. The material may be a naturally occurring material (eg a rubber, a cellulose, sisal, jute, hemp or some other naturally occurring material). It can be a synthetic material (e.g. a polymer (which can be a homopolymer, a copolymer, a terpolymer, a mixture or any combination thereof)). It can be a carbon-derived material (e.g. carbon fiber, graphite, graphene or other). The distributed phase may thus include fibers selected from mineral fibers (organic or inorganic) (e.g. glass fibers such as E glass fibers, S glass, B glass or otherwise), polymeric fibers (e.g. a fiber aramid fiber, a cellulose fiber or otherwise), carbon fibers, metal fibers, natural fibers (e.g. derived from an agricultural source) or any combination thereof. The plurality of elongated fibers may be oriented generally parallel to each other. They can be braided. They can be twisted. The fiber arrangements can be woven and/or non-woven.
[048] The fibrous material may include a plurality of fibers having a length of at least about 1 cm, 3 cm or even 5 cm or more. The fibers can have an average diameter of about 1 to about 50 microns (e.g., about 5 to about 25 microns). The fibers can have a suitable sizing of the coating on them. The fibers may be present in each layer, or in the fibrous insert in general, in an amount of at least about 20%, 30%, 40% or even 50% by weight. The fibers may be present in each layer, or in the fibrous insert in general, in an amount below about 90%, 80%, or even about 70%, by weight. By way of example, the fibers may be present in each layer, or in the fibrous insert, in an amount of from about 50% to about 70% by weight. Fiber contents by weight can be determined in accordance with ASTM D2584-11. The fibers may comprise remoldable thermoplastic polymeric material as described herein.
[049] Tapes and/or sheets (e.g., films) for use in one or more of the portions of a fibrous composite material herein may be made by extrusion, pultrusion or otherwise. Examples of such processes can be found in provisional application US 62/130908, filed March 10, 2015; provisional application US 62/200380, filed on August 3, 2015; and Provisional Application US 62/296378, filed February 17, 2016, all incorporated by reference herein for all purposes. In this way, it may be possible to achieve alignment of the fibers in the tapes and/or sheets. The tape and/or sheet may be formed from the thermoplastic polymeric material. The tape and/or sheet may include a fibrous phase or, alternatively, be substantially free of any fibrous phase. The thermoplastic polymeric material can be formed into fibers which can then form the tape and/or sheet. A method described herein may include a step of impregnating a fibrous mass with the polymeric matrix material and passing the resulting impregnated material through a matrix (e.g., a heated matrix) or other structure having an opening so that the fibrous mass be coated with a generally continuous mass of polymeric matrix material. In this way, it is also possible to obtain the desired ordering of fibers in relation to each other. Composite materials can be formed by keyed extrusion whereby a heat stamping process is used to secure a mechanical fastener, which can be located in a channel formed during the extrusion process. Alternatively, the fastener may be attached in a non-channeling location.
[050] The fibrous composite materials of the present teachings may include one or more layers (e.g., may have 2, 3, 4, 6, or 15 or more layers). The layers may be consolidated in the sense that they include a plurality of individual fibers or other segmented forms of a distributed phase, which may be distributed into a cohesive mass of polymeric matrix material (e.g., a matrix that includes a hydroxyl polymer). phenoxyether, such as a polyetheramine thermoplastic material as described herein). For example, the polymer may be a product (e.g., a thermoplastic condensation reaction product) of a reaction of a mono-functional or di-functional species (i.e., respectively, a species with one or two reactive groups, such as as an amide-containing species), with an epoxide-containing moiety, such as a diepoxide (i.e., a compound with two epoxide functionalities), which reacts under conditions to react the hydroxyl moieties with the epoxy moieties to form a polymer backbone usually linear with ether bonds. Multiple layers can be consolidated so that a cohesive mass, including the multiple layers, is formed. The multiple layers can be consolidated to form a predetermined shape in the form of a three-dimensional shaped insert. For example, the fibrous insert may employ a plurality of layers that include a plurality of elongated fibers (e.g., having a length of at least 1 cm, 3 cm, or even 5 cm or more) that are oriented generally parallel or generally oriented unidirectional to each other and are distributed in a generally continuous polymeric matrix (e.g. in a continuous matrix of the second polymeric material). A molding operation (e.g. thermoforming, molding, passing through a die, rolling, or otherwise) may be performed.
[051] Fibers may be present in an amount, a distribution or both to reinforce the composite article by realizing an improvement of one or more mechanical properties selected from ultimate tensile strength, elongation, flexural modulus, compression modulus , or otherwise, compared to the corresponding property of the polymer matrix material alone.
[052] The fibrous composite materials of the present teachings may be such that the distributed phase is distributed in the polymer matrix material in an ordered array, in a substantially homogeneous array, or both. It is possible for the distributed phase to be distributed in the polymer matrix material in a random arrangement. The individual fibers may be distributed in a predetermined ordered arrangement within the matrix of polymeric material such that at least a portion of the fibers are ordered in their arrangement (e.g. in a generally ordered relationship to one another, such as generally parallel or unidirectional). or otherwise generally axially aligned) and therefore not randomly distributed in the polymer matrix material.
[053] Returning in more detail to materials that may be used in the present teachings, a variety of materials that have thermoplastic thermal characteristics may be suitable. In general, the teachings contained herein also extend to certain thermoplastic polymers (e.g. polyamides such as Nylon 6 or Ulpepespe from BASF). The materials may be used alone, as the matrix material of a multiphase material (e.g., together with a reinforcing phase, such as carbon fibers, glass fibers, polymeric fibers, natural fibers, or some other segmented form, as described herein in another place). It can be employed as a layer of a laminate, as a core or shell of an elongated core/shell material, as a core or shell of core/shell material, or otherwise.
[054] The materials may be thermoplastic in nature, so that it is able to flow when subjected to a temperature above the glass transition temperature (Tg) and/or a temperature at which it melts. A particularly preferred material for use herein is a remouldable resin material and particularly a material which broadly contemplates specific ingredients, reactions and reaction products associated with polymers with an epoxy functionality to impart at least one mechanical characteristic consistent with epoxy thermosetting materials, and at least at least one processing characteristic (e.g., elevated temperature) associated with thermoplastic materials (e.g., a glass transition temperature); and even more particularly, the present teachings relate to the manufacture of additives with a thermoplastic polyether material, such as a thermoplastic epoxy polymer material.
[055] Materials useful in the present teachings (e.g., as remouldable resin material) may have a relatively low glass transition temperature (Tg). It may be possible to have a Tg below about 100°C, below about 90°C, below about 80°C, below about 70°C, below about 65°C as measured by calorimetry sweep differential according to ASTM E1356 - 08 (2014). The material of the present tests may have a glass transition temperature measured by differential scanning calorimetry in accordance with ASTM E1356 - 08 (2014) of at least about 45°C, at least about 55°C, or at least about 60°C. The use of such materials has the ability to substantially increase productivity. Power consumption can be reduced. Build times can be shortened. Still, the resulting materials can result in materials with very attractive mechanical and/or self-adhesive characteristics that make them attractive for additive manufacturing constructs.
[056] As illustrated below, remoldable resin material can have a relatively high Tg. It may be possible to have a Tg in excess of about 115°C, or in excess of about 125°C, or in excess of about 135°C, as measured by differential scanning calorimetry in accordance with ASTM E1356-08 ( 2014). The polymer and/or reaction product of the present assays may have a glass transition temperature measured by differential scanning calorimetry in accordance with ASTM E1356 - 08 (2014) below about 200°C, below about 185°C or below about 170°C. By way of illustration, the polymer and/or reaction product of the present teachings may have a glass transition temperature measured by differential scanning calorimetry in accordance with ASTM E1356 - 08 (2014) of at least about 120°C and below of about 170°C.
[057] The polymeric material may exhibit one or any combination of the following characteristics: a yield point stress (according to ASTM D638 - 14) of at least about 15 MPa (e.g. at least about 30 MPa or even at least at least about 45 MPa), a tensile-to-break elongation force (according to ASTM D638-14) of at least about 40 MPa (e.g. at least about 45 MPa or even at least about 55 MPa) ; an elongation at break (according to ASTM D638-14) of at least about 15% (e.g., at least about 20%, 25%, or 30%); and/or a tensile modulus of elasticity (according to ASTM D638-14) of at least about 0.5 GPa (e.g., at least about 1 GPa, at least about 1.8 GPa, or even at least minus about 2.7 GPa).
[058] By way of illustration of various illustrative materials, several possible reactions are identified that can be used to produce a reformable resin material.
[059] In general, in this case, any reaction suitable to achieve the desired resultant characteristics in a remoldable resin material can be employed. At least two reaction approaches are contemplated within the scope of the present teachings. Either or both in combination may be used. In a first approach, a reaction is used to result in a poly(hydroxyaminoether), (PHAE). In a second approach, a reaction is employed to result in a thermoplastic epoxy polymer that is essentially devoid of nitrogen and/or an amine moiety along its main chain.
[060] Exemplary materials can be made with a di-functional epoxy resin and a primary amine or a secondary diamine, for example, a reaction between bisphenol A diglycidyl ether and monoethanolamine. For some applications that may require a higher glass transition temperature (Tg), it is contemplated that some or all of the bisphenol A diglycidyl ether can be replaced by an epoxy monomer with less mobility. Such epoxy monomers may include fluorene diphenol diglycidyl ether or 1,6 naphthalene diepoxy. Furthermore, it is envisaged that, where fire resistance is desired, some or all of the bisphenol A diglycidyl ether may be replaced by a brominated bisphenol A epoxy resin. According to this approach, materials must be prepared by reacting a diglycidyl ether of dihydric aromatic compounds such as bisphenol A diglycidyl ether, or a diepoxy-functionalized oli(alkylene oxide) or mixture thereof with a primary amine or a diamine. secondary or a monoamine-functionalized poly(alkylene oxide) or mixture thereof.
[061] These materials generally have a relatively high strength and flexural modulus, often much higher than typical polyolefins (ie polyethylene and polypropylene). Such materials can be melt processed at temperatures such as a temperature above about 70°C, about 85°C, or about 90°C, and/or below about 300°C, about 250°C, about 230°C, or about 210°C. Furthermore, the use of the remoldable resin materials described herein for support structures provides improved rigidity and/or improved adhesion when adhesively bonded to another article, for example, compared to another traditional polymeric material such as a polyolefin, a polyamide , a polyester, a polyurethane, a polysulfone or the like.
[062] As the teachings illustrated herein, other epoxide-containing moieties may be employed. The epoxide-containing moieties may include at least one mono-functional epoxide and/or a di-functional epoxide ("diepoxide"). Among the various diepoxides that may be used in the teachings, there may be a diglycidyl ether of a dihydric phenol (e.g. resorcinol, biphenol or bisphenol A). Any epoxide-containing moiety may be an aliphatic and/or aromatic epoxide.
[063] An illustration of a possible example of such a material might be a reaction product of a diglycidyl ether of a dihydroxy organic compound and an amino, namely one that has two amino hydrogens per molecule (e.g. a reaction product of a diglycidyl ether of bisphenol A and a monoethanamine), as described, for example, in col. 1, line 4 to col. 2, line 52 of US Patent 3,317,471 (incorporated by reference).
[064] Additional details of suitable reagents and conditions for this first approach can be found in US patent application 2007/0270515 (see, for example, paragraphs 0014 to 0025), in US patent 5164472 (see, for example, cols 2- 4); and US patent 3317471 (see, for example, col. 1, line 4 through column 2, line 52), all incorporated by reference.
[065] Referring in more detail to the second approach, without limitation, this approach can be used in cases where it is desired to employ a material with a relatively high glass transition temperature. One approach envisions a reaction that may include a step of reacting a dihydric phenol or a combination of different dihydric phenols with a diepoxide or combination of different diepoxides. The reaction can take place in the presence of a catalyst (e.g. a catalyst selected from the group consisting of bis(trihydrocarbylphosphoranylidene)ammonium salt, bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt and tetrakis[tris(dihydrocarbylamino)phosphoranylideneamino salt ] phosphonium). The reaction between the dihydric phenol and the diepoxide can be conducted in an ether or hydroxyether solvent at a temperature high enough to produce a poly(hydroxyether). A particular illustration of such a possible approach to forming a remouldable resin material with a relatively high glass transition temperature can be found in US patent 5401814; incorporated herein by reference. One approach envisions a reaction that may include a step of reacting a dihydric phenol or combining different dihydric phenols with a diepoxide or combining different diepoxides. The reaction can take place in the presence of a catalyst (e.g. a catalyst selected from the group consisting of bis(trihydrocarbylphosphoranylidene)ammonium salt, bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt and tetrakis[tris(dihydrocarbylamino)phosphoranylideneamino salt ] phosphonium). The reaction between the dihydric phenol and the diepoxide can be conducted in an ether or hydroxyether solvent at a temperature high enough to produce a poly(hydroxyether). A particular illustration of such a possible approach to forming a remouldable resin material with a relatively high glass transition temperature can be found in US patent 5401814; incorporated herein by reference.
[066] Approaches other than above to reactions for making materials useful for the present teachings (e.g., a thermoplastic polyether) may include one or more reactions selected from the first and second approaches above, or (a) a reaction product of the diglycidyl ether of a bisphenol with a dihydroxybiphenyl, wherein the repeating unit of the polyhydroxyether contains a hydrocarbon linking group and a hydrocarbon or halogen substituted phenylene radical, as described in US patent 4,647,648 (incorporated herein by reference); (b) a reaction product of a diglycidyl ether of certain amido-dihydric phenols and N-substituted dihydric phenols, as described in US patent 5,115,075 (incorporated herein by reference); (c) a reaction product of a dihydric phenol (e.g. a diglycidyl ether of one or more of a bisphenol ketone, bisphenol sulfone, resorcinol or hydroquinone) and at least one other dihydric phenol such as 4,4'-ispropylidene bisphen (bisphenol A), 4,4'-dihydroxydiphenylethylmethane, 3,3'-dihydroxydiphenyldiethylmethane, 3,4'-dihydroxydiphenylmethylpropylmethane, bisphenol, 4,4'-dihydroxydiphenyloxide, 4,4'-dihydroxydiphenylcyanomethane, 4,4'-dihydroxybiphenyl, 4, 4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylsulfone, 2,6-dihydroxynaphthalene, 1,4'-dihydroxynaphthalene, catechol or the like, as described in US patent 5164472 (incorporated herein by reference) ; (d) a reaction product (e.g. a reactive extrusion product) of a diglycidyl ether of a dihydric phenol with an amine having only two hydrogens under conditions sufficient to form the polyetheramine, as described in US patent 5275853 (incorporated herein by reference); (e) a reaction product of dihydric phenol and a diepoxide in the presence of a catalyst selected from bis(trihydrocarbylphosphoranylidene)ammonium salt, bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt or tetrakis[tris(dihydrocarbylamino) salt phosphoranylideneamino]phosphonium, as described in US patent 5401814 (incorporated herein by reference); (f) a reaction product prepared by reacting (1) a primary amine or bis(secondary) diamine with (2) a diglycidyl ether and (3) an amine or epoxy functionalized poly(alkylene oxide) as described in US patent 5464924 (incorporated herein by reference); (g) a reaction product of a compound having an average of more than one vicinal epoxide group per molecule and a polyhydric phenol or thiophenol, in the presence of a catalytic amount of a tetrahydrocarbyl phosphonium salt in an essentially anhydrous medium, as described in US Patent 4,438,254 (incorporated herein by reference); (h) a reaction product of a diepoxide (e.g., diglycidyl ethers of dihydric phenols) and a difunctional species selected from dihydric phenols, dicarboxylic acids, bis-secondary amines, primary amines, dithiols, disulfonamides and compounds containing two different functionalities capable of reacting with epoxide groups, as described in US patent 6011111 (incorporated herein by reference); or (i) a hydroxy-phenoxyether reaction product polymer prepared by reacting a difunctional species (i.e., a species having two reactive groups), such as a dihydric phenol, with a diepoxide (i.e., a compound with two epoxide functionalities) under conditions sufficient to cause the hydroxyl moieties to react with the epoxy moieties to form ether bonds, as described in WO 98/14498 (incorporated herein by reference).
[067] It is possible that two or more of the remoldable resin compositions described above may be used together. For example, two or more remoldable resins, each with different glass transition temperatures, can be used together for selectively different properties. This can be achieved by blending the two, or by blending preforms of each (for example, a yarn or fabric having upper and lower glass transition fibers).
[068] Remoldable resin materials in accordance with the present teachings may have a generally linear backbone and may also have at least one ether linkage in repeating units of the generally linear backbone. Materials in accordance with the present teachings may be free from cross-linking or any thermoset moiety chemically bonded to a generally linear backbone.
[069] In general, it may also be possible to employ one or more reactions that allow for an optional delayed cross-linking reaction. For example, one or more of the reactants may include one or more moieties that are capable of reacting (e.g., in the presence of a certain stimulus, such as additional heating and/or some other form of predetermined electromagnetic radiation (e.g., , infrared, ultraviolet, microwave or otherwise) to achieve crosslinking of a molecule with itself and/or an adjacent molecule. Preferably, such radiation provides crosslinking while maintaining a resulting article made by manufacturing additives to remain below its Tg. Thus, it may be possible that cross-linking can be performed within and/or between adjacent layers. Thus, the teachings contemplate an optional step to cause at least a portion of an article made in accordance with the teachings to include cross-linking, such as as promoting a crosslinking reaction (e.g. subjecting the feed material and/or the resulting article to electromagnetic radiation as written).
[070] The teachings provided herein make advantageous use of remoldable resin materials for use in various applications, such as in construction, appliances, defence, sporting goods and/or the transportation industry. By way of example, the remouldable resin materials of the teachings find application in transport vehicle components such as structural reinforcements, baffles, sealing devices, panels (e.g. wall panels, automotive body panels, roof panels, etc.), brackets, beams (e.g. cross-vehicle beams, such as useful instrument beams supporting an instrument panel), module structures (e.g. a frame upon which a plurality of components can be mounted , before, during and/or after the frame assembly in a vehicle frame).
[071] The resulting articles can not only be made by taking advantage of beneficial processing characteristics consistent with thermoplastic materials from remoldable resin materials. But, after the articles have been manufactured, the articles may be further modifiable by forming or otherwise molding by heating the article to a temperature above which at least a portion of the remoldable resin material that is incorporated into the article is raised above its Tg. Subsequently, the article can be cooled so that the material is below the Tg, causing the material to retain the desired shape. In one or more times, when the remoldable resin material is above its Tg, the remoldable resin material is such that it becomes tacky and can form an adhesive bond with an item placed on it. Thus, the present teachings contemplate heating an article having a wall to which a component is to be bonded to an elevated temperature above which at least a portion (e.g., below about 60%, about 50%, about (40% (about 30%, about 20%, or about 10% of the average wall thickness) of the remoldable resin material that is incorporated into the wall of the article is elevated above its Tg. At the moment when the portion of the remoldable resin material is above its Tg, a component is brought into contact with it (optionally in the presence of pressure). Subsequently, the article can be cooled so that the material is below the Tg, causing the material to maintain the desired shape and maintain the component by adhesive bonding. It is possible to make use of the Tg and adhesive characteristics of the remouldable resins to simplify the mounting structures, removing the need for certain accessories. This makes it possible to attach a component directly to the article, without a mechanical fastening system, or to overmould a structure in a pultruded bundle (the bundle can be partially or fully encapsulated by the molded material).
[072] With reference to the material of the polymeric matrix, a thermoplastic polymer (for example, a remoldable resin) can be included. The polymer may be a hydroxy-phenoxyether polymer, such as a polyetheramine thermoplastic material. Although other functional species may be used, as taught in US Patent 6011111 (incorporated by reference, see, for example, columns 6-8) and WO 98/14498 (incorporated by reference, see, for example, pages 8-11) examples of mono-functional or di-functional species may include a dihydric phenol, a secondary amine (e.g., a bis-secondary amine), a primary amine, or any combination thereof. Any amine of the functional species can be an aromatic amine, an aliphatic amine, or a combination thereof. Mono-functional or di-functional species may have one or two functionalities capable of reacting with epoxide groups to form a generally uncrosslinked polymer. Some specific, without limitation, examples of functional species for reaction with an epoxy moiety in accordance with the present teachings include an ethanolamine (e.g., monoethanolamine), piperazine, or a combination thereof. Any of the illustrative functional species may be substituted or unsubstituted.
[073] Other examples of illustrative materials, functional species and diepoxides are described in US patents 5115075; US 4438254; US 6011111; and WO patent document 98/14498 (see, for example, pages 3-8) together with illustrative synthesis conditions, all incorporated by reference herein (see also US patents 3317471 and US 4647648, also incorporated herein by reference). Examples of such materials can also be found, without limitation, in paragraphs 15-25 of US patent application 20070270515 (Chmielewski et al.), incorporated by reference for all purposes.
[074] The teachings contained herein also relate to a method for producing a composite article. In general, a method in accordance with the present teachings may employ a step of contacting a plurality of segmented shapes to define a phase distributed with a generally thermoplastic epoxy reaction product of reactants (e.g., a mono-functional or di-functional species). - functional (i.e., respectively, a species with one or two reactive groups, such as an amide-containing species), with an epoxide-containing moiety, such as a diepoxide (i.e., a compound with two epoxide functionalities), i.e. in a softened state (e.g., in a liquefied molten state). For example, a method in accordance with the present teachings may employ forming a composite material by passing a mass of fibers and resin through a matrix (e.g., by extrusion and/or pultrusion), by molding (e.g., injection molding, compression molding, or otherwise), or a combination thereof. One or more other methods may be employed to produce article in accordance with the present teachings. For example, it may be possible to produce a product by thermoforming.
[075] Accordingly, it is envisaged for the teachings herein that there exists a method of manufacturing the fibrous composite article which includes contacting at least a portion of the intended distributed phase material with a generally thermoplastic epoxy reaction product of reagents (e.g. example, a mono-functional or di-functional species (i.e., respectively, a species with one or two reactive groups, such as an amide-containing species), with an epoxide-containing moiety, such as a diepoxide (i.e., a compound with two epoxy functionalities)). For example, in accordance with the teachings contained herein on the proposed polymeric matrix material, the polymeric matrix material may include as a major component an epoxy/amine reaction product material (e.g., a material that is a reaction product of an epoxy resin (e.g. a liquid diepoxide resin) and an amine (e.g. a monoethanolamine) such as a reaction product wherein the reactants as described herein can react in a generally equal molar ratio during one step extrusion, injection molding, pultrusion, or any combination thereof. Contact can be made only after the reaction has completed between the epoxy and the amine (for example, only after the reaction of epoxy and amine reagents). fibrous material can be contacted by the thermoplastic polymer material only in a shaping or molding step. Thus, it is possible that the method presented here does not involve any chemical reaction between any reagents (e.g. o, any epoxy and amine reactants) occurring within a molding or forming machine in which the reaction product and the intended distributed phase materials are brought into contact. That is, the method may include advancing a thermoplastic polymer having at least one epoxide functional group reaction product along a rotating feed screw into a barrel of a polymeric material shaping apparatus, and then contacting the thermoplastic polymer with the desired distributed phase material.
[076] It is also possible for a portion of the intended distributed phase material to be contacted with reactants prior to any reaction to form the thermoplastic polymer reaction product of the present teachings. For example, it may be possible for the intended distributed phase material to be contacted with one or both of the epoxy or amine reactants (eg, in a liquid state) prior to reaction to form the thermoplastic polymer reaction product. For example, a mass of fibers can be infiltrated with a liquid epoxy reagent, a liquid amine reagent, or both. Subsequently, any remaining reactant can be introduced (along with exposure to any necessary heat and/or pressure) to trigger a reaction to form the thermoplastic polymer reaction product in situ within the fiber mass. The use of the remoldable resins described herein as pultrusion polymers, when in a liquid state, are able to provide surprisingly good infiltration of a mass of fibers to provide a cohesive matrix within which the fibers are distributed.
[077] A method of producing an article in accordance with the present teachings may be carried out continuously. For example, fibrous material from a continuous supply (e.g., a spool of the desired fibrous material (e.g., in its desired shape, such as a rope, yarn, weft, non-woven batt or otherwise as described herein) for use as the distributed phase) can be fed continuously to and through a matrix. The fibrous material may be contacted (e.g., by means of a suitable coating operation, such as roll coating, or otherwise) with the thermoplastic polymer reaction product before or at the time the fibrous material is passed through the die. . The fibrous material may be contacted (e.g., by means of a suitable coating operation, such as roll coating, or otherwise) with the reactants for the thermoplastic polymer reaction product before or at the time when the fibrous material is passed through the array. When leaving the matrix, a composite mass is obtained. The fibrous material can thus form a distributed phase within the composite mass. The mass may be cut, molded or otherwise subjected to another operation (e.g. a secondary operation) to produce a composite article suitable for use in an intended application.
[078] It is also possible that a coextrusion step can be used. The co-extrusion step may include a step of passing a composite mass, as described above, through a die while feeding a supply of base material through the die. The base material may be a polymeric material, a metallic material or other material. Conditions can be maintained while materials are passed through the die so that the composite mass is bonded (e.g. mechanically, adhesively, covalently or any combination thereof) to the resulting molded base material. For example, it may be possible that the heat of the base material as it is processed through the die, or essentially immediately thereafter, may be hot enough to cause the thermoplastic polymer reaction product to melt with or otherwise melt. join to the base material. A molding step may be included which may allow a plurality of layers to be assembled in a press which may or may not be a heated press.
[079] Of course, a variety of suitable composite profiles are possible as a result of the teachings. Profiles can include a longitudinal axis. Composite profiles can be symmetrical or asymmetrical in relation to the longitudinal axis. Composite profiles may include one or more longitudinally oriented ribs. Composite profiles may include one or more transversely extending flanges. Composite profiles can include flat and curved portions. Composite profiles can have one or more external surfaces. Composite profiles can have one or more internal surfaces. Composite profiles may include a composite overlay that includes or consists of a composite mass of the present teachings. Composite profiles of the teachings may include a composite overlay that includes or consists of a composite mass of the present teachings. Composite overlay can cover all or part of an external or internal surface. The composite overlay may include or consist of a composite mass of the present teachings may define all or part of a rib, a flange (e.g., a transversely oriented flange), or both. Composite profiles may include a composite mass that is at least partially or even completely embedded in the base material along some or all of the length of the composite profile. The composite profile may include an extruded profile frame that defines a mechanical fixture to secure the profile to another structure (e.g., as described in US patent 7784186 (incorporated by reference, see, for example, Figures 48 and associated description). The composite profile may also have one or more push pin type fasteners, as described in US patent 7,784,186 (incorporated by reference, see, for example, Figures 1-3 and associated description). may be employed for use as an extruded support for structural reinforcement and/or deflector (eg for a transport vehicle).
[080] For use as an extruded support for structural reinforcement and/or deflector (e.g. for a transport vehicle), an activatable material or at least a portion of an external surface of the vehicle may also be employed.
[081] The teachings also provide for a possible manufacturing system that can be employed for an extrusion operation in accordance with the present teachings. The raw material to form a body of base polymeric material is fed into a hopper associated with an extruder. The extruder may have a die through which the raw material is passed to form a molded body profile (eg an extruded profile). The molded body profile can be cooled (eg by a vacuum cooler) to a desired temperature (eg below the material's softening point so that it maintains its molded state). A feed system may feed a fibrous material (e.g., via rollers) to a suitable device to apply a matrix material to define a composite fibrous material (e.g., a roll coater). In such a device, material for forming a polymer matrix is brought into contact with the fibrous material. A suitable device may be used to shape the fibrous composite material, such as a molding roll, heated press or other suitable extrusion and/or pultrusion molding device. The molding roller or other suitable device may also serve to help bond the fibrous composite material to the profile of the molded base body.
[082] In case of joining, the resulting overall composite can be cooled (eg by a cooling tank). Optionally, if it is to be used as a support for a structural reinforcement and/or deflection application, the resulting overall composite may be advanced by a support device (e.g., a pulling or pushing device). An activatable material (eg, a heat-activatable polymeric sealant, acoustic foamable material, and/or structural reinforcement material) can be applied to the composite by an extruder (eg, a T-head extruder). Then the resulting composite (with or without the activatable material in it) can be cut by a suitable cutting device (e.g. a roller cutting saw). By way of illustration, without limitation, the raw material may be a glass filled Nylon® heated to about 260°C. When leaving the refrigerator, the temperature can be from about 150 to about 175°C. The fibers may be glass fibers that are roller coated with a reaction product of a monoethanolamine and bisphenol A diglycidyl ether, while the reaction product is in a softened state. Upon exiting the cooling tank, the composite may be at a temperature of about 120°C. At the time of passing through the extruder, the temperature may be about 90-95°C. The T-head extruder can extrude one or more masses of a heat-activatable epoxy-based structural foam, such as the L-55xx series of materials, available from L&L Products, Inc. See, for example, US patent 7892396, incorporated by reference for all purposes (an illustrative composition is shown in Table I). The heat-activatable material may be foam-activatable to expand and adhere to an adjacent surface (e.g., a wall defining a part of a vehicle, such as a wall defining a cavity in the vehicle). Activation can occur after exposure to heat from a paint-baking oven or induction heating device, following an electrocoating deposition step. The resulting activated material can be scaled up to at least about 50%, 100%, 200%, 400%, 600% or even 1000% of the original volume. The resulting activated material can be expanded from its original volume, but in an amount less than about 2500%, 2000% or even below about 1500% of the original volume.
[083] The composite material of the present teachings offers the benefit of mechanical properties typically obtained through the use of thermoset polymeric materials (e.g., a thermoset epoxy material) as a part or all of a matrix phase of a composite. However, the material has a number of physical attributes that make it suitable for handling and processing, as can be described in the above discussion of processing. The material of the present teachings may also provide post-life recovery, recycling and/or reuse benefits. The current teachings also contemplate methods that include one or more steps of post-life recovery, recycling and/or reuse of the materials of the present teachings. For example, a step of separating the polymeric phase (e.g. the polymeric matrix phase) from the distributed phase may be used. A step may be used to reuse one or more phases of the composite of the present teachings. A recycling step of one or more steps of the present teachings may be used (e.g. processing at least one of the steps to a different shape, size and/or shape from its original shape, size and/or shape in the composite material of the present teachings. The material of the present teachings may exhibit a high elongation factor so that it is not brittle but very strong. The material may be able to bond to a desired part, substrate or location. This provides a benefit that assembly features can be weld-free. Assembly feature can be free of assembly tolerance stacking. As components can be joined (eg, without mechanical fasteners), parts can be hole-free, improving thus accuracy and eliminating inconsistent drilling operations (eg with sheet metal.) Material can facilitate geometric dimensioning and tolerances.
[084] The fibrous composite material of the present teachings may be used in any of several possible ways. Can be used as an overlay on top of a body (eg a molded polymeric body). Can be used as an insert (eg to form a continuous joining surface with a molded polymer body). It may be an insert encapsulated within a molded polymeric body. It can be used as a substitute for sheet metal. It can be used as a substitute for a tube or other generally cylindrical element (eg a roll tube or a molded hydro tube). The fibrous composite material can be a bandage, strip, wrapper, or the like that can be used to provide localized reinforcement to another component of an assembly (eg, a beam that receives some load). The fibrous composite material may be wound into a tubular shape (e.g., for use as or with vehicle cross beams, side intrusion or impact beams or other automotive parts). The fibrous composite material can be thermoformed into the desired shape (eg roof arch, bumper or other automotive part). The fibrous composite material may be molded to provide structure and support for subcomponents of an assembly. For example, the fibrous composite material can be molded to form an internal door module, which can provide an internal structure within a vehicle door, which can also provide an area to mount and/or support sub-components within the door (e.g. , a motor for actuation movement of the windows, locking mechanism, electrical harness, loudspeaker system, ventilation components, mirror control, defroster and the like).
[085] In one aspect of the present teachings, a baffle and/or structural reinforcement for an article is contemplated. The baffle and/or structural reinforcement includes a vehicle that has a mass of polymeric material that has an outer surface and that includes a first polymeric material (e.g., a first thermoplastic material). The carrier may be made from a single polymeric material, or a plurality of polymeric materials. The support may include a fibrous composite material of the present teachings. That is, the support may include a distributed segmented form phase and a polymer matrix phase.
[086] The polymeric material (i.e., the thermoplastic polymeric material) of the fibrous composite material of the teachings may be the same as or different from a polymeric vehicle body. The fibrous composite material of the teachings may be employed on or within a polymeric body of the support.
[087] By way of illustration, the carrier may employ at least one consolidated fibrous insert (which may have a predetermined order of fibers within the insert and/or may have a three-dimensional shape configuration) having an outer surface. The carrier may be a layer of polymeric material adjacent to one or more additional layers, including a fibrous layer and a thermoplastic polymeric layer. The fibrous material may include at least one consolidated fibrous insert including at least one elongate fiber array (e.g., having a mass of continuous fibers, which may be in an ordered array, such as generally axially aligned with respect to one another) distributed into a cohesive mass of a second polymeric material (e.g. a second thermoplastic material). The fibrous insert and associated second polymeric material may gather the bulk of the first polymeric material at a predetermined location to support a predetermined load that is subjected to the predetermined location. The fibrous insert, the second polymeric material, and the bulk of the first polymeric material include compatible materials, structures, or both, to allow the fibrous insert to be joined at least partially (e.g., form a single phase with or be miscible in) the bulk. of the first polymeric material. Structural reinforcement may also include a mass of activatable material applied selectively onto at least a portion of one or both of the outer surfaces of the mass of polymeric material or fibrous insert (e.g., onto the outer peripheral surface of the support, within a cavity support, or both). The mass of activatable material is capable of activation for expansion through an external stimulus (e.g. heat, moisture, radiation or otherwise) and is capable of curing to form an adhesive bond to at least one surface of the article. Desirably, the outer surface of the fibrous insert may be at least partially co-extensive and continuous with the outer surface of the mass of polymeric material.
[088] Materials for a support body here can be a polyamide, a polyolefin (e.g. polyethylene, polypropylene or other), a polycarbonate, a polyester (e.g. a polyethylene terephthalate), an epoxy-based material , a thermoplastic polyurethane, or any combination thereof. It may be preferred to employ a polyamide (e.g. polyamide 6, polyamide 6,6, polyamide 9, polyamide 10, polyamide 12 or the like). The materials of a support body and any overlay and/or insert may be generally compatible with one another insofar as they are capable of forming a mechanical or physical interconnection (e.g. a microscopic interconnection) between them, are capable of form a chemical bond between them, or both. For example, the first and second materials may be such that they melt (e.g., in the absence of any adhesive) when heated above their melting point and/or their softening point. The supports may also be overmolded with a secondary material, such secondary material may be a polymeric material such as a polyolefin, a polyamide, a polyester, a polyurethane, a polysulfone or the like, or an expandable polymer (e.g. a structural foam). or an acoustic foam).
[089] The polymeric body of any vehicle may include a polymeric material that can be filled with chopped fibers (e.g., chopped glass fibers), which may be present in an amount from about 25 to about 40 (e.g., about 30 to about 35) weight percent staple fiber. The average length of such fibers can be less than about 20mm, below about 10mm, or even below about 5mm. They can be randomly oriented. The first and second materials may be free of any metallic materials.
[090] A fibrous insert and/or a fibrous layer may include one or more layers (e.g. they may have 2, 3, 4, 6, 15 or more layers) that are consolidated in the sense that they include a plurality of fibers that are distributed in a cohesive mass of the second polymeric material. The individual fibers may be distributed in a predetermined ordered array within a matrix of the second polymeric material. Preferably, at least a portion of the fibers are ordered in their arrangement (e.g. in a generally ordered relationship to one another, such as generally parallel or unidirectional or otherwise generally axially aligned) and therefore are not distributed. randomly in the second polymeric material. Multiple layers can be consolidated so that a cohesive mass, including the multiple layers, is formed. The multiple layers can be consolidated to form a predetermined shape in the form of a three-dimensional shape insert. It is also possible that a film or interlayer may be located between one or more of the multiple layers. For example, the fibrous insert may employ a plurality of layers that include a plurality of elongated fibers (e.g., having a length of at least 1 cm, 3 cm, or even 5 cm or more) that are oriented generally in a parallel or generally parallel direction. unidirectionally relative to each other and are distributed in a generally continuous polymeric matrix (e.g. in a continuous matrix of the second polymeric material). The fibers can be mineral fibers (e.g. glass fibers such as E-glass, S-glass, B-glass or otherwise), polymeric fibers (e.g. an aramid fiber, a cellulose fiber or otherwise ), carbon fibers, metallic fibers, natural fibers (eg derived from an agricultural source), or otherwise. Desirably, the fibers are glass fibers. The plurality of elongated fibers may be oriented generally parallel to each other. They can be braided. They can be twisted. Fiber collections can be woven and/or non-woven. The fibers can have an average diameter of about 1 to about 50 microns (e.g., about 5 to about 25 microns). The fibers may have a suitable sizing coating thereon. The fibers may be present in each layer, or in the fibrous insert in general, in an amount of at least about 20%, 30%, 40% or even 50% by weight. The fibers may be present in each layer, or in the fibrous insert in general, in an amount below about 90%, 80%, or even about 70%, by weight. By way of example, the fibers may be present in each layer, or in the fibrous insert, in an amount of from about 50% to about 70% by weight. Fiber contents by weight can be determined in accordance with ASTM D2584-11. The tapes and/or sheets for the fibrous insert layers can be made by extrusion, pultrusion or otherwise. In this way, it may be possible to achieve the ordering of the fibers in the tapes and/or sheets. The method described herein may include a step of impregnating a fibrous mass with the polymeric matrix material and passing the impregnated material back through a matrix (e.g. a heated matrix) so that the fibrous mass is coated with a mass generally continuous flow of the polymeric matrix material. In this way, it is also possible to obtain the desired ordering of fibers among themselves.
[091] Each layer of the fibrous insert may be in the form of a sheet, a ribbon or otherwise. The fibers in the sheet and/or tape preferably may be in an ordered relationship with respect to one another. For example, the fibers may be generally parallel to each other and/or unidirectionally oriented. When consolidating multiple layers of sheet, tape, or other form of layer to form a multiple fibrous insert, it is preferred that at least one layer of the fibrous insert exhibits an ordered relationship, as opposed to a random relationship, as found in batts of fibers, which typically employ chopped fibers that are randomly placed together.
[092] It is possible that the layers of the fibrous insert are provided as being wound on a coil. Each layer may have a thickness of at least about 0.1 mm or at least about 0.2 mm. Each layer may have a thickness below about 0.5mm or below about 0.4mm. For example, each layer can be from about 0.2 to about 0.3 mm thick. Some or all of the individual layers may be anisotropic in their mechanical properties. For example, it may have a relatively high flexural modulus and/or strength in a longitudinal direction, but a lower flexural modulus and/or strength in a transverse direction, or vice versa.
[093] The fibrous material may include a plurality of woven strips. For example, it may include a plurality of strips that are interwoven transversely, each strip having a width of at least about 1 mm, at least about 2 mm, or even at least about 3 mm. It may include a plurality of strips that are interwoven transversely, each having a width below about 10 mm, below about 8 mm, or even below about 6 mm. The woven strips may be held together by a polymeric matrix material, for example, a continuous matrix of the polymeric material of the insert. Thus, the strips are fixed in a predetermined position with respect to each other by virtue of the polymeric material. It is preferred that at least some of the strips may each include a plurality of elongated fibers arranged in an ordered relationship with respect to one another, desirably within a continuous matrix of polymeric material. However, it is possible that one or more strips may include fibers in a random orientation relationship relative to each other, such as is derived from typical fiber batts. Strips for forming wefts can be made by cutting a ribbon, sheet or other shape to an appropriate width to form strips. Alternatively, it may be possible for the strips to be pultruded, extruded or otherwise formed (as described herein) to the desired width.
[094] The material defining the fibrous insert may have a flexural strength in accordance with ASTM D79010 of at least about 450 MPa (for example, it can range from about 500 to about 1100 MPa). The fibrous insert material may have a flexural modulus per ASTM D790-10 of at least about 5 GPa, 10 GPa, 20 GPa, or even at least about 25 GPa (e.g., can range from about 30 to about 30 GPa). 35 GPa).
[095] The fibrous insert may employ a fully densified polymer for the polymer matrix. The fibrous insert may have a void content that is less than about 10% by volume of the insert, and more preferably below about 5% or even below about 2% or 1%, as measured by ASTM D2734-09. The fibrous insert may have a density of less than about 40% of the density of steel, below about 33% of the density of steel, or even below about 25% of the density of pure carbon steel.
[096] The fibrous insert may be made to include a plurality of adjacent layers. Adjacent layers may have fiber orientations that are the same or different with respect to each other. The fibrous insert may include a woven layer adjacent to a non-woven layer. The fibrous insert may include a woven layer adjacent to another woven layer. The woven fabric of woven layers within the fibrous insert may be the same or may vary between these woven layers. The width of the strips can vary between adjacent layers. The thickness of adjacent layers can be the same or different.
[097] Examples of woven fabrics include plain fabrics, twill fabrics or otherwise. The overlapping strips may be woven generally orthogonally to each other or at some other angle. The fabric may include a plurality of warp and weft strips. The ratio of warp to weft strips can range from about 30:70 to about 70:30. For example, it might be around 50:50. It is possible that the strips of the warp and weft members are possibly generally of the same width. The width of the warp strip and weft strip may vary relative to each other by 10%, 20%, 30% or more. The width of the warp strip and weft strip may vary relative to each other by less than about 70%, 60%, 50% or less.
[098] Each adjacent layer of tape and/or sheet in the fibrous inserts here may be oriented so that it has fibers (i.e., fibers that are embedded in the polymer matrix of the tape and/or sheet) aligned in a predetermined direction relative to to the fibers of an adjacent layer. Fibers in one layer may generally be at an angle to fibers in an adjacent layer (e.g., the axis of fiber orientation between layers may differ by about 10 to about 90°, such as in the form of a X layer). For example, a multi-layer structure may include a layer that may have fibers oriented in a first direction from a foreground and an adjacent layer oriented with its fibers generally in a second plane parallel to the foreground, but at approximately a 90° angle. degrees.
[099] Desirably, each of the adjacent layers is joined together as a cohesive mass. For example, each of the layers may be bonded together by the polymeric material of the respective layers to form a series of continuous layers. The layers can be bonded together in the absence of any adhesive.
[0100] The fibrous composite material, such as in the form of a sheet or a ribbon (which can serve as a shred or a wrapper), can be applied to control the faulty modes of certain components of an assembly that may be subject to a load, to provide localized reinforcement, or both. For example, a hollow beam (eg, having a rectangular cross section) that receives a load from the top may have a tendency to shear. Strength can be improved and/or failure mode can be changed by the addition of a fibrous composite material as disclosed herein. The fibrous composite material can be bonded to the hollow beam to change its deformation characteristics (e.g. with the composite material generally planar (or in planar contact with a portion of the beam) acting as a wrapper around the beam, enveloping the beam. beam as a shell in a generally helical direction, as a generally cylindrical or tubular structure outside or inside the hollow beam, or other configuration). For example, a woven tape can be applied along the side walls of the beam to help resist having a shear plane that arises substantially along the longitudinal axis of the beam (through the middle of the piece). The tape (or other form of fibrous composite material) can be single-layer or multi-layer, with a combination of fiber orientations (e.g., one layer with fibers generally oriented in the longitudinal direction, another layer having fibers in a that is at an angle to the longitudinal direction (eg, 90 degrees, 45 degrees, or otherwise)). Fiber directions can help resist shear or can provide control and/or predictability of component failure (eg, a beam) when subjected to a particular load. A secondary component can be applied to further increase strength or change the failure mode, such as another fibrous layer with a different orientation, or it can be a metal, a foam component (inside or outside the hollow beam, for example), a fibrous mat or a ductile material (eg, a rubber-like material).
[0101] The fibrous insert may have one or more structural features incorporated into it or linked thereto. For example, one or more fasteners may be employed (eg one or more threaded fasteners). One or more loops may be formed or integrated into the fibrous insert (e.g. to provide a space for the passage of a coating fluid). One or more rivets (eg a self-drilling rivet, a blind rivet or both) can be integrated into the insert. One or more metal parts can be integrated into the insert, which can be adapted to provide a location on the resulting part for spot welding. One or more screws may be integrated into the insert (e.g. with a base which may have openings defined therein, which is located in or on a face of the fibrous insert and which has a column (e.g. a threaded column) which extends out of the base). One or more metal panels, sheets or parts may be integrated into the insert or fixed thereto, for example to provide localized reinforcement.
[0102] One or more structural features may be incorporated into the fibrous insert (or other fibrous composite material) through selective heating, which may be conductive heating. In accordance with the present teachings, it is envisaged that one or more assemblies may be made by selectively heating a portion of a structure that has a wall (e.g., an outer wall of the fibrous insert) of a thickness to raise at least one portion of the wall thickness at a temperature above the glass transition temperature of a polymer (e.g., a polyamide and/or a reformable resin material as taught herein, which may be reinforced as described herein, such as with a fiber or another phase) that forms the wall. While at least a portion of the wall thickness is above the glass transition temperature of the wall-forming polymer, an article is contacted with the structure at least partially within the heated region, optionally under pressure. Subsequently, after the heat leaves the heated region, the polymer forming the wall cools so that the resulting polymer in contact with the article is cooled below the glass transition temperature. Obviously, an adhesive bond is obtained, with the remaining article attached to the structure via the bond. The above method can be used to form an adhesive bond either with or without an additional applied adhesive. That is, it may be possible that the structure material, when heated above its Tg, and then cooled below it, will be able to form an adhesive bond directly with the contacted article. Furthermore, the tenacity of the bond may be sufficient to obviate the need for any fasteners to secure the article to the frame. One option for achieving a bonded assembly in accordance with the above may be to use an adhesive layer, where the adhesive layer (e.g. less than about 5 mm, 4 mm or 3 mm thick and above about 0.05, 0.1 or about 0.5 mm) is made of a reformable resin material as described herein.
[0103] The structure can be any of several suitable shapes. For example, it could be an elongated beam. It can have a length and it can be solid along all or part of the length. It can have a length and be hollow along all or part of the length. The structure may have a wall thickness, measured from a first exposed surface to a generally opposite exposed surface. The wall thickness can be at least about 0.5mm, about 1mm, about 2mm, about 5mm, about 10mm, or about 20mm. The wall thickness can be less than about 100mm, below about 80mm, below about 60mm, or below about 40mm.
[0104] The structure can have a predetermined shape. The shape may include one or more elongated portions. The form may include one or more void portions. The form may include one or more walls defining at least one cavity. The structure may include a plurality of portions each having a different shape. The framework can be configured to define a fascia, which can optionally be supported by an underlying framework. The framework can be configured to define an underlying support for a fascia. The structure may have a panel configuration, for example a configuration that resembles a transport vehicle body (for example a motor vehicle) or an internal trim panel.
[0105] The structure can be configured to receive and support one or more items (eg transport vehicle components) such as to form a module. By way of illustration, one or more articles can be selected from a bracket, a hinge, a latch, a plate, a hook, a latch (e.g. a nut, a bolt or otherwise), a motor, a box component, an electrical harness, a drain tube, a loudspeaker or others.
[0106] Heat may be applied in any suitable manner. One approach may be to employ localized heating. For example, it is possible to employ induction heating for selective heating of at least a portion of the above-described structure. For purposes of illustration, it is possible for the structure to be made with a polymer (e.g., a polyamide and/or a reformable resin material as taught herein, which may be reinforced as described herein, such as with a fiber or other phase). ), and will have a wall thickness. A metallic item (which may be a component desired to be attached to the structure) can be brought close (which may or may not be in contacting relationship) to the structure at the desired joining location. An induction heating device can be brought close to the metallic item to heat the metallic item, which in turn will heat the structure at the affected location when power is supplied to the induction heating device. Other heating devices can also be used for localized heating.
[0107] It is possible that the time that elapses from the time the structure is initially heated until an article is bonded to it by the above steps may be relatively short. For example, the operation may take less than about 1 minute, less than about 30 seconds, or less than about 15 seconds. It may take about 1 second, about 3 seconds, or about 5 seconds.
[0108] Another approach to forming an assembly in accordance with the present teachings provides for forming a molded part by heating a putty material in accordance with the teachings (e.g., a polyamide and/or a reformable resin material as taught herein , which may be reinforced as described herein, such as with a fiber or other phase) at a temperature above the Tg of the material. When at least some of the material is above the Tg, pressure can be applied to the mass of material to define a configured part. For example, it may be thermoformed, molded or otherwise shaped. The configured part can then be joined to another part to form an assembly. The joining of parts can be by an adhesive bond, by a mechanical connection (eg, using a clasp, using a tight joint configuration, or both), or both. For example, without limitation, at least two generally complementary parts may be attached to each other. If one of the parts is made of a reformable resin material as taught herein, they can be joined together by bonding the parts while at least a portion of that part is above the Tg of the reformable cooling material and then cooling to a temperature below Tg. Optionally, this approach can be modified to include the use of a layer of adhesive between the pieces, where the adhesive layer (e.g. less than 5 mm, 4 mm or 3 mm thick and above about 0.05 , 0.1 or about 0.5 mm) is made of a reformable resin material as described herein.
[0109] Parts may be different materials. For example, a portion may include a formable resin material of the present teachings. The other part may include a polyurethane, a polyolefin (e.g. a polypropylene), a polyamide, an acrylate, a methacrylate, a polycarbonate, a polyester or any combination thereof; the other part may include a thermosetting material; the other part can be formed from a sheet molding compound or reaction injection molding.
[0110] As indicated, the fibrous inserts can have a predetermined shape. The shape may be the result of one or more calculations performed during a computer simulation step of a failure, a certain state of stress or otherwise, and may be selected to provide additional local reinforcement in a predetermined region of the part to be subjected to a predisposed stress condition which is determined from these calculations. The fibrous inserts herein may include one or any combination of a generally sinusoidal geometry over some or all of its length, a pair of separate walls that are joined together by a cross wall, one or more edges and/or steps, a portion of concave surface, a convex surface region, or one or more openings. As indicated, the fibrous inserts here may have a three-dimensional configuration, in contrast to a generally planar configuration.
[0111] The characteristics of the fibrous insert may vary from application to application. A benefit of the present teachings is that fibrous insert layers can be selected to meet the needs of a particular application (e.g. in response to computer simulation modeling (such as computer failure or stress state simulation)) . The insert can be individually constructed to include a plurality of layers based on the performance required by the application. In addition, another benefit of the teachings described here is that local reinforcement can be achieved by positioning the inserts at specific locations that are indicated to require additional local reinforcement (e.g., in response to computer simulation modeling (such as computer failure or simulation). of the state of stress)). The teachings presented herein thus provide the skilled artisan with a surprisingly expanded ability to selectively adjust the performance of structural reinforcements. The teachings also contemplate the use of computer simulation modeling to determine the location where a support is expected to support a predetermined load in an accident or under a certain state of stress. Based on the results of this modeling, the location where a fibrous insert should be positioned can be determined. Furthermore, based on the results of such modeling, fiber orientation and/or selection of respective adjacent layers of tape or sheet in a fibrous insert can be targeted. Parts can then be made based on the drawings resulting from this modeling. Methods employing such steps are thus also within the present teachings.
[0112] The supports of the structural reinforcements can be such that the external surface of the fibrous insert is generally co-extensive with the external surface of the mass of polymeric material. This may be over some or all of the perimeter of the fibrous insert. It is also envisaged that the fibrous insert may have opposing surfaces which are exposed and therefore visible on the resulting part. For example, the fibrous insert may have an exposed outer surface and an exposed inner surface. Thus, the fibrous insert may gather the mass of polymeric material only along one or more side edges of the fibrous insert. The resulting visible surfaces of the support can be substantially free of mesh lines or other imperfections that could provide a source of localized weakness of the support.
[0113] The second polymer can be applied directly on the fibrous insert. The second polymeric material may be a liquid poured over the fibrous insert until the insert is saturated with the second polymeric material. The liquid absorbed by the fibrous insert can represent at least about 30% and less than about 70% of the total weight of the fibrous insert after saturation. The saturated insert can polymerize at room temperature or with the addition of heat to form a rigid solid compound. The resulting composite can then receive the first polymeric material by positioning the composite in a tool and molding the first polymeric material (which may be a Nylon material) relative to the composite.
[0114] As appreciated by the foregoing, the support may have (i) a polymeric portion defined by the mass of the first polymeric material, (ii) a localized reinforcement portion defined by at least one fibrous insert, and (iii) an interface portion between the polymeric portion and the localized reinforcing portion wherein the polymeric portion, the interface portion and the localized reinforcing portion are a generally continuous structure. The interface portion may include (i) an interpenetrating network defined by the first and second polymeric materials, (ii) chemical bonds between the first and second polymeric materials, or both (i) and (ii).
[0115] One or more sides of the activatable material may be sticky. Although it is also possible that one or more sides are generally non-sticky to the touch at room temperature. One or more mechanical fasteners may be used bonding or integrally formed with the activatable material, the support, or both.
[0116] Suitable materials that can be used for activatable material include expandable materials and materials that are not expandable. However, it is contemplated that the activatable material may be activated to form a foam. For example, the material may be activated to form a structural foam (eg, the material may include an epoxy ingredient). The material can be activated to form an acoustic foam. Material can be enabled to flow for the purpose of sealing a region within a cavity. The material can include a combination of an expandable material and a material that is not expandable.
[0117] The structural reinforcement of the present teachings can be used to structurally reinforce an article, such as by locating the structural reinforcement within a cavity of the article and activating the activatable material so that it expands and joins a surface of the object. . Structural reinforcement can also be used to seal and/or deflect the cavity. In a preferred application, structural reinforcement is used to reinforce a transport vehicle, such as a motor vehicle.
[0118] By way of example, structural reinforcement can be positioned within a cavity of a transport vehicle (eg, a motor vehicle) prior to vehicle cladding. Activatable material can be activated when subjected to heat during paint baking operations. In applications where the activatable material is a thermally expanding, thermally expanded material, an important consideration relating to the selection and formulation of the material comprising the activatable material is the temperature at which a reaction or expansion of the material, and possibly curing, will occur. . For example, in most applications, it is not desirable for the material to be reactivated at room temperature or otherwise at room temperature in a production line environment. More typically, the activatable material becomes reactive at higher processing temperatures, such as those found in an automobile assembly facility, when the material is processed along with the automobile components at elevated temperatures or at higher applied energy levels. high, for example during painting or curing or baking steps. Although temperatures encountered in an automobile assembly operation can be in the range of about 140°C to about 220°C (for example, about 148.89°C to about 204.44°C (about 300°F to 400°F)), bodyshop and paint shop applications are generally around 93.33°C (about 200°F) or slightly higher. After activating the activatable material, the material will normally cure. Thus, it may be possible that the activatable material can be heated, which can then expand, and then cure to form a resulting foamed material.
[0119] As indicated, the teachings contained herein also pertain to a method for producing a support from an activatable material (e.g., for structural reinforcement for an article). The method may include a step of inserting at least one fibrous insert (which may be consolidated at the time of the inserting step) having an outer surface and including at least one elongated fiber arrangement within a cavity of a tool. A mass of polymeric material may be molded in contact with the fibrous insert, so that a resulting molded mass of polymeric material is integrally joined to the fibrous insert (which is consolidated in its final state) and the outer surface of the fibrous insert is at least partially coextensive and continuous with the outer surface of the resulting molded mass of polymeric material. An activatable mass of material (e.g., overmolded, mechanically bonded or otherwise) may be applied over at least a portion of one or both of the outer surfaces of the resulting mass of polymeric material or fibrous insert. In accordance with the above teachings, the mass of activatable material may be activated for expansion by an external stimulus (e.g., at least partially, if not completely, to fill a space or cavity) and may be capable of healing to form a adhesive bonding to at least one surface of the article to which it is attached.
[0120] The method may include a step of molding at least partially the fibrous insert after its placement in the tool cavity. For example, the tool may be preheated to a temperature above the softening temperature and/or the melting temperature of a polymer of the at least one fibrous insert prior to placing the fibrous insert in the tool cavity. The method may include a step of at least partially molding the fibrous insert after it is placed in the tool cavity and molding the mass of polymeric material. For example, heat and/or pressure resulting from the introduction of the mass of polymeric material into the cavity (e.g. by injection molding) can at least partially cause the fibrous insert to assume a shape dictated by one or more of the walls that define the cavity. Thus, it is possible that the fibrous insert is not preformed prior to placement in the cavity and takes its final shape only in the cavity. Of course, it is also possible for the fibrous insert to be preformed prior to placement in the cavity.
[0121] The fibrous insert, before the insertion step, can be provided in the form of one or more layers of a tape and/or sheet, in which the fibers can be fixed in position with respect to each other (e.g., as a result of consolidation, whereby a cohesive mass of fibers distributed in a continuous polymer matrix is formed). The method may thus include a step of manufacturing the fibrous insert a to include a plurality of layers of tape and/or sheet. For example, the method includes a step of consolidating a plurality of layers of tape and/or sheet while the plurality of layers are subjected to heat and optionally to elevated pressure. For example, a temperature that is above the melting and/or softening point of the polymer of the tape and/or sheet can be used to cause two or more adjacent layers to fuse and remain together after cooling. A pressure of about 0.1 to about 1 MPa can be applied (e.g., about 0.2 to about 0.6 MPa). Temperature and pressure can be used for a desired amount of time to achieve essentially complete densification. Evidently, the teachings provide for the formation of several consolidated insertion structures.
[0122] The fibrous insert can be thermoformed to form a predetermined shape. The fibrous insert can be thermoformed during a consolidation step. A resulting thermoformed fibrous insert can then be placed in a tool cavity and the molten thermoplastic polymeric material can be introduced into contact therewith.
[0123] The molding step may include a step of introducing molten polymer material into the tool cavity through an inlet that is positioned in a generally opposite relationship with at least one fibrous insert. In this way, after introduction into the cavity, the molten polymer comes into contact with the fibrous insert before coming into contact with a wall that defines the cavity.
[0124] Supports made in accordance with the present teachings may have a wall having a first surface and a generally opposite second surface. The wall may have a thickness ranging from about 0.2 to about 6 mm (e.g., about 1.5 to about 4 mm). In selected regions within a support, it is possible that at least about 20%, 40%, 60%, 80%, or even 100% of the wall thickness is defined by the fibrous insert or overlay. The fibrous insert or overlay may have a contoured outer surface portion that is visibly exposed on the support. The fibrous insert or overlay may have a generally flat outer surface portion that is visibly exposed on the support. The first surface and the second surface may be generally parallel to each other.
[0125] The fibrous insert or the overlay may occupy at least about 10%, 20%, 30% or even 40% by weight of the general vehicle. The fibrous insert or overlay can be less than about 90%, 80% or even 70% by weight of the overall support.
[0126] Thus, it is possible that at least a portion of the first surface and the second surface is visibly exposed and is composed of the fibrous insert or the overlay. The supports may have one or more additional structural reinforcements or other structural features, such as one or more ribs, protrusions, or other shape. These features may be free or may include a fibrous insert in accordance with the present teachings.
[0127] It is contemplated that the materials described herein may be pinned. The ability to receive a paint may be desirable, for example, if any surface is visibly exposed. The material can be jet-printed. The material can be painted with conventional electroplating systems. The material can be painted as it may have an affinity for absorbing paint. This may be due, at least in part, to material polarity and/or backbone hydroxyl functionality (e.g. generally linear polymer backbone).
[0128] The parts contained herein may be used for any of several purposes. For example, they can be used to structurally reinforce a transport vehicle, such as a motor vehicle. In this regard, a part may be placed in a cavity of a vehicle body structure, such as a vehicle platform. After applying an electrodeposition coating layer to the vehicle body (e.g. inside the cavity), the part can be subjected to heat from a baking oven, which causes the activatable material to be activated (e.g. expands and fills the cavity), and become attached to the vehicle body.
[0129] Figures 1-11 illustrate examples in accordance with the present teachings. Referring to Figure 1, a support 10 is seen which has one or more masses 12 of a first polymeric material. A fibrous insert 14 is shown joined to one or more masses along an edge of the insert. A portion of the interface 16 is depicted (exaggeratedly for purposes of illustration; for the sake of simplicity this interface is omitted from the remaining drawings, although it is convenient that it may still exist in such embodiments). The support has a top surface 18 and a bottom surface 20. The fibrous insert 14 extends from the top surface to the bottom surface so that the fibrous insert is visibly exposed from above and below. Figure 1 omits any activatable material. However, the activatable material may be located on one or both of the masses 12 or the fibrous insert 14.
[0130] Figure 2 represents a support 110 with a mass of polymeric material 112 and a fibrous insert 114, in which only the upper surface of the fibrous insert is exposed. A bottom surface and side edges are adjacent to the mass of polymeric material. The interface region is omitted from this description, although it may be present. In this design, an expandable material 126 is located over the bulk of the polymeric material and the fibrous insert. However, it can be located on one or the other as well.
[0131] Figure 3 illustrates an example of a support 210 that has a fibrous reinforcement portion 214 with an upper surface 218, from which a rib 222 projects, which is made of a mass of polymeric material (e.g., the same type of material that is otherwise present in the support to which the insert is bonded). The rib includes an outwardly projecting portion having a width w1 and an enlarged neck region having a width (in its greatest dimension) w2 that is greater than width w1, such as by an amount of at least about 10 %, 20% or 30%. The width w2 may be greater than the width w1, such as by an amount not greater than about 100%, 80%, or 60%. A similar rib structure can be used in the Figure 2 embodiment.
[0132] Figures 4a and 4b illustrate two views of an illustrative vehicle 310 that includes a mass of polymeric material 312 and a pair of fibrous inserts 314. In this case, the fibrous inserts have upper and lower surfaces that are exposed. Although it is possible to employ a structure as in Figure 2, in which only an upper surface is exposed. A plurality of ribs 322 are employed (the ribs are shown in a transverse arrangement with respect to a longitudinal axis (e.g., for all embodiments here, the ribs may run longitudinally, transversely, diagonally, or any combination of these directions; the ribs can also be arched)). An activatable material 326 is shown. Although shown in a groove, it may rest on an external surface or otherwise be supported on the stand for all embodiments contained herein.
[0133] Figure 5 illustrates an example of how fibrous inserts 14, 114, 214 or 314 can be multilayered with two or more adjacent layers having different fiber orientations. Although shown as unidirectionally oriented in this example, strips of impregnated fibers can also be provided as a woven layer. Other orientations than those described in Figure 5 are possible. For example, three layers of uniaxially oriented fibers can be oriented at 0/90/0 degrees relative to each other, or five layers can be oriented at 0/45/90/45/0 degrees relative to each other. Other orientations are also possible.
[0134] Figures 6A and 6B illustrate an example of a part in accordance with the present teachings. The part includes a support 610 which is shown as a molded part. It includes a fibrous insert 614. The support includes a plurality of ribs 622. Activatable material 626 is applied over a portion of the support and is shown to partially cover the insert 614. The insert 614, which is overmolded to define the support 610, includes an arcuate surface, and specifically, a concave surface portion 640. In the embodiment shown, it is located toward an end of the insert 614. The insert 614 also includes a through-hole opening 642. The insert includes a pair of opposing walls 644 (which may be generally parallel or otherwise oriented) and a cross wall 646. The insert encompasses a central portion of the bracket.
[0135] Figures 7A and 7B illustrate an example of another part in accordance with the present teachings. The part includes a support 710 which is shown as a molded part. It includes a fibrous insert 714. The support includes a plurality of ribs 722. Activatable material 726 is applied over a portion of the support and is shown to partially cover the insert 714. The insert 714, which is overmolded to define the support 710, includes a rounded portion on the surface 740. In the shown embodiment, it is located toward an end of the insert 714. The insert 714 also includes a through hole opening 742. The insert includes a pair of opposing walls 744 (which may be generally parallel or otherwise oriented) and a cross wall 746. At least one step 748 is defined in the insert.
[0136] Figure 8 schematically illustrates how a support can be made in accordance with the present teachings. A spool of fibrous material 850 can supply material to define an insert 814, shown as sinus. The insert may be overmolded to define overmolded portions 852 (e.g., including a plurality of ribs) of a resulting support 810. The resulting support thus includes the insert 814 and the overmolded portions 852.
[0137] Figure 9 illustrates an example of a profile extruded in accordance with the teachings for use as a support 910. The profile includes a molded fibrous composite material 960 (e.g., by rolling or extrusion) superimposed over an outer surface of the support body 962 (e.g., an extruded polyamide or fiberglass polyamide, such as Nylon®). Support-shaped body 962 has an inner surface 964. A rib 966 extends (e.g., generally orthogonally) from the inner surface 964. Activatable material A is shown. Activatable material A may have been extruded into the support. .
[0138] Figure 10 illustrates an example of a possible fabrication system 1070 that may be used for an extrusion operation in accordance with the present teachings. The raw material to form a body of polymeric base material is fed into a hopper 1072 associated with an extruder 1074. The extruder 1074 features a die 1076 through which the raw material is passed to form a molded body profile 1078 ( e.g. an extruded profile). The molded body profile can be cooled (eg by a 1080 vacuum cooler) to a desired temperature. A feed system 1082 can feed a fibrous material 1084 (e.g., via rollers) to a roller collector 1086 in which the material to form a polymeric matrix is contacted with the fibrous material. A mold roll 1088 (or other suitable extrusion-type molding device) can then further define the desired shape of the resulting fibrous composite material. The mold roll can also serve to help bond the fibrous composite material to the profile of the molded base body. After joining, the resulting overall composite 1090 can be cooled (eg, by a cooling tank 1092). Optionally, if used for use as a support for a structural reinforcement application, the resulting overall composite 1090 may be advanced by a support device 1094 (e.g., a pull or push device). An activatable material can be applied to composite 1090 by an extruder 1096 (eg, a crosshead extruder). Thereafter, the resulting composite (with or without the activatable material in it) can be cut by a cutting device 1098 (e.g., a roller cutting saw). By way of illustration, without limitation, the raw material may be a Nylon® with glass fibers heated to about 260°C. When leaving the refrigerator, the temperature can be from about 150 to about 175°C. The fibers may be glass fibers that are roller coated with a reaction product of a monoethanolamine and bisphenol A diglycidyl ether, while the reaction product is in a softened state. Upon exiting the cooling tank, the composite may be at a temperature of about 120°C. At the time of passing through the extruder, the temperature may be about 90-95°C. The crosshead extruder can extrude one or more masses of a heat-activatable epoxy-based structural foam, such as a structural reinforcement material in the L-55xx series, available from L&L Products, Inc. The production system may also include one or more pultrusion steps.
[0139] As shown, for example, in Figures 11A-11C, profile 1110 may be formed as a continuous fiber pultruded support 1112 that includes a thermoplastic epoxy material. Indeed, the support 1112 may comprise solely the thermoplastic epoxy material and may be free of any additional polymeric materials. Alternatively, only a portion of the carrier 1112 may be formed from the thermoplastic epoxy material. The support may further include a sealing material 1114 which can be added to the support during or after the pultrusion process. The support may also include the addition of one or more film portions 1116. The film portions 1116 may improve bonding between dissimilar materials and/or assist in preventing corrosion such that they may be located near and/or adjacent to a or more openings for receiving a fastening member. The support and one or more of the attached materials mentioned above can also be extruded.
[0140] Of course, although the embodiments of Figures 1 to 11 are shown separately, features of one may be combined with features of another and remain within the present teachings. The representations there must therefore be regarded as generalized and applicable to the teachings as a whole here.
[0141] The teachings described herein are illustrated in connection with a support for a structural reinforcement, in which the support is generally elongated (e.g., may be at least approximately 25 mm in length, at least about 50 mm in length, or even at least about 100 mm long). However, the teachings are not intended to be restrictive. The teachings also contemplate their use for molding supports for deflection and/or sealing. The supports may thus have lengths that are less than about 25 mm (e.g., about 15 mm or less). Supports can be longer than they are wide. Brackets can be wider than they are long.
[0142] As can be appreciated from the teachings presented here, various benefits and/or advantages can be realized. For example, parts can be prepared that have a support that is made of a thermosetting plastic-free material. Parts can be prepared that have at least a portion of the activatable material located on and in contact with a fibrous insert of the present teachings.
[0143] As used herein, unless otherwise noted, the teachings provide that any member of a genre (list) may be excluded from the genre; and/or any member of a Markush cluster can be excluded from the cluster.
[0144] Unless otherwise indicated, any numerical values quoted herein include all values from the lower value to the higher value in increments of one unit, provided there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is indicated that the amount of a component, a property or a value of a process variable, such as, for example, temperature, pressure, time and the like, is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, is intended for values in the mid-range such as (e.g. 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) to be within of the teachings of this specification. In the same way, individual intermediate values are also within the present teachings. For values that are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically envisaged and all possible combinations of numerical values between the lowest and highest enumerated value are to be considered expressly indicated in this application in a similar manner. As can be seen, the teaching of quantities expressed as "parts by weight" here also contemplates the same ranges expressed in terms of percentage by weight. Thus, an expression in a range in terms of "at least 'x' parts by weight of the resulting composition" also contemplates a teaching of ranges of the same quoted amount of "'x' in weight percent of the resulting composition".
[0145] references, including patent applications and publications, are incorporated by reference for all purposes. The term "consisting essentially of" to describe a combination shall include the identified elements, ingredients, components or steps, and other elements, ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising " or "including" to describe combinations of elements, ingredients, components or steps contained herein also contemplate embodiments that consist of, or essentially consist of elements, ingredients, components or steps.
[0146] The plural elements, ingredients, components or steps can be provided by a single element, ingredient, component or integrated step. Alternatively, a single integrated element, ingredient, component or step can be broken down into different elements, ingredients, components or steps. Disclosure of "a" or "an" to describe an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.
[0147] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments, as well as many applications in addition to the examples provided, will be apparent to those skilled in the art upon reading the above description. The scope of the invention should therefore be determined not with reference to the above description, but should rather be determined with reference to the appended claims, together with the full range of equivalents to which such claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of the subject matter that is disclosed herein does not constitute a disclaimer of liability for such subject, nor should the inventors be deemed not to have considered that subject to be part of the described subject.

权利要求:
Claims (45)
[0001]
1. A COMPOSITE ARTICLE MANUFACTURING METHOD, wherein the composite article comprises: (a) a phase distributed in the composite article that includes a plurality of segmented shapes (e.g., fibers, platelets, flakes, chopped fibers or any combination thereof of these); and (b) a polymeric matrix in the composite article in which the distributed phase is distributed, the polymeric matrix including at least 25% by weight of the polymeric matrix of a thermoplastic polymer; wherein the polymer matrix further includes a reaction product of a diepoxide and a primary monoamine or a secondary diamine; wherein the composite article forms at least a portion of a support adapted for use as a baffle, a structural reinforcement of both; and wherein the method includes at least a selected step of mechanically mixing the distributed phase with the reaction product material for use in the polymer matrix and injection molding, extrusion or pultrusion of the resulting mixture.
[0002]
2. METHOD according to claim 1, characterized in that the distributed phase comprises at least 33% by weight of fibers.
[0003]
A METHOD according to claim 1 or 2, characterized in that the distributed phase includes fibers selected from mineral fibers (organic or inorganic), polymeric fibers, carbon fibers, metallic fibers, natural fibers or any combination thereof.
[0004]
4. METHOD according to any one of the preceding claims, characterized in that the distributed phase includes a plurality of fibers with a length of at least 1 mm.
[0005]
A METHOD according to any one of the preceding claims, characterized in that the fibers of the distributed phase are present in an amount, a distribution or both to reinforce the composite article by achieving an increase in one or more mechanical properties selected from the resistance to wear. extreme tensile, elongation, flexural modulus or compression modulus, compared to the corresponding material property of the individual polymer matrix.
[0006]
6. METHOD according to any one of the preceding claims, characterized in that the distributed phase is homogeneously distributed in the polymer matrix.
[0007]
A METHOD according to any one of the preceding claims, characterized in that the distributed phase is in the form of a random distribution, a fabric, a non-woven mat, a plurality of generally axially aligned fibers (e.g. a bundle), a plurality of of axially entwined fibers (e.g. a yarn) or any combination thereof.
[0008]
A METHOD according to any one of the preceding claims, characterized in that the material of at least a portion of the distributed phase is the same as the material of the polymeric matrix.
[0009]
A METHOD according to any one of the preceding claims, characterized in that the polymer matrix includes a reaction product of a hydroxy-phenoxyether polymer (e.g. a polyetheramine thermoplastic material) of a mono-functional or di-functional species with a moiety. containing epoxide, such as a diepoxide, which reacts under conditions to react the hydroxyl moieties with the epoxy moieties to form a generally linear polymeric backbone with ether linkages.
[0010]
10. METHOD according to any one of the preceding claims, characterized in that the distributed phase and the polymeric matrix are present in a relative weight ratio (distributed phase:polymer matrix) of 1:15 to 3:1.
[0011]
A COMPOSITE ARTICLE MANUFACTURING METHOD as defined in any one of the preceding claims, characterized in that it includes a step of advancing a thermoplastic polymer having at least one epoxy functional group reaction product along a rotating feed screw into a drum of a polymeric material molding device.
[0012]
12. DEVICE characterized in that it comprises: (a) a support (10, 110, 210, 310, 610, 710, 810, 910, 1110) that includes: (i) a mass of polymeric material (12, 112, 312, 1112 ) having an outer surface and including a first polymeric material; and (j) at least one fibrous composite material insert (14, 114, 214, 314, 614, 714, 814, 1114) or overlay that has an outer surface and that includes at least one array of elongated fibers having a plurality of ordered fibers distributed in a predetermined manner in a second polymeric material, the fibrous insert joining the mass of polymeric material at a predetermined location to support a predetermined load which is subjected to the predetermined location; wherein the fibrous insert or the overlay and the mass of polymeric material include compatible materials, structures or both, to allow the fibrous insert to be joined at least partially to the mass of polymeric material; and (k) optionally, a mass of activatable material (326, 626, 726) selectively applied to at least a portion of one or both of the outer surface of the mass of polymeric material or at least one fibrous insert, the mass of activatable material being capable of activating to expand upon an external stimulus and being capable of curing to form an adhesive bond to at least one surface of the article; wherein the outer surface of the fibrous insert is at least partially coextensive and continuous with the outer surface of the bulk of polymeric material, (1) wherein the second polymeric material is a hydroxyphenoxyether polymer, such as a thermoplastic material of polyetheramine, which is a product (e.g. a thermoplastic condensation reaction product) of a reaction of a monofunctional or difunctional species (e.g. monoethanolamine) with an epoxide-containing moiety, such as a diepoxide (e.g. for example, bisphenol A) diglycidyl ether which reacts under conditions to react the hydroxyl moieties with the epoxy moieties to form a generally linear polymeric backbone with ether linkages.
[0013]
DEVICE according to claim 12, characterized in that the mass of polymeric material (12, 112, 312, 1112) includes a thermoplastic material.
[0014]
DEVICE as claimed in claim 12 or 13, characterized in that at least one consolidated fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) includes at least one layer in the form of a laminar material that is generally made of the same type of material as the mass of polymeric material.
[0015]
A DEVICE according to any one of claims 12 to 14, characterized in that at least one elongate fiber array of at least one consolidated fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) includes a material which is generally made of the same type of material as the mass of polymeric material (12, 112, 312, 1112).
[0016]
A DEVICE according to any one of claims 12 to 15, characterized in that at least one elongated fiber arrangement of at least one consolidated fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) includes a material which is generally made of the same type of material as the bulk of polymeric material (12, 112, 312, 1112) so that the fibrous insert material and the bulk of polymeric material are chemically fused.
[0017]
A DEVICE according to any one of claims 12 to 16, characterized in that at least one elongate fiber array is a woven fiber array.
[0018]
Device according to any one of claims 12 to 17, characterized in that at least one elongate fiber array is an array of woven fibers that is impregnated with a material that is generally of the same type of material as the material of the mass of material. polymeric (12, 112, 312, 1112).
[0019]
Device according to any one of claims 12 to 18, characterized in that at least one elongate fiber array is an array of woven fibers made of a material that is generally of the same type of material as the bulk of polymeric material (12, 112, 312, 1112) and is impregnated with a material that is generally of the same type of material as the bulk material of polymeric material.
[0020]
Device according to any one of claims 12 to 19, characterized in that a polyamide material is used for one or more of the mass of polymeric material (12, 112, 312, 1112) or at least a portion of the fibrous insert (14). , 114, 214, 314, 614, 714, 814, 1114).
[0021]
A DEVICE according to any one of claims 12 to 20, characterized in that the fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) includes a plurality of layers, each including an arrangement of elongated fibers and each layer being anisotropic in its mechanical properties.
[0022]
DEVICE according to any one of claims 12 to 21, characterized in that the fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) includes a plurality of fibers, including glass fibers, mineral fibers, fibers carbon, polymeric fibers or any combination thereof.
[0023]
Device according to any one of claims 12 to 22, characterized in that the mass of activatable material (326, 626, 726) includes an epoxy-based material.
[0024]
A DEVICE according to any one of claims 12 to 23, characterized in that an orientation of one or more fibers in the elongated fiber array is selected to provide localized rigidity in response to a predetermined load that is applied to the elongated fiber array.
[0025]
DEVICE according to any one of claims 12 to 24, characterized in that the outer surface of the fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) is generally co-extensive with the outer surface of the mass of polymeric material and/or is positioned on top of the outer surface of the mass of polymeric material (12, 112, 312, 1112).
[0026]
DEVICE according to any one of claims 12 to 25, characterized in that a resulting external surface of the support is free of mesh lines or other imperfections that could provide a source of localized weakening of the support.
[0027]
Device according to any one of claims 12 to 26, characterized in that at least one consolidated fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) has an exposed outer surface and an exposed inner surface.
[0028]
DEVICE according to any one of claims 12 to 27, characterized in that the support (10, 110, 210, 310, 610, 710, 810, 910, 1110) has (i) a polymeric portion defined by the mass of polymeric material ( 12, 112, 312, 1112), (ii) a localized reinforcing portion defined by at least one fibrous insert (14, 114, 214, 314, 614, 714, 814, 1114) consolidated or overlapping, and (iii) a portion of interface (16, 1116) between the polymeric portion and the localized reinforcement portion, wherein the polymeric portion, the interface portion and the localized reinforcement portion are a generally smooth and/or continuous structure.
[0029]
A DEVICE as claimed in claim 28, characterized in that the interface portion (16, 1116) includes (i) an interpenetrating network defined by the first and second polymeric materials, (ii) chemical bonds between the first and second polymeric materials, or both (i) and (ii).
[0030]
A DEVICE according to any one of claims 12 to 29, characterized in that the resulting vehicle does not exhibit (i) mesh lines visible to the naked eye, (ii) voids or discontinuities visible to the naked eye through the interface portion, or both ( i) and (ii).
[0031]
Device according to any one of claims 12 to 30, characterized in that the article is a transport vehicle.
[0032]
A METHOD OF MANUFACTURING A DEVICE as defined in any one of claims 12 to 30, characterized in that it comprises impregnating a mass of fibers with the second polymeric material; molding the impregnated mass; and joining the impregnated mass to the mass of polymeric material.
[0033]
33. METHOD according to claim 32, characterized in that the molding step includes passing the impregnated mass, while in a softened state, through an opening to define the desired shape.
[0034]
A METHOD as claimed in claim 32 or 33, characterized in that the molding step includes shaping the device to have a generally continuous profile along its length.
[0035]
35. COMPOSITE comprising: (a) a mass of polymeric material (12, 112, 312, 1112) having an outer surface and including a first polymeric material; and (b) at least one overlay of fibrous material having an outer surface and including at least one array of elongated fibers having a plurality of ordered fibers, at least one fibrous insert (14, 114, 214, 314, 614, 714, 814). , 1114); and (c) a second layer of polymeric material located therebetween and in direct planar contact with each of the mass of polymeric material (12, 112, 312, 1112) and at least one overlay of fibrous material, wherein the second material polymeric is a hydroxy-phenoxyether polymer, such as a polyetheramine thermoplastic material, which is a product (e.g., a thermoplastic condensation reaction product) of a reaction of a mono-functional or di-functional species (e.g., monoethanolamine) with an epoxide-containing moiety, such as a diepoxide (e.g. bisphenol A diglycidyl ether) which reacts under conditions to react the hydroxyl moieties with the epoxy moieties to form a generally linear polymeric backbone with ether linkages.
[0036]
A COMPOSITE as claimed in claim 35, characterized in that the composite comprises a single mass of polymeric material.
[0037]
37. COMPOSITE according to claim 35 or 36, characterized in that the composite includes exactly two overlaps of fibrous material.
[0038]
A COMPOSITE according to any one of claims 35 to 37, characterized in that the composite includes at least two second polymeric layers.
[0039]
The COMPOSITE of any one of claims 35 to 38, characterized in that the composite includes at least four second polymeric layers.
[0040]
A COMPOSITE according to any one of claims 35 to 39, characterized in that the composite includes exactly four second polymeric layers.
[0041]
COMPOSITE according to any one of claims 35 to 40, characterized in that the second polymeric layer is a film.
[0042]
COMPOSITE according to any one of claims 35 to 41, characterized in that the mass of polymeric material includes a polyethylene material.
[0043]
A COMPOSITE as claimed in any one of claims 35 to 42, characterized in that at least one overlay of fibrous material includes glass fibers.
[0044]
44. METHOD characterized in that it comprises molding the composite as defined in any one of claims 35 to 43 in a heated press.
[0045]
45. DEVICE comprising: (a) a pultruded elongated thermoplastic epoxy support; (b) a sealing material located in direct planar contact with a portion of the support; (c) one or more portions of the thermoplastic epoxy film layer located in direct planar contact with the support.

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