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    • 专利摘要:
    METHOD FOR DEPOSITING A CONFORMAL COATING, CONFORMAL COATING DISPLAYED IN A TUBULAR STRUCTURE AND SYSTEM TO FORM A CONFORMAL COATING IN A TUBULAR STRUCTURE. The present invention relates to a method for depositing a coating that includes creating a vacuum within an inner volume of a tubular structure, the tubular structure also including an inner surface. A gas is supplied to the inner volume of the tubular structure, the gas including a plasma precursor in the gas phase. The tubular structure is skewed relative to the floor. Plasma having a density is formed and positioned cylindrically along the length of the tubular structure. The positive ions of the plasma precursor gas are generated and are deposited on the inner surface forming a coating on the inner surface, with the coating showing an angle of contact with water greater than 120 °.
    公开号:BR112015011794B1
    申请号:R112015011794-5
    申请日:2013-11-20
    公开日:2021-01-12
    发明作者:Michael A. Miller；Ronghua Wei；Gregory J. Hatton
    申请人:Southwest Research Institute；Shell Global Solutions；
    IPC主号:
    专利说明:

    CROSS REFERENCE WITH RELATED REQUESTS
    [001] The present application claims the benefit of the filing date of U.S. Patent Application Serial No. 13 / 683,690 filed on November 21, 2012, the teachings of which are hereby incorporated by reference. FIELD OF THE INVENTION
    [002] The present disclosure relates to conformal superhydrophobic coatings presented on the inner surface of relatively long tubular structures and processes for forming such coatings. In particular, the present invention relates to superhydrophobic coatings that mitigate the nucleation, growth and adhesion of hydrocarbon hydrates and inorganic scales on the inner surface of tubular structures. BACKGROUND
    [003] Hydrates, in particular, clathrate hydrates are understood to be solids based on crystalline water physically resembling ice, in which methane or other relatively small hydrocarbons are weights. Methane hydrate deposits found on and below the ocean floor and in certain regions of permanent ice make up the majority of known natural gas reserves on the planet. In addition, methane hydrates and other relatively minor forms of hydrocarbons in the production of oil and gas wells or pipelines. However, the formation of hydrates within the production of wells and pipelines leads to solid ice plugs with gas trapped within that blocked product flow when not mitigated.
    [004] Approximately 10 to 15% of production costs can be invested in preventing the formation of hydrates using technologies based on chemical additives (for example, methanol, siloxane oligomers, poly-N-vinylpyrrolidone, and aluminum sulfate) and physical methods (for example, high frequency electromagnetic fields). However, when such preventive methods fail, removing a continuous hydrate plug, for example, in a marine pipeline is expensive. Mitigation strategies that are not dependent on chemical additives or external physical methods can offer extraordinary cost savings for pipeline operations if an intrinsic property of the surface on which it contacts oil, and therefore such hydrates can be manipulated to reduce or eliminate nucleation and / or adhesion of hydrates on such surfaces.
    [005] It was tried to provide a functionalization of organosilicone and coatings that reduce the adhesion of hydrates to these surfaces. The hydrophobization of the metal surface comes into contact, for example, in reacting the iron oxyhydroxide functional groups present on the surface of the carbon steel with trimethyl chlorosilane or chlorosiloxane oligomers, as well as fluorine-analogues of these reagents. While these strategies can result in surfaces that can be classified as hydrophobic in relation to water, with contact angles with water approaching 120 °, these levels of hydrophobicity have been considered insufficient to inhibit nucleation, growth and adhesion of the hydrate on metal surfaces. SUMMARY
    [006] One aspect of the present disclosure relates to a method for depositing a conformal coating. The method includes creating a vacuum within an inner volume of a tubular structure, the tubular structure also including an internal surface. The gas is supplied in the inner volume of the tubular structure, and the gas includes a plasma precursor in the gas phase. The tubular structure is skewed relative to the floor. The plasma is formed so that it can be positioned cyclically along the length of the tubular structure. The positive ions of the plasma precursor gas are generated and can then be accelerated to the inner surface and deposited on the inner surface to form a coating, the coating having a contact angle with water greater than 120 °.
    [007] In a related aspect, the present disclosure refers to a conformal coating disposed in a tubular structure, comprising a tubular structure having an internal surface and an internal volume, and a carbo-siloxane coating disposed on the internal surface, being that the coating has a water contact angle greater than 120 °. The coating comprises 50 to 60 percent atomic carbon, 20 to 30 percent atomic oxygen, and 15 to 25 percent atomic silicon. The coating, at a depth of up to 300 Angstroms, includes the following types of chemical bonds: (a) Si-O- at a relative concentration of 38.5 (± 12)%; and a relative concentration of 25.6 (± 5)%; (c) C-O at a relative concentration of 4.5 (± 3)%; and (d) C-C at a relative concentration of 31.4 (± 2)%.
    [008] Another aspect of the present disclosure relates to a system for forming a conformal coating on a tubular structure. The system includes a tubular structure including an internal surface defining an interior volume and at least two opposite ends, each of the opposite ends including an opening. The system also includes at least two vacuum pumping stations, with each vacuum pumping station attached to one of the openings. The system also includes a gas supply port coupled to the interior volume via a small diameter tubular electrode (ie, 0.125-0.5 inches OD) on the floor (or positive) potentially covering the length of the tubular and suspended structure centrally under tension, through which the gas is supplied and eliminated in the internal volume of the tubular structure approximately halfway along the length of the tubular structure through a gas diffuser. In addition, as an optional feature, the system may include a plurality of magnetic field coils, with each magnetic field coil being arranged around the tubular structure and the magnetic field coils being spaced along the length of the tubular structure. In addition, the optional aspect of the system includes an arbitrary waveform generator electrically connected to the magnetic field coils configured to impose a variable current on the magnetic field coils and configured to provide a phase shift between at least two field coils magnetic. These optional aspects of the system can be used to assist the static or dynamic positioning of a plasma when formed within the tubular structure. BRIEF DESCRIPTION OF THE DRAWINGS
    [009] Other aspects and those mentioned above of this disclosure, and the way to achieve them, may become apparent and better understood by reference the following description of the modalities described here taken together with the accompanying drawings, being that:
    [010] Figure 1 illustrates a scheme for measuring the angle of contact with water;
    [011] Figure 2a illustrates a schematic of an exemplary embodiment of a system for carrying out the process of the present disclosure;
    [012] Figure 2b illustrates a schematic of another exemplary embodiment of a system for carrying out the process of the present disclosure;
    [013] Figure 3 illustrates an exemplary method for carrying out the process of this disclosure;
    [014] Figure 4 illustrates the rupture displacement versus a rupture force for water ice in coated and uncoated structures;
    [015] Figure 5 illustrates the relationship between the angle of contact with the oil in water and the breaking strength at maximum force (Mpa) versus the surface roughness of the water ice in stainless steel;
    [016] Figure 6 illustrates the breaking force versus the breaking displacement for both coated and uncoated carbon steel relative to solid asphaltenes; and
    [017] Figure 7 illustrates the Raman spectrum for coating production by the process and system described here versus the discharge of plasma of conventional brightness increased by chemical vapor deposition. DETAILED DESCRIPTION
    [018] The present disclosure relates to conformal superhydrophobic coatings present on the internal surface of relatively long tubular structures and processes for forming such coatings. In particular, the present invention relates to superhydrophobic coatings that mitigate the nucleation, growth and adhesion of hydrocarbon hydrates, organic deposits, and inorganic scales on the inner surface of tubular structures.
    [019] As noted above, hydrates, and in particular clathrate hydrates, are understood to be solids based on crystalline water in which relatively small hydrocarbons or other low molecular weight compounds are trapped within the hydrogen bonded water molecule. . Stated differently, hydrates are crystalline compounds, which comprise two constituents including host molecules (or water molecules) that form a solid lattice structure bonded to hydrogen and guest molecules (including hydrocarbons or other relatively low molecular weight compounds) host molecules. Hydrocarbons are trapped without a chemical bond within three three-dimensional lattice structures formed by the hydrogen bonding of water molecules. Non-limiting examples of hydrocarbons can include methane, ethane, propane, isobutene, 2-methyl butane, methylcyclopentane, methylcyclohexane, cyclooctane and combinations thereof. Other non-hydrocarbon hydrates include carbon dioxide, hydrogen sulfide, nitrogen, chlorine, etc.
    [020] Hydrates can form if gas and water are present under the appropriate state-phase conditions. In the case of a pipe or a well, hydrates can form in the volume flow or on the metal surfaces (that is, on the surfaces inside or delimiting the flow. Typically, the flow delimiting a metal surface is colder than the cooler temperatures promote the formation of hydrates on metal surfaces, which can provide nucleation sites for the formation of crystalline lattice. water can wet the metal, and subsequently hydrates with clathrate gas can form from of gas molecules originally dissolved in the aqueous phase. The nucleation of the hydrates can occur in the core size ranging from 5 nm to 30 nm. These nuclei are metastable and can cluster in larger stable groups of hydrates ranging in size from 100 to 2000 nm .
    [021] Under conditions of supersaturated gas in the aqueous phase, nucleation proceeds much more actively at the metal-water interface compared to water-gas interfaces far from the metal surface. In particular, the surface roughness of an unmodified metal substrate, having a relatively greater surface energy, can play two relatively important roles in the hydrate nucleating activity. First, the surface roughness can create areas of disruption of the aqueous phase on the surface, lowering the barrier to hydrate formation. Second, the formation of microscopic gas pockets within the surface roughness allows the hydrate to grow by creating a relatively large number of liquid gas interfaces.
    [022] The present disclosure is aimed at modifying the surface state of the inner surfaces of the tube wall, so that the surfaces exhibiting superhydrophobicity, reduce the surface energy and water wettability on the tube wall in relation to water. Hydrophobicity can be understood as the repulsion of water from a surface of a given metal, this is opposite to hydrophilicity in that water is attracted to the surfaces of a given material. Hydrophobicity can be quantified in terms of contact angle, which, as illustrated in figure 1, is the angle θ that a drop of water 100 forms in relation to a given surface 102. The smaller the contact angle, the more water is attracted to and wets the surface. The greater the contact angle, the less water will wet the surface. The ability of water to "wet" or "moisten" a surface indicates the ability of water to flow and cover the surface to maximize the contact area and the attractive forces between the water and the surface. In figure 1, the contact angle can be measured in a mineral oil environment as opposed to an air environment.
    [023] Hydrophobic materials can generally be understood as materials having contact angles with water that are 90 ° or greater. Superhydrophobic materials can be understood here as materials having an angle of contact with water that is 120 ° or greater. In this way, the internal surfaces of the tubular structures discussed here are modified to reduce the energy of the surfaces in relation to water, therefore, it increases the hydrophobicity to a contact angle of 120 or greater. As understood here, measurements can be made in mineral oil. This serves as a reference environment for approaching the environment in a well producing oil or a flow line.
    [024] The inner surface of the tubular structures can be modified by coating the structure with a superhydrophobic material that provides a conformal coating. Using high resolution X-ray photoelectronic spectrometry, the relative contribution of different bonding states comprising the superhydrophobic coating was determined from the variation of the XPS-measured states of each element involved in a given bonding type. It was determined that from these quantitative results that superhydrophobic coatings may include, consist essentially of, or consist of one or more substantially amorphous domains of the following types of chemical bonds: (a) Si-O- at a relative concentration of 38.5 (± 12)%; (b) Si-C at a relative concentration of 25.6 (± 5)%; (c) C-O at a relative concentration of 4.5 (± 3)%; (d) C-C at a relative concentration of 31.4 (± 2)%. The reference to the aspect that the domains are substantially amorphous can be understood as a situation where 90% or more of the domains are amorphous or non-crystalline.
    [025] Coatings may include, consist essentially of, or consist of 50 to 60 percent atomic carbon, including all values and variations here, 20 to 30 percent atomic oxygen, including all values and variations here, and 15 to 25 atomic percentage of silicon, including all values and variations here. The elements are present in a total amount of 100 percent atomic; however, impurities can be present in up to 1 percent atomic of the total composition. Preferably, the coatings can be composed of 56 to 57 percent atomic carbon, including all values and variations here, 20 to 26 atomic percentage of oxygen, including all values and variations here, and 17 to 23 percent atomic silicon, including all values and variations here. In addition, such atomic percentage concentrations and the types of bonds mentioned above are such that they are present on surfaces and at depths of 100 Angstroms, 200 Angstroms and 300 Angstroms in the coating. Thus, the atomic percentage concentration of C, O and Si is present in a relatively uniform profile from the surface to a depth of 300 Angstroms.
    [026] The coatings here can preferably be formed of silane compounds providing C, H, O and Si. Preferably a plasma precursor can include hexamethyldisiloxane (HMDSO) having the formula (CH3) 3Si-O-Si (CH3) 3. It can be appreciated that the precursors then identified can then form a plasma themselves or with the help of a noble gas such as Ar (preferably), or He, and coat the inner surfaces of the tubular structure to provide the amorphous domains noted above. In addition, other preferred precursors useful in forming superhydrophobic coatings on the inner surface of tubular structures, according to the process methods described here, include: (1) hexamethyldisilazane (CH3) 3Si-N-Si (CH3) 3; (2) bis-trifluoropropyl tetramethyldisiloxane (CF3C2H4) Si (CH3) 2-O-Si (CH3) 2 (CF3C2H4; and (3 combinations of HMDSO or (1) or (2) with a volatile fluorocarbon including, but not limited to , perfluoropropane (C3F8), hexafluoropropylene oxide (C3F6O), perfluorocyclohexane (C6F12), and hexafluorobenzene (C6F6).
    [027] The tubular structures to which the superhydrophobic coating is applied can be understood as structures having a length for diameter ratio (or a larger linear cross section) of 10: 1 or greater, such as 20: 1, 30: 1, 100: 1, and up to 1,000: 1. The tubular structure can be 10 feet or more in length, including all values and variations between 10 feet and 100 feet, including all values and increments there, such as in the range of 10 to 50 feet, from 20 to 70 feet, etc. . tubular structures can generally be circular in the cross section. However, in other modalities, tubular structures can exhibit rectangular, square, triangular or geometric cross sections. Additional modalities may include non-linear hollow shapes (in the plane), such as "S", curves, and split rings, or spiral shapes (outside the plane). In these cases, the internal electrode / various gases on the potential (or positive) floor are suspended with periodic dielectric supports making contact with the internal wall of the structure, as opposed to an unsupported, although tensioned, electrode for most linear shapes smaller than than or equal to 40-ft in length. Such dielectric supports are translated during the coating process in such a way that the '[area of the support making direct contact with the internal wall of the structure is unmasked, thus avoiding the potential to leave behind the periodic uncoated stains or changes in coating when along the length of the wall structure at the periodic locations of such supports.
    [028] Tubular structures can exhibit an initial average surface roughness (Ra) of less than 10 μm. The tubular structures can be based on iron and can include steel and preferably stainless steel or carbon steel.
    [029] The coatings can be deposited on a structure using a magnetically aided plasma chemical vapor deposition system, an example of which is illustrated in figure 2a. however, it must be understood that the aid of the magnetic field is not a necessary requirement of the process conditions, but can be used as necessary to assist the deposition process by concentrating or translating - both dynamically and statically - the plasma formed within the tubular structures . The system includes the tubular structure 200, on which the liner will be deposited, mounted between two high vacuum pump stations 204a, 204b at each end 206a, 206b of the tubular structure 200, that is, at each opening of the tubular structure. Therefore, additional openings must be provided in the tubular structure, additional high vacuum pumps can be fitted in these openings. Alternatively, additional openings can be sealed to prevent process gases from escaping. The high vacuum pumps 204a, 204b are operatively connected directly or indirectly to the tubular structure in such a way that the gas can be evacuated from the inner volume of the tubular structure. A combination of vacuum pumps can be arranged at high vacuum pump stations. For example, a positive displacement pump to achieve vacuum and a turbomolecular vacuum pump to achieve a high vacuum can be used. The high vacuum pump station can achieve a vacuum in the range of 1 * 10-1 Torr to 1 * 10-7 Torr.
    [030] The tubular structure is electrically isolated from the high vacuum pumping stations using vacuum compatible insulators 280a, 208b. In addition, the components connected to the vacuum pumping stations 204 are connected to an electrical ground G. A gas supply system 210 is connected to a gas inlet port 211a, 211b located in the distal parts of the apparatus 212a, 212b. an internal gas distribution tube 214 (see figure 2b), which also serves as an electrode on the potential ground, running along the axial length L of the tubular structure, including a plurality of gas ports 216 can also be provided to distribute process gases even throughout the inner volume 220 of the tubular frame 200. The gas ports are operatively coupled to the inner volume of the tubular frame in such a way that the path for the gas to pass from the storage tanks to the gas ports is provided, filling the inner volume of the tubular structure with process gases. The gas supply system 210 may include storage tanks or devices 222a, 222b in which the gas is stored in both a gas and a liquid form. The gas supply system 210 may also include mass flow controllers 224a, 224b to control the rate of gas flow entering the system. The gases are passed through supply lines 226a, 226b, 226c, and 226d at the gas inlet ports 211a, 211b. While only two storage tanks and mass flow controllers are illustrated, more than two can be present, such as three, four or even ten. The gases used in the system, process and coatings here include a chemical precursor used alone, or in combination with an inert gas, such as argon. Inert gases may be supplied to the interior volume at a ratio of 1:40 to 10: 1 from the inert gas to the plasma precursor.
    [031] A high voltage pulsed DC power source 230 is electrically connected to a 200 tubular structure. The negatively polarized pulsed voltage can vary from 0.5-10 kV, including all values and variations here with a pulsed frequency ranging from 500-5000 Hz, including all values and variations here and a pulse width ranging from 1 to 100 μs, including all values and variations here. The pulsed voltage of the power supply can be negatively polarized in relation to the ground system, forming a plasma in a hollow space of the structure. Plasma consists of electrons, ions and neutrons in various states of energy. When chemical precursors (for example, HMDSO) are fed into the plasma it can fragment, resulting in the formation of ionized and non-ionized fragments (radicals) of HMDSO molecules. The negatively polarized voltage extracts the positively charged ions from the plasma and accelerates the ions to the inner surface of the tubular structure. The acceleration is with relatively high terminal speeds and relatively high kinetic energy. When energetic ions and radicals from fragments of deposits of HMDSO molecules on the inner surface of the tubular structure a coating with the required composition can be formed.
    [032] As illustrated in figure 2a, the system preferably includes two or more magnetic field coils 240a, 240b, 240c, 240d, that is, solenoids, are configured or arranged around the outside of the tubular structure. While the four coils are illustrated, up to 10 or 20 coils can be provided depending on the length of the tube. Each magnetic field coil can exhibit a cross-sectional shape of a collar and wrap around the periphery of the tubular structure 200, spaced along the axial length L of the tubular structure 200. The magnetic field coils are connected to one or more constant current power suppliers DC 242a, 242b producing a magnetic field. The magnetic field can penetrate the thickness of the wall, depending on the magnetic permeability of the structure. The magnetic flux densities in the range of 0.1 mT (1 G) to 200 mT (2,000 G), including all values and ranges there, can appear in the hollow region or in the inner volume 220 of the tubular structure, that is, in the plasma region.
    [033] An arbitrary waveform generator 244 is also provided and electrically connected to the magnetic field coils to impose a variable current on each field coil 240 combined with a phase shift β between at least two, and even all coils magnetic field, for example, from 0 ° to 180 ° displacement phase. The density of the plasma can therefore be scanned cylindrically or positioned over the length of the structure. This is a reference to the aspect that plasma can be confined and relatively enhanced (for example, a higher relative plasma concentration) at selected locations along the length of the tubular structure. The swept magnetic flux can therefore form a relatively more uniform plasma within the tubular structures when compared to those situations where no magnetic flux or a static magnetic flux is provided. Therefore, a more uniform coating deposition across the internal surface of the relatively long hollow structure can now be achieved as needed.
    [034] A process for forming superhydrophobic coatings is further described here with reference to figure 3. The process can optionally start with a cleaning step 300, such as a spray cleaning, to remove contamination including organic species or surface oxides inorganic, from the inner surfaces of tubular structures. Initially, a vacuum is created or drawn in the inner volume of the tubular member for a pressure in the range of 1 * 10-6 Torr to 1 * 10-7 Torr, including all values and ranges here. Argon gas and, optionally hydrogen gas as a reactive gas, is introduced into the tubular substrate through the gas supply system, so that a pressure in the range of 1.33 Pa (10 mTorr) to 6.66 Pa (50 mTorr ), including all values and ranges here, is achieved. Other inert gases (eg, xenon, helium, neon, krypton or combinations thereof) can be used alone or in combination with argon gas.
    [035] While maintaining the gas pressures noted above, a negatively polarized pulsed voltage ranging from 0.5 to 10 kV, including all values and ranges here, with a pulse frequency ranging from 500 to 5000 Hz, including all values and ranges here, and a pulse width of 1 to 100 microseconds, including all values and ranges here. The positive ions (and / or positive ion radicals) generated by the plasma are accelerated towards the negatively polarized internal interface of the tubular member with relatively high kinetic energy, resulting in spray cleaning of the surface contaminants from the surface of the structure. During the process, negatively charged surfaces, including electrons and ionic radicals, accelerate towards the set of gas pipes / internal electrodes in the potential soil.
    [036] Following optional plasma spray cleaning, the chemical precursor gas, such as the HMDSO described above, can be supplied alone or co-mixed with an inert gas, such as argon, and measured in the inner volume of the tubular structure at a constant flow rate 302. The precursor gas can be supplied at a flow rate of 1 to 100 cm3 / min, including all values and variations there, while inert gas can be supplied at a flow rate of 1 to 200 cm3 / min, including all values and variations there. The gas space, or interior volume, of the tubular structure is maintained at a total pressure ranging from 1.33 Pa (10 mTorr) to 13.33 Pa (100 mTorr), including all values and variations there.
    [037] To initiate the deposition of the coating on the inner surface of the tubular structure, a plasma is formed 304 in the inner volume electrically exciting the tubular structure through negatively polarizing the tubular structure with a pulsed voltage in the range of 0.5 kV to 10 kV , including all values and variations there, relative to the ground at a pulse frequency of 500 Hz to 5000 Hz, including all values and variations there, and a pulse width ranging from 1 microsecond to 100 microseconds, including all values and variations there. The deposition period 306 can vary from 60 minutes to 120 minutes, including all values and variations there. The resulting coating has a thickness of up to 2.0 micrometers, as in the range of 0.2 to 2 micrometers, including all values and variations. Furthermore, the resulting coating is conformal, that is, in conformity with the surface aspects of the substrate and exhibiting a thickness deviation of less than 50% through the coating. After deposition, a durable and soft coating is formed having a structural and chemical composition that exhibits hydrophobic surface properties and still exhibits the nucleation, growth and adhesion of gas hydrates and / or the adhesion of asphaltenes, waxes and inorganic scales in their surface.
    [038] The resulting coating compositions are characterized along with the lines noted above. The water contact angle (WCA) of a drop of liquid water resting on the surface of a coated steel substrate immersed in mineral oil is determined to exceed 120 ° and reaches a value of 155 °, including all values and variations there . As the surface roughness increases, the angle of contact with water increases. Referring to figure 1, the contact angle is determined by the angle θ formed between the surface plane 102 of the coated substrate, parallel with the solid water interface, and the tangent line 104 at the oil-in-water interface crossing the plane of surface at the triple point of oil in solid water, measured through the drop of water, the oil being mineral. The measurement of the contact angle with water can be achieved by conventionally practiced methods, which include, for example, a goniometer coupled with a relatively high resolution camera.
    [039] In addition, the resulting compositions exhibit reduced water-ice shear pressures (i.e., shear forces). Specifically, ice-water shear pressures can be reduced by more than half when using superhydrophobic coatings (having a coating angle of 120 ° or greater) versus hydrophobic coatings (having a contact angle less than 120 °). The ice-water shear pressure can, for example, be less than or equal to 0.2 Mpa, such as 0.001 Mpa to 0.2 Mpa, including all values and variations there. The ice-water shear pressure is understood as the amount of shear stress required to move the water-ice drop attached to a surface, the water-ice drop on an electro-polished, uncoated steel surface of 1,089 Mpa. Stated differently, the ice-water shear pressure of the coated surface is half, or more than half, i.e., 1% to 50% of the water-ice shear pressure of the uncoated surfaces of the same roughness.
    [040] In addition, the resulting compositions exhibit a reduced shear pressure relative to hydrocarbon materials such as asphaltene and wax. Shear pressures can also be reduced by half or more than half, i.e., 1% to 50%, when using superhydrophobic coatings, such as less than or equal to 0.010 Mpa. Thus, the coating also exhibits oleophobic characteristics, which can be understood as a molecule that is repelled from the oil. In the case of an inorganic scale, a shear pressure less than or equal to 0.040 Mpa can be used to move the inorganic scale composed of carbonate salts adhered to this surface, compared to 0.16 Mpa for the unprotected surface.
    [041] The oleophobic and superhydrophobic nature of coatings are useful in mitigating or inhibiting nucleation, growth and adhesion of asphaltenes, waxes, and gas hydrates on the inner surface of steel pipe materials. Such properties carry significant benefits for the marine piping industry by reducing the frequency at which the product flow can be overloaded by stops due to gas hydrate, asphaltene or wax occlusions formed in the pipeline.
    [042] The compositions in question of the preferred coatings described here are understood to be accessible through a unique combination of the deposition process, the process conditions, and the preferred chemical precursors described here. This, in part, provides the superhydrophobicity and adhesion properties to the bottom surface necessary to inhibit nucleation, growth, and the adhesion of gas hydrates and the adhesion of asphaltenes, waxes and inorganic scales to steel substrates. In addition, the coating is able to resist wear and abrasion. In addition, the process is capable of coating the inner surface of long tubular structures. EXAMPLES
    [043] A number of steel substrates have been provided having a range of surface roughness average (Ra) ranging from 7.0 micro-inches to 30 micro-inches. The surface roughness of each substrate was measured using a style-type surface profilometer (Dektak 150, Veeco Instruments, Inc.) and collecting the surface profile over a scanning distance of 1 cm. The roughness average, Ra, was determined by computing the arithmetic mean of the absolute values of the vertical deviations (mountains and valleys) in the surface profile. The coatings were produced in each sample 0.4 microns and 0.8 microns in thickness as further described in Table 1 below. Specifically, each sample was first spray-cleaned and then a coating was deposited using an HMDSO precursor and an Ar gas.
    [044] The hydrophobicity of each coating was characterized by measuring the angle of contact with water in mineral oil using a goniometer coupled with a high resolution digital camera. As previously illustrated in figure 1, the water contact angle (WCA) was defined as an angle θ formed between the surface plane 102 of the coated substrate, parallel to the solid water interface, and the tangent line 104 at the water interface. oil in water crossing the surface plane at the triple point oil solid water, the Angle passing through the bubble. Digital image processing software (SIMAGIS®, Smart Imaging Technologies, Inc.) was used to derive precisely such WCAs from the captured images of the water droplet and the coated surface. The contact angles with water for each example are given below in Table 1. As illustrated, the greater the roughness and thickness of the coating, the greater the contact angle with water in oil. However, this effect is expected to reach a maximum, beyond which the contact angle decreases and the shear pressure, as described below, increases. TABLE 1. Hydrophobicity and Adhesion Characteristics of Carbon Steel Coatings

    [045] Ice-water adhesion characterized by ice-water shear pressure (ie, shear stress) was also measured for each coating. Specifically, the ice-water shear pressure was characterized using a device that measures the adhesion between an ice-water drop and a coating on a steel substrate. A description of this device and its application has been reported elsewhere [Zou, M .; Beckford, S .; Wei, R .; Ellis, C; Hatton, G., Miller, M.A., Applied Surface Science 257 (2011) 3786-3792]. The test was performed at 262 K. Figure 4 illustrates a comparison of the shear force (N) used to break the adhesion between the unprotected electropolished stainless steel A having a surface roughness of 0.5 micro-inch (0.13 micrometer) ) and stainless steel having the same roughness and a coating having a thickness of 0.8 micron B. As can be seen in figure 4, the shear stress required to displace an ice-water drop attached to the coated surface was determined to reaching a value lower than 0.0363 Mpa at 262 K, while the electrode-polished uncoated steel surface requires a shear stress of approximately one order or greater magnitude to displace a drop of ice-water of the same volume of bond to its surface at a similar temperature. Table 1 lists the ice-water shear pressures for each coating and surface roughness on carbon steel substrates. In addition, figure 5 illustrates the relationship of the contact angle θ oil in water and the shear stress at a maximum force (Mpa) S versus the surface roughness.
    [046] The adhesion of solidified asphaltenes and waxes was also determined using a measuring device described above at 262K. in this example, the substrates were formed from carbon steel having a surface roughness of 30 micro-inches (0.76 micrometers). Figure 6 illustrates the shear force versus the shear displacement for both sample A of unprotected carbon steel and sample B of coated carbon steel. The peak shear stress required to displace a drop of solid asphaltene from the surface of the carbon steel that is coated in this example was 30.2 kPa, compared with 9.86 for coated steel.
    [047] The elemental composition and bonding states in question of the preferred coatings derived from the process conditions can be characterized in relation to the depth or thickness of the coating using an X-ray photoelectronic spectrometry (XPS) also known as electron for chemical analysis (ESCA). XPS (or ESCA) can be understood as an elementary analysis technique to detect elements with the exception of hydrogen and helium, with a nominal detection limit of approximately 0.1% atomic. A high resolution XPS can also provide information regarding the connection states of the elements in question. The elemental composition of the coatings formed here is described in Table 2. Tables 3 to 5 provide the bonding state of the coatings. TABLE 2. Relative Elementary Composition by Atomic Percentage of the Preferred Coating as a Depth Function
    Table 3. Relative Concentration of Liaison States for the 1st Region of
    TABLE 4. Relative Binding State Concentration for the XPS High Resolution Oxygen Region as a Depth Function

    TABLE 5. Relative Liaison State Concentration for the 2nd Region of
    * Combination of Si 2p3 / 4 and Si 2p1 / 2 peaks
    [048] In addition, the coatings were examined using Raman spectroscopy to identify the unique molecular structural characteristics of that obtained using the processes claimed here. A comparison was made between the Raman spectrum of the coating and the process described here for that chemical vapor deposition increased by conventional discharged plasma (PECVD). In both cases, the precursor HMDSO was used in combination with the process gas Ar. The spectra are illustrated in figure 7, with the spectrum displayed by the present process being indicated as I and the spectrum displayed by the conventional process is indicated as II .
    [049] As seen in the graph, the process described here yields a coating that contains a substantially higher proportion of Si - O - Si structural groups than the conventional process. This is indicated by the asymmetric Si - O - Si stretching vibrations over a wide region of the spectrum close to 500 cm-1, at point A, which is markedly depressed in the coating prepared by the glow discharge. The wide spectral region close to 793 cm-1, point B, indicates a proportionally greater contribution of di- and trimethyl silanes [- Si (CH3) x] terminals, which emerge in the Raman spectrum as asymmetric Si - C elongation vibrations. Finally, the spectral region between 1309 cm-1 and 1350 cm-1, point C, can be attributed to the cutting models associated with the formation of carbosilanes [Si - CH2 - Si] in the coating. The relative contribution of this structural aspect is again greater in the coating described here than in the conventional coating.
    [050] While the particular modalities have been described, it must be understood that various changes, adaptations and modifications can be made here without departing from the spirit of the invention and the scope of the attached claims. The scope of the invention must therefore be determined not with reference to the above description, but rather with reference to the appended claims along with its full scope of equivalents. In addition, it should be understood that the appended claims do not necessarily comprise the broader scope of the invention whose claimant is entitled to claim, or only the manner (s) in which the invention can be claimed, or that all aspects recited are necessary .
    权利要求:
    Claims (12)
    [0001]
    1. Method for depositing a conformal coating, CHARACTERIZED by the fact that it comprises: creating a vacuum within an inner volume (220) of a tubular structure (200) of steel having an average initial roughness (Ra) equal to or greater than 0.3 μm and less than 10 μm, where such tubular structure (200) includes an internal surface and such an internal volume (220); introducing an inert gas and optionally hydrogen in such interior volume (220) and maintaining a pressure in the range of 1.33 Pa (10 mTorr) to 6.66 Pa (50 mTorr); spraying such an internal surface by applying to such a tubular structure (200) a negatively polarized pulsed voltage ranging from 0.5 to 10 kV, with a pulsed frequency ranging from 500 to 5000 Hz at a pulse width of 1 to 100 μs per 30 to 120 minutes, while maintaining such pressure in the range of 1.33 Pa (10 mTorr) to 5.33 Pa (40 mTorr); after said spray cleaning, supply a) precursor gas at a flow rate of 1 to 100 cm3 / min and b) inert gas at a flow rate of 1 to 200 cm3 / min for such interior volume (220) of such structure tubular (200), in which the inner volume (220) of such tubular structure (200) is maintained at a total pressure ranging from 1.33 Pa (10 mTorr) to 13.33 Pa (100 mTorr) and such gas precursor is hexamethyldisiloxane; negatively polarize such tubular structure (200) in relation to the ground with a pulsed voltage ranging from 0.5 to 10 kV at a pulsed frequency of 500 to 5000 Hz at a pulse width of 1 to 100 μs; forming a plasma having a density and cyclically positioning that plasma density along the length of such tubular structure (200); generate positive ions from such a plasma precursor gas that are deposited on such an internal surface; and forming a coating with a thickness ranging from greater than or equal to 0.8 μm to 2 μm on such an internal surface during a deposition period (306) of 60 minutes to 120 minutes, where such coating exhibits a contact angle with water greater than 120 ° in mineral oil and such coating comprises, a depth of up to 300 Angstroms, 50 to 60 of atomic percentage of carbon, 20 to 30 of atomic percentage of oxygen, and 15 to 25 of atomic percentage silicon measured by XPS.
    [0002]
    2. Method, according to claim 1, CHARACTERIZED by the fact that it also comprises ordering at least two coils of magnetic field (240a, 240b, 240c, 240d) externally around such tubular structure (200) and forming a magnetic field having a density in the range of 0.1 mT (1 G) to 200 mT (2,000 G) in the hollow region of the tubular structure (200).
    [0003]
    3. Method, according to claim 2, CHARACTERIZED by the fact that a variable current is imposed on each magnetic field coil (240a, 240b, 240c, 240d) with a phase shift between each magnetic field coil (240a, 240b, 240c, 240d) to cyclically position such plasma density.
    [0004]
    4. Method according to claim 1, CHARACTERIZED by the fact that such gases are supplied to such an interior volume (220) in a ratio of 1:40 to 10: 1 of such inert gas to such a plasma precursor.
    [0005]
    5. Method, according to claim 1, CHARACTERIZED by the fact that, at such a depth of up to 300 Angstroms, such coating comprises 56 to 57 atomic percentage of carbon, 20 to 26 atomic percentage of oxygen and 17 to 23 percent atomic silicon.
    [0006]
    6. Method, according to claim 1, CHARACTERIZED by the fact that such a coating, at such depth of up to 300 Angstroms, comprises the following types of bond: (a) Si-O in a relative concentration of 38.5 (± 12)%; (b) Si-C at a relative concentration of 25.6 (± 5)%; (c) C-O at a relative concentration of 4.5 (± 3)%; (d) C-C at a relative concentration of 31.4 (± 2)%.
    [0007]
    7. Method, according to claim 1, CHARACTERIZED by the fact that such coating has a contact angle with water greater than 120 ° to 155 ° in mineral oil.
    [0008]
    8. Conformal coating arranged in a tubular structure (200), CHARACTERIZED by the fact that it comprises: a tubular structure (200) of steel having an initial average roughness (Ra) greater than or equal to 0.3 μm and less than 10 μm, an internal surface and an internal volume (220); and a carbo-siloxane coating disposed on such an internal surface having a thickness ranging from greater than or equal to 0.8 μm to 2 μm, in which such coating is deposited according to the method, as defined in claim 1, and has an angle of contact with water greater than 120 ° in mineral oil, in which such coating comprises 50 to 60 percent atomic carbon, 20 to 30 percent atomic oxygen and 15 to 25 percent atomic silicon .
    [0009]
    9. Conformal coating arranged in a tubular structure (200), according to claim 8, CHARACTERIZED by the fact that such coating has an angle of contact with water greater than 120 ° to 155 ° in mineral oil.
    [0010]
    10. Conformal coating arranged in a tubular structure (200), according to claim 8, CHARACTERIZED by the fact that such tubular structure (200) is a pipe configured to transport gas or oil.
    [0011]
    11. System for forming a conformal coating having a thickness ranging from greater than or equal to 0.8 μm to 2 μm and an angle of contact with water greater than 120 ° in mineral oil in a tubular structure (200) according with the method, as defined in claim 1, CHARACTERIZED by the fact that it comprises: a tubular structure (200) of steel having initial average roughness (Ra) greater than or equal to 0.3 μm and less than 10 μm including a inner surface defining an interior volume (220) and at least two opposite ends (206a, 206b), each opposite end (206a, 206b) including an opening; at least two vacuum pumping stations (204), wherein each vacuum pumping station (204) is coupled to one of such openings; a gas supply port (211a, 211b) coupled to such an interior volume (220); a gas supply line (226a, 226b, 226c, 226d) coupled to such a gas supply port (211a, 211b), wherein said gas supply line (226a, 226b, 226c, 226d) includes a controller mass flow (224a, 224b); a high voltage pulsed DC power source (230) electrically connected to such a tubular structure (200); a plurality of magnetic coils (240a, 240b, 240c, 240d), wherein each magnetic field coil (240a, 240b, 240c, 240d) is arranged around such a tubular structure (200) and such magnetic field coils (240a , 240b, 240c, 240d) are spaced along the length of such tubular structure (200); and an arbitrary waveform generator (244) electrically connected to such magnetic field coils (240a, 240b, 240c, 240d) configured to impose a variable current on such magnetic field coils (240a, 240b, 240c, 240d) and configured to provide a phase shift between at least two such magnetic field coils (240a, 240b, 240c, 240d).
    [0012]
    12. System according to claim 11, CHARACTERIZED by the fact that such a gas supply port (211a, 211b) includes an internal gas collector extending along the axial length of such tubular structure (200).
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    同族专利:
    公开号 | 公开日
    US20170306182A1|2017-10-26|
    US9701869B2|2017-07-11|
    EP2923137B1|2020-05-27|
    EP2923137A2|2015-09-30|
    CN105308212A|2016-02-03|
    US20140137976A1|2014-05-22|
    CN105308212B|2017-08-08|
    AU2018204117A1|2018-06-28|
    AU2013348056A1|2015-06-11|
    US20150337170A1|2015-11-26|
    BR112015011794A2|2017-07-11|
    MY181527A|2020-12-25|
    WO2014081858A3|2015-08-20|
    EP2923137A4|2017-03-29|
    US9926467B2|2018-03-27|
    AU2018204117B2|2020-01-02|
    AU2013348056B2|2018-07-12|
    US9121540B2|2015-09-01|
    WO2014081858A2|2014-05-30|
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-07-14| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/683,690|US9121540B2|2012-11-21|2012-11-21|Superhydrophobic compositions and coating process for the internal surface of tubular structures|
    US13/683,690|2012-11-21|
    PCT/US2013/071059|WO2014081858A2|2012-11-21|2013-11-20|Superhydrophobic compositions and coating process for the internal surface of tubular structures|
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