LOW FRICTION COATING WITH IMPROVED ABRASION AND WEAR PROPERTIES AND PRODUCTION METHODS

专利摘要:
low friction coating with improved abrasion and wear properties and production methods. Low friction coatings with improved resistance to abrasion wear and methods of producing such coatings are provided. in one form, the coating includes: i) a bottom layer selected from the group consisting of crn, tin, tialn, tialvn, tialvcn, tisin, tisicn, tialsin and combinations thereof, wherein the bottom layer varies in thickness by 0.1 at 100 (mi)m, ii) an adhesion promoting layer selected from the group consisting of cr, ti, si, w, crc, tic, sic, wc, and combinations thereof, wherein the adhesion promoting layer varies in thickness from 0.1 to 50 (mi)m and is contiguous with a surface of the lower layer, and iii) a functional layer selected from the group consisting of a fullerene-based composite, a diamond-based material, coal sediment, and combinations thereof, wherein the functional layer ranges from 0.1 to 50 (mi)m and is contiguous with a surface of the adhesion-promoting layer.
公开号:BR112015009709B1
申请号:R112015009709-0
申请日:2013-11-19
公开日:2021-09-08
发明作者:Srinivasan Rajagopalan；Tabassumul Haque；Mehmet Deniz Ertas；Adnan Ozekcin；HyunWoo Jin；Bo Zhao
申请人:Exxonmobil Research And Engineering Company；
IPC主号:

专利说明:

FIELD
[0001] The present disclosure relates to the field of coatings with improved properties. More particularly it relates to multi-layer low friction coatings with improved abrasion and wear resistance, methods of preparing such coatings and methods of using such coatings to reduce friction and improve abrasion resistance. FUNDAMENTALS
[0002] Extended Reach Rotary Drilling Devices:
[0003] In rotary drilling operations, a drill bit is attached to the end of a set of lower holes that is connected to a drill string comprising pipe joints and drilling tools that can be rotated on the surface by a rotary table or top drive unit. The weight of the drill string and lower set of holes cause the rotary bit to cut a hole in the ground. As the operation progresses, new sections of drill pipe are added to the drill string to increase its overall length. Periodically during the drilling operation, the open well is covered to stabilize the walls, and the drilling operation is resumed. As a result, the drill string generally operates both in the open pit and within the cover that has been installed on the well. Alternatively, the coiled tubing can replace the drill string in the drill assembly. The combination of a drill string and bottom hole set or coiled tubing and bottom hole set is referred to herein as a drill rod set. The rotation of the drill string supplies power through the drill string and lower set of holes to the drill. In coiled pipe drilling, energy is released into the bit by drilling fluid pumps. The amount of energy that can be transmitted per rotation is limited to the maximum torque that a drill string or coiled pipe can experience.
[0004] When drilling a well through underground formations, the set of drill rods undergoes considerable sliding contact with both the steel cover and rock formations. This sliding contact mainly results from the rotational and axial movements of the drill rod assembly in the well. Friction between the moving surface of the drill rod assembly and the stationary surfaces of the cover and formation creates considerable drag on the drill rod and results in excessive torque and drag during drilling operations. The problem of friction is inherent in any drilling operation, but is especially problematic in directionally drilled wells or Extended Reach Drilling (ERD) wells. Directional drilling or ERD is the intentional deviation of a well drilling from the vertical. In some cases, the angle to the vertical can be as large as ninety degrees from the vertical. Such wells are commonly referred to as horizontal wells and can be drilled to a considerable depth and considerable distance from the drilling rig.
[0005] In all drilling operations, the drill rod assembly has a tendency to downtime compared to the well or well cover side, but this tendency is much greater in directionally drilled wells due to the effect of gravity. As the drill string increases in length or degree of vertical deflection, the amount of friction created by the rotating drill rod assembly also increases. To overcome this increase in friction, additional energy is required to rotate the drill rod assembly. In some cases, the friction between the drill rod assembly and the cover wall or well exceeds the maximum torque that can be tolerated by the drill rod assembly and/or the maximum torque capability of the drilling rig and drilling operations must cease. Consequently, the depth to which wells can be drilled using available directional drilling equipment and techniques is limited.
[0006] Friction reduction is a fundamental requirement in such ultra-long-range underground oil and gas rotary drilling applications. One method of reducing friction caused by contact between the drill rod assembly and casing (in the case of a covered well) or well (in the case of an open hole) is to improve the lubricity of the drilling muds. In industrial drilling operations, attempts have been made to reduce friction mainly through the use of water and/or oil based mud solutions containing various types of expensive and often environmentally harmful additives. Diesel and other mineral oils are also often used as lubricants, but there is a problem with sludge disposal. Certain minerals such as bentonite are known to help reduce friction between the drill rod assembly and an open well. Materials such as Teflon have been used to reduce friction, however, they lack durability and strength. Other additives include vegetable oils, asphalt, graphite, detergents and nutshells, but each has its own limitations. While these sludges had some benefit, sludge disposal is a problem. Additionally, a bigger problem is the fact that COF increases with increasing temperature, especially with water-based sludges.
[0007] Yet another method for reducing friction between the drill rod assembly and the well cover or well is to use a solid casing material over the drill string assembly (also referred to herein as solid ligation or solid casing ). US Patent No. 4,665,996, incorporated herein by reference in its entirety, discloses the use of solid coating the main bearing surface of a drill pipe with an alloy having a composition of: 50 to 65% cobalt, 25 to 35 % Molybdenum, 1-18% Chromium, 2-10% Silicon and less than 0.1% Carbon to reduce friction between the drill string and the roof or rock. As a result, the torque required for rotary drilling operation, especially directional drilling, is reduced. The disclosed alloy also provides excellent wear resistance over the drill string, while reducing wear to the well cover. Solid coating can be applied to parts of the drill rod assembly using either the solder coat or thermal spray methods.
[0008] Although solid ligation has been effective in protecting tool joints to some extent, carbide particles are known to cause severe abrasive wear of the capping material, thus limiting the effectiveness of this technique.
[0009] Another method for reducing friction between the set of drill rods and the well cover or well is to use the aluminum drill string because aluminum is lighter than steel. However, the aluminum drill string is expensive and difficult to use in drilling operations, and is not compatible with many types of drilling fluids (eg high pH drilling fluids).
[0010] US Patent Nos. 7,182,160, 6,349,779 and 6,056,073 disclose the designs of grooved segments in drill strings for the purpose of improving fluid flow in the annular space and reducing contact and friction with the wall of the well.
[0011] Yet another problem encountered during underground rotary drilling operations, especially directional drilling, is the wear of the cover and drill rod assembly that occurs when metal surfaces are in contact with each other. This abrasion between metal surfaces when drilling oil and gas wells results in excessive wear on both the drill rod assembly and casing cover. Currently, a preferred solution to reduce wear on drill rod assemblies is hard coating on the parts of the drill rod assembly. Alloys containing tungsten carbide, such as Stellite 6 and Stellite 12 (trademark of Cabot Corporation), have excellent wear resistance as a hard coating material. The hard casing protects the drill rod assembly but tends to cause excessive abrasion of the well cover. This problem is especially serious during directional drilling because the drill rod assembly, which has a tendency to rest on the well cover, continually wears down the well cover as the drill string rotates. Also, some of these hard-coated alloys, such as tungsten carbide, can make the friction problem worse.
[0012] Oil and Gas Well Production Devices with Coated Gloves:
[0013] In addition to rotary underground oil and gas drilling devices, friction is also a problem in oil and gas well production devices. Oil and gas well production suffers from basic mechanical problems that can be costly, or even prohibitive, to correct, repair or mitigate. Friction is ubiquitous in the oilfield, in devices that are in moving contact that wear out and lose their original dimensions, and in devices that are degraded by erosion, corrosion and deposits. These are impediments to successful operations that can be mitigated through the selective use of oil and gas well production devices with coated sleeves as described below. These oil and gas well production devices include, but are not limited to, drilling rig equipment; marine flexible tube systems; tubular goods; wellhead, trees and valves; production equipment including artificial lifting equipment, completion columns and equipment; sand formation and wall findings; and well intervention equipment.
[0014] Equipment and Devices for the Petrochemical and Chemical Industry:
[0015] Components for equipment in petrochemical and chemical production suffer from degradation ranging from mechanical and chemical effects. For example, components wear out due to repeated friction of surfaces, resulting in damage that requires repair or replacement. Under certain circumstances, debris produced by wear can also contaminate the product, making it unacceptable. In addition to wear, excessive friction between surfaces can also increase the energy required for operation. Higher energy costs can also be realized when pumping fluids into operation due to excessive friction or resistance between the fluid and the surface of the component that drives it. Another example of component degradation can be related to corrosion where components need to be replaced periodically. Corrosion can also lead to fouling on the inside diameter of heat exchanger tubulars, which results in degradation of heat transfer efficiency. These are all potential impediments to successful petrochemical operations that can be costly, or even prohibitive, to fix, repair or mitigate.
[0016] Exemplary non-limiting applications of such coatings include extruders, barrels, gearboxes, bearings, compressors, pumps, pipes, tubes, molding dies, valves and reactor vessels.
[0017] Required for Current Disclosure:
[0018] Given the expansive nature of these requirements for extended-range rotary drilling devices, coated sleeve oil and gas well production devices, and chemical petrochemical industry equipment and devices, there is a need for low-friction coatings with improved properties such as friction, wear, abrasion, corrosion, erosion and deposits. Considering the operating environments for these applications, which typically include high loads and severe abrasive conditions, traditional and conventional low friction coatings (eg graphite, MoS2, WS2) may not meet the durability requirements in some cases. Thus, there is a need to develop low-friction coatings that demonstrate adequate durability in these environments, through improved abrasion resistance and reduced wear on both the coated part and the counterface material (eg, overlay steel) relative to to prior art coatings. SUMMARY
According to one aspect of the present disclosure, an advantageous low friction multilayer coating comprises: i) a back layer selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations, in which the lower layer varies in thickness from 0.1 to 100 µm, ii) an adhesion promoting layer selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and its combinations, in which the adhesion promoting layer ranges in thickness from 0.1 to 50 µm and is contiguous with a surface of the lower layer, and iii) a functional layer selected from the group consisting of a fullerene-based composite, a material diamond-based, diamond-like carbon (DLC), and combinations thereof, where the functional layer ranges from 0.1 to 50 µm and is contiguous with a surface of the tackifying layer. The adhesion promoting layer is interposed between the lower layer and the functional layer, and can also provide the additional strength enhancing function. The friction coefficient of the low friction coating functional layer as measured by the block in the annular friction test is less than or equal to 0.15, and the abrasion resistance of the low friction coating as measured by the modified ASTM G105 abrasion test produces a sign of deep wear less than or equal to 20 µm and a weight loss less than or equal to 0.03 grams.
[0020] According to another aspect of the present disclosure, a method of producing a low friction multilayer coating comprises: i) providing a substrate for the coating, (ii) depositing on a surface of the substrate a lower layer selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations, in which the lower layer varies in thickness from 0.1 to 100 µm, iii) deposit a layer on the surface of the lower layer adhesion promoter selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and combinations thereof, wherein the adhesion promoter layer varies in thickness from 0.1 to 50 µm and is contiguous with a surface of the lower layer, and iv) depositing on the surface of the adhesion promoting layer a functional layer selected from the group consisting of a fullerene-based composite, a diamond-based material, diamond-like carbon (DLC), and your combinations, in which the cam Each functional range ranges from 0.1 to 50 µm and is contiguous with a surface of the adhesion promoting layer. The friction coefficient of the low friction coating functional layer as measured by the block in the annular friction test is less than or equal to 0.15, and the abrasion resistance of the low friction coating as measured by the modified ASTM G105 abrasion test produces a sign of deep wear less than or equal to 20 µm and a weight loss less than or equal to 0.03 grams.
[0021] These and other aspects and attributes of the disclosed multilayer low friction coatings, methods of preparing such coatings and methods of using such coatings for underground rotary drilling devices, oil and gas well production devices with coated glove and petrochemical and chemical industry equipment and devices and their advantageous applications and/or uses will be apparent from the following detailed description, particularly when read in conjunction with the accompanying figures. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] To assist those of practical skill in the relevant art in the production and use of the subject matter in this regard, reference is made to the attached drawings, in which:
[0023] Figure 1 represents micrographs in a sectional plane X of the test specimens deposited with different coating architectures after the CETR-BOR high sand content test in which the lower layer constitutes a substrate (ferrous), a layer of CrN adhesion promoter (enhancement of strength) that separates the upper functional layers of the substrate. More detailed information about the architectures can be found in Table 1 below. DEFINITIONS
[0024] The "bottom hole set" (BHA) is comprised of one or more devices, including, but not limited to: stabilizers, variable capacity stabilizers, reverse countersinks, drill collars, flexible drill collars, steerable tools rotary, rolling countersinks, shock subs, mud motors, logging tools during drilling (LWD), measuring tools during drilling (MWD), core tools, bottom countersinks, hole openers, centralizers, turbines, curved housings , tilted motors, drill vessels, accelerator vessels, pass-through subs, shock vessels, torque reduction tools, float subs, fishing tools, fishing vessels, washdown tubes, profiling tools, drilling tool search subs, non-magnetic counterparts of any of these devices, and their combinations and their associated external connections.
[0025] "Cover" is the pipe installed in a well bore to prevent the hole from collapsing and allow the drilling to continue below the bottom of the cover column with higher fluid density and no fluid flow within the covered training. Typically, multiple columns of cover are installed when drilling smaller and smaller diameter wells.
[0026] "Cover centerers" are sleeves connected with the outside of the cover when being operated in the cavity. Centralizers are often equipped with steel springs or metal fingers that push against the formation to achieve the formation wall balance, with an aim to center the cover to provide a more uniform annular space around the cover to achieve a better seal. of cement. Centralizers can include finger-like devices to scrape the well to dislodge the filter cake from the drilling fluid which can inhibit direct cement contact with the formation.
[0027] "Contiguous" refers to objects that are adjacent to each other in such a way that they can share a common edge or face. "Non-contiguous" refers to objects that do not have a common edge or face because they are offset or offset from each other. For example, tool joints are larger diameter cylinders that are noncontiguous because a smaller diameter cylinder, the drill pipe, is positioned between the tool joints.
[0028] "Coupling" is a connecting device between two pieces of pipe, often, but not exclusively, a separate piece that is threadably fitted into two parts longer than coupling the joint together. For example, a coupling is used to join two parts of the suction rods on the pumping equipment of the artificial lifting rod.
[0029] "Drill collars" are heavy wall tubes in the set of lower holes near the drill. The rigidity of the drill collars helps the bit drill straight, and the weight of the collars is used to apply weight to the bit to drill forward.
[0030] "Drill rod" is defined as the entire length of the tubular pipes, comprised of kelly (if present), the drill pipe and the drill collars, which make up the drilling assembly from the surface to the part bottom of the cavity. Drill rod does not include drill bit. In the special case of casing operations during drilling, the casing string that is used to drill within the ground formations will be considered part of the drill rod.
[0031] "Drill rod set" is defined as a combination of a drill string and bottom hole set or coiled tubing and bottom hole set. Drill rod set does not include drill bit.
[0032] "Drilling column" is defined as the column, or series of drill pipes with attached tool joints, transition tube between the drill string and the set of lower holes including the tool joints, the pipe of heavy weight drilling including tool gaskets and durability plugs that carry fluid and rotational energy from the upper transmission or kelly to the drill collars and bit. In some references, but not in this document, the term "drill column" includes both the drill tube and the drill collars in the lower set of holes.
[0033] "Elbow pipes, T-tubes and couplings" are pipe equipment commonly used for the purpose of connecting flow lines to complete a flow path with respect to fluids, for example, to connect a well bore with the surface production facilities.
[0034] "Kelly" is a flat-sided polygonal piece of tubing that passes through the drill rig floor over rigs equipped with older rotary table equipment. Torque is applied to this four, six, or maybe eight-sided piece of pipe to rotate the drill pipe, which is connected below.
[0035] "Profiling tools" are instruments that are typically operated in a well to take measurements; for example, when drilling in the drill rods or in the open or covered hole in the fixed net. Instruments are installed with a series of brackets configured to operate within a well, such as cylindrical shaped devices, which provide environmental isolation for the instruments.
[0036] "Plunger elevator" is a device that moves up and down a column of pipe to purge the pipe of water, similar to a pipeline "pipe cleaning" operation. With the plunger elevator at the bottom of the tube, the tube scraper device is configured to block fluid flow, and therefore it is pushed up into the orifice by fluid pressure from below. When it moves up the well, it displaces the water because the water is not allowed to separate and flow beyond the limits of the plunger elevator. At the top of the pipeline, a device triggers a change in the piston elevator configuration such that it now deflects the fluids, after which gravity pulls it down the pipeline against the upward flowing current. Friction and wear are important parameters in piston elevator operation. Friction reduces the speed of the plunger lifter as it falls or rises, and outer surface wear provides an opening that reduces the device's effectiveness as it travels up through the hole.
[0037] "Production device" is a broad term defined to include any device relating to the drilling, completion, stimulation, reconditioning or production of an oil and/or gas well. A production device includes any device described herein used to the purpose of producing oil or gas. For convenience of terminology, the injection of fluids into a well is defined to be production at a negative rate. Therefore, references to the word "production" will include "injection" unless otherwise noted.
[0038] "Shock sub" is a modified piercing collar that features a molar-like impact-absorbing element to provide relative axial movement between the two ends of the shock sub. Sub shock is sometimes used for drilling very resistant formations where high levels of axial impacts can occur.
[0039] "Sleeve" is a tubular part designed to fit over another part. The inner and outer surfaces of the sleeve may be circular or non-circular in cross-sectional profile. The inner and outer surfaces may generally have different geometries, ie , the outer surface may be cylindrical with a circular cross section, while the inner surface may have an elliptical or other non-circular cross section. Alternatively, the outer surface may be elliptical and the inner surface circular, or some other combination. The use of pins, grooves and other means can be used to restrict the sleeve to a body in one or more degrees of freedom, and sealing elements can be used if there are pressure or differential fluid containment issues. More generally, a sleeve can be considered to be a generalized hollow cylinder with one or more variable radii or profiles in cross-section along the axial length of the cylinder.
[0040] "Sliding contact" refers to frictional contact between two bodies in relative motion, either separated by fluids or solids, these including particles in the fluid (bentonite, glass globules, etc.) or by devices designed to cause rolling to ease friction. A part of the contact surface of two bodies in relative motion will always be in a sliding state, and thus sliding.
[0041] "Suction rods" are steel bars which connect a beam pumping unit at the surface with a suction rod pump at the bottom of a well. These rods can be hinged and lined or they can be continuous rods that are manipulated like coiled tubing. Since the rods reciprocate up and down, there is friction and wear at the contact points between the rod and the piping.
[0042] "Tool joint" is a conical rowed coupling element for pipe that is generally produced from a special steel alloy in which the pin and housing connections (outer and inner row, respectively) are secured to the ends of the pipe. Tool joints are commonly used in drill pipe, but can also be used in work strings and other OCTG, and they can be friction welded to the pipe ends.
[0043] "Top Drive" is a method and equipment used to rotate the drill pipe from a drive system located on a cart that moves up and down on rails connected to the drill rig mast. The top drive is the preferred means of drill pipe operation because it facilitates the simultaneous rotation and reciprocation of the pipe and drilling fluid circulation. In directional drilling operations, there is often less risk of pipe sticking when using the upper drive equipment.
[0044] "Pipe" is the pipe installed in a well within the cover to allow fluid flow on the surface.
[0045] "Valve" is a device that is used to control the flow rate in a flow line. There are many types of valve devices, including check valve, gate valve, globe valve, ball valve, gate valve. needle and plug valve. Valves can be operated manually, remotely or automatically, or a combination of these. Valve performance is highly dependent on the seal establishment between well-tuned mechanical devices.
[0046] "Valve seat" is the surface on which the dynamic seal secures when the valve is operated to prevent flow through the valve. For example, a hinge of a subsurface safety valve will seal against the seat valve when it is closed.
[0047] "Fixed net" is a cable that is used to operate tools and devices in a well drilling. Fixed netting is often made up of many smaller filaments twisted together, but fixed monofilament netting, or "smooth thread", also exists. Fixed netting is generally deployed in large drums mounted on roll forming trucks or skidding units.
[0048] "Working columns" are joined pieces of pipe used to perform a well drilling operation, such as operating a logging tool, fishing materials outside of well drilling, or performing a compaction task of cement.
[0049] A "cladding" is comprised of one or more adjacent layers and any interfaces included. A liner can be placed over the base substrate material of a body assembly, over the solid bandage placed on a base substrate material, or over another liner.
[0050] A "low friction coating" is a coating for which the coefficient of friction is less than 0.15 under reference conditions. A typical low friction coating may include one or more backsheets, tackifier layers and functional layers.
[0051] A "layer" is the thickness of a material that can serve a specific functional purpose, such as reduced coefficient of friction, high stiffness, or mechanical support for overlapping layers or protecting underlying layers.
[0052] A "low friction layer" or "functional layer" is a layer that provides low friction in a low friction coating. It can also provide better resistance to abrasion and wear.
[0053] An "adhesion promoting layer" provides enhanced adhesion between the functional layers and/or underlayers in a multilayer coating. It can also provide greater strength.
[0054] An "inner layer" is applied between the outer surface of the substrate material of the body assembly or solid bandage or buttery layer and adhesion-promoting layer or functional layer or between the functional layers and/or adhesion-promoting layers in a coating of multiple layers.
[0055] A "graded layer" is a layer in which at least one constituent, element, component or intrinsic property of the layer alters the thickness of the layer or some fraction thereof.
[0056] A "buttery layer" is a layer interposed between the outer surface of the substrate material of the body assembly or solid bandage and a layer, which may be another buttery layer, or a layer comprising the low friction coating. There may be one or more buttery layers interposed in one way. The buttery layer may include, but is not limited to, lower layers comprising the low friction coating.
[0057] "Solid bandage" is a layer interposed between the outer surface of the substrate material of the body assembly and the buttery layers, or one of the layers comprising the low friction coating. Solid ligation can be used in the oil and gas drilling industry to prevent wear on the tool joint and cover.
[0058] An "interface" is a transition region from one layer to an adjacent layer, in which one or more of the constituent material composition and/or property value changes from 5% to 95% of the values that characterize each. from adjacent layers.
[0059] A "graded interface" is an interface that is designed to have a gradual change of constituent material composition and/or property value from one layer to the adjacent layer. For example, a graduated interface can be created as a result of gradually interrupting the processing of a first layer, while gradually simultaneously starting the processing of a second layer.
[0060] The "unscaled interface" is an interface that has a sudden change in the composition of the constituent material and/or property value from one layer to the adjacent layer. For example, an unscaled interface can be created as a result of interrupting the processing of one layer and subsequently starting the processing of a second layer.
[0061] (Note: Several of the above definitions are from A Dictionary for the Petroleum Industry, Third Edition, The University of Texas at Austin, Petroleum Extension Service, 2001.) DETAILED DESCRIPTION
[0062] All numerical values within the detailed description and appended claims are modified by "about" or "approximately the" indicated value, and account is taken of experimental error and variations that should be expected by a person who has practical skill in technique.
[0063] Related Applications:
U.S. Patent No. 8,220,563, incorporated herein by reference in its entirety, discloses the use of ultra-low friction coatings on drill rod assemblies used in oil and gas drilling applications. Other oil and gas well production devices can benefit from the use of the coatings disclosed herein. A set of drill rods is an example of a production device that can benefit from the use of liners. The geometry of a set of drill shanks in operation is an example of a class of applications comprising a cylindrical body. In the case of the drill rod, the actual drill rod assembly is an inner cylinder that is in sliding contact with the cover or open cavity, an outer cylinder. These devices can have variable radii and alternatively can be described as comprising multiple contiguous cylinders of variable radii. As described below, there are several other examples of cylindrical bodies in oil and natural gas well production operations, in sliding contact due to relative motion or stationary object to be contacted by fluid flow currents. The coatings of the invention can be used advantageously for each of these applications, considering the relevant problem to be addressed, through the evaluation of the contact or flow problem to be solved to alleviate friction, wear, corrosion, erosion or deposits, and through judicious consideration of how to apply such coatings to specific devices for maximum utility and benefit.
[0065] U.S. Patent No. 8,261,841, incorporated herein by reference in its entirety, discloses the use of ultra-low friction coatings in oil and gas well production devices and methods of manufacturing and using such coated devices. In one form, the coated oil and gas well production device includes an oil and gas well production device including one or more organisms, and a coating over at least a portion of the one or more organisms, wherein the coating is selected from an amorphous alloy, a chemical-based nickel-phosphorus composite or heat-treated electrogalvanized with a phosphorus content greater than 12% by weight, graphite, MoS2, WS2, a fullerene-based composite, a cermet boride base, a quasi-crystalline material, a diamond-based material, diamond-like carbon (DLC), boron nitride, and combinations thereof. Coated oil and gas well production devices can provide reduced friction, wear, corrosion, erosion and deposits for oil and gas well construction, completion and production.
[0066] US Patent No. 8,286,715, incorporated herein by reference in its entirety, discloses the use of ultra-low friction coatings in coated oil and gas well production devices and methods of making and using such coated devices . In one configuration, the sleeved oil and gas well producing device includes an oil and gas well producing device including one or more organisms and one or more sleeves proximal to the outer or inner surface of the one or more organisms, and a coating on at least a portion of the inner surface of the gloves, the outer surface of the gloves, or a combination thereof, wherein the coating is selected from an amorphous alloy, a heat treated electroplated or chemically based nickel-phosphorus composite with a phosphorus content greater than 12% by weight, graphite, MoS2, WS2, a fullerene-based composite, a boride-based cermet, a quasi-crystalline material, a diamond-based material, diamond-like carbon (DLC), boron nitride, and combinations thereof. Oil and gas well production devices with coated sleeves can provide reduced friction, wear, erosion, corrosion and deposits for oil and gas well construction, completion and production.
[0067] Patent Publication No. 2011-0220415A1, incorporated herein by reference in its entirety, discloses drill rod assemblies with ultra-low friction coatings for underground drilling operations. In one configuration, coated drill rod assemblies for underground rotary drilling operations include a body assembly with an exposed outer surface, including a drill string attached to a set of lower cavities, a coiled tubing attached to an assembly of lower cavities, or a cover column coupled to a set of lower cavities and an ultra-low friction coating on at least a portion of the exposed outer surface of the body assembly, solid ligature on at least a portion of the exposed outer surface of the body assembly, an ultra-low friction coating over at least a portion of the solid bandage, wherein the ultra-low friction coating comprises one or more ultra-low friction layers, and one or more buttery layers interposed between the bandage. solid and the ultra-low friction coating. Coated Drill Rod Assemblies provide reduced friction, vibration (stick-slide and twist), abrasion and wear during straight or directional cavity drilling allowing for the best penetration rates and allowing ultra-long reach drilling with transmissions existing superiors.
[0068] U.S. Patent Publication No. 2011-0220348A1, incorporated herein by reference in its entirety, discloses coated oil and gas well production devices and methods of producing and using such coated devices. In one form, the coated device includes one or more cylindrical bodies, solid bandage over at least a portion of the exposed outer surface, the exposed inner surface, or a combination of both the exposed outer or inner surfaces of the one or more cylindrical bodies, and a coating over at least a part of the inner surface, the outer surface, or a combination thereof of one or more cylindrical bodies. The coating includes one or more ultra-low friction layers, and one or more buttery layers interposed between the solid bandage and the ultra-low friction coating. Coated oil and gas well production devices can provide reduced friction, wear, erosion, corrosion and deposits for oil and gas well construction, completion and production.
[0069] U.S. Patent Publication No. 2011-0203791A1, incorporated herein by reference in its entirety, discloses coated oil and gas well production devices and methods of producing and using such devices with coated gloves. In one form, the sleeved coated oil and gas well producing device includes one or more cylindrical bodies, one or more sleeves proximal to the outer diameter or inner diameter of the one or more cylindrical bodies, solid ligature in at least one portion of the exposed outer surface, the exposed inner surface, or a combination of the equally exposed outer or inner surface of the one or more gloves, and a coating on at least a portion of the inner surface of the glove, the outer surface of the glove, or a combination thereof gives one or more gloves. The coating includes one or more ultra-low friction layers, and one or more buttery layers interposed between the solid bandage and the ultra-low friction coating. Oil and gas well production devices with coated sleeves can provide reduced friction, wear, erosion, corrosion and deposits for oil and gas well construction, completion and production.
[0070] U.S. Patent Publication No. 2011-0162751A1, incorporated herein by reference in its entirety, discloses coated petrochemical and chemical industry devices and methods of making and using such coated devices. In one configuration, the coated petrochemical and chemical industry device includes a petrochemical and chemical industry device that encompasses one or more organisms, and a coating on at least a portion of one or more organisms, wherein the coating is selected from an alloy amorphous, chemical-based or electro-galvanized nickel-phosphorus composite heat treated with a phosphorus content greater than 12% by weight, graphite, MoS2, WS2, a fullerene-based compound, a boride-based cermet, an almost material -crystalline, a material based on diamond, diamond-like carbon (DLC), boron nitride, and combinations thereof. Coated petrochemical and chemical industry devices can provide reduced friction, wear, corrosion and other properties required for superior performance.
[0071] Provisional Patent Application US 61/542,501 filed on October 3, 2012, incorporated herein by reference in its entirety, discloses methods and systems for vacuum coating the external surface of tubular devices for use in oil prospecting and gas, drilling, completions and production operations for friction reduction, erosion reduction and corrosion protection. These methods include embodiments for the tubular sealing devices within a vacuum chamber such that the entire device is not contained within the chamber. These methods also include embodiments for treating the surface of tubular devices prior to coating. In addition, these methods include embodiments for vacuum coating tubular devices using a plurality of devices, a plurality of vacuum chambers, and various coating source configurations.
[0072] Exemplary Embodiments of Low Friction Multilayer Coating:
[0073] Applicants have discovered multi-layer low friction coatings that produce improved coating durability under severe abrasive/load conditions. In a preferred form, these low friction coatings include a diamond-like carbon (DLC) as one of the layers in the coating.
[0074] DLC coatings offer an attractive option to mitigate the negative effects discussed above, as (a) very low COF values can be perceived (<0.15, and even <0.1), (b) COF remains largely stable as a function of temperature, and (c) abrasive wear problems caused by solid particles such as carbides are greatly reduced. The typical structure of DLC coatings requires a very rigid amorphous carbon layer in variable forms of hybridization (ie, characters like sp2 or sp3). Typically, as the sp3 content increases, the DLC layer becomes more rigid, but it can also develop a more residual compressive stress. Resistance and residual stress can be controlled by varying the sp2/sp3 ratio. Increasing the sp2 content (ie, graphite-like nature) typically reduces strength and compressive strength. The sp2/sp3 ratio and overall chemistry can be varied by controlling various parameters during the deposition process (eg PVD, CVD or PACVD), such as substrate polarization, gas mixture ratio, creep of laser (if applicable), substrate, deposition temperature, level of hydrogenation, use of dopants in the DLC layer (metallic and/or non-metallic), etc. However, the reduction in residual stress in the DLC layer is generally accompanied by a reduction in DLC strength (and reduction in sp3 content). Although highly sp3-like DLC coatings can achieve very high strength values (~4500 to 6000 Hv), these coatings have compression stresses >> 1GPa, detrimental to the durability of the applications described above.
[0075] Therefore, there is a need for new DLC compositions with variable sp2/sp3 ratios, designed to provide higher resistance values (in the range of 1700 to 5500 Hv) for use in extended range rotary drilling devices, devices production of coated oil and gas wells (with gloves and without gloves) and equipment and devices for the petrochemical and chemical industry. Resistance values lower than ~1500 Hv are considered unsuitable for the intended application space, as the abrasive nature of relatively solid particles (eg sand, oil-based mud components, etc.) is expected from quickly wear off the DLC coating.
[0076] Although typical DLC coatings offer better strength (in the range of 2500 Hv), there is a need to consider more solid versions (Hv > 3000) during residual stress management for optimal coating thickness formation. In addition, there is a need to minimize plastic deformation of the underlying substrate in the presence of 3-body abrasive contact scenarios.
[0077] The durability of diamond-like carbon (DLC) coatings under three-body contact scenarios (i.e., in the presence of abrasive particles) is limited by the total abrasion resistance of the coating and coating fragmentation/delamination that can be instigated by plastic deformation of the underlying substrate due to the creation of high local stresses. For DLC coatings to last longer in harsh abrasive/loading environments, techniques to suppress existing failure modes to improve overall durability are required.
[0078] In one embodiment, a low friction, multi-layer coating of the present disclosure includes a backsheet that must be contiguous with a surface of a substrate for the coating, an adhesion promoting and strength enhancing layer contiguous with a surface of the coating. lower layer, and a functional layer contiguous with a surface of the adhesion promoting layer. Therefore, the adhesion promoting layer is interposed between the lower layer and the functional layer. The functional layer is the outermost exposed layer of the low friction multi-layer coating.
[0079] The substrate surface for the coating can be produced from a variety of different materials. Exemplary non-limiting substrates for coating include steel, stainless steel, solid ligation, an iron alloy, an aluminum-based alloy, a titanium-based alloy, ceramic, and a nickel-based alloy. Non-limiting exemplary solid bandage materials include cermet-based materials, metal matrix composites, nanocrystalline metal alloys, amorphous alloys, and hard metal alloys. Other exemplary non-limiting types of solid ligation include carbides, nitrides, borides and elemental tungsten oxides, titanium, niobium, molybdenum, iron, chromium and silicon dispersed within a metallic alloy matrix. Such solid ligature can be deposited by solder coating, thermal spraying, or laser/electron beam capping. The thickness of the solid bandage layer can vary from several orders of magnitude to or equal to the thickness of the outer coating layer. Exemplary non-limiting solid ligature thicknesses are 1mm, 2mm and 3mm above the surface of the drill rod assembly. The solid bandage surface can have a patterned design to reduce the drag of abrasive particles that contribute to wear. The multi-layer low friction coatings disclosed herein can be deposited on top of the solid bandage pattern. The solid ligature pattern can include both recessed and raised regions and the thickness variation in the solid ligature can be as much as its total thickness.
[0080] The multi-layer low friction coatings of the present disclosure can be applied to a portion of the surface of a device selected from the following non-limiting exemplary types: a drill bit for underground rotary drilling, a set of drill rods for underground rotary drilling, a cover, a pipe, couplings, a working column, the coiled pipe, a tube, a riser, a piston, centralizers, a completion column, a production column, and a petrochemical production device and chemistry. In addition, the multi-layer low friction coatings of the present disclosure can be applied to a portion of the surface of the devices described in the defining section of the present disclosure.
[0081] The low friction coating bottom layer disclosed herein can be produced from a variety of different materials, including, but not limited to, CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations. The thickness of the lower layer can range from 0.1 to 100 μm, or from 1 to 75 μm, or from 2 to 50 μm, or from 3 to 35 μm, or from 5 to 25 μm. The lower layer can have a resistance ranging from 800 to 4000 VHN, or from 1000 to 3500 VHN, or from 1200 to 3000 VHN, or from 1500 to 2500 VHN or from 1800 to 2200 VHN.
[0082] The adhesion promoting layer of the low friction coating described here not only improves the adhesion between the lower layer and the functional layer, but also enhances the overall strength of the coating. For this reason, it can also be referred to herein as a strength reinforcing layer. The adhesion promoting layer of the low friction coating disclosed herein can be produced from a variety of different materials including, but not limited to, Cr, Ti, Si, W, CrC, TiC, SiC, WC, and their combinations. The thickness of the adhesion promoting layer can vary from 0 to 60 μm, or from 0.01 to 50 μm, or from 0.1 to 25 μm, or from 0.2 to 20 μm, or from 0.3 to 15 μm , or from 0.5 to 10 µm. The adhesion promoting layer can have a strength ranging from 200 to 2500 VHN, or from 500 to 2000 VHN, or from 800 to 1700 VHN, or from 1000 to 1500 VHN. There is also generally a compositional gradient or transition at the interface of the lower layer and the adhesion promoting layer, which may vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0083] The functional layer of the low friction coating disclosed herein can be produced from a variety of different materials including, but not limited to, a fullerene-based composite, a diamond-based material, carbon similar to diamond (DLC) and its combinations. Non-limiting exemplary diamond-based materials include chemical vapor deposited diamond (CVD) or compact polycrystalline diamond (PDC). The functional layer of the low friction coating described herein is advantageously the diamond-like carbon (DLC) coating, and more particularly the DLC coating can be selected from amorphous tetrahedral carbon (ta-C), amorphous hydrogenated carbon tetrahedral (ta- C:H), hydrogenated diamond-like carbon (DLCH), hydrogenated polymer-like carbon (PLCH), hydrogenated graphite-like carbon (GLCH), diamond-like carbon containing silicon (Si-DLC), diamond-like carbon containing titanium (Ti-DLC), diamond-like carbon containing chromium (Cr-DLC), diamond-like carbon containing metal (Me-DLC), diamond-like carbon containing oxygen (O-DLC), diamond-like carbon containing nitrogen (N -DLC), boron-containing diamond-like carbon (B-DLC), fluorinated diamond-like carbon (F-DLC), sulfur-containing diamond-like carbon (S-DLC), and combinations thereof. The functional layer can be graded for improved durability, reduced friction, adhesion and mechanical performance. The thickness of the functional layer can vary from 0.1 to 50 μm, or from 0.2 to 40 μm, or from 0.5 to 25 μm, or from 1 to 20 μm, or from 2 to 15 μm, or 5 at 10 µm. The functional layer can have a Vickers resistance ranging from 1000 to 7500 VHN, or from 1500 to 7000 VHN, or from 2000 to 6500 VHN, or from 2200 to 6000 VHN, or from 2500 to 5500 VHN, or from 3000 to 5000 VHN . The functional layer may have a surface roughness ranging from 0.01 μm to 1.0 μm Ra, or from 0.03 μm to 0.8 μm Ra, or from 0.05 μm to 0.5 μm Ra, or from 0.07 μm to 0.3 μm Ra, or from 0.1 μm to 0.2 μm Ra. There is usually also a compositional gradient or transition at the interface of the adhesion promoting layer and the functional layer, which may vary in thickness from 0.01 to 10 μm, or from 0.05 to 9 μm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0084] In another form of the present disclosure, multi-layer low friction coating is multiple layers including a bottom layer contiguous with a surface of a substrate for the coating, an adhesion promoting layer contiguous with a surface of the bottom layer, and a functional layer contiguous with a surface of the tackifier layer may further include a second tackifier layer which is contiguous with a surface of the functional layer, and a second functional layer which is contiguous with a surface of the second tackifier layer. Therefore, the second adhesion-promoting layer is interposed between the functional layer described above and a second functional layer. The second functional layer is the outermost exposed layer of the low friction multi-layer coating.
[0085] The second adhesion promoting layer can be produced from the following non-limiting exemplary materials: Cr, Ti, Si, W, CrC, TiC, SiC, WC, and combinations thereof. The thickness of the second adhesion promoting layer may vary from 0 to 60 μm, or from 0.1 to 50 μm, or from 1 to 25 μm, or from 2 to 20 μm, or from 3 to 15 μm, or from 5 to 10μm. The second adhesion promoter layer can have a Vickers strength ranging from 200 to 2500 VHN, or from 500 and 2000 VHN, or from 800 to 1700 VHN, or from 1000 to 1500 VHN. There is also generally a compositional or transition gradient at the interface of the functional layer and the second adhesion-promoting layer, which can vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0086] The second functional layer can also be produced from a variety of different materials, including, but not limited to, a fullerene-based composite, a diamond-based material, diamond-like carbon (DLC) and their combinations. Non-limiting exemplary diamond-based materials include chemical vapor deposited diamond (CVD) or compact polycrystalline diamond (PDC). Non-limiting exemplary diamond-like carbon includes ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, N-DLC, O-DLC, B-DLC, Me-DLC, F-DLC and theirs combinations. The thickness of the second functional layer can vary from 0.1 to 50 μm, or from 0.2 to 40 μm, or from 0.5 to 25 μm, or from 1 to 20 μm, or from 2 to 15 μm, or from 5 to 10 µm. The second functional layer can have a resistance ranging from 1000 to 7500 VHN, or from 1500 to 7000 VHN, or from 2000 to 6500 VHN, or from 2500 to 6000 VHN, or from 3000 to 5500 VHN, or from 3500 to 5000 VHN . The second functional layer may have a surface roughness ranging from 0.01 μm to 1.0 μm Ra, or from 0.03 μm to 0.8 μm Ra, or from 0.05 μm to 0.5 μm Ra, or from 0.07 μm to 0.3 μm Ra, or from 0.1 μm to 0.2 μm Ra. There is also generally a compositional or transition gradient at the interface of the second adhesion-promoting layer and the second functional layer, which may vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or 0.1 to 8 µm, or from 0.5 to 5.
[0087] The low friction multi-layer coating which includes a second tack-promoting layer and a second functional layer may also optionally include a second lower layer interposed between the functional layer and the second tack-promoting layer. The second low friction coating bottom layer disclosed herein can be produced from a variety of different materials including, but not limited to, CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and combinations thereof. The thickness of the second lower layer can vary from 0.1 to 100 μm, or from 2 to 75 μm, or from 2 to 75 μm, or from 3 to 50 μm, or from 5 to 35 μm, or from 10 to 25 μm . The second lower layer can have a resistance ranging from 800 to 3500 VHN, or from 1000 to 3300 VHN, or from 1200 to 3000 VHN, or from 1500 to 2500 VHN, or from 1800 to 2200 VHN.
[0088] In yet another embodiment of the present disclosure, the low friction multilayer coating including a bottom layer contiguous with a surface of a substrate for the coating, an adhesion promoting layer contiguous with a surface of the bottom layer, and a layer functional contiguous with a surface of the tackifying layer may further include from 1 to 100 series of incremental coating layers, wherein each series of incremental coating layers includes a combination of an incremental tackifying layer, an incremental functional layer and an optional incremental bottom layer, wherein each series of incremental coating layers is configured as follows: A) the optional incremental bottom layer contiguous with a surface of the functional layer and the incremental adhesion promoting layer; wherein the optional incremental lower layer is interposed between the functional layer and the increment adhesion promoting layer; B) the incremental adhesion promoting layer contiguous with a surface of the functional layer or the optional lower incremental layer, and the incremental functional layer; and the incremental adhesion promoting layer is interposed between the functional layer and the functional incremental layer or between the lower optional incremental layer and the functional incremental layer; and C) the incremental functional layer is contiguous with a surface of the incremental adhesion promoting layer.
[0089] The optional incremental lower layer of the low friction coating disclosed herein can be produced from a variety of different materials including, but not limited to, CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations. The thickness of the optional incremental bottom layer can range from 0.1 to 100 μm, or from 2 to 75 μm, or from 2 to 75 μm, or from 3 to 50 μm, or from 5 to 35 μm, or from 10 to 25 µm. The optional incremental bottom layer can have a resistance ranging from 800 to 3500 VHN, or from 1000 to 3300 VHN, or from 1200 to 3000 VHN, or from 1500 to 2500 VHN, or from 1800 to 2200 VHN.
[0090] The incremental adhesion promoting layer can be produced from the following non-limiting exemplary materials: Cr, Ti, Si, W, CrC, TiC, SiC, WC, and combinations thereof. The thickness of the incremental adhesion promoting layer can vary from 0 to 60 μm, or from 0.1 to 50 μm, or from 1 to 25 μm, or from 2 to 20 μm, or from 3 to 15 μm, or from 5 to 10μm. The incremental adhesion promoter layer can have a strength ranging from 200 to 2500 VHN, or from 500 to 2000 VHN, or from 800 to 1700 VHN, or from 1000 to 1500 VHN. There is also generally a compositional or transition gradient at the interface of the optional incremental bottom layer and the incremental adhesion promoting layer, which can vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or 0, 1 to 8 µm, or from 0.5 to 5 µm.
[0091] The incremental functional layer can be produced from a variety of different materials, including, but not limited to, a fullerene-based composite, a diamond-based material, diamond-like carbon (DLC) and combinations thereof . Non-limiting exemplary diamond-based materials include chemical vapor deposited diamond (CVD) or compact polycrystalline diamond (PDC). Non-limiting exemplary diamond-like carbon includes ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, N-DLC, O-DLC, B-DLC, Me-DLC, F-DLC and theirs combinations. The thickness of the incremental functional layer can range from 0.1 to 50 μm, or from 0.2 to 40 μm, or from 0.5 to 25 μm, or from 1 to 20 μm, or from 2 to 15 μm, or from 5 to 10 µm. The incremental functional layer can have a resistance ranging from 1000 to 7500 VHN, or from 1500 to 7000 VHN, or from 2000 to 6500 VHN, or from 2200 to 6000 VHN, or from 2500 to 5500 VHN, or from 3000 to 5000 VHN . The incremental functional layer may have a surface roughness ranging from 0.01 μm to 1.0 μm Ra, or from 0.03 μm to 0.8 μm Ra, or from 0.05 μm to 0.5 μm Ra, or from 0.07 μm to 0.3 μm Ra, or from 0.1 μm to 0.2 μm Ra. There is also usually a compositional or transition gradient at the interface of the incremental adhesion promoting layer and the incremental functional layer, which may vary in thickness from 0.01 to 10 μm, or from 0.05 to 9 μm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0092] The total thickness of the multilayer low friction coatings of the present disclosure can range from 0.5 to 5000 microns. The lower limit of the total multilayer coating thickness can be 0.5, 0.7, 1.0, 3.0, 5.0, 7.0, 10.0, 15.0 or 20.0 microns of thickness. The upper limit of the total multilayer coating thickness can be 25, 50, 75, 100, 200, 500, 1000, 3000, 5000 microns thick.
[0093] The multilayer low friction coatings of the present disclosure produce a functional layer friction coefficient of the low friction coating as measured by the block-in-ring friction test that is less than or equal to 0.15, or less or equal to 0.12, or less than or equal to 0.10, or less than or equal to 0.08. Friction force can be calculated as follows: Friction force = normal force x Coefficient of Friction. The low friction multi-layer coating of the present disclosure produces a counterface wear scar depth as measured by the block-in-ring friction test of less than or equal to 500 µm, or less than or equal to 300 µm, or less or equal to 100 µm, or less than or equal to 50 µm.
[0094] The multi-layer low friction coatings of the present disclosure also show an unexpected improvement in abrasion resistance. The modified ASTM G105 abrasion test can be used to measure abrasion resistance. In particular, the multi-layer low friction coatings of the present disclosure produce an abrasion resistance as measured by the modified ASTM G105 abrasion test with respect to wear scar depth and weight loss that is at least 5 times less, or at least 5 times less. at least four times smaller, or at least 2 times smaller than an insulated layer coating of the same functional layer. The multi-layer low friction coatings of the present disclosure provide a wear mark depth through the modified ASTM G105 abrasion test less than or equal to 20 µm, or less than or equal to 15 µm, or less than or equal to 10 µm, or less than or equal to 5 µm, or less than or equal to 2 µm. The multi-layer low friction coatings of the present disclosure generate a weight loss through the modified ASTM G105 abrasion test less than or equal to 0.03 gram, or less than or equal to 0.02 gram, or less than or equal to 0. 01 gram, or less than or equal to 0.005 gram, or less than or equal to 0.004 gram, or less than or equal to 0.001 gram.
[0095] Exemplary Method of Preparation of Forms of Realization of Low Friction Coatings of Multiple Layers:
[0096] The multilayer low friction coatings of the present disclosure can be produced by a variety of process techniques. In an exemplary form, a method of manufacturing a low friction coating includes the following steps: i) providing a substrate for the coating, ii) depositing on a substrate surface a lower layer, iii) depositing on the surface of the lower layer an adhesion promoting layer which is contiguous with a surface of the lower layer, iv) depositing on the surface of the adhesion promoting layer a functional layer which is contiguous with a surface of the adhesion promoting layer.
[0097] The lower layer of the low friction coating fabrication method disclosed herein can be produced from a variety of different materials including, but not limited to, CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations. The thickness of the lower layer can range from 0.1 to 100 μm, or from 2 to 75 μm, or from 2 to 75 μm, or from 3 to 50 μm, or from 5 to 35 μm, or from 10 to 25 μm. The lower layer can have a resistance ranging from 800 to 3500 VHN, or from 1000 to 3300 VHN, or from 1200 to 3000 VHN, or from 1500 to 2500 VHN, or from 1800 to 2200 VHN.
[0098] The adhesion promoting layer of the manufacturing method of a low friction coating disclosed herein not only improves the adhesion between the lower layer and the functional layer, but also improves the strength of the coating. For this reason, it can also be referred to herein as a strength-enhancing layer. The adhesion promoting layer of the low friction coating disclosed herein can be prepared from a variety of different materials, including, but not limited to, Cr, Ti, Si, W, CrC, TiC, SiC, WC, and the like. combinations. The thickness of the adhesion promoting layer can vary from 0 to 60 μm, or from 0.1 to 50 μm, or from 1 to 25 μm, or from 2 to 20 μm, or from 3 to 15 μm, or from 5 to 10 µm. The adhesion promoting layer can have a strength ranging from 200 to 2500 VHN, or from 500 to 2000 VHN, or from 800 to 1700 VHN, or from 1000 to 1500 VHN. There is also generally a compositional or transition gradient at the interface of the lower layer and the adhesion promoting layer, which may vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0099] The functional layer of the low friction coating fabrication method disclosed herein can be produced from a variety of different materials, including, but not limited to, a fullerene-based composite, a diamond-based material , diamond-like carbon (DLC) and combinations thereof. Non-limiting exemplary diamond-based materials include chemical vapor deposited diamond (CVD) or compact polycrystalline diamond (PDC). Non-limiting exemplary diamond-like carbon includes ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, N-DLC, O-DLC, B-DLC, Me-DLC, F-DLC and theirs combinations. The thickness of the functional layer can vary from 0.1 to 50 μm, or from 0.2 to 40 μm, or from 0.5 to 25 μm, or from 1 to 20 μm, or from 2 to 15 μm, or 5 at 10 µm. The functional layer can have a resistance ranging from 1000 to 7500 VHN, or from 1500 to 7000 VHN, or from 2000 to 6500 VHN, or from 2200 to 6000 VHN, or from 2500 to 5500 VHN, or from 3000 to 5000 VHN. The functional layer may have a surface roughness ranging from 0.01 μm to 1.0 μm Ra, or from 0.03 μm to 0.8 μm Ra, or from 0.05 μm to 0.5 μm Ra, or from 0.07 μm to 0.3 μm Ra, or from 0.1 μm to 0.2 μm Ra. There is usually also a compositional or transition gradient at the interface of the adhesion-promoting layer and the functional layer, which may vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0100] The method of manufacturing a low friction coating described above may further include the additional deposition layers of the adhesion promoting layers, the functional layers and the optional underlayers (between the functional layers and the adhesion promoting layers) to further increase the abrasion resistance, coefficient of friction and other properties of low friction multilayer coating. In another exemplary form, the method of producing a low friction coating including a bottom layer contiguous with a surface of a substrate for the coating, an adhesion promoting layer contiguous with a surface of the bottom layer, and a functional layer contiguous with a surface of the tackifying layer may further include the step of depositing 1 to 100 series of incremental coating layers, wherein each series of incremental coating layers includes a combination of an incremental tackifying layer, an incremental functional layer. and an optional incremental back layer, wherein each series of incremental coating layers is configured as follows: A) the optional incremental back layer contiguous with a surface of the functional layer and the incremental adhesion promoting layer; wherein the optional incremental lower layer is interposed between the functional layer and the increment adhesion promoting layer; B) the incremental adhesion promoting layer contiguous with a surface of the functional layer or the optional lower incremental layer, and the incremental functional layer; and the incremental adhesion promoting layer is interposed between the functional layer and the functional incremental layer or between the lower optional incremental layer and the functional incremental layer; and C) the incremental functional layer is contiguous with a surface of the incremental adhesion promoting layer.
[0101] The optional incremental bottom layer of the low friction coating production method disclosed herein can be produced from a variety of different materials including, but not limited to, CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations. The thickness of the optional incremental bottom layer can range from 0.1 to 100 μm, or from 2 to 75 μm, or from 2 to 75 μm, or from 3 to 50 μm, or from 5 to 35 μm, or from 10 to 25 µm. The optional incremental bottom layer can have a resistance ranging from 800 to 3500 VHN, or from 1000 to 3300 VHN, or from 1200 to 3000 VHN, or from 1500 to 2500 VHN, or from 1800 to 2200 VHN.
[0102] The incremental adhesion promoting layer of the production method of a low friction coating can be produced from the following non-limiting exemplary materials: Cr, Ti, Si, W, CrC, TiC, SiC, WC, and their combinations . The thickness of the incremental adhesion promoting layer can vary from 0 to 60 μm, or from 0.1 to 50 μm, or from 1 to 25 μm, or from 2 to 20 μm, or from 3 to 15 μm, or from 5 to 10μm. The incremental adhesion promoter layer can have a strength ranging from 200 to 2500 VHN, or from 500 to 2000 VHN, or from 800 to 1700 VHN, or from 1000 to 1500 VHN. There is also generally a compositional or transition gradient at the interface of the optional incremental bottom layer and the incremental adhesion promoting layer, which can vary in thickness from 0.01 to 10 µm, or from 0.05 to 9 µm, or 0, 1 to 8 µm, or from 0.5 to 5 µm.
[0103] The incremental functional layer of the production method of a low friction coating can be produced from a variety of different materials, including, but not limited to, a fullerene-based composite, a diamond-based material, diamond-like carbon (DLC) and combinations thereof. Non-limiting exemplary diamond-based materials include chemical vapor deposited diamond (CVD) or compact polycrystalline diamond (PDC). Non-limiting exemplary diamond-like carbon includes ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, N-DLC, O-DLC, B-DLC, Me-DLC, F-DLC and theirs combinations. The thickness of the incremental functional layer can range from 0.1 to 50 μm, or from 0.2 to 40 μm, or from 0.5 to 25 μm, or from 1 to 20 μm, or from 2 to 15 μm, or from 5 to 10 µm. The incremental functional layer can have a resistance ranging from 1000 to 7500 VHN, or from 1500 to 7000 VHN, or from 2000 to 6500 VHN, or from 2200 to 6000 VHN, or from 2500 to 5500 VHN, or from 3000 to 5000 VHN . The incremental functional layer may have a surface roughness ranging from 0.01 μm to 1.0 μm Ra, or from 0.03 μm to 0.8 μm Ra, or from 0.05 μm to 0.5 μm Ra, or from 0.07 μm to 0.3 μm Ra, or from 0.1 μm to 0.2 μm Ra. There is also usually a compositional or transition gradient at the interface of the incremental adhesion promoting layer and the incremental functional layer, which may vary in thickness from 0.01 to 10 μm, or from 0.05 to 9 μm, or from 0.1 to 8 µm, or from 0.5 to 5 µm.
[0104] The Production Method of the multi-layer low friction coatings of the present disclosure produces a coefficient of friction of the low friction coating functional layer as measured by the block-in-ring friction test that is less than or equal to 0.15 , or less than or equal to 0.12, or less than or equal to 0.10, or less than or equal to 0.08. The low friction multi-layer coating of the present disclosure produces a counterface wear scar depth as measured by the block-in-ring friction test of less than or equal to 500 µm, or less than or equal to 300 µm, or less or equal to 100 µm, or less than or equal to 50 µm.
[0105] The low friction coating production method of the present disclosure also shows an unexpected improvement in abrasion resistance. The modified ASTM G105 abrasion test can be used to measure abrasion resistance. In particular, the multi-layer low friction coatings of the present disclosure produce an abrasion resistance as measured by the modified ASTM G105 abrasion test with respect to wear scar depth and weight loss that is at least 5 times less, or at least 5 times less. at least four times smaller, or at least 2 times smaller than an insulated layer coating of the same functional layer. The multi-layer low friction coatings of the present disclosure provide a wear mark depth through the modified ASTM G105 abrasion test less than or equal to 20 µm, or less than or equal to 15 µm, or less than or equal to 10 µm, or less than or equal to 5 µm, or less than or equal to 2 µm. The multi-layer low friction coatings of the present disclosure generate a weight loss through the modified ASTM G105 abrasion test less than or equal to 0.03 gram, or less than or equal to 0.02 gram, or less than or equal to 0. 01 gram, or less than or equal to 0.005 gram, or less than or equal to 0.004 gram, or less than or equal to 0.001 gram.
[0106] For the low friction coating manufacturing method of the present disclosure, the steps of depositing the lower layers, the adhesion promoting layers and/or the functional layers, can be selected from the following non-limiting exemplary methods: vapor deposition physical, plasma-assisted chemical vapor deposition, and chemical vapor deposition. Exemplary non-limiting physical vapor deposition coating methods are electron tube sputter deposition, ion beam assisted deposition, cathodic arc deposition, and pulsed laser deposition.
[0107] The manufacturing method of the low friction coatings of the present disclosure may further include the post-processing step of the outermost functional layer to achieve a surface roughness between 0.01 to 1.0 μm Ra, or 0.03 mm to 0.8 μm Ra, or 0.05 μm to 0.5 μm Ra, or 0.07 μm to 0.3 μm Ra, or 0.1 μm to 0.2 μm Ra. Exemplary non-limiting post-processing steps may include a mechanical polishing, a chemical polishing, deposition of smoothing layers, an ultra-fine superpolishing process, a tribochemical polishing process, an electrochemical polishing process, and combinations thereof.
[0108] The low friction coating fabrication method of the present disclosure can be applied to the surface of various substrates for coating. Exemplary non-limiting substrates for the disclosed coating methods include steel, stainless steel, solid ligation, an iron alloy, an aluminum-based alloy, a titanium-based alloy, ceramic, and a nickel-based alloy. Non-limiting exemplary solid bandage materials include cermet-based materials, metal matrix composites, nanocrystalline metal alloys, amorphous alloys, and hard metal alloys. Other exemplary non-limiting types of solid ligation include carbides, nitrides, borides and elemental tungsten oxides, titanium, niobium, molybdenum, iron, chromium and silicon dispersed within a metallic alloy matrix. Such solid ligation can be deposited by solder coating , thermal spray, or laser/electron beam capping. Solid ligation layer thickness can vary from several orders of magnitude times to or equal to the thickness of the outer coating layer. Exemplary non-limiting solid ligature thicknesses are 1mm, 2mm and 3mm above the surface of the drill rod assembly. The solid bandage surface can have a patterned design to reduce the drag of abrasive particles that contribute to wear. The multi-layer low friction coatings disclosed herein can be deposited on top of the solid bandage pattern. The solid ligature pattern can include both recessed and raised regions and the thickness variation in the solid ligature can be as much as its total thickness.
[0109] The low friction coating production method of the present disclosure can be applied to a portion of the surface of a device selected from the following non-limiting exemplary types: a drill bit for underground rotary drilling, a set of drill rods for underground rotary drilling, a cover, a pipe, couplings, a working column, a coiled pipe, a tube, a riser, a piston, centralizers, a completion column, a production column, and a petrochemical production device and chemistry. In addition, the low friction, multi-layer coating methods of the present disclosure can be applied to a portion of the surface of the devices described in the definition section of the present disclosure.
[0110] Exemplary Method of Using Multi-Layer Low Friction Coating Embodiments:
[0111] The multi-layer low friction coatings disclosed herein may be applied to a portion of the surface of a device selected from the group consisting of a drill bit for underground rotary drilling, a set of drill rods for underground rotary drilling , a cover, a pipe, couplings, a work column, a coiled pipe, a tube, a riser, a plunger, centralizers, a completion column, a production column, and a petrochemical and chemical production device.
[0112] More particularly, the multi-layer low friction coatings disclosed herein can be used to improve the performance of drilling tools, particularly a drill head for drilling in formations containing clay and similar substances. The present disclosure uses the novel low surface energy materials or coating systems to provide thermodynamically low energy surfaces, e.g., waterless wetting surface for the lower cavity components. The multi-layer low friction linings disclosed herein are suitable for drilling oil and gas in clay prone areas, such as in deep shale drilling with high clay contents using water-based muds (here abbreviated as WBM) to prevent the drilling bit and the mounting component from the bottom of the cavity from waxing.
[0113] In addition, the multi-layer low friction coatings disclosed herein when applied to drill string assembly can simultaneously reduce contact friction, drill waxing and reduce wear without compromising the durability and mechanical integrity of the cover on the covered cavity situation. Thus, the multi-layer low friction coatings disclosed herein are "cover friendly" in that they do not degrade the life or functionality of the cover. The multi-layer low friction coatings disclosed herein are also characterized by low or no sensitivity to friction behavior in speed reduction. In this way, the drill rod assemblies provided with the multi-layer low friction coatings disclosed herein provide low friction surfaces with advantages both in attenuating clamp-slip vibrations and reducing parasitic torque to further allow for drilling of ultra-long reach.
[0114] The multi-layer low friction coatings disclosed herein for drill rod assemblies thus provide the following exemplary non-limiting advantages: i) attenuate clamp-slide vibrations, ii) reduce torque and drag to extend the reach of the extended reach wells, and iii) soften the wax-up of the drill bit and other component of the lower part of the cavity. These three advantages together with the minimization of parasitic torque can lead to significant improvements in the penetration drilling rate, as well as the durability of downhole drilling equipment, thus also contributing to the reduction of non-productive time (abbreviated here as NPT ). The multi-layer low-friction coatings disclosed herein not only reduce friction, but also withstand aggressive downhole drilling environments that require chemical stability, corrosion resistance, impact resistance, durability against wear, erosion, and mechanical integrity (interface resistance of coating substrate). The multi-layer low friction coatings disclosed herein are also amenable to application of complex shapes without damaging the properties of the substrate. In addition, the multi-layer low friction coatings disclosed herein also provide low energy surfaces necessary to provide resistance to waxing of lower cavity components.
[0115] The body mount or coated drill rod assembly may include solid ligation on at least a portion of the exposed outer surface to provide enhanced strength and durability to wear. Drill rod assemblies experience significant wear in the solid ligature regions as these are the main points of contact between the drill rod and the casing or borehole. Wear can be exacerbated by abrasive sand and stone particles that are dragged across the interface and rub the surfaces. The coatings on the coated drill rod assembly disclosed herein exhibit high strength properties to help mitigate abrasive wear. Using a solid bandage that has a surface with a patterned design can promote the flow of abrasive particles beyond the coated solid bandage region and reduce the amount of wear and damage to the coating and the solid bandage portion of the component. The use of coatings in conjunction with the standardized solid bandage will further reduce wear due to abrasive particles.
[0116] Therefore, another aspect of the disclosure is the use of multi-layer low friction coatings over a solid ligature on at least a portion of the exposed outer surface of the body assembly, where the solid ligature surface has a patterned design that reduces the drag of abrasive particles that contribute to wear. During drilling, abrasive sand and other rock particles suspended in the drilling fluid may move into the interface between the body assembly or drill string assembly and the cover or borehole. These abrasive particles, once entrained into this interface, contribute to accelerated wear of the body assembly, drill string assembly and casing. There is a need to extend the life of equipment to maximize drilling and economic efficiency. Since the solid bandage that is produced imposingly above the surface of the body mount or drill string mount makes maximum contact with the casing or borehole, it experiences maximum abrasive wear due to the drag of sand and stone particles. Therefore, it is advantageous to use solid bandage and multi-layer low friction coatings together to provide wear protection and low friction. It is further advantageous to apply the solid bandage in a standard configuration where the grooves between the solid bandage material allow particles to flow past the solid bandage region without becoming drawn and rubbing the interface. It is even more advantageous to reduce the contact area between the solid bandage and the roof or open borehole to ease sticking or waxing through rock cuts. Multi-layer low friction coatings can be applied in any layout, but preferably should be applied to the entire area of the model as the material passing through the model aisle should have a reduced chance of adhering to the pipe.
[0117] One aspect of the present disclosure relates to a coated drill rod assembly advantageous for underground rotary drilling operations comprising: a body assembly with an exposed outer surface including a drill string coupled to a cavity bottom assembly , a coiled tubing coupled to a cavity bottom mount, or a cover column coupled to a cavity bottom mount, solid ligature on at least a portion of the exposed outer surface of the body assembly, where the solid ligature surface can or not having a standard configuration, a low friction multilayer coating on at least a portion of the solid bandage, and one or more buttery layers interposed between the solid bandage and the low friction multilayer coating.
[0118] Another aspect of the present disclosure relates to an advantageous method for reducing friction together with coated drill rods during underground rotary drilling operations comprising: providing a set of drill rods comprising a body assembly with an exposed outer surface, including a drill string coupled to a cavity bottom mount, a coiled tubing coupled to a cavity bottom mount, or a cover column coupled to a cavity bottom mount, ligature solid on at least a portion of the exposed outer surface of the body assembly, where the solid bandage surface may or may not have a patterned design, a low friction, multi-layer coating over at least a portion of the solid bandage, and one or more buttery layers interposed between the solid bandage and the low-friction multi-layer coating, and use of the joint. of coated drill shanks in underground rotary drilling operations.
[0119] Yet another aspect of the present disclosure relates to the interposition of one or more buttery layers between the outer surface of the body assembly or solid bandage, and the low friction multi-layer coating. The buttery layer can be created or deposited as a result of one or more techniques including electrochemical or currentless deposition methods, Plasma Vapor Deposition (PVD) or Plasma Assisted Chemical Vapor Deposition (PACVD) methods. carburetion, nitriding or boration, or ultra-fine super-polishing methods. The buttery layer can be graded, and can serve a variety of functional purposes, including, but not limited to: decreasing surface roughness, enhancing adhesion with other layers, enhanced mechanical integrity, and performance.
[0120] Yet another aspect of the present disclosure relates to the advantageous method of forming one or more buttery layers interposed between the outer surface of the body assembly or solid bandage, and where low friction multi-layer coating. The buttery layer can be created or deposited as a result of one or more techniques including electrochemical or currentless deposition methods, Plasma Vapor Deposition (PVD) or Plasma Assisted Chemical Vapor Deposition (PACVD) methods. carburetion, nitriding or boration, or ultra-fine super-polishing methods. The buttery layer can be graded, and can serve a variety of functional purposes, including, but not limited to: decreasing surface roughness, enhancing adhesion with other layers, enhanced mechanical integrity, and performance.
[0121] In another embodiment, the buttery layer can be used in conjunction with the solid bandage, where the solid bandage is on at least a portion of the exposed outer or inner surface to provide marked wear resistance and durability to the rod assembly of coated perforation, where the surface of the solid bandage may have a patterned design that reduces the drag of abrasive particles that contribute to wear. In addition, the low friction multi-layer coating can be deposited on top of the buttery layer.
[0122] Other Details regarding Individual Layers and Interfaces:
[0123] Other details regarding the functional layers for use in the multi-layer low friction coatings described herein are as follows:
[0124] Fullerene-Based Composites:
[0125] Coating layers of fullerene-based composites that include fullerene-like nanoparticles can also be used as the functional layers. Fullerene-like nanoparticles have advantageous tribological properties compared to typical metals, while alleviating the deficiencies of conventional layered materials (eg graphite, MoS2). Nearly spherical fullerenes can also behave like nanoscale ball bearings. The main favorable benefit of hollow fullerene-like nanoparticles can be attributed to the following three effects, (a) friction by rotation, (b) fullerene nanoparticles function as spacers, which eliminate metal-to-metal contact between the roughness of the two mated metal surfaces, and (c) material transfer from the body. The sliding/rotation of the fullerene-like nanoparticles at the interface between the friction surfaces may be the main friction mechanism at low loads when the nanoparticle shape is preserved. The beneficial effect of fullerene-like nanoparticles increases with loading. Exfoliation of outer leaves of fullerene-like nanoparticles has been observed to occur at high contact loads (~1GPa). The transfer of delaminated fullerene-like nanoparticles appears to be the dominant friction mechanism under severe contact conditions. The mechanical and tribological properties of fullerene-like nanoparticles can be exploited by incorporating these particles into the binding phases of the coating layers. In addition, composite coatings that incorporate fullerene-like nanoparticles in a metal binder phase (eg, currentless deposition of Ni-P) can provide a self-lubricating film with excellent non-stick characteristics suitable for the functional layer of multilayer low friction coatings disclosed herein.
[0126] Super-Tough Materials (Diamond, Diamond-like Carbon):
[0127] Super-strength materials such as diamond and diamond-like carbon (DLC) can be used as the functional layer of the multi-layer low friction coatings disclosed herein. Diamond is the hardest material known to man and under certain conditions it can produce a low coefficient of friction when deposited by chemical vapor deposition (herein abbreviated as CVD).
[0128] In an advantageous embodiment, diamond-like carbon (DLC) can be used as the functional layer of the multi-layer low friction coatings disclosed herein. DLC refers to amorphous carbon material that exhibits some of the unique properties similar to those of natural diamond. Suitable diamond-like carbon (DLC) layers or coatings may be selected from ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, diamond-like carbon containing (Ti-DLC), like carbon to chromium containing diamond (Cr-DLC), Me-DLC, F-DLC, S-DLC, other types of DLC layers, and combinations thereof. DLC coatings include significant amounts of sp3 hybrid carbon atoms. These sp3 bonds can occur not only with crystals - in other words, with solids in the long-range order - but also with amorphous solids where the atoms are in a random arrangement. In this case, there will only be binding between a few individual atoms, which is the short-range order, and not a long-range order that extends over a large number of atoms. Bond types have a considerable influence on the material properties of amorphous carbon films. If the sp2 type is predominant the DLC film can be lighter, while if the sp3 type is predominant, the DLC film can be stronger.
[0129] DLC coatings can be manufactured as amorphous, flexible, and still primarily "diamond" bonded to sp3. The most resistant is such a mixture known as amorphous tetrahedral carbon, or ta-C. Such ta-C includes a high volume fraction (~80%) of carbon atoms bonded to sp3. Optional fillers for DLC coatings include, but are not limited to, hydrogen, sp2 graphite carbon, and metals, and can be used in other forms to achieve a desired combination of properties depending on the particular application. Various forms of DLC coatings can be applied to a variety of substrates that are compatible with a vacuum environment and that are also electrically conductive. DLC coating quality is also dependent on the fractional content of the alloy and/or doping elements such as hydrogen. Some DLC coating methods require hydrogen or methane as a precursor gas, and therefore a considerable percentage of hydrogen may remain in the finished DLC material. In order to further improve their tribological and mechanical properties, DLC films are often modified by incorporating other alloying elements and/or dopants. For example, the addition of fluorine (F), and silicon (Si) to DLC films reduces surface energy and wetting capacity. The reduction in surface energy in fluorinated DLC (F-DLC) is attributed to the presence of CF2 and CF3 groups in the film. However, higher F contents can lead to lower strength. The addition of Si can reduce surface energy by decreasing the surface energy dispersive component. Addition of Si can also increase the strength of DLC films by promoting sp3 hybridization in DLC films. The addition of metallic elements (eg W, Ta, Cr, Ti, Mo) to the film can reduce residual compressive stresses, resulting in better mechanical integrity of the film after compressive loading.
[0130] The diamond-like or carbon-like phase bonded to sp3 of DLC is a thermodynamically metastable phase while the sp2 bonded graphite is a thermodynamically stable phase. Thus, the formation of DLC coating films requires unbalanced processing to obtain metastable sp3 bound carbon. Equilibrium processing methods such as graphitic carbon evaporation, where the average energy of the vaporized species is low (close to kT, where k is the Boltzman constant and T is the temperature on the absolute temperature scale), lead to formation 100% carbon bonded to sp2. The methods disclosed herein for producing DLC coatings require that the carbon in the sp3 bond length be significantly less than the sp2 bond length. Therefore, the application of pressure, impact, catalysis, or some combination of these at the atomic scale can force the carbon atoms bonded to sp2 closer together into sp3 bonding. This can be done with sufficient force such that the atoms cannot simply bounce back apart in characteristic sp2 bond separations. Typical techniques combine such compression with a push of the new sp3 bonded carbon agglomerate deeper into the coating so that there is no room for expansion back to the separations necessary for sp2 bonding; or the new cluster is covered by the arrival of new carbon destined for the next cycle of impacts.
[0131] The DLC coatings disclosed herein can be deposited by the coating techniques of physical vapor deposition, chemical vapor deposition or plasma assisted chemical vapor deposition. Physical vapor deposition coating methods include sputter deposition with RF-DC plasma reactive electron tube, ion beam assisted deposition, cathodic arc deposition and pulsed laser deposition (PLD). Chemical vapor deposition coating methods include beam assisted deposition of CVD ions, plasma accentuated deposition using a glow discharge of hydrocarbon gas, using a radio frequency (rf) glow discharge of a hydrocarbon gas, plasma-immersed ion processing and microwave discharge. Plasma enhanced chemical vapor deposition (PECVD) is an advantageous method for deposition of DLC coatings over large areas at high deposition rates. The plasma-based CVD coating process is a non-line-of-sight technique, that is, the plasma conformally covers the part to be coated and the entire exposed surface of the part that is coated to a uniform thickness. The surface finish of the part can be maintained after applying DLC coating. An advantage of PECVD is that the temperature of the substrate part generally does not rise above about 150 °C during the coating operation. Fluorine-containing DLC (F-DLC) and silicon-containing DLC (Si-DLC) films can be synthesized using the plasma deposition technique that uses an acetylene process gas (C2H2) mixed with fluorine-containing precursor gases. silicon, respectively (eg tetra-fluoro-ethane and hexa-methyl-disiloxane).
[0132] The DLC coatings disclosed herein may have friction coefficients within the ranges described above. The low COF can be based on the formation of a thin graphite film in the actual contact areas. Since the sp3 bond is a thermodynamically unstable carbon phase at elevated temperatures of 600 to 1500 oC, depending on environmental conditions, it can turn into graphite that can function as a solid lubricant. These high temperatures can occur as very short instantaneous temperatures (referred to as the incipient temperature) in collisions or roughness contacts. An alternative theory for the low COF of DLC coatings is the presence of a hydrocarbon-based slippery film. The tetrahedral structure of a carbon bonded to sp3 can result in a situation on the surface where there may be a vacant electron exiting the surface that has no carbon atom to attach to, which is referred to as an orbital "pending bond". If a hydrogen atom with its own electron is placed on such a carbon atom, it can bond with the orbital pendant bond to form a two-electron covalent bond. When two such smooth surfaces with an outer layer of isolated hydrogen atoms slide together, shear will occur between the hydrogen atoms. There is no chemical bond between the surfaces, just very weak van der Waals forces, and the surfaces have the properties of a heavy hydrocarbon wax. Carbon atoms on the surface can create three strong bonds leaving an electron in the orbital pendant bond that points from the surface. Hydrogen atoms attach to such a surface that it becomes hydrophobic and has low friction.
[0133] DLC coatings for the functional layer of the multi-layer low friction coatings disclosed herein also prevent wear due to their tribological properties. In particular, the DLC coatings disclosed herein demonstrate improved wear and abrasion resistance making them suitable for use in applications that experience extreme contact pressure and harsh abrasive environments.
[0134] Buttered Layers:
[0135] In yet another embodiment of the included multi-layer low friction coatings, the device may further include one or more buttery layers interposed between the outer surface of the body assembly or solid bandage layer and the layers comprising the coating of multiple layers of low friction on at least a portion of the exposed outer surface.
[0136] In an embodiment of the nickel-based alloy used as a buttery layer, the layer can be formed by electroplating. Electrogalvanized nickel can be deposited as a buttery layer with adapted resistance ranging from 150 to 1100, or from 200 to 1000, or from 250 to 900, or from 300 to 700 Hv. Nickel is a silver-white metal, and therefore the appearance of the buttery nickel-based alloy layer can range from a matte gray to an off-white glossy finish. In one form of the buttery nickel bond layers disclosed herein, nickel sulfamate can be deposited from a bath of nickel sulfamate using electroplating. In another form of the buttered nickel alloy layers disclosed herein, nickel watts can be deposited from a nickel sulfate bath. Nickel watts typically produce a brighter finish than sulfamate nickel, as even the weaker watt bath contains a grain refiner to improve deposit. Nickel watts can also be deposited as a semi-gloss finish. Semi-bright nickel watts achieve a brighter deposit because the bath contains organic and/or metallic brighteners. Rinse aids in a watt bath even out the deposit, producing a smoother surface than the underlying part. The semi-gloss watt deposit can be easily polished to an ultra-smooth, high-gloss surface. A shiny nickel bath contains a higher concentration of organic brighteners which have a leveling effect on the deposit. Sulfur based brighteners are normally used to achieve leveling at the beginning of deposits, and a sulfur free organic such as formaldehyde is used to achieve a full gloss deposit when the coating layer thickens. In another form, the nickel alloy used for the buttery layer can be formed from black nickel, which is often applied over an electrolytic or chemical nickel sub-galvanizing. Among the advantageous properties provided by a buttered nickel-based layer include, but are not limited to, corrosion prevention, magnetic properties, smooth surface finish, appearance, lubricity, strength, reflectivity and emissivity.
[0137] In another embodiment, the nickel-based alloy used as a buttery layer can be formed as a chemical nickel plating. In this form, chemical nickel plating is an autocatalytic process and does not use externally applied electrical current to produce the deposit. Electrolytic process deposits of a uniform coating of metal, regardless of the shape of the part or its surface irregularities; therefore, it overcomes one of the main disadvantages of electroplating, the variation in the thickness of the galvanizing that results from the variation in current density caused by the geometry of the galvanized part and its connection with the galvanizing anode. A currentless deposition solution produces a deposit wherever it comes in contact with a properly prepared surface, without the need to shape complicated anodes and accessories. Since the chemical bath maintains a uniform deposition rate, the plater can precisely control the deposit thickness simply by controlling the immersion time. Low phosphorus chemical nickel used as a buttery coating can produce the brightest and toughest deposits. Resistance ranges from 60 to 70 RC (or 697Hv ~1076Hv). In another form, the middle or mid-phos phosphor can be used as a buttery layer, which has a resistance of approximately 40 to 42 RC (or 392Hv ~412Hv). Resistance can be improved by heat treatment in the range of 60 to 62 RC (or 697Hv ~746Hv). Porosity is lower and, conversely, corrosion resistance is higher than chemical nickel with low phosphorus content. Chemical nickel with high phosphorus content is dense and dull compared to deposits with medium and low phosphorus content. The high phosphorus content has the best corrosion resistance of the chemical nickel family; however, the deposit is not as resistant as the lower phosphorus form. Chemical nickel with high phosphorus content is a virtually non-magnetic coating. For the buttered nickel alloy layers disclosed herein, nickel boron can be used as an underlying plate for metals that require heating for adhesion. The amorphous NiP matrix can also include a second dispersed phase. Exemplary non-limiting dispersed second phases include: i) fine nano-sized second phase particles incorporated in the diamond chemical NiP matrix, ii) chemical NiP matrix with hexagonal boron nitride particles dispersed within the matrix, and iii) matrix of chemical NiP with submicron PTFE particles (eg 20-25% by volume Teflon) evenly dispersed throughout the coating.
[0138] In yet another embodiment, the buttery layer can be formed from a galvanized chrome layer to produce a smooth and reflective surface finish. Buttered layers of hard chrome or functional chrome plating provide high strength that is in the range 700 to 1000, or 750 to 950, or 800 to 900 HV, have a smooth, glossy surface finish, and are weather resistant. corrosion with thicknesses ranging from 20 μm to 250, or 50 to 200, or from 100 to 150 μm. Chrome plating butter coats can be easily applied at low cost. In another form of this embodiment, a decorative chrome plating can be used as a buttery layer to provide a durable coating with a smooth surface finish. The buttery decorative chrome layer can be deposited in a thickness range from 0.1 μm to 0.5 μm, or 0.15 μm to 0.45 μm, or 0.2 μm to 0.4 μm, or 0.25 µm to 0.35 µm. The buttery decorative chrome layer can also be applied during bright nickel plating.
[0139] In yet another embodiment, the buttery layer can be formed over the body assembly or solid bandage from a super-polishing process, which removes machining/grinding grooves and provides a surface finish below 0 .25 µm mean surface roughness (Ra).
[0140] In yet another embodiment, the buttery layer can be formed on the solid body or ligature assembly by one or more of the following exemplary non-limiting processes: PVD, PACVD, DCV, ion implantation, carburization, nitriding, borization, sulfation, siliconization, oxidation, an electrochemical process, a currentless deposition process, a thermal spray process, a kinetic spray process, a laser-based process, a friction-stirring process, a detonation hammering process, a laser detonation hammering process, a welding process, a brazing process, an ultra-fine super polishing process, a tribochemical polishing process, an electrochemical polishing process, and combinations thereof.
[0141] Interfaces:
[0142] The interfaces between various layers in the coating can have a substantial impact on the performance and durability of the coating. In particular, ungraded interfaces can create sources of weakness including one or more of the following: stress concentrations, voids, residual stresses, nuclear reaction, delamination, fatigue cracking, poor adhesion, chemical incompatibility, mechanical incompatibility. An exemplary non-limiting means to improve coating performance is to use graded interfaces.
[0143] Graded interfaces take into account a gradual change in material and physical properties between layers, which reduces the concentration of weakness sources. An exemplary non-limiting means of creating a graded interface during a manufacturing process is to progressively stop processing a first layer while simultaneously gradually starting processing a second layer. The graduated interface thickness can be optimized by varying the rate of change of processing conditions. The thickness of the graduated interface can range from 0.01 to 10 μm, or from 0.05 to 9 μm, or from 0.1 to 8 μm, or from 0.5 to 5 μm. Alternatively, the thickness of the graduated interface can range from 5% to 95% of the thickness of the thinner adjacent layer. TEST METHODS
[0144] CETR Ring Block Test with High Sand Content
[0145] The test is designed to simulate a high load (ie high contact pressure) and high abrasion environment. The ring specimens were rotated at various speeds and loads against a 6.36 mm wide steel block (~300 to 350 Hv resistance) at room temperature. The steel counterface was translated at a reciprocal speed of 1 mm/s perpendicular to the axis of rotation of the ring, in order to maintain uniform wear across the ring. The lubrication medium used for this study consisted of an oil-based slurry (oil : water = 1 : 9) where water was used as a continuous phase. A poly-alpha-olefin oil of viscosity 8 cSt at 100°C was used. This oil produced an emulsion viscosity of approximately 0.009 Pa.S at the test temperature, which is comparable to the viscosity of a typical oil-based slurry under similar conditions. The slurry contained 50% by weight of sand (silica) of 150 µm average diameter. The slurry was introduced into a chamber in which the ring was partially immersed for the duration of the test. The sand was completely homogenized in the lubrication medium prior to testing by introducing the slurry (in a sealed container) into a magnetic stirrer for 30 minutes. The rotation of the ring prevented the sedimentation of particles in the reservoir during the test. The coefficient of friction values during each wear test were automatically recorded by a computer. Block wear (mark depth) was measured by scanning the wear marks on a style prophylometer, while liner wear was estimated based on visual inspection. Block wear was used as the measure of counterface friendliness for any given coating. It should be noted that all coatings produced a low coefficient of friction (typically < 0.1), while the DLC remained intact during the CETR-BOR test.
[0146] Modified ASTM G105 Abrasion Test:
[0147] This is a wet sand/rubber rotating abrasion test designed to simulate a lower load and very harsh abrasion environment. The standard ASTM G105 test is performed using rubber wheels of four different Shore hardnesses. However, in order to avoid complexity, the ASTM G105 test was modified for this study where the specimen was tested in contact against a rotating rubber wheel of certain Shore hardness (A 58-62). Tests were performed on a Falex wear tester by keeping the rubber wheel partially submerged in a mixture of sand and water. The wheel was rotated at 200 rpm for 30 minutes against a vertically placed flat test specimen (1" x 3") under a load of 30 lbf. The wheel diameter and width were 9" and 0.5", respectively. The slurry contained 60% SiO2 sand (circular) and 40% water. At the conclusion of the tests, the specimens were investigated for coating durability and performance determined by (a) residual coating on the plate (visual examination - percentage of wear area covered by the top layer coating after testing), (b) loss of mass, (c) profilometry to measure wear scar depth and (d) microscopy. The reported wear scar depth is the maximum wear groove depth measured by sweeping the style along the length of the wear scar created by the rubber wheel through the middle of the wear zone width. EXAMPLES
[0148] Illustrative example 1:
[0149] The two steps as outlined below were used to improve coating durability under severe abrasive/load conditions.
[0150] Step 1: Thick/super-thick lower layer structures:
[0151] The deposition of the DLC layers and adhesion promoters can be performed through a process such as PACVD, where a source and/or a target is used to deposit the DLC layer and the lower layer (for example, CrxN, TixN etc.). In some cases, the DLC layer (usually 1 to 5 µm) is deposited directly onto a substrate, without any underlay. In other cases, a bottom layer (typically 2 to 5 µm) is deposited onto the substrate prior to deposition of DLC (over the bottom layer). The bottom layer provides some integrity and mechanical strength through load protection, while also providing some strength bonding with the substrate. Generally, lower back layer thicknesses help to improve overall coating performance in less severe conditions (eg low abrasion/load), coating durability remains very poor under conditions where high abrasion/loads are encountered, especially due to plastic deformation of the substrate and abrasive wear of the DLC itself.
[0152] Finite Element Analysis (FEA) indicates that load transmission through sand grains can initiate significant deformation of the underlying substrate at notch depths of < 1 µm, which is possible under high load operating conditions. In fact, with larger sand grains (~25 to 50 μm), the level of plastic deformation of the substrate (locally) can be quite high (>10 %), leading to delamination and coating cracks near the bottom/layer interface. substrate. In addition, plastic deformation in the substrate can change the stress state at the DLC/bottom layer interface, further reducing the load bearing capacity of the DLC coating. Coating delamination/cracking is accelerated by high residual compressive stress within the DLC coating which creates a complex local stress state leading to coating removal (detachment).
[0153] By systematically increasing the thickness of the lower layer (by > 10 to 15 µm), a more effective load protection layer can be created, thus significantly minimizing the plastic deformation of the substrate. The abrasion test experiments and results (discussed below) illustrate the beneficial effect on coating durability as a function of increasing backsheet thickness (CrN). Deposition of such thick underlays is a technically challenging process, and may require good stoichiometry control (eg alternating CrN and Cr2N layers to control residual stress) and longer deposition times (typical deposition rates for CrN: 1 µm for 40 to 50 minutes).
[0154] Step 2: Thick/Super-Thick, Super-Strong and/or Composite DLC Structures
[0155] Although Step 1 (above) helps to minimize plastic deformation of the substrate, it does not directly address the issue of DLC performance (ie durability) under severe abrasive conditions.
[0156] In wear involving an abrasion medium (ie, sand), the strength ratio of the abrasion medium and coating (ie, the surface being rubbed) determines overall abrasion rate (according to open literature) . Under this premise, increasing coating strength can help reduce abrasive wear. However, the increased strength of DLC coatings comes at the expense of increased residual stress, which causes problems with cracking / delamination / nuclear reaction of the coating. Thus, this aspect leads to a focus on "ideal" resistance as opposed to "extreme" resistance. Our experiences indicate that resistance values from 2500 to 5500 (Hv) can be targeted, in combination with the effective thicknesses of the lower layer, while not compromising the durability of the coating (through cracking/nuclear reaction) severely with respect to structure architectures. thicker coating.
[0157] Given a coating strength, which in turn determines the rate of abrasion (assuming a gradual abrasion mechanism dominates as opposed to the cracking/nuclear reaction of the coating), the overall durability of the coating depends on the coating thickness. By systematically increasing the thickness of the DLC layer (to values > 15 µm), it has been shown that the durability of the coating can be improved under severe abrasive/load conditions (discussed below). The deposition of such DLC layers is a technically challenging process that requires good control over intercoat adhesion (where applicable) and chemical control, residual stress control and process control to prevent chamber contamination, while requiring long deposition times (typical DLC deposition rates: 1 µm for every 80 to 100 minutes). In some cases, the beneficial effects of using stronger functional layers such as ta-C, in combination with thicker underlayers and adhesion promoting layers, can also be seen.
[0158] The intrinsic abrasion resistance of DLC depends on the coating chemistry. A multiple layer of a-C:H alternating with CrC can be created to improve the overall intrinsic strength and abrasion resistance of the multiple layer. The a-C:H phase is essential to provide the low friction properties, while the CrC phase provides strength and greater resistance to abrasion. Results indicating superior abrasion resistance of such a multiple layer are also presented (below). Alternatively, a combination of a stronger functional layer (eg Ta-C) with a target underlayer thickness (such as CrN) can also produce superior abrasion resistance, along with better coating strength and durability.
[0159] Results that summarize the combined benefits of Step 1 and Step 2:
[0160] Table 1 below shows a summary of the nine different coating architectures tested to assess the effect of the approaches/steps outlined above (in some cases, adhesion promoting layer thickness values are not explicitly reported). Two types of tests/experiments were designed and conducted to assess the durability of the coating: CETR (high sand) block-in-ring test, and modified ASTM G105 test. These tests and associated measurements of each are described above.TABLE 1: SUMMARY OF LINING ARCHITECTURES AND TEST RESULTS




[0161] Figure 1 illustrates the microscopy investigations in some selective coatings (A-F of Table 1). Indications of good coating performance and durability are: low block wear (ie good coating friendliness), high % residual coating after CETR-BOR or ASTM test (ie good coating durability in abrasive test high load), low weight loss and depth of marks in the ASTM G105 test (ie, minimal coating removal and/or substrate removal during testing).
[0162] The beneficial effects of (a) thick underlays, (b) thick DLC structures and multilayer composites, and (c) super-resistant topsheet coatings are evident from the results presented in this study. The cumulative effects of these approaches can produce a coating architecture (eg similar to E, F architecture) with significantly improved overall durability among the specimens evaluated, under test conditions designed to simulate high load/abrasion environments. When using weight loss in ASTM tests as a measure, it can be seen that Architecture E (thick bottom layer + thick multi-layer DLC) is approximately 20 times better than Architecture A (thin DLC). In addition, Architecture F (thick undercoat + thick C-tap) is about 70 to 100 times better than Architecture A (thin DLC) in terms of overall durability as measured by wear/abrasion resistance in the G105 test . The significant improvement in abrasion resistance using the thick undercoat and thick coating was also evident for the super tough ta-C coating (Architecture I vs. Architecture H).
[0163] Applicants have attempted to disclose all embodiments and applications of the disclosed subject matter that may be reasonably foreseeable. However, there may be unpredictable insubstantial modifications that remain equivalent. Although the present disclosure has been described in conjunction with its specific exemplary embodiments, it is evident that many changes, modifications and variations will be manifest to those skilled in the art in light of the foregoing description, without departing from the spirit or scope of the present disclosure. Accordingly, the present disclosure is intended to cover all such changes, modifications and variations from the description detailed above.
[0164] All patents, test procedures, and other documents cited herein, including priority documents, are fully incorporated by reference, to the extent that such disclosure is not inconsistent with this disclosure and for all jurisdictions in which such incorporation is allowed.
[0165] When numerical lower limits and numerical upper limits are listed here, the ranges of any lower limit than any upper limit are contemplated.

权利要求:
Claims (16)
[0001]
1.Multi-layer low friction coating, characterized in that it comprises: i) a lower layer selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and their combinations, in which the lower layer varies in thickness from 3 to 35 µm, ii) an adhesion promoting layer selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and combinations thereof, wherein the adhesion promoter layer adhesion ranges in thickness from 0.1 to 50 µm and is contiguous with a surface of the lower layer, and iii) a diamond-like carbon functional layer (DLC), where the thickness of the functional layer ranges from 2 to 15 µm and the functional layer is contiguous with a surface of the adhesion promoting layer, if present, wherein the adhesion promoting layer, if present, is interposed between the lower layer and the functional layer, wherein the coefficient of friction of the functional layer of the coating low friction as measured by the block in the back test. annular iso is less than or equal to 0.15, and where the abrasion resistance of the low friction coating as measured by the modified ASTM G105 abrasion test produces a wear scar depth less than or equal to 20 µm and a loss in weight less than or equal to 0.03 grams.
[0002]
2. Coating according to claim 1, characterized in that the lower layer is contiguous with a surface of a substrate, preferably wherein the substrate is selected from the group consisting of steel, stainless steel, solid ligature, an alloy of iron, an aluminum based alloy, a titanium based alloy, ceramic and a nickel based alloy, most preferably wherein the solid ligature comprises a cermet based material, metallic matrix composite or a hard metallic alloy.
[0003]
3. Coating according to claim 1, characterized in that the functional layer is selected from the group consisting of ta-C, ta-C:H, DLCH, PLCH, GLCH, Si-DLC, N-DLC, O- DLC, B-DLC, Me-DLC, F-DLC and combinations thereof.
[0004]
4. Coating according to claim 1, characterized in that the resistance of the lower layer ranges from 800 to 3500 VHN, the resistance of the adhesion promoting layer ranges from 200 to 2500 VHN, and the strength of the functional layer ranges from 1000 to 7500 VHN.
[0005]
5. Coating according to claim 1, characterized in that the adhesion promoting layer is present and the coating further includes a gradient at the interface of the lower layer and the adhesion promoting layer ranging from 0.01 to 10 μm and it further includes a gradient at the interface of the adhesion promoting layer and the functional layer ranging from 0.01 to 10 µm.
[0006]
6. Coating according to claim 1, characterized in that the adhesion promoting layer is present and the coating further includes a second adhesion promoting layer selected from the group consisting of Cr, Ti, Si, W, CrC, TiC , SiC, WC, and combinations thereof, in which the second adhesion promoting layer ranges in thickness from 0.1 to 50 µm and is contiguous with a functional layer surface, and a second functional layer of diamond-like carbon (DLC) , wherein the second functional layer ranges from 2 to 15 µm and is contiguous with a surface of the second tackifier layer, and preferably includes a second lower layer interposed between the functional layer and the second tackifier layer, wherein the second bottom layer is selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and combinations thereof, where the thickness of the second bottom layer ranges from 5 to 35 µm.
[0007]
7. The coating according to claim 1, further comprising from 1 to 100 series of incremental coating layers, wherein each series of incremental coating layers includes a combination of an incremental adhesion promoting layer, an incremental functional layer and an optional incremental bottom layer, wherein each series of incremental coating layers is configured as follows: (i) wherein the optional incremental bottom layer is selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and combinations thereof; ranges in thickness from 5 to 35 µm; and is contiguous with a surface of the functional layer and the incremental adhesion promoting layer; wherein the optional incremental lower layer is interposed between the functional layer and the incremental adhesion promoting layer, (ii) wherein the incremental adhesion promoting layer is selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and their combinations; ranges in thickness from 0.1 to 50 µm; and is contiguous with a surface of the functional layer or optional bottom incremental layer, and the incremental functional layer; wherein the incremental adhesion promoting layer is interposed between the functional layer and the functional incremental layer or between the lower optional incremental layer and the functional incremental layer; (iii) where the incremental functional layer is diamond-like carbon (DLC); ranges from 2 to 15 µm in thickness; and is contiguous with a surface of the incremental adhesion promoting layer.
[0008]
8. Coating according to claim 7, characterized in that the strength of the optional incremental lower layer ranges from 800 to 3500 VHN, the strength of the incremental adhesion promoting layer ranges from 200 to 2500 VHN, and the strength of the layer incremental functional ranges from 1000 to 7500 VHN.
[0009]
9. Coating according to claim 7, characterized in that it further includes a gradient at the interface of the optional incremental lower layer and the incremental adhesion promoting layer ranging from 0.01 to 10 μm, and further includes a gradient at the interface the incremental adhesion promoter layer and the incremental functional layer that ranges from 0.01 to 10 μm.
[0010]
10. Coating according to claim 1, characterized in that the surface roughness of the functional layer varies from 0.01 μm to 1.0 μm Ra; the depth of the counterface wear scar as measured by the ring block friction test is less than or equal to 500 µm; the abrasion resistance of the low friction coating as measured by the modified ASTM G105 abrasion test produces a wear scar depth and weight loss at least 5 times lower than a single coating layer of the same functional layer.
[0011]
11. Coating according to claim 7, characterized in that the surface roughness of the outermost incremental functional layer varies from 0.01 μm to 1.0 μm Ra.
[0012]
12. Coating according to any one of claims 1 or 7, characterized in that the coating is applied to a part of the surface of a device selected from the group consisting of a drill bit for underground rotary drilling, a set of drill rods for underground rotary drilling, a cover, a pipe, couplings, a work string, a coiled pipe, a tube, a riser, a piston, centralizers, a completion column, a production column, and a device of petrochemical and chemical production.
[0013]
13. Method of manufacturing a low friction multilayer coating as defined in any one of claims 1 to 12, characterized in that it comprises: 1) providing a substrate for the coating, ii)) depositing on a substrate surface a lower layer selected from the group consisting of CrN, TiN, TiAlN, TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and combinations thereof, wherein the lower layer varies in thickness from 5 to 35 µm, iii) optionally deposit on the surface of the lower layer an adhesion promoting layer selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and combinations thereof, wherein the adhesion promoting layer varies in thickness from 0.1 to 50 μm and is contiguous with a surface of the lower layer, and iv) deposit on the surface of the adhesion promoting layer or on the lower layer, if the adhesion promoting layer is not present, a functional layer of diamond-like carbon (DLC ), in which and the functional layer ranges from 2 to 15 µm and is contiguous with a surface of the tack-promoting layer, if the tack-promoting layer is present. wherein the coefficient of friction of the low friction coating functional layer as measured by the modified ASTM G105 abrasion test produces a deep wear signal less than or equal to 20 µm, and a weight loss less than or equal to 0.03 grams.
[0014]
14. Method according to claim 13, characterized in that it further includes depositing from 1 to 100 series of incremental coating layers, wherein each series of incremental coating layers includes a combination of an incremental adhesion promoting layer , an incremental functional layer and an optional incremental bottom layer, where each series of incremental coating layers is configured as follows: (i)where the optional incremental bottom layer is selected from the group consisting of CrN, TiN, TiAlN , TiAlVN, TiAlVCN, TiSiN, TiSiCN, TiAlSiN and combinations thereof; ranges in thickness from 5 to 35 µm; and is contiguous with a surface of the functional layer and the incremental adhesion promoting layer; wherein the optional incremental lower layer is interposed between the functional layer and the incremental adhesion promoting layer, (ii) wherein the incremental adhesion promoting layer is selected from the group consisting of Cr, Ti, Si, W, CrC, TiC, SiC, WC, and their combinations; ranges in thickness from 0.1 to 50 µm; and is contiguous with a surface of the functional layer or optional bottom incremental layer, and the incremental functional layer; wherein the incremental adhesion promoting layer is interposed between the functional layer and the incremental functional layer or between the optional lower incremental layer and the incremental functional layer, (iii) wherein the incremental functional layer is diamond-like carbon (DLC); ranges from 2 to 15 µm in thickness; and is contiguous with a surface of the incremental adhesion promoting layer.
[0015]
15. Method according to claim 13, characterized in that the steps of deposition of the lower layer, depositing of the adhesion promoting layer or deposition of the functional layer are selected from the group consisting of physical vapor deposition, chemical vapor deposition assisted by plasma and chemical vapor deposition; preferably wherein the physical vapor deposition coating method is selected from the group consisting of electron tube sputter deposition, ion beam assisted deposition, cathodic arc deposition and pulsed laser deposition.
[0016]
16. Method according to claim 13, characterized in that it further includes a post-processing step in the functional layer to achieve a surface roughness between 0.01 to 1.0 μm Ra, preferably in which the powder step -processing is selected from the group consisting of mechanical polishing, chemical polishing, depositing polished layers, an ultra-fine super polishing process, a tribochemical polishing process, an electrochemical polishing process, and combinations thereof.

类似技术:

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公开号 | 公开日 | 专利标题

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BR112015009709B1|2021-09-08|LOW FRICTION COATING WITH IMPROVED ABRASION AND WEAR PROPERTIES AND PRODUCTION METHODS

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AU2009340498B2|2016-03-03|Coated oil and gas well production devices

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同族专利:

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公开号 | 公开日

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EP2938754B1|2018-12-19|

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BR112015009709A2|2017-07-04|

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RU2653379C2|2018-05-08|

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CN104870692B|2018-07-06|

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RU2015123296A|2017-01-27|

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AU2013364110A1|2015-07-09|

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US20140178637A1|2014-06-26|

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CA2890522A1|2014-06-26|

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US9617654B2|2017-04-11|

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CA2890522C|2019-07-02|

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EP2938754A1|2015-11-04|

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AU2013364110B2|2016-05-05|

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WO2014099211A1|2014-06-26|

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CN104870692A|2015-08-26|

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

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

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

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

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2021-04-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-08| 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 19/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/724,403|2012-12-21|

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US13/724,403|US9617654B2|2012-12-21|2012-12-21|Low friction coatings with improved abrasion and wear properties and methods of making|

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PCT/US2013/070681|WO2014099211A1|2012-12-21|2013-11-19|Low friction coatings with improved abrasion and wear properties and methods of making|

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