JP2017512902A - Method for producing a corrosion protection coating or adhesion promoting coating - Google Patents

Abstract

A method of treating a substrate, wherein the method includes impregnating a surface of the substrate with a first particle set including a dopant and a second particle set including an abrasive on the substrate. Including substantially simultaneously supplying a fluid jet to a surface of the substrate, wherein the dopant forms a corrosion-inhibiting species or a corrosion-inhibiting coating or adhesion promoting coating on or on the surface of the substrate. Includes adhesion promoting species. Also provided is an article comprising a substrate having a corrosion-inhibiting coating or an adhesion-promoting coating, the coating comprising particles of corrosion-inhibiting or adhesion-promoting species that are impregnated on the surface of the substrate (eg, produced by the above method). To be)

Description

  The present invention relates to surface treatment techniques in the field of materials science.

  Abrasion can be defined as the action or process of rubbing or rubbing things, or rubbing things by friction, as well as the action or fact so worn. Spraying abrasive materials onto metal surfaces has increased in technical application in recent years. Techniques such as grit blasting, shot blasting, sand blasting, and micro abrasion are included in the surface treatment technology category. In each technique, an abrasive material, typically a shot or grit, is mixed with the fluid and fed at high speed to impact the surface to be treated. The method of supplying an abrasive material is classified as wet or dry depending on the choice of fluid (typically water or air) used to supply the abrasive material to the surface. Alternatively, the abrasive can be propelled to the surface with a spinning wheel or paddle using a wheelblast machine. As the wheel rotates, the abrasive particles are accelerated and directed toward the target, impacting and wearing the target, similar to a standard fluid ablation system. Such a system does not require any fluid or compressed gas to propel the particles. The generic term “abrasive bombardment” is used herein to mean all such techniques. Such techniques differ from shot peening techniques where round particles are applied to the surface to alter the stress level in the substrate so as not to cause significant material polishing or to induce a dimple surface texture. . (However, it is understood that to avoid uncertainties, the abrasive impact technique can change the stress level at the surface of the substrate and cause material polishing.)

  Abrasive impact applications include metal cutting, surface cleaning, and pretreatment that induces the desired surface texture (surface roughness) to enhance the adhesion of additional coating materials. (Solomon et al., Welding Research, 2003. October: p. 278-287; Momber et al., Tribology International, 2002. 35: p. 271-281; Arola et al., J. Biomed. Mat. Res. , 2000. 53 (5): p. 536-546; and Arola and Hall, Machining Science and Technology, 2004. 8 (2): p. 171-192.) The latter example is found in the biomedical field. There, alumina or silica is used to grit blast titanium implants to achieve a surface roughness that optimizes the adhesion of the plasma sprayed hydroxyapatite (HA) coating to the surface of the implant. Although HA coated implants are preferred due to the biomimetic properties of the apatite layer, an optimum bond strength between the apatite layer and the titanium surface is also required.

  When impacting these surfaces, it has long been known that some of the abrasive material penetrates the surface of the metal itself, and thus this technique is a candidate for a method that generally changes the chemistry at the surface. Attracted interest. (See Arola et al. And Arola and Hall, supra.) Another study in the biomedical field is investigating shot blasting as a method of depositing an HA layer directly on the titanium surface, which is an expensive plasma spray. Trying to avoid the process (Ishikawa, K., et al., Blast coating method: new method of coating titanium surface with Hydroxyapatite at room temperature. J. Biomed. Mat. Res., 1997. 38: p. 129-134). In this study, HA particles whose particle size distribution is not specified are used as abrasives. However, since the deposited apatite layer can be easily removed by a gentle cleaning method, it seems that strong bonding with the metal surface could not be achieved.

  Choi et al. (KR2003-0078480) describe the use of a single calcium phosphate particle as a medium for grit blasting to embed grit into the surface of a dental implant, but discloses particles over 190 μm.

  US Pat. No. 6,502,442 describes the use of sintered HA as an abrasive with water as the fluid medium. In this case, since the HA has been heat-treated, a certain degree of HA embedding can be achieved.

  Müller et al (US 2004/158330) describe blasting particles comprising calcium phosphate contained in a glassy matrix. In other references (eg, US Pat. No. 4,752,457 and US Pat. No. 6,210,715), methods for producing calcium phosphate microspheres, usually containing polymer components, and for producing the same Although complex methods are described, their effectiveness as blasting media has not been elucidated.

  The Rocatec® system for silicization of metal surfaces and other surfaces also uses solid particles with multiple elements. This technique is widely used in the dental field. In this case, the alumina particles having the silica outer adhesion layer are sent to a previously roughened surface, and the heat generated from the collision at that time causes the silica outer adhesion layer crushed around the collision site to be fused to the surface. . This process is called ceramicization.

  Bru-Magniez et al. (US Pat. No. 6,431,958) describe hard abrasive materials with multiple layers as abrasives used in blast abrasive impact techniques for surface treatment. In this case, the purpose of the processing step is to embed or deposit a plurality of layers surrounding the abrasive particles on the surface to be processed. The outer side contains at least one polymer and the preferred core ceramic material is oxide, carbide, nitride, or carbonitride.

  The use of multiple polymer layers has already been proposed. Lange et al. (US Pat. No. 6,468,658) describe particles for blasting that include a basic core material and an outer adhesive layer of titanium dioxide.

  Further applications of abrasive impact for surface processing can be found in the biomedical field, for example, the use of microabrasion to clean oxide slag from the struts of laser-processed coronary stents And the use of microabrasion to embed silica on the surface of pacemakers and defibrillators to deposit additional polymer coatings on each device.

  The commonality between these examples is the use of one type of solid particles in the fluid stream. This can also be a pretreatment step prior to subsequent coating.

  U.S. Pat. No. 3,754,976 proposes a different approach using two separate particles. The patent includes spraying a surface of a mixture of metallic powder and small peening particles at a high speed, the speed being sufficient to bond the metallic powder to the surface and form a metal laminate layer. Describe the process. This process is limited to the combination of non-abrasive shot peening particles and metallic powder. U.S. Pat. No. 4,552,784 is a similar approach in which a metal powder is exposed to a metal surface as it strikes a substrate with a stream of shot peening particles and a stream of rapidly solidifying metal powder particles. We propose an approach that can be combined to be deposited as a laminate layer on top. In this process, no abrasive is used and deposition is limited to metal precursors. U.S. Pat. No. 4,753,094 involves spraying a stream of molybdenum disulfide powder mixed with a steel shot onto a substrate at a predetermined speed, which is microscopically applied to the substrate as it strikes the substrate. A process is described that is sufficient speed to bind the plate-like molybdenum disulfide particles and form a surface that reduces friction there. The process does not mention abrasive particles and the steel shot used is usually used in a non-abrasive shot peening process.

  US Pat. No. 8,119,183 and WO 2008/033867, filed under the name of EnBio Limited, propose an alternative approach, in which the abrasive flow and coating precursor ( Abrasive blasting and coating deposition are performed simultaneously by combining the dopant) flow into one step of processing the surface of the metal implant. The abrasive is used as a step to remove the oxide layer and bond the dopant to the metal, thus providing a new method for modifying the metal surface of the medical device, and this Various bio-related dopants for the coating process are described. The dopant material is used to improve the biomedical properties of the surface of the device. Since the materials used to make medical implants are naturally corrosion resistant and do not require a coating to prevent corrosion, no corrosion resistant dopants have been considered.

[Corrosion prevention coating]
However, in industrial application areas other than medical implants, there are corrosive species in the vicinity of the substrate (for example, during use of the substrate, during subsequent processing, or during storage of the substrate, etc.), the substrate is likely to corrode. Accordingly, it would be desirable to provide a corrosion-inhibiting surface treatment for such substrates. In this document, the term “corrosion prevention” should be broadly interpreted to include a process that reduces the susceptibility of the substrate to corrosion and also includes a process that generally prevents corrosion.

  The two main types of corrosion protection surface treatments considered in this document are conversion coatings and mechanically-bonded coatings.

[Chemical conversion coating]
Chemical conversion coatings are routinely used to protect metal articles in the aerospace, shipping, petrochemical, and many other industries. A conversion coating is a treatment of a metal substrate where at least a portion of the surface is converted to a coating by a chemical or electrochemical process. Examples include chromate conversion coating, phosphate conversion coating, and anodizing. The most common reasons for applying conversion coatings are to increase the protection against corrosion, to change the color of the surface, to increase the hardness of the surface, or to deposit a primer layer on the surface in order to improve the adhesion of subsequent layers It is. Chromate conversion coatings have gained an advantage in several sectors of the corrosion coating market, but such coatings are a natural part of the chromate conversion process, mainly due to the toxicity of hexavalent chromium used in the coating process. Its popularity is declining due to its negative impact on the environment. Therefore, the significance of phosphate coatings, and in particular zinc phosphate coatings, is gradually increasing.

  All of this coating requires a pretreatment step, which often involves polishing blasting the surface prior to coating. For example, phosphate conversion coating is a complex process that involves a significant number of steps and requires a multi-stage surface treatment strategy. In general, the first step involves cleaning the surface. This can be accomplished by a variety of methods, including immersion in solvents, etchants, acids, basic agents, degreasing agents, physical cleaning using ultrasonic tanks, and physical polishing using methods such as grit blasting. Can be achieved. Many of this processes are performed at elevated temperatures using hazardous or toxic chemicals. Following the cleaning step, the surface can be further activated. This involves a grit blasting or mechanical polishing process that breaks down the natural oxide layer, roughens the surface, and makes the active site available for subsequent bonding to the conversion coating during subsequent steps. It may be physical activation to be used. Alternatively, the surface may be activated by chemical means. For example, in the case of zinc phosphate coating, a method in which the surface is pretreated with a colloidal titanium compound immediately before application of the chemical conversion coating is often used. Other compounds such as dilute solutions of copper sulfate and nickel sulfate, oxalic acid, and polyphosphonates promote the increase in initial nuclei generated during subsequent phosphorylation steps, and these pretreatments are thin and compact, A fine particulate phosphate coating is formed. The activation step can include a combination of subsequent chemical activations following an initial grit blasting process.

  The actual phosphate deposition is a stand-alone process step, usually performed using a wet chemical solution. The substrate is usually immersed in a bath of chemical conversion agent. The composition of such baths varies from manufacturer to manufacturer, but usually includes dilute solutions based on phosphoric acid, all containing suitable accelerators along with alkali metal / heavy metal ions. Such baths are usually heated to improve the reaction rate and optimize the surface finish. The chemical concentrations of reactants and waste in the bath change steadily as the chemical reaction proceeds and the bath needs to be closely monitored and adjusted to maintain optimal performance. For larger parts, because of the physical size of the article, the chemical bath becomes very large and complex and difficult to control. For such substrates, spray phosphorylation is used. Similar to the wet chemical bath method, but instead a chemical solution is sprayed onto the metal surface to allow it to react.

  Following the phosphorylation step, the article is typically cleaned, dried, and sent to undergo further processing that may include additional layers, sealants, passivation treatments, or paint deposition. The phosphorylation process is generally slow, complex, requires considerable heat input, and uses harsh toxic chemicals.

  Therefore, it is still readily available to process both large and small elements, easy to use, and does not require a multi-step processing process that uses large amounts of energy and harsh chemicals to prevent corrosion. Is required to generate.

[Mechanical bond coating]
Next, when considering mechanically bonded coatings, these form a mechanical interlock between the coating and the underlying substrate, rather than as a result of a chemical or electrochemical reaction of the surface of the substrate. By the coating that is bonded to the underlying substrate. In order to prepare a substrate surface that receives a coating that mechanically bonds to the substrate, conventionally, the substrate surface is subjected to another pretreatment process to roughen the surface of the substrate. This produces, on a microscale, numerous cracks, indentations, or other non-planar areas on the surface of the substrate, into which subsequently applied coatings can be interlocked. Such a roughening process is generally performed by sandblasting, after which the roughened surface is cleaned. The coating is then applied in another process such as spraying. Using such sandblasting, cleaning, and spraying processes in this way (ie, as a multi-stage process) is time consuming and requires that such processes be more efficient. .

[Adhesion promoting coating (including primer layer)]
Although the above discussion focuses primarily on applying a corrosion protection coating directly to the surface of the substrate, it is understood that similar problems arise when forming an adhesion promoting coating on the substrate. As used herein, expressions such as “adhesion-promoting” and “adhesion-promoting coating” refer to a coating that is applied to a substrate to improve the adhesive properties of the surface of the substrate: Allowing, promoting or enhancing the adhesion of the substrate to another material or article with which the substrate subsequently contacts; or enabling, promoting or enhancing the adhesion of subsequently deposited layers to the substrate (The coating thereby serves as a primer layer for subsequently deposited layers).

  One skilled in the art understands that the primer layer is a coating formed on the surface of the substrate. Subsequent coating is applied to the primer layer. The primer layer is selected so that it bonds well to the substrate and that the subsequently applied coating bonds well to the primer layer. Thus, the primer layer acts as an intermediate layer between the substrate and the subsequently applied coating, and the overall effect is a better bond between the subsequently applied coating and the substrate compared to the absence of the primer layer.

  Similar to the anti-corrosion coating, the adhesion promoting coating can be formed as a conversion coating or a mechanical bond coating on the underlying substrate. In any case, the above problems with conversion coatings and mechanical bond coatings (in the context of corrosion protection) are equally applicable.

  According to a first aspect of the present invention, there is provided a method of treating a metal substrate, the method comprising: a first particle set including a dopant; a second particle set including an abrasive; and the dopant of the metal substrate. Including substantially simultaneously supplying from at least one fluid jet to the surface of the metal substrate to impregnate the surface, wherein the dopant forms a corrosion-inhibiting conversion coating on the surface of the metal substrate. Including corrosion-inhibiting species.

  The expression “metal substrate” as used herein is not to be interpreted as including only a substantially pure metal substrate or an alloy substrate, but a composite material having a metallic element, eg a metal matrix composite material. Should be interpreted broadly to include

  By this substantially simultaneous supply method, the action of the abrasive particles on the surface of the metal substrate promotes the impregnation of the corrosion-inhibiting dopant particles on the surface of the metal substrate. This provides a method for producing an anti-corrosion conversion coating that is readily available for processing both large and small elements and is easy to use without requiring a multi-step processing process.

  A further advantage obtained as a result of supplying the abrasive particles substantially simultaneously with the corrosion-inhibiting dopant particles is to work harden the surface of the metal substrate and / or apply compressive stress to the surface of the metal substrate. Both, including, promote the improvement of metal resistance to stress corrosion cracking. Since these effects occur substantially simultaneously with the impregnation of the corrosion-inhibiting dopant species on the metal surface (which is also promoted by the action of the abrasive particles), the abrasive particles are supplied together with the corrosion-inhibiting dopant particles. Is understood to provide a synergistic benefit in improving the corrosion resistance of the treated metal. That is, physical modifications to the metal surface (ie, work hardening and / or compressive stress) can be achieved in conjunction with chemical modifications (ie, addition of corrosion inhibiting dopant species).

  Preferably, the corrosion inhibiting species is chemically bonded to the substrate.

  According to a second aspect of the present invention, there is provided a method for treating a metal substrate, the method comprising: a first particle set including a dopant; a second particle set including an abrasive; and the dopant of the metal substrate. Including substantially simultaneously supplying from at least one fluid jet to the surface of the metal substrate to impregnate the surface, wherein the dopant is mechanically bonded to the surface of the metal substrate. Includes corrosion-inhibiting species that form a protective coating.

  By this substantially simultaneous method, the action of abrasive particles on the surface of the metal substrate facilitates the impregnation of the corrosion-inhibiting dopant particles into the surface of the metal substrate and folds at the interface between the substrate and the coating. Or bending, thus improving the degree of mechanical bond between the substrate and the coating and the overall strength of the bond. Such a process is particularly applicable to substrate materials where a conversion coating cannot be formed, is readily available to handle both large and small elements, and is easy to use, multi-step processing A method is provided for producing an anticorrosion coating so that no process is required.

  With respect to the first and second aspects, preferably the coating has properties such that a dopant laminate layer does not occur.

  In practice, the method further comprises removing a metal oxide from the surface of the metal substrate by abrasive blasting, thereby exposing the metal surface, and at least adding a corrosion-inhibiting dopant to impregnate the substrate surface with the dopant. It may further comprise providing substantially simultaneously from one fluid jet to the metal surface. The physical process by which the abrasive particles impinge on the surface of the metallic material functions to remove surface oxides and substantially simultaneously embed dopant particles into or on the surface. In addition, abrasive blasting can change the microstructure of the underlying metal, compress the surface, and impart compressive force to the metal. Since the compressive force of this surface opposes the tensile force required for crack propagation, it can promote the reduction of stress corrosion cracking.

  Removal of the passivating metal oxide layer exposes the underlying reactive metal. When combined with the impact energy from the dopant particles impinging on the surface and the energy dissipated by the impact of the abrasive particles, sufficient energy can be released to chemically bond the coating to the substrate. Moreover, the bond formed by the combination of the abrasive and the dopant can improve the adhesion and / or durability of the dopant material. Furthermore, the abrasive can not only be present as an outer surface layer, but can also stir and bend the surface of the substrate so that it is physically mixed with the surface.

  Surprisingly, it has been discovered that deposits have very little evidence of abrasive particles. Instead, the surface of the substrate appears to be preferentially doped with a corrosion-inhibiting material. The abrasive material appears to bounce off the surface and the surface is impregnated with minimal abrasive grit. Generally, more than 90% of the deposit is formed by a corrosion resistant dopant and less than 10% is derived from the abrasive. In some cases, more than 99% of the deposit is formed by corrosion resistant dopants and less than 1% is derived from abrasive particles.

  The layer of corrosion-inhibiting material can be used as a final surface finish that functions as a corrosion-resistant layer. Alternatively, the corrosion-inhibiting material can be further coated with one or more additional coating layers in order to improve the corrosion resistance (and / or scratch-resistance) of the surface. Such one or more additional different layers may be applied by spraying, painting, dipping, vapor deposition, or any suitable method for applying subsequent layers. Corrosion protection materials can function as a primer to which such additional layers can adhere, thus improving the adhesion of subsequent layers to the substrate metal. Adjusting the abrasive properties, dopant properties, or blasting conditions can change the surface shape and interfacial chemistry of the deposited layer of corrosion resistant material, and thus the primer surface to provide improved primer performance. Can be optimized.

  A layer of corrosion-inhibiting material can be deposited over the repair area of the metal surface. In order to apply certain repairs, such as welding or brazing, it is necessary to remove all outer coating and oxide layers to leave a workable metal. After completion of this repair step, the bullion is still exposed and susceptible to corrosion. Since field repairs are generally performed in situations where complex wet chemical deposition methods are not available, application of corrosion resistant materials cannot be easily completed using conventional deposition methods. Thus, in many cases, the repaired area can be excessively corroded and damaged again. Simple particle blasting as described herein can be readily used in such situations to apply a corrosion-preventing surface treatment that can protect the repair area and extend the life of the product.

  The method described herein provides a one-step process that cleans and roughens the surface while changing the native oxide layer to a corrosion resistant surface. This is accomplished without the use of thermal energy and without the need for hazardous chemicals, toxic chemicals, or corrosive chemicals. Advantageously, the treatment is not limited to the size of the substrate and is not limited to pipe sections, wind turbine elements, civil engineering structures, outer walls, large engineering elements, marine elements, automobile body articles, or routine It is easily applicable to other such large metallic elements that corrode. In one specific application, the element is a tubular pipe and the coating is applied to the inner or outer surface of the pipe. When applied to the inner surface of the pipe, the coating can reduce corrosion and further reduce friction when pumping liquid through the pipe.

  In certain embodiments, the dopant is provided in a gaseous carrier fluid such as nitrogen, hydrogen, argon, helium, air, ethylene oxide, and combinations thereof. In another embodiment, the dopant is provided in a liquid carrier liquid. In some embodiments, the liquid is also an etching liquid (basic or acidic). In certain embodiments, the dopant is provided in an inert environment.

  The corrosion-inhibiting dopant material may be a chromate, phosphate, polymer (eg thermosetting or thermoplastic), oxide, or nitride. The dopant may be cerium oxide (ceria). In certain preferred methods, the coating is derived from a phosphate compound. The phosphate can include a corrosion-inhibiting transition metal phosphate, such as iron phosphate, manganese phosphate, or zinc phosphate, or combinations thereof. Since phosphate is not deposited by an electrochemical process, various materials can be incorporated into the surface by changing the starting dopant powder.

  In certain embodiments, the abrasive has at least one suitable property selected from size, shape, hardness, and density to destroy the oxide layer of the metal substrate. In certain embodiments, the abrasive has a Mohs hardness of 0.1-10, such as a Mohs hardness of 1-10, or a Mohs hardness of 5-10. In certain preferred methods, the abrasive has a Mohs hardness of 7-10. In another embodiment, the abrasive has a particle size of 0.1 μm to 10,000 μm, such as a particle size of 1 μm to 5000 μm, or a particle size of 50 μm to 500 μm. In one preferred method, the abrasive particle size has a Mohs hardness of 10 μm to 150 μm.

  Abrasive materials used in this method include, but are not limited to, silica, sand, alumina, zirconia, zirconate, barium titanate, calcium titanate, sodium titanate, titanium oxide, glass, biocompatible glass , Diamond, silicon carbide, boron carbide, dry ice, boron nitride, calcium phosphate, calcium carbonate, metallic powder, carbon fiber composite, polymer composite, titanium, stainless steel, hardened steel, carbon steel chromium alloy, or any of them A shot or grit formed by a combination of

  Abrasive impact can be used to work harden the surface, and it can interact synergistically with corrosion inhibiting dopants to limit stress corrosion cracking. This degree of work hardening can be accommodated by changing the abrasive properties. By changing the size, shape, or chemistry of the abrasive, the effect on the substrate can be changed. Due to the presence of the dopant, the surface is very deformed and chemically altered, while the underlying layers are also altered. While the dopant does not penetrate into this subsurface zone, the impact process can alter the grain structure of the underlying metal. This zone can be extended to 10-50 microns and the depth of the zone can be controlled by changing the particle size, hardness, and abrasive speed. Increasing the energy of the abrasive improves the depth of the change effect. The grains in this altered region can exhibit twinning. Twins were observed in previously shot peened metals. Twin formation is facilitated by high strain rates, impact loading, and relatively large grain sizes. Underneath this structurally altered layer is an undeformed substrate.

  The pressure of the fluid jet is also a factor in determining the impact energy of the abrasive. Abrasive and dopant may not be provided to the surface through the same jet. It can be in any number of individual jets as long as they provide a solid element to the surface at substantially the same time (e.g., prior to reformation of the oxide layer). This can provide a high degree of flexibility in optimizing the invention for certain specific needs. For large substrates, multiple nozzles can be used to simultaneously provide abrasive and dopant to multiple points on the surface, thus accelerating the overall process speed.

  In certain embodiments, the fluid jet is selected from a wet blaster and an abrasive water jet peening machine. In certain embodiments, the at least one fluid jet operates at a pressure of 0.5 to 100 bar, such as 1 to 30 bar, or 1 to 10 bar.

  In yet another embodiment, the at least one fluid jet is selected from a drive blasting machine, a wheel polishing machine, a grit blasting machine, a sand blasting machine, and a microblasting machine. In certain embodiments, the at least one fluid jet operates at a pressure of 0.5-100 bar, such as 1-30 bar, or 3-10 bar.

  In other embodiments, the blasting instrument can be used in conjunction with controlled motion such as CNC or robotic control. Blasting can be performed in an inert environment.

  In some embodiments, the dopant and abrasive are contained in the same reservoir and provided to the surface from the same jet (nozzle). In yet another embodiment, the dopant is contained in one reservoir, the abrasive is contained in another reservoir, and a plurality of nozzles provide the dopant and the abrasive. The plurality of nozzles may be in the form of a jet within the jet, i.e., particles from each jet impact the surface at the same angle of incidence. In yet another embodiment, the plurality of nozzles impact the surface at different angles of incidence but are spatially separated so as to hit the same point on the surface at the same time.

  In certain embodiments, the article to be treated is a metal such as a metal selected from pure metals, metal alloys, intermetallic compounds, or mixtures thereof. Typical metals are iron, zinc, cadmium, tin, silver, titanium, titanium alloys (eg NiTi or Nitinol), alloy iron, stainless steel, and stainless steel alloys, carbon steel, carbon steel alloys, aluminum, aluminum alloys, Includes nickel, nickel alloys, nickel titanium alloys, tantalum, tantalum alloys, niobium, niobium alloys, chromium, chromium alloys, cobalt, cobalt alloys, noble metals, and noble metal alloys.

  Those skilled in the art will appreciate the effect of mechanical parameters, including jet velocity, operating pressure, venturi configuration, angle of incidence, and surface-to-nozzle distance, on the extent of dopant impregnation on the surface when using these mixed media. Can understand.

  One skilled in the art can understand the effect of the size, shape, density, and hardness of the abrasive material on the extent of dopant impregnation on the surface when using these mixed media.

  Those skilled in the art will know that when using these mixed media, the fluid stream itself, the blasting device using a gas media (usually air), and the inert gas (e.g. Or a rare gas such as Ar or He) can be understood.

  According to a third aspect of the present invention, there is provided a method of treating a substrate, the method comprising: a first particle set including a dopant; a second particle set including an abrasive; and the dopant on a surface of the substrate. Including substantially simultaneously supplying from at least one fluid jet to the surface of the substrate for impregnation, wherein the dopant forms an adhesion promoting coating on or on the surface of the substrate; Includes adhesion promoting species.

  The adhesion promoting species may form a conversion coating on the surface of the substrate.

  The adhesion promoting species can also be chemically bonded to the substrate.

  Alternatively, the adhesion promoting species may form a mechanically bonded adhesion promoting coating on the surface of the substrate.

  Similar to the anti-corrosion coating described above, the action of the abrasive particles on the surface of the substrate promotes the impregnation of adhesion promoting dopant particles on the surface of the substrate by the method provided at the same time applied in the third aspect. To do. This is an easy-to-use, easy-to-use, multi-step treatment process that does not require a multi-step processing process (chemical coating or mechanical bonding) to handle both large and small elements. As a layer).

  In certain embodiments, the adhesion promoting species forms a primer layer on the substrate, ie, the adhesion promoting species functions as a primer forming species. Such primer-forming species may include fluoropolymers such as PTFE, perfluoroalkoxy polymers such as Teflon, polyvinylidene fluoride, perfluoropolyethers, perfluorinated elastomers, or polyvinyl fluoride. Alternatively, or in addition, the primer-forming species includes silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compounds, or materials that include one or more functional groups of vinyl, peroxyester, peroxide, acetate, or carboxylate. obtain.

  One or more subsequent layers can be applied to the primer layer, such as a scratch suppression layer, a corrosion protection layer, an adhesive layer, a non-stick surface, or a solid low friction layer (eg, a fluoropolymer such as PTFE).

  Alternatively, instead of functioning as the primer layer itself, an adhesion promoting coating may be provided to improve the adhesion of the substrate to another material or article that the coated substrate will later contact. In such cases, the adhesion promoting layer includes, for example, a silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound, or a material that includes one or more functional groups of vinyl, peroxyester, peroxide, acetate, or carboxylate. obtain.

  With respect to all the above aspects, preferably the second particle set (ie abrasive particles) has an average particle size of 1 μm to 150 μm, more preferably an average particle size of 10 μm to 150 μm, particularly preferably an average particle size of 50 μm to 150 μm. Have By using such small abrasive particles, the destruction of the surface of the substrate is improved, so that the penetration of the dopant particles into the surface of the substrate is promoted, and the intermixing between the substrate surface and the dopant particles is promoted.

  Preferably, the first particle set (i.e., dopant particles) has an average particle size in the range of 1 [mu] m to 100 [mu] m.

  Preferably, the weight ratio of the first particle set and the second particle set is between 20:80 and 80:20. Particularly preferably, the weight ratio of the first particle set and the second particle set is between 40:60 and 60:04.

  In certain embodiments, the first particle set and the second particle set may be provided without the use of a carrier fluid.

  More generally, according to a fourth aspect of the present invention, there is provided a method of treating a substrate, the method comprising: a first particle set comprising a dopant; and a second particle set comprising an abrasive comprising the dopant. Including substantially simultaneously supplying from at least one fluid jet to the surface of the substrate to impregnate the surface of the substrate, wherein the dopant is applied to or on the surface of the substrate. A corrosion-inhibiting or adhesion promoting species is included to form an adhesion promoting coating.

  According to a fifth aspect of the present invention there is provided an article comprising a metal substrate having a corrosion-inhibiting conversion coating, wherein the conversion coating comprises particles of corrosion-inhibiting species impregnated on the surface of the metal substrate. In this context, impregnation means a process in which the dopant is present in the top 20 microns of the metal surface and is intimately intermixed with the metal. The impregnating material may spread on or over the metal surface but also penetrates into the metal. The dopant material is not formed as a laminate layer just located on the metal substrate.

  The expression “article” as used herein should be interpreted broadly to include a portion of a larger product and the entire product.

  According to a sixth aspect of the present invention there is provided an article comprising a metal substrate having a mechanically bonded corrosion protection coating, wherein the mechanically bonded corrosion protection coating is impregnated on the surface of the metal substrate. Contains particles of corrosion-inhibiting species.

  According to a seventh aspect of the present invention there is provided an article comprising a substrate having an adhesion promoting coating, the adhesion promoting coating comprising particles of an adhesion promoting species impregnated on a surface of the substrate.

  According to an eighth aspect of the present invention there is provided an article comprising a substrate having a corrosion inhibiting coating or an adhesion promoting coating, wherein the corrosion inhibiting coating or the adhesion promoting coating is a first, second, third or fourth aspect. It is produced | generated by the method concerning.

Embodiments of the present invention will now be described by way of example only and with reference to the following drawings in which:
1a, 1b, and 1c schematically illustrate a process for processing a metal substrate. Figures 2a, 2b, and 2c schematically illustrate three different nozzle configurations for providing abrasive and dopant particles on the surface. FIG. 3 is a schematic cross-sectional view of a metal substrate having a corrosion-inhibiting chemical conversion coating. FIG. 4 is a schematic cross-sectional view of a metal substrate having a corrosion-inhibiting chemical conversion coating on which a second layer is formed. FIG. 5 is a schematic cross-sectional view of a substrate having an adhesion promoting coating. FIG. 6 is a schematic cross-sectional view of a substrate having an adhesion promoting coating that functions as a primer layer with a subsequent coating formed thereon. FIG. 7 shows the results of a lap-shear strength test after various surface treatments on titanium (for Example 5 described below).

  This embodiment represents the best way to implement the present invention as far as the applicant knows. However, it does not include all the methods achieved in the present invention.

[Overview of deformation]
The present embodiment provides a method for treating a substrate, wherein the method impregnates the surface of the substrate with a first particle set containing a dopant and a second particle set containing an abrasive. And at least one fluid jet to the surface of the substrate substantially simultaneously, wherein the dopant forms a corrosion protection coating or adhesion promoting coating on or on the surface of the substrate. , Including corrosion-inhibiting species or adhesion promoting species.

  The action of abrasive particles on the surface creates a rough interface between the substrate material and the coating formed thereon. Also, the degree of intermixing between the substrate and the dopant species is such that no dopant laminate layer is produced.

  This embodiment can be subdivided into three main variants.

  According to a first variant, certain embodiments provide a method of treating a metal substrate, the method comprising a first particle set comprising a dopant and a second particle set comprising an abrasive comprising the dopant. A method of substantially simultaneously supplying from at least one fluid jet to the surface of the metal substrate for impregnating the surface of the metal substrate, wherein the dopant is applied to the surface of the metal substrate. Including corrosion-inhibiting species such as

  According to a second variant, another embodiment provides a method of treating a metal substrate, the method comprising: a first particle set comprising a dopant; and a second particle set comprising an abrasive comprising the dopant. Including impregnating the surface of the metal substrate substantially simultaneously from at least one fluid jet to the surface of the metal substrate, wherein the dopant is mechanically bonded to the surface of the metal substrate. A corrosion-inhibiting species that forms a formed anti-corrosion coating.

  According to a third variant, a further embodiment provides a method of treating a substrate (which may not be a metal), the method comprising a first set of particles comprising a dopant and a second comprising an abrasive. Providing a set of particles substantially simultaneously from at least one fluid jet to the surface of the substrate for impregnating the surface of the substrate with the dopant, wherein the dopant is applied to the surface of the substrate, or It includes an adhesion promoting species such as to form an adhesion promoting coating thereon (eg, by chemical conversion coating or mechanical bonding).

[Substantially simultaneous particle providing method]
For details of performing the method according to each of the first, second, and third variations, the reader first begins with the substantially simultaneous deposition of the first and second sets of particles. Reference is made to WO 2008/033867 which describes the technology of However, WO2008 / 033867 forms a corrosion-inhibiting conversion coating or a mechanically bonded corrosion-inhibiting coating on or on the surface of a metal substrate (as in the first and second variants). It should be noted that no dopants are included that contain corrosion-inhibiting species such as Also, WO2008 / 033867 does not describe forming an adhesion promoting coating on or on the surface of the substrate (as in this third variant).

  Of course, those skilled in the art understand that the first particle set and the second particle set are different from each other (ie, the dopant species is different from the abrasive).

[Embodiment for forming a corrosion-preventing coating on or on the surface of a substrate (first and second variants)]
Embodiments of the method are encompassed by, but not limited to, the schematic diagrams shown in FIGS. 1a, 1b, and 1c.

  FIG. 1 a schematically shows a fluid jet (nozzle) 2 that provides a stream 3 containing a set 4 of abrasive particles substantially simultaneously with a set 6 of dopant particles. The dopant particle 6 contains a corrosion-inhibiting species. The particle sets 4 and 6 impact the surface 10 of the metal substrate 8 in order to impregnate the surface of the metal substrate with the corrosion-preventing dopant.

  According to the first variant, a chemical or electrochemical reaction can occur between the dopant species and the substrate material, resulting in the formation of a corrosion-inhibiting conversion coating on the surface of the metal substrate 8. The energy required to initiate these reactions can be provided by the impact force of both particle sets on the surface. Abrasive particles do not necessarily have to be directly related to a chemical reaction, but their impact force on a surface can provide energy to initiate a conversion reaction.

  Alternatively, according to the second variant, some of the corrosion-inhibiting dopant particles are mechanically interlocked with the surface of the substrate, and the surface is roughened by the action of abrasive particles and mechanically bonded to the surface of the metal substrate. An anticorrosion coating can be formed.

  The formation of the corrosion protection coating can include a combination of both conversion coating and mechanical bonding of the dopant particles to the surface of the substrate.

  For both the first and second variations, during the deposition process, the deposited dopant particles are subjected to continued abrasive particle bombardment, and the dopant particles are repeatedly driven onto and into the surface of the substrate. As a result, the substrate and dopant species are intimately mixed, resulting in a hard bond and interlock between the two so that the anti-corrosion coating does not result in a dopant laminate layer.

  In the embodiment illustrated in FIGS. 1a, 1b, and 1c, the surface 10 is a layer of metal oxide. As a result of the impact by the abrasive particles 4, the oxide layer on the surface is destroyed, and the breakthrough in the oxide layer 10 exposes the new surface 10a of the substrate 8 (FIG. 1b). In the case of a metal substrate, the newly exposed surface is a metal surface. As the particle stream 3 subsequently strikes the substrate 8, the dopant particles 6 are integrated into the surface 10 of the substrate 8 (FIG. 1c). Such destruction of the oxide layer to produce a newly exposed metal surface is particularly applicable when a chemical or electrochemical reaction is caused between the dopant and the substrate species. Allow the substrate metal to react (instead of the surface oxide layer). However, the breakdown of the oxide layer is also advantageous when the coating is mechanically bonded to the substrate 8.

  In some embodiments, the blasting instrument can be used in conjunction with controlled motion such as CNC (computer numerical control) or robot control. Blasting can be performed in an inert environment.

  In some embodiments, the dopant and the abrasive are contained in the same reservoir and provided to the surface from the same jet (nozzle). In yet another embodiment, the dopant is contained in one reservoir, the abrasive is contained in another reservoir, and a plurality of nozzles provide the dopant and the abrasive. The plurality of nozzles may be in the form of a jet within the jet, i.e., particles from each jet impact the surface at the same angle of incidence. In yet another embodiment, the plurality of nozzles are spatially separated to impact the surface at different angles of incidence while simultaneously hitting the same point on the surface.

  Figures 2a, 2b, and 2c are schematic diagrams of three different nozzle configurations that provide dopant and abrasive on the surface: a single nozzle (Figure 2a); multiple nozzles with separate dopant and abrasive From one reservoir, with one nozzle positioned within the other nozzle (FIG. 2b); and with multiple individual nozzles, dopant and abrasive are provided from another reservoir (FIG. 2c). More specifically, FIG. 2 a shows a single nozzle 20 for providing a single stream 23 of abrasive particles 24 and corrosion inhibiting dopant particles 26 to a substrate 28. FIG. 2b shows that multiple nozzles and dopants and abrasives provided from separate reservoirs can be used, and FIG. 2b shows the abrasiveness located in the nozzle 40 that provides a stream 43 of corrosion inhibiting dopant particles 26. Illustrated is a nozzle 30 that provides a stream 33 of particles 24, where streams 33 and 43 are coaxial streams. As shown in FIG. 2c, a plurality of individual nozzles and dopants and abrasives provided from separate reservoirs can also be used, and FIG. 2c shows the abrasive particles 24 and the corrosion-inhibiting dopant particles 26, respectively. Nozzles 30 and 40 providing streams 33 and 43 are shown.

  The distance D between the nozzle (s) and the substrate surface may be in the range of 0.1 mm to 100 mm, for example in the range of 0.1 mm to 50 mm, or in the range of 0.1 mm to 20 mm. The angle of the nozzle relative to the surface may be in the range of 10 degrees to 90 degrees, such as 30 degrees to 90 degrees, or 70 to 90 degrees.

  One or more dopant species may be used. It is readily understood that when more than one dopant is used, the dopant may be provided from a single nozzle, or each type may be provided from a separate nozzle.

  As shown in FIG. 3, the layer 52 of corrosion inhibiting material can be used as a final surface finish that functions as a corrosion resistant layer of the substrate 8. As described above, such a corrosion resistant layer 52 may be formed as a conversion coating on the surface of the substrate 8 or may be formed as a layer that is mechanically bonded to the substrate 8.

  Alternatively, as shown in FIG. 4, the corrosion protection layer 52 may be further coated with one or more additional coating layers 54 to improve surface corrosion resistance (and / or scratch-resistance). . Such one or more additional layers may be applied by spraying, painting, dipping, vapor deposition, or any suitable method for applying subsequent layers. The anticorrosion material 52 functions as a primer to which such an additional layer 54 can adhere, thus improving the adhesion of the subsequent layer 54 to the substrate metal 8. Adjusting the abrasive properties, dopant properties, or blasting conditions can alter the surface shape and interfacial chemistry of the deposited layer of the corrosion resistant material 52, and thus the primer surface to provide improved primer performance. Can be optimized.

Applications of the above techniques to form corrosion protection coatings include (but are not limited to) providing corrosion protection to:
● Large-scale engineering elements such as pipe sections ● Wind turbine elements ● Civil engineering structures ● Exterior walls ● Marine elements ● Automotive vehicle goods ● Oil and gas industry elements ● Aerospace elements

[Embodiment in which an adhesion promoting coating is formed on or on the surface of a substrate (third modification)]
Similar to the above method for forming a corrosion-inhibiting coating, embodiments for forming an adhesion promoting coating are also included in the schematic diagrams shown in FIGS. 1a, 1b, and 1c, but are not limited thereto, in this case The dopant particles 6 contain adhesion promoting species. Particle sets 4 and 6 may be metallic in some embodiments, but in other embodiments non-metallic (eg, polymer or ceramic) so that the surface of substrate 8 is impregnated with adhesion promoting species. Or the surface 10 of the board | substrate 8 which may be a composite material is impacted.

  If the substrate 8 is metal, the surface 10 can also include a metal oxide layer. As a result of the impact by the abrasive particles 4, the oxide layer on the surface is destroyed, and the breakthrough in the oxide layer 10 exposes the new surface 10a of the substrate 8 (FIG. 1b). In the case of a metal substrate, the newly exposed surface is a metal surface. As the particle stream 3 subsequently strikes the substrate 8, the adhesion promoting dopant particles 6 are integrated into the surface 10 of the substrate 8 (FIG. 1c). Such destruction of the oxide layer to produce a newly exposed metal surface is particularly applicable when a chemical or electrochemical reaction is caused between the dopant and the substrate species. Allow the substrate metal to react (instead of the surface oxide layer). However, the breakdown of the oxide layer is also advantageous when the adhesion promoting coating is mechanically bonded to the substrate 8.

  Similar to the above method, three possible different nozzle configurations are schematically illustrated in FIGS. 2a, 2b and 2c.

  A chemical or electrochemical reaction can occur between the adhesion promoting species and the substrate material, resulting in the formation of an adhesion promoting conversion coating on the surface of the substrate 8.

  Alternatively, some of the adhesion promoting dopant particles are mechanically interlocked with the surface of the substrate, and the surface is roughened by the action of abrasive particles to form an adhesion promoting coating that is mechanically bonded to the surface of the substrate. Can be done.

  Formation of the adhesion promoting coating may include a combination of both conversion coating and mechanical bonding of the dopant particles to the surface of the substrate.

  With respect to the third variant, during the deposition process, the deposited dopant particles are subjected to continued abrasive particle bombardment, and the dopant particles are repeatedly driven onto and into the surface of the substrate, resulting in adhesion promotion. The substrate and dopant species are intimately mixed to create a high degree of bonding and interlock between them so that the coating does not result in a dopant laminate layer.

  FIG. 5 shows a schematic cross-sectional view of a substrate 8 having an adhesion promoting coating 56 formed as a conversion coating on the surface of the substrate or formed as a mechanically bonded coating on the surface of the substrate.

  Optionally, in certain embodiments, adhesion promoting coating 56 is deposited in an uncured or semi-cured state for curing in another step using heat, radiation, moisture, etc. prior to subsequent coating application. May be. Such curing can be performed in a site-limited manner (eg, using localized infrared curing).

  An adhesion promoting coating 56 may be provided to improve the adhesion of the substrate 8 to another material or article that the coated substrate will later contact. That is, the creation of the adhesion promoting coating 56 may be the only surface treatment process performed on the substrate.

  However, as shown in FIG. 6, the adhesion promoting coating 56 may instead function as a primer layer to which additional coatings 58 (or multiple subsequent coatings) may be applied later. The coating 58 can be, for example, an anti-scratch coating, or an anti-corrosion coating (which prevents corrosion of the underlying substrate 8), or a non-stick coating such as low friction or polytetrafluoroethylene (PTFE), or the underlying substrate 8 It may be an adhesive layer that adheres and bonds to another article. In other embodiments, the coating 58 may include other types of fluoropolymer layers, paint layers (eg, epoxy layers), ceramic coatings, and the like. Subsequent fluoropolymer layers can be applied to minimize unwanted scale, debris, asphaltene, paraffin, or dirt accumulation and deposition that can impair the operation of the underlying substrate. As such a fluoropolymer layer, a fluoropolymer primer such as PTFE has been found to be particularly advantageous in order to allow a thick fluoropolymer coating to be effectively adhered to the underlying substrate. This was surprising because the first fluoropolymer layer impregnated on the substrate was expected to function as a release layer that minimizes adhesion of subsequent layers. In contrast, it was found that the later fluoropolymer coating adhered to the fluoropolymer primer layer, and the presence of the primer layer improved the adhesion of the later layer. This process can be further improved by heating the multi-layer structure so that the fluoropolymer layers coalesce thermally. Such a coating has been found to be of great advantage when applied to the inner surface of the pipe, where it reduces corrosion and reduces maintenance requirements.

  Optionally, in certain embodiments, a subsequently applied coating 58 may be deposited in an uncured or semi-cured state for curing in another step using heat, radiation, moisture, and the like. Such curing may be performed in a site-limited manner (eg, using infrared curing).

Applications of the above techniques for the formation of adhesion promoting coatings or primer layers include (but are not limited to):
● Improved adhesion of protective coatings to the inner and outer surfaces of pipes to minimize scale buildup or to minimize corrosion ● Glue to metal elements for improved bond strength ● Improved adhesion of protective coatings for use in marine, aerospace, or industrial applications ● Improved adhesion of anti-scratch coatings ● “Non-stick” (Non-stick) "coating formation, such as utensils, pots, or other items used for cooking food (home and industrial) to prevent food sticking during cooking Formation on the article. For such applications, the non-stick coating is bonded to the substrate using a primer layer and may include a fluoropolymer such as PTFE.
● In a mold release application, that is, use of a mold, a non-stick coating is formed on the inner surface of the mold (usually the mold is made of metal) to facilitate removal of the molded article from the mold. The non-stick coating is bonded to the mold surface using a primer layer and may include a fluoropolymer such as PTFE. Molds coated in this way have a number of possible applications including vehicle tires, engineering elements, consumer products and the like.
• Treatment of engineering element surfaces that require a low coefficient of friction by using a primer layer to bond a low friction coating (eg, including a fluoropolymer such as PTFE) to the engineering element surface.
● An adhesive coating is formed on the substrate to improve the degree of bonding application, that is, the bonding between the substrate and another material or article that the coated substrate will later contact. For example, it can be treated with a binder to improve the extent to which the metal wire is bonded to rubber (in such a case, the wire is the substrate). Such a wire can then be used, for example, in the manufacture of vehicle tires, and the wire is wrapped in rubber to reinforce the tire.
● Improved general bonding of metals to composites and plastics.

Examples of Abrasive Species Abrasive species that can be used in this method (as a different second particle set provided at substantially the same time as the first, particle set comprising a dopant) are not limited to this, Silica, sand, alumina, zirconia, barium titanate, calcium titanate, sodium titanate, titanium oxide, glass, biocompatible glass, diamond, silicon carbide, boron carbide, dry ice, boron nitride, calcium phosphate, calcium carbonate, metal Or a shot or grit formed of carbon powder composite, carbon fiber composite, polymer composite, titanium, stainless steel, hardened steel, carbon steel chromium alloy, or any combination thereof.

  Preferably, the abrasive particles have a Mohs hardness of at least 7.

  The abrasive particles preferably have an average particle size (diameter) in the range of 1 μm to 150 μm, more preferably 10 μm to 150 μm, and particularly preferably 50 μm to 150 μm. By using such small abrasive particles, the destruction of the surface of the substrate is improved, so that the penetration of the dopant particles into the surface of the substrate is promoted, and the intermixing between the substrate surface and the dopant particles is promoted. Thus, the dopant species are impregnated into the substrate so that a dopant laminate layer does not occur.

Examples of corrosion-inhibiting dopant species For the first and second variants described above, the corrosion-inhibiting dopant species that can be used in the method (as a first particle set different from the second particle set) are not limited to these. , Chromates, phosphates, polymers (eg thermosetting or thermoplastic), oxides or nitrides. For example, the dopant may be ceria. In certain preferred methods, the coating is derived from a phosphate compound. The phosphate may include iron phosphate, manganese phosphate, zinc phosphate, or combinations thereof. Since phosphate is not deposited by an electrochemical process, various materials can be incorporated into the surface by changing the starting dopant powder.

  Of particular note is that the corrosion inhibiting dopant species need not be a sacrificial metal or metal salt. A polymer-based dopant that forms a stable deposit on the surface of the substrate, prevents the accumulation of corrosive substances on the surface, or prevents corrosion by physically isolating the corrosive species from the underlying substrate. Can be deposited. Fluoropolymer based, acrylate based, acetic acid (acetate) based and epoxy based layers can all perform this function.

  The dopant particles preferably have an average particle size (diameter) in the range of 1 μm to 100 μm.

  Preferably, the weight ratio of dopant particles to abrasive particles is between 20:80 and 80:20, particularly preferably between 40:60 and 60:40.

Examples of adhesion promoting dopant species For the third variation, the adhesion promoting dopant species that can be used in the method (as the first particle set different from the second particle set) are not limited to these, such as PTFE, etc. Fluoropolymers, perfluoroalkoxy materials such as Teflon, polyvinylidene fluoride, perfluoropolyethers, fully fluorinated elastomers, and polyvinyl fluoride. It may also include materials containing silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compounds, or vinyl, peroxyester, peroxide, acetate, or carboxylate functional groups.

  In certain instances, when forming an adhesion promoting coating that functions as a primer layer for a polymer-based subsequent layer, the primer layer may be composed of the same material that is present in the subsequent layer. Good. PTFE or other fluoropolymer may be used as a primer-forming dopant species to improve adhesion of subsequent fluoropolymer layers.

  The dopant particles preferably have an average particle size (diameter) in the range of 1 μm to 100 μm.

  Preferably, the weight ratio of dopant particles to abrasive particles is between 20:80 and 80:20, particularly preferably between 40:60 and 60:40.

Examples The following examples include the use as a primer layer and illustrate the use and efficacy of the above method in forming corrosion protection coatings and adhesion promoting coatings.

Example 1: Zinc phosphate deposition on various metal substrates (aluminum, copper, grade 2 and grade 5 titanium, hastelloy, inconel, magnesium, mild steel, stainless steel (316)), aluminum, copper, grade 2 and grade 5, respectively. A series of metal substrates made from titanium, hastelloy, inconel, magnesium, mild steel, and stainless steel (316) were obtained. Zinc phosphate powder (<5 micron average particle size) was mixed with alumina grit (100 micron average particle size) at an even volume fraction and loaded into an Accuflow powder feeder. The powder is supplied to a grit blast nozzle from which it is moved across the surface of the metal substrate, and the powder is blasted to the surface at a pressure of 75 psi. After blasting, the substrate is cleaned with compressed air to remove loose powder. All of the treated samples were found to have a significant level of zinc phosphate deposited on the surface. Surface characterization was performed by SEM and EDX analysis. EDX was used to determine the coating concentration by measuring and adding the Zn and P concentrations. A moderate (> 30%) zinc phosphate coverage was observed on all tested surfaces, confirming that the abrasive blasting process was able to efficiently deposit corrosion protection materials. Inspection of the deposited corrosion protection material suggested that it was formed by a combination of both a chemical conversion process and a mechanical bond. Since the surface oxide was removed, zinc phosphate was bound to the surface as in the case of the conversion coating, but some mechanical interlocking was also observed as a result of the impact process.

Example 2: Mild Steel Corrosion Protection Mild steel coupons and buttons were blasted with a mixture of zinc phosphate powder and alumina grit. After deposition, the samples were analyzed using EDX, and both types of treated samples were found to have about 40% zinc phosphate on the surface. The coated sample was then immersed in a 3.5% w / w NaCl solution. Untreated mild steel coupons and buttons were used as controls. After 72 hours, the untreated steel sample was visibly discolored and the sample container had a significant accumulation of brown precipitate that had settled to the bottom of the jar. Samples treated with zinc phosphate showed no visible change to the initial state. There was no evidence of any signs of deposition, discoloration, or other corrosion. The test continues until 7 days, while untreated samples continue to deteriorate, while samples blasted with zinc phosphate do not change much, thus confirming the protective corrosion protection properties of abrasive blasting. It was.

Example 3: Primer for epoxy paint Mild steel (grade SAE 1008) was used as a sample for all. The following surface treatment was then applied to some samples.
● Raw blank sample (that is, as-received)
● Grit blasting (as per ISO8501-1, based on Sa2 (1/2))
● Iron phosphate (Henkel Bonderite M-FE 1000 from Q-Panel)
● Zinc (Meath Metal, “Tri-eco Zinc” from Ireland)
● Commercial dry zinc phosphate primer (Johnstones)
● Pre-mixed dry zinc phosphate powder (supplied by Delaphos) and two powders of zinc phosphate produced by blasting metal with 100 micron alumina, pressure 75 psi through the De Laval nozzle to the surface It is blasted with.

  Each element is then coated with an SP320 two-part epoxy laminate obtained from www.UnionChandlery.ie. This particular paint provides a clear coat that allows observation of rust / corrosion growth from the introduced scratch.

  Corrosion tests were performed using a neutral salt spray cabinet as per ISO 9227. As per ISO 18782, a “T” scribe was introduced into each sample using a carbide tip. Over the test period, each sample was periodically removed and photographed to record corrosion growth from scratch. The sample was washed in deionized water to remove excessive rust / corrosion on the sample before taking a picture. The width / growth of corrosion from scratch was measured with the free public imageJ software. Each coupon was removed from the salt spray cabinet at predetermined intervals over a period of 56 days. Corrosion width was measured using imageJ software. The scale was adjusted with a steel ruler.

  Somewhat surprisingly, the performance of the “iron phosphate” and “zinc-plated” samples was not good. In particular, the galvanized sample showed significant delamination of the epoxy paint after 28 days and a complete catastrophic failure occurred after 56 days.

  Blank coupons and grit blast coupons initially performed well and the superficial results were identical to those of the zinc phosphate coating. However, when cut and inspected in detail, this sample proved to be more corroded against any of the zinc phosphate treatments. Both zinc phosphate treatments were significantly superior to other commercial treatments. The blasted zinc phosphate tie layer was very close to the performance of commercial dry zinc phosphate primer (which utilized a significantly thicker coating).

Example 4: Primer for fluoropolymer adhesion Four 3 "x5" mild steel Q-panels were pretreated with the following abrasive blasting process.
(I) Two were 100: micron alumina with a weight ratio of 80:20 and PTFE (Zonyl MP 1300) and blasted using a standoff distance of 40 psi and 30 mm.
(Ii) The other two were blasted with alumina only under the same conditions.

  All samples were then washed with deionized water, dried with compressed air, and given a subsequent coating of PTFE fluoropolymer. PTFE was sprayed from a 150 mm stand-off at 2 psi. In order to obtain a thick coating, it was necessary to run the surface three times. All samples were then heated to 400 ° C. in a carbolite furnace and air cooled.

  The adhesion test was then performed using a modified version of ISO 2409.

  This aggressive version of ISO 2409 used a more advanced “tack” tape (tesa 4613) due to the weak adhesion between the standard scotch tape and the PTFE coating and repeated tape tensions. Prior to cutting, the sample was boiled in DIW for 20 minutes, completely dried and cooled. Cutting was performed with a multi-blade cutter at 2 mm intervals as per ISO 2409. For each coating, four separate areas were tested and tape tension was repeated four times in each test area. According to the ISO classification up to level 5, such as 0 for samples that did not break in the tape test, 1 for surfaces with 5% or less separation, 2 for surfaces with 5-15% separation, etc. .

  After one tape test, the sample prepared using the abrasive blast pretreatment gave a value of 1, but the sample blasted with both abrasive and PTFE showed no effect, Classified as 0. After performing four tape tests on the same area, abrasive blasted samples were classified in levels 2-4, while samples blasted with both abrasive and PTFE remained in the 0 or 1 classification. It was shown that the adhesion was significantly improved by the PTFE primer.

  After this, the samples were cut, mounted, polished and observed with a light microscope. The coating thickness in each sample was measured at 5 points at a magnification of 10 × and the two coatings yielded a thickness of 43 microns and were in agreement. There was no visible interface between the PTFE primer layer and the topcoat, indicating complete bonding.

Example 5: Improved bonding of adhesive to metal element In this case, the substrate was grade V titanium. Five different surface treatments were adhesion tested. this is,
(i) Untreated titanium, the following is called blank.
(ii) A grit blasted titanium surface produced by abrasive blasting titanium with 50 micron alumina.
(iii) Commercial aerospace primer This follows the Chromic Acid Anodized (CAA) surface and includes the Cytec BR127 Solgel primer. This is referred to as “CAA + primer”.
(iv) A surface produced by blasting titanium with a mixture of alumina and a thermosetting epoxy (LT3366) (referred to as "epoxy") from Huntsman.
(v) Surface produced by blasting titanium with a mixture of alumina and zinc phosphate powder (Heubach ZP10)

  All samples were then bonded to carbon fiber reinforced plastic (CFRP). The CFRP was Hexcel 8552 / 5H, prepared for bonding using a wet peel ply (Henkel Hysol EA9895). The adhesive was Cytec FM300 epoxy film adhesive (0.03 gsm weight) and was cured at 177 ° C. for 1 hour at 45 psi pressure.

  Once the adhesive was fully cured, the sample was cooled to room temperature and lap shear tested according to ISO 2243-1. The specimens had a 25 mm wide and 12.5 mm adhesive overlap. Lap shear strength was calculated by dividing the strength at failure by the overlap area. Four iterations were performed for each surface treatment.

  The results of this test are shown in FIG. All surface treatments exceeded the performance of the untreated blank. Simply roughing with an alumina abrasive was sufficient to significantly increase adhesion, but interface failure occurred in both the untreated and grit blast joint systems. However, the deposition of chemical primers was much more successful and all three chemical primers showed a cohesive failure mode. Both zinc phosphate and epoxy dopants significantly improved joint adhesion and performed as well as commercial aerospace primers. It should be noted that the abrasive blasting method was able to achieve this level of performance without the use of toxic chromate conversion coatings or aggressive wet chemical primers.

Examples of industrial application fields
The method is applicable in a wide range of industries, including but not limited to large engineering elements such as pipe sections, wind turbine elements, civil engineering structures, outer walls, marine elements, automobile vehicles Includes goods, petroleum and gas industry elements, and aerospace elements.

Claims (73)

A method of processing a metal substrate, comprising:
A first particle set including a dopant and a second particle set including an abrasive are impregnated onto the surface of the metal substrate substantially simultaneously from at least one fluid jet and the surface of the metal substrate is impregnated with the dopant. Including providing for
The method, wherein the dopant includes a corrosion-inhibiting species so as to form a corrosion-inhibiting conversion coating on the surface of the metal substrate.   The method of claim 1, wherein the corrosion-inhibiting species is chemically bonded to the substrate. A method of processing a metal substrate, comprising:
A first particle set including a dopant and a second particle set including an abrasive are impregnated onto the surface of the metal substrate substantially simultaneously from at least one fluid jet and the surface of the metal substrate is impregnated with the dopant. Including providing for
The method wherein the dopant comprises a corrosion inhibiting species that forms a corrosion inhibiting coating that is mechanically bonded to the surface of the metal substrate.   The method according to claim 1, wherein the anticorrosion coating has a property such that a laminate layer of the dopant does not occur.   Abrasive blasting of the metal oxide from the surface of the metal substrate with the second particle set substantially simultaneously with the supply of the first particle set to expose the metal surface. 5. The method according to any one of claims 1 to 4, further comprising a step of removing by.   The method according to claim 1, wherein a pretreatment process is not performed prior to the supply of the first particle set and the second particle set.   The method of any of claims 1-6, wherein the corrosion protection coating forms a first layer and the method further comprises applying a second layer to the first layer.   8. The method of claim 7, wherein the first layer functions as a primer to improve the adhesion of the second layer.   9. A method according to claim 7 or 8, wherein the second layer is an anti-scratch layer.   10. A method according to any one of claims 7 to 9, wherein the second layer is an additional corrosion protection layer.   The method according to claim 1, wherein the corrosion-inhibiting species comprises chromate, phosphate, polymer, oxide, or nitride.   The method of claim 11, wherein the corrosion-inhibiting species comprises a transition metal phosphate.   The method of claim 12, wherein the corrosion-inhibiting species comprises iron phosphate, manganese phosphate, or zinc phosphate, or a combination thereof.   The method of claim 11, wherein the corrosion-inhibiting species comprises cerium oxide. A method of processing a substrate, comprising:
In order to impregnate the surface of the substrate with the first set of particles comprising a dopant and the second set of particles comprising an abrasive material from at least one fluid jet substantially simultaneously on the surface of the substrate. Including the step of providing,
The method, wherein the dopant comprises an adhesion promoting species so as to form an adhesion promoting coating at or on the surface of the substrate.   The method of claim 15, wherein the adhesion promoting species forms a conversion coating on the surface of the substrate.   The method of claim 16, wherein the adhesion promoting species is chemically bonded to the substrate.   The method of claim 15, wherein the adhesion promoting species forms an adhesion promoting coating that is mechanically bonded to the surface of the substrate.   The method according to any one of claims 15 to 18, wherein a pretreatment process is not performed before the supply of the first particle set and the second particle set.   The method according to any one of claims 15 to 19, wherein the adhesion promoting species forms a primer layer on the substrate.   21. The method of claim 20, wherein the adhesion promoting species comprises a fluoropolymer such as PTFE, a perfluoroalkoxy material such as Teflon, polyvinylidene fluoride, perfluoropolyether, perfluorinated elastomer, or polyvinyl fluoride.   22. The adhesion promoting species comprises silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound, or a material comprising one or more vinyl, peroxyester, peroxide, acetate, or carboxylate functional groups. The method described in 1.   23. A method according to any of claims 20-22, wherein the primer layer forms a first layer and the method further comprises applying a second layer to the first layer.   24. The method of claim 23, wherein the second layer is an anti-scratch layer.   24. The method of claim 23, wherein the second layer is a corrosion protection layer.   24. The method of claim 23, wherein the second layer is an adhesive layer.   24. The method of claim 23, wherein the second layer is a solid low friction layer.   24. The method of claim 23, wherein the second layer is a non-stick layer.   20. The adhesion promoting species comprises silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound, or a material comprising one or more vinyl, peroxy ester, peroxide, acetate, or carboxylate functional groups. The method in any one of.   30. A method according to any of claims 15 to 29, wherein the adhesion promoting coating has a property such that a laminate layer of the dopant does not occur.   Abrasive blasting the metal oxide from the surface of the substrate with the second set of particles substantially simultaneously with the supply of the first set of particles to expose the metal surface. 31. A method according to any of claims 15 to 30, further comprising the step of removing by.   32. A method according to any of claims 1-31, wherein the second set of particles has an average particle size in the range of 1 [mu] m to 150 [mu] m.   33. The method of claim 32, wherein the second set of particles has an average particle size in the range of 10 [mu] m to 150 [mu] m.   34. The method of claim 33, wherein the second set of particles has an average particle size in the range of 50 [mu] m to 150 [mu] m.   35. A method according to any of claims 1-34, wherein the first set of particles has an average particle size in the range of 1 [mu] m to 100 [mu] m.   36. A method according to any of claims 1-35, wherein the ratio of the first particle set to the second particle set is between 20:80 and 80:20 by weight.   37. The method of claim 36, wherein the ratio of the first particle set to the second particle set is between 40:60 and 60:40 by weight.   38. The method of claims 1-37, further comprising work hardening the surface of the metal substrate via the supply of the second particle set.   The method according to any one of claims 1 to 38, wherein compressive stress is introduced into the surface of the metal substrate via the supply of the second set of particles.   40. The method of any of claims 1-39, wherein the first particle set and the second particle set are supplied without the use of a carrier fluid. A method of processing a substrate, comprising:
In order to impregnate the surface of the substrate with the first set of particles comprising a dopant and the second set of particles comprising an abrasive material from at least one fluid jet substantially simultaneously on the surface of the substrate. Including the step of providing,
The method, wherein the dopant comprises a corrosion-inhibiting or adhesion-promoting species so as to form a corrosion-inhibiting coating or adhesion-promoting coating on or on the surface of the substrate.   An article comprising a metal substrate having a corrosion-inhibiting conversion coating, wherein the conversion coating comprises particles of corrosion-inhibiting species impregnated on the surface of the metal substrate.   43. The article of claim 42, wherein the corrosion-inhibiting species is chemically bonded to the substrate.   An article comprising a metal substrate having a corrosion-resistant coating that is mechanically bonded, wherein the mechanically-bonded coating includes particles of corrosion-inhibiting species impregnated on the surface of the metal substrate. , Goods.   45. An article according to any of claims 42 to 44, wherein the article does not have a laminate layer of the corrosion-inhibiting species.   46. The article of any of claims 42-45, wherein the corrosion protection coating forms a first layer, and the article further comprises a second layer disposed on the first layer.   47. The article of claim 46, wherein the first layer functions as a primer for improving the adhesion of the second layer.   48. The article of claim 46 or 47, wherein the second layer is an anti-scratch layer.   49. An article according to any of claims 46 to 48, wherein the second layer is an additional corrosion protection layer.   50. The article of any of claims 42-49, wherein the corrosion-inhibiting species comprises chromate, phosphate, polymer, oxide, or nitride.   51. The article of claim 50, wherein the corrosion inhibiting species comprises a transition metal phosphate.   52. The article of claim 51, wherein the corrosion-inhibiting species comprises iron phosphate, manganese phosphate, or zinc phosphate, or a combination thereof.   51. The article of claim 50, wherein the corrosion-inhibiting species comprises cerium oxide.   An article comprising a substrate having an adhesion promoting coating thereon, wherein the adhesion promoting coating comprises particles of adhesion promoting species impregnated on a surface of the substrate.   55. The article of claim 54, wherein the adhesion promoting species is chemically bonded to the substrate.   55. The article of claim 54, wherein the adhesion promoting species is mechanically coupled to the substrate.   57. The article according to any of claims 54 to 56, wherein the article does not have a laminate layer of the adhesion promoting species.   58. The article of any of claims 54 to 57, wherein the adhesion promoting coating functions as a primer layer on the substrate.   59. The article of claim 58, wherein the adhesion promoting species comprises a fluoropolymer such as PTFE, a perfluoroalkoxy material such as Teflon, polyvinylidene fluoride, perfluoropolyether, perfluorinated elastomer, or polyvinyl fluoride.   60. The adhesion promoting species comprises a silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound, or material comprising one or more vinyl, peroxyester, peroxide, acetate, or carboxylate functional groups. Articles described in 1.   61. The article of any of claims 58-60, wherein the primer layer forms a first layer, and the article further comprises a second layer disposed on the first layer.   62. The article of claim 61, wherein the second layer is an anti-scratch layer.   62. The article of claim 61, wherein the second layer is a corrosion protection layer.   62. The article of claim 61, wherein the second layer is an adhesive layer.   62. The article of claim 61, wherein the second layer is a solid low friction layer.   62. The article of claim 61, wherein the second layer is a non-stick layer.   58. The adhesion promoting species comprises a silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound, or material comprising one or more vinyl, peroxyester, peroxide, acetate, or carboxylate functional groups. The article according to any one of the above.   68. The article of any of claims 42 to 67, wherein the substrate is a metal and the microstructure of the surface of the metal substrate indicates work hardening.   69. The article of any of claims 42 to 68, wherein the surface of the substrate is under an inherent compressive stress.   42. An article comprising a substrate having a corrosion inhibiting coating or adhesion promoting coating produced by the method of any of claims 1-41. Large-scale engineering elements such as pipe sections,
Wind turbine elements,
Civil engineering structure,
outer wall,
Marine elements,
Automobile vehicle goods,
71. An article according to any of claims 42 to 70, which is at least part of an element of the petroleum or gas industry, or an aerospace element.   A method of processing a substrate described and illustrated with reference to substantially any combination of the accompanying drawings.   An article comprising a substrate having a corrosion protection coating or adhesion promoting coating, described and illustrated with reference to substantially any combination of the accompanying drawings.

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