阅读说明：本技术 一种金属表面微织构及强粘接性聚合物润滑层制备方法 (Preparation method of metal surface micro-texture and strong-adhesion polymer lubricating layer ) 是由 张国亮 王燕霜 宁飞浪 杨立军 王而强 徐龙涛 于 2019-03-06 设计创作，主要内容包括：通过不同表面处理工艺,如：喷砂、激光加工、阳极氧化等,调控金属表面凹凸阵列,并采用过渡金属溶液反应处理表面微结构空间产生聚合物聚合催化活性位,构筑金属表面催化转化层,为聚合物润滑层原位聚合提供反应空间。同时,使用金属表面改性剂多取代基多巴胺分子,该改性剂具有羟基(-OH)聚合官能团及胺基与季胺(-NH、-NH-、=N-)固化官能团,研究该化合物在酸碱度(pH=4-9)与氧气条件下,经金属表面催化层诱导形成界面粘附层。基于改性剂的聚合官能团,与环氧分子官能共聚反应产生交联网络键合结构,该工艺克服了传统环氧单体聚合物与外加固化剂反应的形成润滑层的低粘附强度、不均匀或易脱落的难题,可用于制备金属表面界面强粘接性润滑层,为金属表面的耐磨防护提供一种新方法。(By different surface treatment processes, such as: sand blasting, laser processing, anodic oxidation and the like, regulating and controlling the concave-convex array on the metal surface, adopting a transition metal solution to react and treat the surface microstructure space to generate a polymer polymerization catalytic activity site, constructing a metal surface catalytic conversion layer, and providing a reaction space for in-situ polymerization of a polymer lubricating layer. Meanwhile, a polysubstituted dopamine molecule of a metal surface modifier is used, the modifier is provided with a hydroxyl (-OH) polymerization functional group and an amino and quaternary amine (-NH, -NH-, = N-) curing functional group, and the compound is researched to form an interface adhesion layer through the induction of a metal surface catalysis layer under the conditions of pH value (pH = 4-9) and oxygen. The process overcomes the problems of low adhesion strength, non-uniformity or easy falling of the lubricating layer formed by the reaction of the traditional epoxy monomer polymer and an external reinforcing agent, can be used for preparing the lubricating layer with strong bonding property on the metal surface interface, and provides a new method for wear-resistant protection of the metal surface.)

1. A preparation method of a metal surface micro-texture and strong-adhesion polymer lubricating layer is characterized by comprising the following steps: the method for preparing the microtexture comprises the steps of treating the metal surface by adopting different surface texture processes such as sand blasting, laser etching, anodic oxidation and the like, then immersing the metal surface into a transition metal solution, and activating the concave-convex microspace of the metal to form a catalytic conversion layer and a micro-scale rough active site.

2. The method comprises the following specific steps:

firstly, early preparation: preparing a material sample and related equipment, and pretreating the metal surface: oil removal, rust removal, scale removal and the like; preparing a catalytic activity solution: 100-200 g/L of nickel sulfate, 50-100 g/L of cobalt sulfate, 40-60 g/L of ruthenium chloride, 5-40 g/L of boric acid and deionized water as a solvent;

secondly, surface texture technology: a sand blasting process, wherein the granularity of alumina abrasive particles is about 100-300 mu m, the pressure of a nozzle outlet of a sand blasting machine is 0.7-2.0 MPa, the distance between the nozzle and a sample is 30-60 mm, after the acid etching process is finished, the sample is cleaned by distilled water and dried for 30 min at 100-120 ℃; laser photoetching, wherein a nanometer laser is used, the pulse energy is 2-14 mJ, the average power of the laser is adjusted to be 4-36W, the opening and closing of a gate are set, and the moving platform is controlled by a computer to enable the laser to form interference fringes on the surface of a sample; closing the pulse laser system, taking out the sample, and drying for 30 min at the temperature of 60-100 ℃; an anodic oxidation process, which uses aluminum alloy as a material and regulates and controls the current density to be 1.4-2.0A/m²The concentration of sulfuric acid is 50-200 g/L, the concentration of aluminum ions is 8-10 g/L, the oxidation time is 25-30 min, the temperature of electrolyte is 25-30 ℃, after oxidation is finished, distilled water is used for washing for several times, and drying is carried out for 30 min at the temperature of 60-100 ℃;

thirdly, dipping: the pH value range of the catalytic active solution is 0.4-8, the dipping time is 12-24 h, dipping is increased, the sample is taken out for times, and the sample is naturally dried.

3. Based on the fact that the surface concave-convex array is used as a space, the metal performance is organically modified by using polysubstituent dopamine molecules of the surface adhesive, and the metal surface bifunctional catalytic-crosslinking composite coating is obtained, so that the optimization of the interface adhesion characteristic of the metal surface lubricating layer is realized.

4. The method of claim 2, wherein the polysubstituted functional groups of the dopamine adhesive are hydroxyl (-OH) functional groups, amine groups and quaternary amine (-NH) functional groups₂-NH-, = N-) curing functional groups.

5. The method for preparing a lubricating layer with strong surface adhesion according to claim 2, wherein the catalytic-crosslinking composite plating layer is a catalytic layer composed of active elements such as nickel, cobalt and ruthenium, and an adhesion layer composed of an adhesive dopamine.

6. A method of forming a highly adherent lubricating layer on a surface as claimed in claim 2, wherein the dopamine adherent is reacted with a catalyst to form a plurality of intermediates comprising:

and fifthly, mixing the intermediate with an epoxy polymer monomer to perform ring-opening polymerization reaction.

7. The method for forming a highly adhesive surface lubricating layer according to claim 5, wherein the epoxy-based polymer monomer comprises a bisphenol A-type epoxy compound, a brominated bisphenol A-type epoxy compound, and a phenol-type epoxy compound.

8. A lubricating layer with strong adhesion on the metal surface, which is prepared by the method for preparing the lubricating layer on the metal surface according to claim 6.

Technical Field

The invention belongs to the technical field of solid lubrication, and particularly relates to a metal surface strong-adhesion lubricating layer and a preparation method thereof.

Background

The oil resource reserves in the east of China are reduced, and the land deep oil reservoir in the Chinese and western China becomes the main battlefield for oil field development. Aiming at complex stratum conditions in the middle and western part, drilling and production technologies such as a highly deviated well, a highly displaced well, a cluster well and the like are rapidly developed, compared with the traditional straight well drilling technology, the drilling technology has the characteristics of long drilling period, large friction resistance, harsh working condition conditions and the like, and the self friction reduction characteristic of the traditional lubricating oil or lubricating grease is difficult to meet the specific requirements of the harsh working condition, so that drilling tools such as a casing and the like are seriously abraded.

In the process of developing a drilling tool in a deep oil and gas field, the working conditions are very complex, such as: high temperature (200-260 ℃), high formation pressure, high gas-liquid corrosion and the like, and the drilling tool material is required to have good performances of high temperature resistance, wear resistance, corrosion resistance, fatigue resistance and the like, even high-strength drill rod steel such as X-95, G-105, S-135 and the like cannot meet the specific working condition requirements.

In recent years, a lot of research is being conducted on the lubrication and wear resistance problems of metal materials such as special steel, aluminum alloy, and stainless steel, and surface modification and coating are more. The methods for improving the wear resistance of the metal surface are mainly divided into three categories: (1) the surface treatment improves the wear resistance, and the main research methods comprise: surface carburization, nitriding and the like, but carburization and nitriding layers are thin, and the service life of a lubricating layer is limited; (2) the surface self-assembled film, the coating and the grease lubricating layer generate abrasion resistance reduction resistance, but the uniformity and the timeliness of the lubricating layer need to be improved. (3) The surface of the material is constructed with a polymer-based, ceramic-based or composite material protective layer, which can generate solid self-lubricating property, but the problems of protective layer shedding, abrasive wear and the like need to be overcome; obviously, realizing high-efficiency service performance of metal materials under severe working condition environments is a long-term objective, and creating a polymer composite protective layer with strong adhesion and excellent self-lubricating property on the metal surface is not slow enough.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a multifunctional protective layer integrating strong interface adhesion, self-repairing and self-lubricating functions and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

a metal surface microtexture and strong adhesive polymer lubricating layer comprises the following parts:

the metal surface microtexture comprises surface sand blasting, laser etching and anodic oxidation processes,

the adhesive contains dopamine molecule monomer with polyfunctional group,

polymeric lubricating layer, epoxy group-containing polymeric monomer

A preparation method of a metal surface micro-texture and strong-adhesion polymer lubricating layer comprises the following steps:

(1) carrying out pretreatment processes such as oil removal on a bearing steel sample with a certain size, adjusting parameters such as abrasive particle size, nozzle outlet pressure of a sand blasting machine, distance between a nozzle and the sample, and the like to obtain proper surface roughness, and carrying out aftertreatment on the surface of the sample to finally obtain a metal surface with a microtexture;

(2) carrying out pretreatment processes such as oil removal and the like on a bearing steel sample with a certain size, selecting a nano laser, adjusting pulse energy, adjusting laser average power and other laser etching processes to finally obtain proper surface roughness, and carrying out aftertreatment on the surface of the sample;

(3) an anodic oxidation process, namely using aluminum alloy as a material, regulating and controlling current density, electrolyte sulfuric acid concentration, aluminum ion concentration, oxidation time, electrolyte temperature and other oxidation processes, and finally obtaining a proper surface porous morphology, and then cleaning a sample;

(4) preparation: dissolving nickel sulfate, cobalt sulfate, ruthenium chloride, boric acid and the like with certain mass in deionized water, and regulating and controlling proper pH to prepare a catalytic activity solution with certain concentration;

(5) soaking the metal plate with the surface microstructure obtained in the steps (1) to (3) in a catalytic activity solution at a certain temperature to finally obtain a metal surface catalytic layer;

(6) and (4) uniformly coating the sample obtained in the step (5) with dopamine molecular monomers, and keeping the sample at a certain temperature for 12 hours to obtain the metal surface adhesion layer. And then, coating a molecular polymer monomer with an epoxy group on the surface of the metal composite layer by using a spin coater, and carrying out in-situ polymerization for 8-16 h at a certain temperature to finally obtain the strong-adhesion composite lubricating layer.

Preferably, the sand blasting process in the step (1) is as follows: the granularity of the sand blasting machine is about 100-200 mu m, the pressure of the outlet of a nozzle of the sand blasting machine is about 0.7-1.0 MPa, and the distance between the nozzle and a sample is about 30-40 mm.

Preferably, the laser etching process in the step (2) is as follows: the pulse energy is about 8-10 mJ, and the average power of the laser is adjusted to about 10-20W.

Preferably, the anodic oxidation process in the step (3) is as follows: the current density is 1.4-1.8A/m²The concentration of sulfuric acid is 100-150 g/L, the concentration of aluminum ions is 8-10 g/L, the oxidation time is 30 min, and the temperature of the electrolyte is 30 ℃.

Preferably, the concentration of the catalytically active impregnation liquid in step (4) is: 110 g/L of nickel sulfate, 55g/L of cobalt sulfate, 58 g/L of ruthenium chloride and 35g/L of boric acid, and the pH value is about 1.5.

Preferably, the time and temperature of the impregnation in the step (5) are respectively: at 40 ℃ for 20 h.

Preferably, the in-situ copolymerization temperature of the adhesive and the epoxy molecules in the step (6) is 40-60 ℃, and the in-situ copolymerization time is 12 hours.

Detailed description of the preferred embodiments

The following examples are given to illustrate the present invention and it should be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that one of ordinary skill in the art would be able to make insubstantial adjustments and modifications to the present invention, including other types of surface microtexturing techniques and adhesives, to prepare strongly adherent lubricating layers at the interface.