Polymer micro-nano additive manufacturing method and system based on mechanochemical action

Abstract

The invention provides a polymer micro-nano additive manufacturing method and system based on mechanochemical action, and relates to the technical field of additive manufacturing. According to the polymer micro-nano additive manufacturing method based on the mechanochemical effect, friction contact is generated between a friction pair and a base material sample in a certain medium environment, and friction movement is carried out under a certain load and a certain sliding speed; and directional and quantitative growth of the polymer micro-nano structure is realized in a set movement track. According to the method for achieving negative abrasion through friction, the medium environment, the friction load and the sliding speed are controlled, the mechanochemical effect of a contact area is promoted, activation energy needed by polymer film forming is reduced, construction of the micro-nano structure is achieved in a preset movement track under friction chemical induction, the precision of the prepared micro-nano structure can reach the nanometer magnitude, and the performance of the micro-nano structure is improved. Meanwhile, the patterned micro-nano structure can be prepared on the base material through the design of the motion trail, so that further function expression is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of additive manufacturing, and in particular to a polymer micro-nano additive manufacturing method and system based on mechanochemical action. Background Art

[0002] Micro-nano additive manufacturing technology combines two cutting-edge fields of advanced manufacturing - micro-nano manufacturing and additive manufacturing. It can realize the controllable formation of microstructures and structures by manufacturing materials in layers and stacking them layer by layer in a "bottom-up" manner at the micrometer and nanometer scales. Different from traditional micro-nano manufacturing methods such as lithography, etching, laser micromachining, and focused ion beam, micro-nano additive manufacturing has multi-scale, multi-material, and multi-dimensional manufacturing capabilities. Therefore, as a disruptive new technology, it has become a key research direction.

[0003] The micro-nano additive manufacturing method based on mechanochemical action is a new type of green chemical preparation method. For most chemical syntheses, the reaction is carried out in solution, while mechanochemistry relying on mechanical force basically does not require solvents. It has low energy consumption, fast speed, and can basically react and synthesize a series of functional molecules quantitatively. It is a green, simple and efficient synthetic power. In recent years, researchers have realized a new means of micro-nano additive manufacturing by utilizing the formation of friction transfer film or friction chemical reaction film or negative wear phenomenon. For example, Kim et al. from Pennsylvania State University in the United States used pinene, pinane and n-decane as additives and polyalphaolefin (PAO) as base oil to achieve friction polymerization of small molecules on the steel surface through friction; in addition, Q. Jane Wang et al. from Northwestern University in the United States used cyclopropanecarboxylic acid (CPCa) or its analogues dissolved in polyalphaolefin base oil to form a lubricant, which can form an in-situ carbon film under moderate sliding conditions.

[0004] However, the micro-nano structures formed by the friction principle are random and uncontrollable, and it is impossible to achieve directional and quantitative formation of micro-nano structures at the microscopic scale. During the friction process, based on the driving effect of mechanochemistry, the polymerization of small molecules or the recombination of functional groups can be achieved, but how to achieve precise control and achieve nanometer-level precision is a difficulty that has not yet been solved in the above research. In addition, most of the micro-nano additive manufacturing systems currently studied are presented in the form of wear debris accumulation, which cannot be patterned and lacks functional expression. The above shortcomings result in the method of micro-nano additive manufacturing using friction far from meeting the requirements of practical applications. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a polymer micro-nano additive manufacturing method and system based on mechanochemical action. The method provided by the present invention can prepare patterned micro-nano structures, and the precision of the micro-nano structures can reach the nanometer level.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a polymer micro-nano additive manufacturing method based on mechanochemical action, comprising the following steps:

[0008] The friction pair is subjected to friction motion on the surface of the substrate according to a set motion trajectory, and a polymer micro-nano structure with a nanometer height is oriented and grown at the position of the motion trajectory;

[0009] During the friction movement, there is a lubricating liquid between the friction pair and the surface of the substrate, and the lubricating liquid is a polymerized monomer or includes a polymerized monomer and a lubricating oil; during the friction movement, the load is 0.01 to 3N, the sliding speed is 10 to 2000 μm / s, and the ambient temperature is 20 to 150°C.

[0010] Preferably, the friction pair is a spherical friction pair, and the diameter of the spherical friction pair is 0.1-3 mm.

[0011] Preferably, the friction pair is made of a material that has a catalytic effect on the growth of polymer micro-nano structures.

[0012] Preferably, the material of the substrate includes metal element, silicon, alloy, ceramic, polymer or ITO glass.

[0013] Preferably, when the lubricating liquid is a polymerized monomer, the polymerized monomer comprises pinene or cyclopropanecarboxylic acid.

[0014] Preferably, when the lubricating liquid comprises polymerized monomers and lubricating oil, the polymerized monomers comprise pinene, cyclopropanecarboxylic acid or cyclopropanedicarboxylic acid, and the mass fraction of the polymerized monomers in the polymerized monomers and the lubricating oil is ≥5%.

[0015] Preferably, during the friction movement, the relative humidity of the environment is 10-60%.

[0016] Preferably, the friction motion is a reciprocating friction motion, the reciprocating distance of the reciprocating friction motion is 100 to 2000 μm, and the friction cycle is 200 to 10,000 times.

[0017] Preferably, the height of the polymer micro-nano structure is 10 to 500 nm.

[0018] The present invention provides a polymer micro-nano additive manufacturing system based on mechanochemical action, comprising a friction pair, a substrate and a lubricating liquid. The lubricating liquid is a polymer monomer or comprises a polymer monomer and a lubricating oil. The lubricating liquid is used to be applied between the friction pair and the substrate surface.

[0019] The present invention provides a polymer micro-nano additive manufacturing method based on mechanochemical action, comprising the following steps: a friction pair is subjected to friction motion on the surface of a substrate according to a set motion trajectory, and a polymer micro-nano structure with a nanometer height is oriented and grown at the position of the motion trajectory; during the friction motion, there is a lubricating liquid between the friction pair and the surface of the substrate, and the lubricating liquid is a polymer monomer or includes a polymer monomer and a lubricating oil; during the friction motion, the load is 0.01-3N, the sliding speed is 10-2000μm / s, and the ambient temperature is 20-150°C. The present invention causes friction contact between the friction pair and the substrate sample in a certain medium environment (including lubricating liquid and ambient temperature), performs friction motion under a certain load and sliding speed, and realizes oriented (i.e., accurately controlling the formation and growth of the micro-nano structure at the position of the motion trajectory) and quantitative (referring to the growth height of the micro-nano structure) growth of the polymer micro-nano structure in the set motion trajectory. The present invention utilizes friction to achieve negative wear. By controlling the medium environment, friction load and sliding speed, the mechanochemical action in the contact area is promoted, the activation energy required for polymer film formation is reduced, and the construction of micro-nano structures is achieved in a preset motion trajectory under the induction of tribochemical factors. The precision of the prepared micro-nano structures can be as low as nanometers. At the same time, through the design of the motion trajectory, specific patterned micro-nano structures can be prepared on the substrate sample to facilitate further functional expression. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The local three-dimensional microscopic morphology (a) and two-dimensional profile curve (b) of the sample prepared on the surface of the substrate material in Example 1;

[0021] Figure 2 Elemental composition analysis of samples prepared on the surface of the substrate material in Example 1;

[0022] Figure 3 The local three-dimensional microscopic morphology (a) and two-dimensional profile curve (b) of the sample prepared on the surface of the substrate material in Example 4;

[0023] Figure 4 This is the three-dimensional microscopic morphology of the sample prepared on the surface of the substrate material in Example 5. DETAILED DESCRIPTION

[0024] The present invention provides a polymer micro-nano additive manufacturing method based on mechanochemical action, comprising the following steps:

[0025] The friction pair is subjected to friction motion on the surface of a substrate (i.e., a base material) according to a set motion trajectory, and a polymer micro-nano structure with a nanometer height is oriented and grown at the position of the motion trajectory;

[0026] During the friction movement, there is a lubricating liquid between the friction pair and the surface of the substrate, and the lubricating liquid is a polymerized monomer or includes a polymerized monomer and a lubricating oil; during the friction movement, the load is 0.01 to 3N, the sliding speed is 10 to 2000 μm / s, and the ambient temperature is 20 to 150°C.

[0027] In the present invention, the friction pair is preferably a spherical friction pair, and the diameter of the spherical friction pair is preferably 0.1 to 3 mm, and can be 0.1, 0.3, 0.5, 1, 1.5 or 3 mm. In the present invention, the contact pressure can be changed by controlling the ball diameter of the friction pair, thereby achieving controllable growth of polymer micro-nano structures.

[0028] In the present invention, the material of the friction pair is preferably a material that has a catalytic effect on the growth of polymer micro-nano structures, that is, the type of friction pair can be matched according to the catalytic activity of different polymers. If there is a catalytic reaction between the friction pair material itself and the polymerized monomer (such as the friction pair made of copper material in the embodiment of the present invention has a catalytic effect on the polymerization of cyclopropanecarboxylic acid), it can promote the formation of micro-nano structures, significantly improve the friction catalytic effect, optimize the friction polymerization process, and thus achieve efficient and directional growth of micro-nano structures. In the embodiment of the present invention, the material of the friction pair is steel, zirconium oxide, copper or nickel.

[0029] In the present invention, the material of the substrate (i.e., the sample to be processed) preferably includes metal, silicon, alloy, ceramic, polymer or ITO glass, the alloy is such as steel or GCr15, the ceramic is such as zirconia, alumina or Si 3 N 4 In the present invention, the substrate is a material with a certain hardness. The inherent hardness of the substrate affects the growth rate of the micro-nano structure. Specifically, the growth of the micro-nano structure requires the substrate to have sufficient hardness to maintain the stability and durability of the structure and prevent damage during processing and application. The hardness of the substrate directly affects the formation, performance and adhesion of the coating of the micro-nano structure. In an embodiment of the present invention, the substrate is a sheet.

[0030] In the present invention, during the friction movement, there is a lubricating liquid between the friction pair and the surface of the substrate, and the lubricating liquid is a polymerized monomer (ie, a pure small molecule compound) or includes a polymerized monomer and a lubricating oil.

[0031] In the present invention, when the lubricating liquid is a polymerized monomer, the polymerized monomer preferably includes pinene or cyclopropanecarboxylic acid (CPCa).

[0032] In the present invention, when the lubricating fluid includes a polymerized monomer and a lubricating oil, the polymerized monomer preferably includes pinene, cyclopropanecarboxylic acid (CPCa) or cyclopropane dicarboxylic acid, and the mass fraction of the polymerized monomer in the polymerized monomer and the lubricating oil is preferably ≥5%, which can be 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%. In an embodiment of the present invention, the cyclopropane dicarboxylic acid is 1,1-cyclopropane dicarboxylic acid. The present invention has no special requirements for the lubricating oil, and lubricating oils well known to those skilled in the art can be used, such as PAO10, PAO4, PAO6, SN500, DBE, ethylene glycol. The presence of the lubricating oil can reduce the friction heat between the contact surfaces, reduce the roughness of the contact surface, thereby reducing the friction coefficient, avoiding wear of the substrate, and improving the contact state of the friction interface, which helps to form micro-nano structures in a directional and localized manner. In the present invention, when the polymerizable monomer is in liquid state (such as pinene and cyclopropanecarboxylic acid), the polymerizable monomer is directly mixed with lubricating oil to obtain lubricating liquid, and ultrasonic or magnetic stirring can be performed to achieve uniform mixing of the polymerizable monomer and lubricating oil; in the present invention, when the polymerizable monomer is in solid state (such as cyclopropanedicarboxylic acid), the present invention preferably grinds the polymerizable monomer and performs oleic acid modification, and then mixes with lubricating oil to obtain lubricating liquid; the oleic acid modification method preferably comprises the following steps:

[0033] The oleic acid, the polymerization monomer powder and the petroleum ether solvent are mixed to carry out a modification reaction to obtain a suspension;

[0034] The suspension is sequentially subjected to solid-liquid separation, solid phase drying and grinding to obtain oleic acid-modified polymerized monomer powder (nano powder).

[0035] In the present invention, the mass ratio of the oleic acid to the polymerized monomer powder is preferably 5:1. The present invention has no special requirements for the amount of the petroleum ether solvent, as long as the oleic acid and the polymerized monomer powder can be completely dissolved. In the present invention, the temperature of the modification reaction is preferably 70-80°C, the time is preferably 2-4h, and the modification reaction is preferably carried out under the conditions of a constant temperature water bath and magnetic stirring. In the present invention, the solid-liquid separation method can be centrifugation, and the centrifugation is preferably performed multiple times to fully separate the oleic acid and the petroleum ether solvent. In the present invention, the temperature of the solid phase drying is preferably 80-85°C, and the time is preferably 3-4h.

[0036] In the present invention, during the friction movement, the load is 0.01-3N, which can be 0.01, 0.05, 0.1, 0.5, 0.7, 1, 1.2, 1.5, 2, 2.5 or 3N, the sliding speed is 10-2000μm / s, which can be 10, 50, 100, 400, 700, 800, 1000 or 2000μm / s, and the ambient temperature is 20-150℃, which can be 20, 25, 50, 80, 100, 120 or 150℃. When the ambient temperature is higher than room temperature, it can be achieved by an external heating field. In the present invention, the size of the load will affect the speed at which the micro-convex peaks on the contact surface of the friction pair are removed, thereby affecting the stabilization time of the friction factor. The micro-convex peaks on the contact surface of the friction pair under a larger load are removed faster, but the friction factor under different normal loads after stabilization does not change much, and the growth rate of the micro-nano structure gradually increases with the load, presenting a trend of first increasing, then stabilizing, and then decreasing. In the present invention, the change of sliding speed will affect the friction coefficient, and the sliding speed will also affect the relationship between friction and normal load. At the nanometer scale, the friction increases with the logarithmic growth of the sliding speed. After exceeding the critical sliding speed, the friction is almost unaffected by the change of sliding speed. These reasons will also affect the growth of micro-nano structures. In the present invention, during the friction polymerization process, the increase in temperature can promote the polymerization reaction of small molecule compounds, increase the reaction rate, help reduce the activation energy required for polymer film formation, promote the formation of tribochemical reaction film, thereby accelerating the growth of micro-nano structures and improving the preparation efficiency of micro-nano structures; the increase in temperature may cause microstructural changes in the contact interface, such as changes in crack morphology and the formation of an oxide layer, and these changes will affect the friction performance and stability of the micro-nano structure. The present invention uses a method for realizing negative wear by friction, and by controlling the medium, friction load, sliding speed and ambient temperature, the mechanochemical action of the contact area is promoted, the activation energy required for polymer film formation is reduced, and the directional (i.e., the formation and growth of the micro-nano structure is precisely controlled in a specific area or position) and quantitative (i.e., the controllable growth of the growth height) growth of the micro-nano structure is achieved in a preset motion trajectory under tribochemical induction.

[0037] In the present invention, during the friction movement, the relative humidity of the environment is preferably 10-60%, and can be 10%, 20%, 30%, 40%, 50%, or 60%. In the present invention, the relative humidity of the environment has an impact on friction and wear, and the change in humidity may affect the properties of the material surface, such as the friction coefficient and wear rate, and further affect the growth of the micro-nano structure.

[0038] In the present invention, the friction motion is preferably a reciprocating friction motion, the reciprocating distance of the reciprocating friction motion is preferably 100-2000 μm, and can be 100, 200, 300, 500, 1000, 1500 or 2000 μm, and the friction cycle is preferably 200-10000 times, and can be 3000, 5000, 7000 or 10000 times. In the present invention, the reciprocating distance and the friction cycle affect the growth height and uniformity of the micro-nano structure. With the extension of the friction cycle and the extension of the reciprocating distance, it is conducive to obtaining a more uniform micro-nano structure.

[0039] In the present invention, the motion trajectory can be a straight line, a curve, letters (such as the crossed double E-shaped motion trajectory in the embodiment) and other designable patterns. The pattern setting and size setting (such as width, length and curvature) of the motion trajectory can be performed according to actual needs.

[0040] The specific operation of the polymer micro-nano additive manufacturing method provided by the present invention is preferably as follows:

[0041] Pre-treating the surface of the substrate, wherein the pre-treatment includes grinding, polishing, cleaning and drying;

[0042] Fix the pre-treated substrate on a groove with a precision displacement stage and place it directly below the friction pair. Use a pipette to place the lubricating liquid between the friction pair and the substrate so that the substrate is completely immersed in the lubricating liquid.

[0043] Set the friction motion trajectory, which can be constructed in straight lines, curves and other patterns according to needs; set the corresponding friction parameters (load, sliding speed, reciprocating distance, etc.) and medium environment (temperature, humidity, etc.);

[0044] Start the friction test device and perform micro-nano additive manufacturing according to the set parameters;

[0045] After the test, the substrate surface is cleaned and dried using a suitable reagent (such as petroleum ether).

[0046] In the present invention, the height of the polymer micro-nano structure is nanometer-scale, preferably 10 to 500 nm, and can be 10, 30, 40, 60, 80, 100, 140, 200, 300, 400 or 500 nm.

[0047] The present invention provides a friction-driven micro-nano additive manufacturing method, which utilizes the mechanochemical effect generated by friction, and realizes the growth of polymer micro-nano structures in a specific area on a substrate sample through the polymerization of small molecules or the chain breakage and recombination of chemical bonds under the action of the mutual coupling of heat and force. Compared with the prior art, the micro-nano structure prepared by the present invention has a precision control at the nanometer level, and can be prepared in a directional and quantitative manner, and patterned to facilitate further functional expression; and the technology belongs to the category of green chemistry, providing a new idea for chemical synthesis, which is conducive to green, low-carbon, high-quality and sustainable development.

[0048] The present invention provides a polymer micro-nano additive manufacturing system based on mechanochemical action, comprising a friction pair, a substrate and a lubricating liquid, wherein the lubricating liquid is a polymer monomer or comprises a polymer monomer and a lubricating oil, and the lubricating liquid is applied between the friction pair and the surface of the substrate. In the present invention, the conditions of the friction pair, the substrate and the lubricating liquid are the same as those in the above technical solution, and are not repeated here. The polymer micro-nano additive manufacturing system provided by the present invention can realize the directional and quantitative growth of polymer micro-nano structures.

[0049] In order to further illustrate the present invention, the polymer micro-nano additive manufacturing method and system based on mechanochemical action provided by the present invention are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present invention.

[0050] Example 1

[0051] A steel ball with a diameter of 1 mm was used as the friction pair, a Si wafer was used as the base material, and a pinene solution with a purity of 98% was used as the lubricant. Before processing, the surface of the base material was ground, polished, cleaned and dried, and it was fixed in the groove and placed directly below the friction pair. A pipette was used to add 100 μL of lubricating liquid into the groove so that the base material was completely immersed in the lubricating liquid. The friction trajectory was set to a straight line. During the friction process, the load used was 1 N, the sliding speed was 1000 μm / s, the reciprocating distance was 200 μm, and the friction cycle was 5000 times. The set medium environment was: temperature of 100 ° C, relative humidity of 30%. After preparation, the sample was taken out, cleaned with petroleum ether and dried. The height of the sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment is 80 nm, the width is 50 μm, and the length is 200 μm. The local three-dimensional microscopic morphology photos and two-dimensional contour curves of the surface prepared samples are shown in Figure 2. Figure 1 As shown ( Figure 1 Profile1, Profile2 and Profile3 represent two-dimensional profile analysis at three different locations on the surface. The chemical composition is as follows: Figure 2 shown.

[0052] Example 2

[0053] Zirconia balls with a diameter of 1 mm were used as friction pairs, Si wafers were used as base materials, and 50 wt.% of pinene solution was mixed with 50 wt.% of PAO10 as lubricating liquid. The surface of the base material was ground, polished, cleaned and dried before processing, and it was fixed in the groove and placed directly below the friction pair. 100 μL of lubricating liquid was added to the groove using a pipette gun so that the base material was completely immersed in the lubricating liquid. The friction trajectory was set to a straight line. During the friction process, the load used was 1 N, the sliding speed was 400 μm / s, the reciprocating distance was 200 μm, and the friction cycle was 10,000 times. The set medium environment includes: temperature of 50 ° C and relative humidity of 30%. After preparation, the sample was taken out, cleaned with petroleum ether and dried. The sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment has a height of 60 nm, a width of 40 μm, and a length of 200 μm.

[0054] Example 3

[0055] A steel ball with a diameter of 0.5 mm is used as the friction pair, a steel sheet is used as the base material, and a pinene solution with a purity of 98% is used as the lubricant. Before processing, the surface of the base material is ground, polished, cleaned and dried, and it is fixed in the groove and placed directly below the friction pair. A pipette is used to add 50 μL of lubricating liquid into the groove so that the base material is completely immersed in the lubricating liquid. The friction trajectory is set to a straight line. During the friction process, the load used is 0.5 N, the sliding speed is 800 μm / s, the reciprocating distance is 100 μm, and the friction cycle is 3000 times. The set medium environment includes: temperature of 80 ° C and relative humidity of 30%. After preparation, the sample is taken out, cleaned with petroleum ether and dried. The height of the sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment is 50 nm, the width is 30 μm, and the length is 100 μm.

[0056] Example 4

[0057] A copper ball with a diameter of 1 mm was used as a friction pair, a steel sheet was used as a base material, and 5wt.% of cyclopropanecarboxylic acid (CPCa) was mixed with 95wt.% of PAO10 as a lubricant. The surface of the base material was ground, polished, cleaned and dried before processing, and it was fixed in a groove and placed directly below the friction pair. A pipette gun was used to place 100μL of lubricant between the friction pair and the base material. The friction trajectory was set to a straight line. During the friction process, the load used was 0.7N, the sliding speed was 700μm / s, the reciprocating distance was 200μm, and the friction cycle was 10,000 times. The set medium environment includes: temperature of 100°C and relative humidity of 30%. After preparation, the sample was taken out, cleaned with petroleum ether and dried. The height of the sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment is 140nm, the width is 40μm, and the length is 200μm. The local three-dimensional microstructure and two-dimensional profile curve of the surface prepared sample are as follows: Figure 3 As shown ( Figure 3 Profile1, Profile2 and Profile3 represent three different positions selected from the surface for two-dimensional profile analysis).

[0058] Example 5

[0059] A steel ball with a diameter of 1 mm was used as the friction pair, a Si wafer was used as the base material, and a pinene solution with a purity of 98% was used as the lubricant. Before processing, the surface of the base material was ground, polished, cleaned and dried, and it was fixed in the groove and placed directly below the friction pair. A pipette was used to add 100 μL of lubricating liquid into the groove so that the base material was completely immersed in the lubricating liquid. The friction trajectory was set to double E for the patterned construction of the forked electrode. During the friction process, the load used was 1.2 N, the sliding speed was 2000 μm / s, the reciprocating distance was 300 μm, and the friction cycle was 7000 times. The set medium environment includes: temperature of 120°C and relative humidity of 20%. After the preparation is completed, the sample is taken out, cleaned with petroleum ether and dried. The three-dimensional microscopic morphology of the sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment is as follows Figure 4 shown.

[0060] Example 6

[0061] A copper ball with a diameter of 1 mm was used as a friction pair, and a Si wafer was used as a matrix material. The 1,1-cyclopropanedicarboxylic acid powder was ground and oleic acid was modified. A solution consisting of 10wt.% oleic acid-modified nanopowder and 90wt.% PAO4 was used as a lubricant. The oleic acid modification method is as follows: oleic acid and 1,1-cyclopropanedicarboxylic acid powder were dissolved in a petroleum ether solvent at a mass ratio of 5:1; magnetic stirring was performed in a constant temperature water bath, the temperature was raised to 70°C, and the reaction was performed for 2 hours to obtain a suspension; the suspension after the reaction was centrifuged and repeatedly separated and precipitated until there was no oleic acid; the washed precipitate was placed in a vacuum environment at 80°C and dried for 3 hours, and after drying, it was ground into powder to obtain oleic acid-modified nanopowder, i.e., oleic acid-modified cyclopropanedicarboxylic acid powder.

[0062] Before processing, the surface of the base material is ground, polished, cleaned and dried, and it is fixed in the groove and placed directly below the friction pair. Use a pipette to add 100μL of lubricating liquid into the groove so that the base material is completely immersed in the lubricating liquid. The friction trajectory is set to a straight line. During the friction process, the load used is 1.5N, the sliding speed is 400μm / s, the reciprocating distance is 200μm, and the friction cycle is 5000 times. The set medium environment includes: temperature of 80℃ and relative humidity of 40%. After preparation, take out the sample, clean it with petroleum ether and dry it. The height of the sample prepared on the surface of the base material using the friction-driven micro-nano additive manufacturing method of this embodiment is 30nm, the width is 30μm, and the length is 200μm.

[0063] Example 7

[0064] A nickel ball with a diameter of 1 mm was used as a friction pair, a steel sheet was used as a base material, 1,1-cyclopropanedicarboxylic acid powder was ground, oleic acid modified (the modification method was the same as in Example 6), and a solution consisting of 20wt.% oleic acid-modified nanopowder and 80wt.% PAO4 was used as a lubricant. The surface of the base material was ground, polished, cleaned and dried before processing, and it was fixed in the groove and placed directly below the friction pair. A pipette gun was used to add 100μL of lubricating liquid into the groove so that the base material was completely immersed in the lubricating liquid. The friction trajectory was set to a straight line. During the friction process, the load used was 2.0N, the sliding speed was 800μm / s, the reciprocating distance was 200μm, and the friction cycle was 10,000 times. The set medium environment includes: temperature of 120°C and relative humidity of 40%. After preparation, the sample was taken out, cleaned with petroleum ether and dried. The sample prepared on the surface of the base material by the friction-driven micro-nano additive manufacturing method of this embodiment has a height of 40 nm, a width of 30 μm, and a length of 200 μm.

[0065] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A polymer micro-nano additive manufacturing method based on mechanochemical action, characterized in that: The following steps are involved: The friction pair is subjected to friction motion on the surface of the substrate according to a set motion trajectory, and a polymer micro-nano structure with a nanometer height is oriented and grown at the position of the motion trajectory; During the friction movement, there is a lubricating liquid between the friction pair and the surface of the substrate, and the lubricating liquid is a polymerized monomer or includes a polymerized monomer and a lubricating oil; during the friction movement, the load is 0.01 to 3N, the sliding speed is 10 to 2000 μm / s, and the ambient temperature is 20 to 150°C.

2. The method according to claim 1, characterized in that The friction pair is a spherical friction pair, and the diameter of the spherical friction pair is 0.1-3 mm.

3. The method according to claim 1 or 2, characterized in that: The material of the friction pair is a material that has a catalytic effect on the growth of polymer micro-nano structures.

4. The method according to claim 1, characterized in that: The material of the substrate includes metal element, silicon, alloy, ceramic, polymer or ITO glass.

5. The method according to claim 1, characterized in that When the lubricating liquid is a polymerized monomer, the polymerized monomer includes pinene or cyclopropanecarboxylic acid.

6. The method according to claim 1, characterized in that When the lubricating liquid comprises polymerized monomers and lubricating oil, the polymerized monomers comprise pinene, cyclopropanecarboxylic acid or cyclopropanedicarboxylic acid, and the mass fraction of the polymerized monomers in the polymerized monomers and the lubricating oil is ≥5%.

7. The method according to claim 1, characterized in that During the friction movement, the relative humidity of the environment is 10-60%.

8. The method according to claim 1 or 7, characterized in that: The friction motion is a reciprocating friction motion, the reciprocating distance of the reciprocating friction motion is 100 to 2000 μm, and the friction cycle is 200 to 10000 times.

9. The method according to claim 1, characterized in that: The height of the polymer micro-nano structure is 10-500 nm.

10. A polymer micro-nano additive manufacturing system based on mechanochemical action, characterized in that: The invention comprises a friction pair, a substrate and a lubricating liquid. The lubricating liquid is a polymerized monomer or comprises a polymerized monomer and lubricating oil. The lubricating liquid is applied between the friction pair and the substrate surface.

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