A high-hardness wear-resistant composite material and a preparation method and application thereof

Abstract

The application discloses a kind of high-hardness wear-resistant composite material and its preparation method and application, high-hardness wear-resistant composite material includes iron-based alloy, amine group urea-containing polymer and additive;Additive includes 7-methyl-(1,2,4) triazolone (1,5-a) pyridine-2 (3H) -imine and benzotriazole-6-sulfonic acid;Iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni.The application introduces iron-based alloy, amine group urea-containing polymer and composite additive synergistic effect, utilizes its functional group and metal surface coordination to form protective film, enhances dispersibility, adhesion and wear resistance, insulates corrosive medium, promotes self-repairing ability, maintains stability under high temperature, high load condition, meets actual application demand.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of self-repairing materials, more particularly, to a high-hardness wear-resistant composite material and a preparation method and application thereof. BACKGROUND

[0002] Wear is one of the main modes of material failure, accounting for about 80% of equipment damage and failure. According to the investigation and analysis of the United States, the United Kingdom, Japan and Germany in the past 20 years, the economic loss caused by wear failure is huge, accounting for about 2% of the total national economic output. At present, the problem of wear failure is mainly solved by using wear-resistant technology, friction-reducing technology and repair technology, but these technologies are mostly independent, and the effectiveness, reliability and universality are limited.

[0003] Metal wear self-repairing technology (ART) is a new surface engineering technology and product that integrates wear resistance, friction reduction and dynamic self-repairing functions. The core of this technology is to use the force-chemical reaction conditions of the metal friction surface to transfer the micro-nano powder materials of special components to the metal surface and form a metal ceramic protective layer. This protective layer can significantly improve the hardness and smoothness of the friction surface, reduce the friction coefficient, and restore the wear area to its original size.

[0004] Although the metal wear self-repairing technology has achieved remarkable application results in the industrial field, it still faces some technical problems in actual application. The existing metal wear self-repairing materials are usually composed of multiple mineral components and various additives. These materials have poor dispersibility in lubricating oil and are prone to sedimentation or agglomeration. This not only affects the uniform distribution of the materials, but also may cause local wear to intensify; secondly, with the passage of time, the self-repairing materials may exhibit instability, affecting long-term performance and reliability, ultimately resulting in poor self-repairing performance and low repair efficiency, which cannot meet the actual application requirements. In addition, under high temperature and high load conditions, the friction coefficient of the materials is unstable, it is difficult to resist high-load wear, and it cannot effectively reduce the friction coefficient, leading to increased energy consumption and wear. SUMMARY

[0005] The present application aims to overcome the above-mentioned defects in the prior art and provide a high-hardness wear-resistant composite material and a preparation method and application thereof. By introducing Mn, Mo, Co, Cr, Fe and Ni to enhance the wear resistance of the iron-based alloy, adding benzotriazole-6-sulfonic acid and 7-methyl-(1,2,4)triazolo(1,5-a)pyridine-2(3H)-imine for synergistic effect, using the functional groups to form a protective film on the metal surface, enhancing the adhesion and wear resistance, and isolating the corrosion medium. The imine group modifies the alloy particles, improves the dispersibility, and enhances the self-repairing ability. The amine group urea polymer forms a concave-convex surface, maintains stability under high temperature and high load conditions, ensures the reliability of long-term use, improves the repair efficiency, and meets the actual application requirements.

[0006] To achieve the above object, the technical scheme of the present application is as follows:

[0007] A high-hardness wear-resistant composite material, comprising an iron-based alloy, an amine urea-containing polymer and an additive; the additive comprises 7-methyl-(1,2,4) triazol(1,5-a) pyridine-2(3H)-imine and benzotriazole-6-sulfonic acid in a mass ratio of 1:(0.1-0.5); the iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni, wherein the atomic percentage of Fe is 20-40%, the atomic percentage of Mn is 5-10%, the atomic percentage of Mo is 15-30%, the atomic percentage of Co is 5-20%, the atomic percentage of Cr is 5-15%, and the atomic percentage of Ni is 5-10%; the mass fraction of the iron-based alloy is 100 parts, the mass fraction of the amine urea-containing polymer is 1-3 parts, and the mass fraction of the additive is 10-25 parts.

[0008] Optionally, the amine urea-containing polymer is alkyl dimethyl ammonium chloride.

[0009] Optionally, the Mn, Mo, Co, Cr, Fe and Ni are pure metal powders with a purity of ≥99.5%.

[0010] Optionally, the average particle size of the iron-based alloy is <1 um.

[0011] The present application also discloses a preparation method of the high-hardness wear-resistant composite material as described above, comprising the following steps:

[0012] (1) preparing metal raw materials by proportioning Mn, Mo, Co, Cr, Fe and Ni raw materials according to atomic percentages;

[0013] (2) obtaining the iron-based alloy with an average particle size of <1 um by sequentially subjecting the metal raw materials to rough grinding and fine grinding;

[0014] (3) obtaining the high-hardness wear-resistant composite material by adding the iron-based alloy and the amine urea-containing polymer into an aqueous solution containing the additive for homogenizing dispersion, and then centrifugally separating the solid, drying, and preparing.

[0015] Optionally, in step (2), the rough grinding is performed for 5-8 h; and the fine grinding is performed for 10-15 h.

[0016] Optionally, in step (2), the liquid medium for fine grinding is alcohol.

[0017] The application further discloses application of the high-hardness anti-wear composite material in lubricating oil.

[0018] Optionally, the volume ratio of the high-hardness anti-wear composite material to the base lubricating oil is (0.1-0.5) : 100.

[0019] The application has the following beneficial effects:

[0020] The application first introduces Mn, Mo, Co, Cr, Fe and Ni, which can significantly improve the wear resistance of the material through different mechanisms; further, a composite synergistic dispersant is added in the iron-based alloy, wherein the multiple nitrogen atoms on the triazole ring in the benzotriazole-6-sulfonic acid can coordinate with the metal surface to form stable chemical bonds, the sulfonic acid group introduced on the triazole ring can further enhance the adhesion of the material to the metal surface; the triazole functional group and the pyridine functional group in 7-methyl-(1,2,4) triazol (1,5-a) pyridine-2 (3H) -imine can chemically adsorb to the active sites on the metal surface to form stable coordination bonds, thereby being adsorbed on the metal surface, so as to form a dense protective film, ensure the wear resistance and stability of the material, effectively isolate the external corrosive medium, and reduce the oxidation and corrosion of the metal; at the same time, the imine group modifies the alloy particles, improves the characteristics of the self-repairing material that is difficult to disperse and suspend in the lubricating oil, and further improves the ability of the self-repairing material as a friction damage self-repairing material; the amine group-containing urea polymer can form a dense concave-convex surface on the metal surface, and can also maintain the stability of the material.

[0021] The raw materials of the application cooperate with each other and synergistically act, the lubricating oil of the high-hardness anti-wear composite material of the application generates a metal ceramic protective layer with excellent wear-reducing performance on the metal friction surface when the mechanical equipment is rubbed, the hardness and smoothness of the friction surface are improved, the friction coefficient is greatly reduced, and the worn parts are restored to the original size, the self-repairing of the metal wear parts is completed, the service life of the equipment is greatly prolonged, and the energy consumption is saved. Therefore, not only the friction coefficient of the surface of the machine part itself can be reduced, the wear due to friction can be reduced, but also the wear of the machine part surface caused by the abrasive particles due to wear can be reduced, and the working temperature of the lubricating oil can be reduced. DETAILED DESCRIPTION

[0022] The application will be further described below in combination with specific embodiments, but the application is not limited in any way by the embodiments.

[0023] Embodiment 1

[0024] The high-hardness wear-resistant composite material of the embodiment comprises an iron-based alloy (average particle size <1 um), alkyl dimethyl ammonium chloride and an additive; the additive comprises 7-methyl-(1, 2, 4) triazol (1, 5-a) pyridine-2 (3H) -imine and benzotriazole-6-sulfonic acid in a mass ratio of 1:0.25; the iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni, wherein the atomic percentage of Fe is 30%, the atomic percentage of Mn is 10%, the atomic percentage of Mo is 15%, the atomic percentage of Co is 20%, the atomic percentage of Cr is 15%, and the atomic percentage of Ni is 10%;

[0025] The mass fraction of the iron-based alloy is 100 parts, the mass fraction of the amido urea-containing polymer is 3 parts, and the mass fraction of the additive is 24 parts.

[0026] The preparation method of the high-hardness wear-resistant composite material of the embodiment comprises the following steps:

[0027] (1) raw materials of Mn, Mo, Co, Cr, Fe and Ni are prepared according to atomic percentages to obtain metal raw materials;

[0028] (2) the metal raw materials are sequentially subjected to coarse grinding for 8 hours and fine grinding for 10 hours to obtain an iron-based alloy with an average particle size of less than 1 um;

[0029] (3) the iron-based alloy and the amido urea-containing polymer are added into an aqueous solution containing the additive for homogenization and dispersion, and then subjected to centrifugal separation to obtain a solid, which is dried to prepare the high-hardness wear-resistant composite material.

[0030] Embodiment 2

[0031] The high-hardness wear-resistant composite material of the embodiment comprises an iron-based alloy (average particle size <1 um), alkyl dimethyl ammonium chloride and an additive; the additive comprises 7-methyl-(1, 2, 4) triazol (1, 5-a) pyridine-2 (3H) -imine and benzotriazole-6-sulfonic acid in a mass ratio of 1:0.1; the iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni, wherein the atomic percentage of Fe is 40%, the atomic percentage of Mn is 5%, the atomic percentage of Mo is 25%, the atomic percentage of Co is 10%, the atomic percentage of Cr is 15%, and the atomic percentage of Ni is 5%;

[0032] The mass fraction of the iron-based alloy is 100 parts, the mass fraction of the amido urea-containing polymer is 1 part, and the mass fraction of the additive is 15 parts.

[0033] The preparation method of the high-hardness wear-resistant composite material of the embodiment comprises the following steps:

[0034] (1) Mn, Mo, Co, Cr, Fe and Ni raw materials are prepared according to atomic percentage to obtain metal raw materials;

[0035] (2) The metal raw materials are sequentially coarsely ground for 7h and finely ground for 15h to obtain an iron-based alloy with an average particle size of less than 1um;

[0036] (3) The iron-based alloy and the amido urea-containing polymer are added into an aqueous solution containing additives for homogenously dispersing, and then centrifuged to obtain a solid, which is dried to prepare a high-hardness wear-resistant composite material.

[0037] Example 3

[0038] The high-hardness wear-resistant composite material of the present example comprises an iron-based alloy (average particle size <1um), alkyl dimethyl ammonium chloride and additives; the additives comprise 7-methyl-(1,2,4) triazolo(1,5-a) pyridine-2(3H)-imine and benzotriazole-6-sulfonic acid with a mass ratio of 1:0.5; the iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni, wherein the atomic percentage of Fe is 20%, the atomic percentage of Mn is 10%, the atomic percentage of Mo is 30%, the atomic percentage of Co is 15%, the atomic percentage of Cr is 15%, and the atomic percentage of Ni is 10%;

[0039] The mass fraction of the iron-based alloy is 100 parts, the mass fraction of the amido urea-containing polymer is 3 parts, and the mass fraction of the additives is 15 parts.

[0040] The preparation method of the high-hardness wear-resistant composite material of the present example comprises the following steps:

[0041] (1) Mn, Mo, Co, Cr, Fe and Ni raw materials are prepared according to atomic percentage to obtain metal raw materials;

[0042] (2) The metal raw materials are sequentially coarsely ground for 8h and finely ground for 10h to obtain an iron-based alloy with an average particle size of less than 1um;

[0043] (3) The iron-based alloy and the amido urea-containing polymer are added into an aqueous solution containing additives for homogenously dispersing, and then centrifuged to obtain a solid, which is dried to prepare a high-hardness wear-resistant composite material.

[0044] Example 4

[0045] The present example is different from Example 1 only in that the mass ratio of 7-methyl-(1,2,4) triazolo(1,5-a) pyridine-2(3H)-imine and benzotriazole-6-sulfonic acid is 1:0.1.

[0046] Example 5

[0047] The present example differs from Example 1 only in that the mass ratio of 7-methyl-(1,2,4)triazolo(1,5-a)pyridin-2(3H)-imine and benzotriazole-6-sulfonic acid is 1 :0.5.

[0048] Example 6

[0049] The present example differs from Example 1 only in that the mass fraction of the iron-based alloy is 100 parts, the mass fraction of the urea-amine group-containing polymer is 1 part, and the mass fraction of the additive is 25 parts.

[0050] Example 7

[0051] The present example differs from Example 1 only in that the mass fraction of the iron-based alloy is 100 parts, the mass fraction of the urea-amine group-containing polymer is 3 parts, and the mass fraction of the additive is 10 parts.

[0052] Comparative Example 1

[0053] The present comparative example differs from Example 1 only in that the present comparative example does not add the urea-amine group-containing polymer.

[0054] Comparative Example 2

[0055] The present comparative example differs from Example 1 only in that the present comparative example does not add 7-methyl-(1,2,4)triazolo(1,5-a)pyridin-2(3H)-imine.

[0056] Comparative Example 3

[0057] The present comparative example differs from Example 1 only in that the present comparative example does not add benzotriazole-6-sulfonic acid.

[0058] Comparative Example 4

[0059] The present comparative example differs from Example 1 only in that the mass ratio of 7-methyl-(1,2,4)triazolo(1,5-a)pyridin-2(3H)-imine and benzotriazole-6-sulfonic acid is 1 :2.

[0060] Comparative Example 5

[0061] The present comparative example differs from Example 1 only in that the mass ratio of 7-methyl-(1,2,4)triazolo(1,5-a)pyridin-2(3H)-imine and benzotriazole-6-sulfonic acid is 10:0.1.

[0062] Comparative Example 6

[0063] The present comparative example differs from Example 1 only in that the mass fraction of the iron-based alloy is 100 parts, the mass fraction of the urea-amine group-containing polymer is 5 parts, and the mass fraction of the additive is 5 parts.

[0064] Comparative Example 7

[0065] The present comparative example is compared with Example 1, the only difference being that the mass fraction of the iron-based alloy is 100 parts, the mass fraction of the amido urea-containing polymer is 5 parts, and the mass fraction of the additive is 30 parts.

[0066] Application Example 1

[0067] A lubricating oil, the lubricating oil comprising the composite material provided in Examples 1-7 and Comparative Examples 1-7 and base oil (Class II base oil, model XHH-150N); the preparation method of the lubricating oil comprising: mixing the composite material provided in Examples 1-7 and Comparative Examples 1-7 and the base oil, and stirring and premixing, shear infiltration, ultrasonic dispersion, and homogenization treatment, to obtain the lubricating oil. The volume ratio of the high-hardness anti-wear composite material and the base lubricating oil is 0.5:100, the stirring rate in the stirring and premixing is 5000 r / min, and the stirring time is 10 min; the strong mechanical dispersion is carried out in a shear dispersion machine, the shear rotation speed is 4000 rpm, the shear time is 40 min, and the circulating temperature is controlled at 10-35°C; the ultrasonic dispersion power is 800 W, the ultrasonic frequency is 20 kHz, the ultrasonic temperature is not more than 35°C, and the ultrasonic time is 40 min; the homogenization pressure is 1000 bar, the homogenization temperature is 10-35°C, and the homogenization is carried out 150 times.

[0068] Comparative Application Example 1

[0069] A lubricating base oil, the lubricating base oil (Class II base oil, model XHH-150N) is not added with the composite material.

[0070] Performance test

[0071] 1. The SRV micro-tribological tester is used to determine the change of the friction-reducing and wear-resisting performance of the lubricating base oil provided in Application Example 1 compared with Comparative Application Example 1, the test conditions are: load 200 N, frequency 50 Hz, temperature 50°C, stroke 1 mm, and the friction coefficient and wear scar diameter are recorded; and the friction coefficient and wear scar diameter reduction percentage of the lubricating oil added with the composite material in Application Example 1 compared with the lubricating base oil is calculated; the smaller the friction coefficient and wear scar diameter, the better the anti-wear and friction-reducing performance.

[0072] Friction coefficient reduction percentage = (friction coefficient of the lubricating base oil - friction coefficient of the lubricating oil) / friction coefficient of the lubricating base oil * 100%;

[0073] Wear scar diameter reduction percentage = (wear scar diameter of the lubricating base oil - wear scar diameter of the lubricating oil) / wear scar diameter of the lubricating base oil * 100%.

[0074] 2. The low-temperature corrosion resistance and high-temperature corrosion resistance of the material including the application example 1 were determined by GB / T5096. The low-temperature corrosion resistance was determined according to GB / T5096, and the test temperature was set to 50℃, and the determination was performed after 3h. The high-temperature corrosion resistance was determined according to GB / T5096, and 120℃ was used as the initial temperature, and the test temperature was increased at a rate of 1℃ / min, and the determination was performed after 3h.

[0075] 3. The change of the self-repairing performance of the material including the application example 1 was determined by using a MRH-3 type high-speed ring block wear tester. The test conditions were as follows: on the MRH-3 type high-speed ring block wear tester, the load was 200N, the rotation speed was 100r / min, and the time was 20s, and a wear scar of 12mm×0.6mm was dry ground on the surface of the test block. The self-repairing effect of the above-mentioned application example 1 was investigated by using the MRH-3 type high-speed ring block wear tester at a speed of 0.257m / s and a time of 4h. The self-repairing performance evaluation: the self-repairing effect was investigated by comparing the wear amount before and after repair.

[0076] Table 1: Performance test results

[0077] coefficient of friction wear scar diameter (mm) low temperature corrosion high temperature corrosion example 1 0.108 0.208 2b 1b example 2 0.114 0.223 2b 1b example 3 0.129 0.215 2b 1b example 4 0.133 0.237 2b 1b example 5 0.141 0.241 2b 1b example 6 0.127 0.219 2b 1b example 7 0.147 0.246 2b 1b comparative example 1 0.249 0.349 3a 3b comparative example 2 0.245 0.341 3a 3a comparative example 3 0.244 0.336 3a 3b comparative example 4 0.236 0.324 3a 3b comparative example 5 0.242 0.318 3a 3b comparative example 6 0.211 0.313 3a 3b comparative example 7 0.203 0.302 3a 3b comparative application example 1 0.218 0.45 / /

[0078] Table 2: Self-repairing performance test results

[0079] 200N example 1 0.48 mg example 2 0.41 mg example 3 0.47 mg example 4 0.27 mg example 5 0.22 mg example 6 0.23 mg example 7 0.30 mg comparative example 1 0.023 mg comparative example 2 0.029 mg comparative example 3 0.041 mg comparative example 4 0.037 mg comparative example 5 0.046 mg comparative example 6 0.052 mg comparative example 7 0.049 mg

[0080] From Tables 1-3, it can be seen that, compared with the comparative examples 1-7, the friction coefficient of the material provided by the application examples 1-7 is significantly reduced, the wear scar diameter is significantly reduced, the low-temperature corrosion resistance and high-temperature corrosion resistance test results are improved, and the self-repairing performance is better. Therefore, the addition of the composite material can improve the anti-wear and friction-reducing performance, corrosion resistance and self-repairing performance to different degrees. In addition, the addition ratio of each component has a significant influence on the friction-reducing and wear-resisting performance and the self-repairing performance.

[0081] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be noted that, for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A high-hardness wear-resistant composite material, characterized in that, The high-hardness wear-resistant composite material includes an iron-based alloy, alkyl dimethyl ammonium chloride, and additives; The additive comprises 7-methyl-(1,2,4)triazolo(1,5-a)pyridine-2(3H)-imine and benzotriazol-6-sulfonic acid in a mass ratio of 1:(0.1~0.5); The iron-based alloy is composed of Mn, Mo, Co, Cr, Fe and Ni, wherein the atomic percentage of Fe is 20% to 40%, the atomic percentage of Mn is 5% to 10%, the atomic percentage of Mo is 15% to 30%, the atomic percentage of Co is 5% to 20%, the atomic percentage of Cr is 5% to 15%, and the atomic percentage of Ni is 5% to 10%. By mass, the iron-based alloy comprises 100 parts, the alkyl dimethyl ammonium chloride comprises 1 to 3 parts, and the additive comprises 10 to 25 parts.

2. The high-hardness wear-resistant composite material according to claim 1, characterized in that, The Mn, Mo, Co, Cr, Fe and Ni are pure metal powders with a purity of ≥99.5%.

3. The high-hardness wear-resistant composite material according to claim 1, characterized in that, The average particle size of the iron-based alloy is <1 μm.

4. A method for preparing a high-hardness wear-resistant composite material as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) Prepare the metal raw materials by mixing Mn, Mo, Co, Cr, Fe and Ni according to atomic percentages; (2) The metal raw material is subjected to coarse grinding and fine grinding in sequence to obtain the iron-based alloy with an average particle size of less than 1 μm; (3) The iron-based alloy and alkyl dimethyl ammonium chloride are added to an aqueous solution containing additives for homogeneous dispersion, and then the solid is obtained by centrifugation and dried to prepare the high-hardness wear-resistant composite material.

5. The preparation method according to claim 4, characterized in that, In step (2), the coarse grinding time is 5h~8h; The fine grinding time is 10h~15h.

6. The preparation method according to claim 4, characterized in that, In step (2), the liquid medium for fine grinding is alcohol.

7. The application of a high-hardness anti-wear composite material as described in any one of claims 1-3 in lubricating oil, characterized in that, The lubricating oil includes a base lubricating oil and the high-hardness anti-wear composite material.

8. The application according to claim 7, characterized in that, The volume ratio of the high-hardness anti-wear composite material to the base lubricating oil is (0.1~0.5):100.