A highly wear-resistant composite material, its preparation method, and a water-lubricated bearing

Abstract

The present invention relates to the field of composite materials, and specifically to a highly wear-resistant composite material, a preparation method thereof, and a water-lubricated bearing. Calculated by weight parts, it includes: 80-100 parts of carboxylated nitrile rubber, 10-20 parts of chlorinated polyethylene rubber, 50-70 parts of ultra-high molecular weight polyethylene, 5-10 parts of epoxy resin, 20-30 parts of amino molybdenum disulfide, 1-2 parts of lubricant, 0.1-0.5 part of crosslinking agent, 5-10 parts of inorganic filler, 0.01-0.1 part of organic amine, and 1-3.5 parts of vulcanization assistant. The highly wear-resistant composite material of the present invention has good wear resistance and is an excellent material for making water-lubricated bearings.

Description

Technical Field

[0001] The present invention relates to the field of composite materials, and particularly to a highly wear-resistant composite material, a preparation method thereof, and a water-lubricated bearing. Background Art

[0002] Water has the characteristics of being pollution-free, widely sourced, energy-saving, and safe as a lubricating medium, while rubber has the characteristics of shock absorption, anti-friction, anti-abrasive wear, anti-fatigue, and easy processing. If the advantages of water and rubber are combined to prepare an environment-friendly water-lubricated bearing, a series of problems existing in current traditional bearing friction pairs using precious metals and consuming strategic resources can be solved, such as large wear, strong vibration, high noise, high non-functional power consumption, poor reliability, short service life, and oil leakage polluting water resources. At present, there have been reports on developing new water-lubricated composite materials by adding additives such as UHMWPE and graphite to nitrile-butadiene rubber using the method of mechanical melt blending, but the application effect is not ideal. How to further improve its wear resistance under water-lubricated conditions has become the current research focus. Summary of the Invention

[0003] Object of the Invention: Aiming at the above technical problems, the present invention provides a highly wear-resistant composite material, a preparation method thereof, and a water-lubricated bearing.

[0004] The technical solution adopted is as follows:

[0005] A highly wear-resistant composite material, in parts by weight, includes:

[0006] 80 - 100 parts of carboxylated nitrile rubber, 10 - 20 parts of chlorinated polyethylene rubber, 50 - 70 parts of ultra-high molecular weight polyethylene, 5 - 10 parts of epoxy resin, 20 - 30 parts of aminoated molybdenum disulfide, 1 - 2 parts of lubricant, 0.1 - 0.5 parts of cross-linking agent, 5 - 10 parts of inorganic filler, 0.01 - 0.1 parts of organic amine, and 1 - 3.5 parts of vulcanization assistant.

[0007] Further, it also includes high-density polyethylene and low-density polyethylene.

[0008] Further, the dosages of the high-density polyethylene and the low-density polyethylene are respectively 20 - 30% and 10 - 20% of the weight of the ultra-high molecular weight polyethylene.

[0009] Further, the preparation method of the aminoated molybdenum disulfide is as follows:

[0010] Hydroxylate molybdenum disulfide with piranha solution, and then carry out a hydrolysis reaction with silane coupling agent KH-900 to aminoate molybdenum disulfide.

[0011] Further, the lubricant is any one or a combination of liquid paraffin, solid paraffin, polyethylene wax, ethylene bisstearamide, glycerol monostearate, metal soap, stearic acid, stearyl alcohol, oleamide, zinc stearate, calcium stearate.

[0012] Further, the crosslinking agent includes di-tert-butyl peroxide and vinyl silane with a weight ratio of 1-5:1-5;

[0013] The vinyl silane is any one or a combination of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltri-tert-butoxysilane, vinyltri-tert-butylperoxysilane, vinyltriacetoxysilane.

[0014] Further, the inorganic filler is the pyrolysis product of petroleum coke at 900-1500°C.

[0015] Further, the organic amine is any one or a combination of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, trimethylhexamethylenediamine.

[0016] The present invention also provides a preparation method of a highly wear-resistant composite material:

[0017] Carboxy nitrile rubber and chlorinated polyethylene rubber are first stage mixed and then discharged from the mill. The obtained rubber compound is second stage mixed with ultra-high molecular weight polyethylene, epoxy resin, amino molybdenum disulfide, lubricant, crosslinking agent, inorganic filler, and organic amine. A vulcanization aid is added to the obtained rubber compound, and after mixing evenly, it is passed through a thin sheet, placed and then vulcanized. The vulcanization temperature is 150-180°C, the vulcanization time is 20-40 min, and the vulcanization pressure is 15-30 MPa.

[0018] The present invention also provides a water-lubricated bearing prepared from the above highly wear-resistant composite material.

[0019] The beneficial effects of the present invention:

[0020] The introduction of carboxyl groups into carboxylated nitrile rubber has improved its tensile strength, tear strength, hardness, wear resistance, ozone aging resistance, etc. to varying degrees. However, it has also increased the polarity of nitrile rubber molecules. As a non-polar material, ultra-high molecular weight polyethylene has poor compatibility with nitrile rubber. The addition of chlorinated polyethylene rubber can improve the compatibility between the two and play an obvious compatibilizing role. The appropriate cross-linking of epoxy resin can improve the processing performance of ultra-high molecular weight polyethylene. The amino groups on amino-functionalized molybdenum disulfide can cross-link with epoxy resin, thus establishing a "bridging" effect between the interface of molybdenum disulfide and the resin matrix, making the interface layer more firm and stable and having better wear resistance. The pyrolysis products of petroleum coke have an ordered carbon microcrystalline structure, a high degree of graphitization, and a large specific surface area. Its addition can significantly increase the crystallinity of ultra-high molecular weight polyethylene, thereby improving the mechanical strength and wear resistance of the material. After testing, the high-wear-resistant composite material of the present invention has good wear resistance and is an excellent material for making water-lubricated bearings. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 FIG. is the SEM scanning electron microscope image of the high-wear-resistant composite material prepared in Example 1 of the present invention. It can be seen that Figure 1 amino-functionalized molybdenum disulfide and inorganic fillers are evenly distributed in the tissue matrix, the material is fully melted and mixed, and the tissue structure is relatively compact.

[0022] Figure 2 FIG. is the relationship curve of friction coefficient - rotational speed when the high-wear-resistant composite material prepared according to the formula in Example 1 is used as a sample for friction performance testing. DETAILED DESCRIPTION OF THE INVENTION

[0023] For those not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase. Technologies not mentioned in the present invention refer to the prior art.

[0024] Example 1:

[0025] A high-wear-resistant composite material, by weight, includes:

[0026] 90 parts of carboxylated nitrile rubber, 15 parts of chlorinated polyethylene rubber, 60 parts of ultra-high molecular weight polyethylene, 18 parts of high-density polyethylene, 10 parts of low-density polyethylene, 6 parts of E44 type epoxy resin, 20 parts of amino-functionalized molybdenum disulfide, 1.5 parts of polyethylene wax, 0.25 parts of di-tert-butyl peroxide, 0.1 parts of vinyltriethoxysilane, 10 parts of inorganic filler, 0.05 parts of triethylenetetramine, 2 parts of sulfur, 1 part of accelerator DM, and 0.5 part of accelerator M.

[0027] Among them, the preparation method of amino-functionalized molybdenum disulfide is as follows:

[0028] 100 g of molybdenum disulfide with a particle size of 100 - 200 nm was added to 250 mL of piranha solution. After ultrasonic oscillation treatment at 50 °C for 4 h, it was filtered out, washed successively with deionized water and absolute ethanol, dried at 105 °C for 2 h, then mixed with 5 L of toluene and 80 mL of water. While stirring, 240 mL of KH-900 was added. After ultrasonic oscillation treatment at 40 °C for 40 min, 116 mL of 0.1 mol / L dilute hydrochloric acid solution was dropped in. After dropping, the temperature was raised to 50 °C and ultrasonic oscillation treatment was carried out for 4 h. The obtained product was filtered out, washed successively with toluene, absolute ethanol and deionized water, and finally vacuum dried at 50 °C for 10 h to obtain amino-functionalized molybdenum disulfide.

[0029] The inorganic filler is the pyrolysis product of petroleum coke. Specifically, a tube furnace was used to pyrolyze petroleum coke at a working temperature of 1350 °C. First, the tube furnace was heated to the working temperature, then nitrogen was introduced at 800 ml / min to sweep for 15 min to discharge air. The porcelain boat loaded with petroleum coke was quickly pushed into the high-temperature core area of the tube furnace. After pyrolysis for 60 min, the porcelain boat was taken out and cooled to room temperature in a nitrogen atmosphere, and the pyrolysis product was ground.

[0030] The preparation method of the above high wear-resistant composite material:

[0031] Carboxy nitrile rubber and chlorinated polyethylene rubber were first mixed and kneaded, and then discharged. The temperature of the first-stage mixing was 120 °C, the time of the first-stage mixing was 10 min, and the rotor speed was 80 r / min. The obtained rubber compound was mixed with ultra-high molecular weight polyethylene, E44-type epoxy resin, amino-functionalized molybdenum disulfide, polyethylene wax, di-tert-butyl peroxide, vinyltriethoxysilane, inorganic filler, and organic amine in the second-stage mixing. The temperature of the second-stage mixing was 160 °C, the time of the second-stage mixing was 5 min, and the rotor speed was 120 r / min. Then sulfur, accelerator DM, and accelerator M were added to the obtained rubber compound, and after mixing evenly, it was passed through a thin roll 5 times to produce a sheet. After standing overnight, it was vulcanized on a flat vulcanizer. The vulcanization temperature was 180 °C, the vulcanization time was 30 min, and the vulcanization pressure was 25 MPa.

[0032] Example 2:

[0033] A high wear-resistant composite material, by weight, includes:

[0034] 100 parts of carboxy nitrile rubber, 20 parts of chlorinated polyethylene rubber, 70 parts of ultra-high molecular weight polyethylene, 15 parts of high-density polyethylene, 10 parts of low-density polyethylene, 10 parts of E44-type epoxy resin, 30 parts of amino-functionalized molybdenum disulfide, 2 parts of polyethylene wax, 0.25 part of di-tert-butyl peroxide, 0.1 part of vinyltriethoxysilane, 10 parts of inorganic filler, 0.1 part of triethylenetetramine, 2 parts of sulfur, 1 part of accelerator DM, and 0.5 part of accelerator M.

[0035] Among them, the preparation methods of amino-functionalized molybdenum disulfide and inorganic filler (pyrolysis product of petroleum coke) are the same as those in Example 1.

[0036] The preparation method of the above high wear-resistant composite material:

[0037] Mix carboxyl nitrile rubber and chlorinated polyethylene rubber in the first stage and then discharge the rubber. The temperature of the first-stage mixing is 120 °C, the time of the first-stage mixing is 10 min, the rotor speed is 80 r / min. The obtained rubber compound is subjected to second-stage mixing with ultra-high molecular weight polyethylene, E44-type epoxy resin, amino-functionalized molybdenum disulfide, polyethylene wax, di-tert-butyl peroxide, vinyltriethoxysilane, inorganic filler, and organic amine. The temperature of the second-stage mixing is 160 °C, the time of the second-stage mixing is 5 min, and the rotor speed is 120 r / min. Then, sulfur, accelerator DM, and accelerator M are added to the obtained rubber compound. After mixing evenly, it is passed through the mill 5 times to make sheets. After standing overnight, it is vulcanized on a flat vulcanizer. The vulcanization temperature is 180 °C, the vulcanization time is 40 min, and the vulcanization pressure is 30 MPa.

[0038] Example 3:

[0039] A high wear-resistant composite material, by weight, includes:

[0040] 80 parts of carboxyl nitrile rubber, 10 parts of chlorinated polyethylene rubber, 50 parts of ultra-high molecular weight polyethylene, 15 parts of high-density polyethylene, 5 parts of low-density polyethylene, 5 parts of E44-type epoxy resin, 20 parts of amino-functionalized molybdenum disulfide, 1 part of polyethylene wax, 0.25 part of di-tert-butyl peroxide, 0.1 part of vinyltriethoxysilane, 5 parts of inorganic filler, 0.01 part of triethylenetetramine, 2 parts of sulfur, 1 part of accelerator DM, and 0.5 part of accelerator M.

[0041] Among them, the preparation methods of amino-functionalized molybdenum disulfide and inorganic filler (pyrolysis product of petroleum coke) are the same as those in Example 1.

[0042] The preparation method of the above high wear-resistant composite material:

[0043] Mix carboxyl nitrile rubber and chlorinated polyethylene rubber in the first stage and then discharge the rubber. The temperature of the first-stage mixing is 120 °C, the time of the first-stage mixing is 10 min, the rotor speed is 80 r / min. The obtained rubber compound is subjected to second-stage mixing with ultra-high molecular weight polyethylene, E44-type epoxy resin, amino-functionalized molybdenum disulfide, polyethylene wax, di-tert-butyl peroxide, vinyltriethoxysilane, inorganic filler, and organic amine. The temperature of the second-stage mixing is 160 °C, the time of the second-stage mixing is 5 min, and the rotor speed is 120 r / min. Then, sulfur, accelerator DM, and accelerator M are added to the obtained rubber compound. After mixing evenly, it is passed through the mill 5 times to make sheets. After standing overnight, it is vulcanized on a flat vulcanizer. The vulcanization temperature is 150 °C, the vulcanization time is 20 min, and the vulcanization pressure is 15 MPa.

[0044] Example 4:

[0045] A highly wear-resistant composite material, by weight, includes:

[0046] 100 parts of carboxylated nitrile rubber, 10 parts of chlorinated polyethylene rubber, 60 parts of ultra-high molecular weight polyethylene, 12 parts of high-density polyethylene, 10 parts of low-density polyethylene, 5 parts of E44 type epoxy resin, 30 parts of amino molybdenum disulfide, 1 part of polyethylene wax, 0.25 part of di-tert-butyl peroxide, 0.1 part of vinyltriethoxysilane, 10 parts of inorganic filler, 0.01 part of triethylenetetramine, 2 parts of sulfur, 1 part of accelerator DM, 0.5 part of accelerator M.

[0047] Among them, the preparation methods of amino molybdenum disulfide and inorganic filler (pyrolysis product of petroleum coke) are the same as those in Example 1.

[0048] The preparation method of the above highly wear-resistant composite material:

[0049] Mix the carboxylated nitrile rubber and chlorinated polyethylene rubber in the first stage and then discharge the rubber. The temperature of the first-stage mixing is 120 °C, the time of the first-stage mixing is 10 min, the rotor speed is 80 r / min. The obtained rubber compound is mixed with ultra-high molecular weight polyethylene, E44 type epoxy resin, amino molybdenum disulfide, polyethylene wax, di-tert-butyl peroxide, vinyltriethoxysilane, inorganic filler, and organic amine in the second stage. The temperature of the second-stage mixing is 160 °C, the time of the second-stage mixing is 5 min, the rotor speed is 120 r / min. Then add sulfur, accelerator DM, and accelerator M to the obtained rubber compound, mix evenly, pass through the mill 5 times and take out the sheet. After standing overnight, vulcanize on a flat vulcanizer. The vulcanization temperature is 180 °C, the vulcanization time is 20 min, and the vulcanization pressure is 30 MPa.

[0050] Example 5:

[0051] A highly wear-resistant composite material, by weight, includes:

[0052] 80 parts of carboxylated nitrile rubber, 20 parts of chlorinated polyethylene rubber, 50 parts of ultra-high molecular weight polyethylene, 10 parts of high-density polyethylene, 5 parts of low-density polyethylene, 5 parts of E44 type epoxy resin, 20 parts of amino molybdenum disulfide, 2 parts of polyethylene wax, 0.25 part of di-tert-butyl peroxide, 0.1 part of vinyltriethoxysilane, 5 parts of inorganic filler, 0.1 part of triethylenetetramine, 2 parts of sulfur, 1 part of accelerator DM, 0.5 part of accelerator M.

[0053] Among them, the preparation methods of amino molybdenum disulfide and inorganic filler (pyrolysis product of petroleum coke) are the same as those in Example 1.

[0054] The preparation method of the above highly wear-resistant composite material:

[0055] Carboxy nitrile rubber and chlorinated polyethylene rubber are kneaded in one stage and then discharged. The temperature of the one-stage kneading is 120 °C, the time of the one-stage kneading is 10 min, the rotor speed is 80 r / min. The obtained rubber compound is subjected to two-stage kneading with ultra-high molecular weight polyethylene, E44 type epoxy resin, aminoated molybdenum disulfide, polyethylene wax, di-tert-butyl peroxide, vinyltriethoxysilane, inorganic filler, and organic amine. The temperature of the two-stage kneading is 160 °C, the time of the two-stage kneading is 5 min, and the rotor speed is 120 r / min. Then, sulfur, accelerator DM, and accelerator M are added to the obtained rubber compound, and after mixing evenly, it is passed through a thin roll 5 times to produce a sheet. After standing overnight, it is vulcanized on a flat vulcanizer. The vulcanization temperature is 150 °C, the vulcanization time is 40 min, and the vulcanization pressure is 15 MPa.

[0056] Comparative Example 1:

[0057] It is basically the same as Example 1, except that chlorinated polyethylene rubber is not added.

[0058] Comparative Example 2:

[0059] It is basically the same as Example 1, except that molybdenum disulfide is not subjected to aminoation treatment.

[0060] Comparative Example 3:

[0061] It is basically the same as Example 1, except that inorganic filler (pyrolysis product of petroleum coke) is not added.

[0062] Comparative Example 4:

[0063] It is basically the same as Example 1, except that white carbon black is used to replace the inorganic filler (pyrolysis product of petroleum coke).

[0064] Performance test:

[0065] The water lubricated friction and wear test equipment is: Rtec MFT-5000 high-speed ring-block friction and wear tester;

[0066] The high wear-resistant composite material prepared according to the formula in Example 1 is used as a specimen. The friction performance test conditions are: load 40 N, rotation speeds are 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200 rpm respectively, temperature 25 °C, and each rotation speed is maintained for 15 min. The friction coefficient value in the stable state is recorded, and the results are as Figure 1 shown;

[0067] The highly wear-resistant composite materials prepared according to the formulations in Examples 1-5 and Comparative Examples 1-4 were used as specimens. The wear performance test conditions were: load 40 N, rotational speed 400 rpm, temperature 25 °C, time 60 min; lubricating medium: water; test index: volume wear rate, and the volume wear rate was calculated according to the following formula:

[0068] K = (m1 - m2) / ρNL, where m1 is the mass of the specimen before the experiment, m2 is the mass of the specimen after the experiment, ρ is the density of the specimen, N is the load, and L is the final friction distance. The test results are shown in Table 1.

[0069] Table 1:

[0070]

[0071] As can be seen from Table 1 above, the highly wear-resistant composite material of the present invention has good wear resistance.

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A highly wear-resistant composite material, characterized in that, By weight parts, it includes: 80 - 100 parts of carboxylated nitrile rubber, 10 - 20 parts of chlorinated polyethylene rubber, 50 - 70 parts of ultra-high molecular weight polyethylene, 5 - 10 parts of epoxy resin, 20 - 30 parts of amino molybdenum disulfide, 1 - 2 parts of lubricant, 0.1 - 0.5 parts of crosslinking agent, 5 - 10 parts of inorganic filler, 0.01 - 0.1 parts of organic amine, 1 - 3.5 parts of vulcanization accelerator; It also includes high-density polyethylene and low-density polyethylene; The dosages of the high-density polyethylene and low-density polyethylene are respectively 20 - 30% and 10 - 20% of the weight of the ultra-high molecular weight polyethylene; The preparation method of the amino molybdenum disulfide is as follows: The molybdenum disulfide is hydroxylated with piranha solution, and then undergoes a hydrolysis reaction with the silane coupling agent KH-900 to amino-functionalize the molybdenum disulfide; The crosslinking agent includes di-tert-butyl peroxide and vinyl silane with a weight ratio of 1 - 5:1 - 5; The vinyl silane is any one or a combination of vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(β-methoxyethoxy)silane, vinyl tri-tert-butoxysilane, vinyl tri-tert-butylperoxysilane, vinyl triacetoxysilane; The inorganic filler is the pyrolysis product of petroleum coke at 900 - 1500 °C; The organic amine is any one or a combination of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, trimethylhexamethylenediamine; The lubricant is any one or a combination of liquid paraffin, solid paraffin, polyethylene wax, ethylene bisstearamide, glycerol monostearate, stearic acid, stearyl alcohol, oleic acid amide, zinc stearate, calcium stearate; The preparation method of the above high wear-resistant composite material: The carboxylated nitrile rubber and chlorinated polyethylene rubber are first stage-mixed and then discharged. The obtained rubber compound is second stage-mixed with ultra-high molecular weight polyethylene, epoxy resin, amino molybdenum disulfide, lubricant, crosslinking agent, inorganic filler, and organic amine. The vulcanization accelerator is added to the obtained rubber compound, and after mixing evenly, it is passed through a thin sheet, placed and vulcanized. The vulcanization temperature is 150 - 180 °C, the vulcanization time is 20 - 40 min, and the vulcanization pressure is 15 - 30 MPa.

2. A water-lubricated bearing, characterized in that, Prepared from the high wear-resistant composite material described in claim 1.

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