CN116478530A - Wear-resistant antistatic polyamide composite material and preparation method thereof - Google Patents

Wear-resistant antistatic polyamide composite material and preparation method thereof Download PDF

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Publication number
CN116478530A
CN116478530A CN202310344901.1A CN202310344901A CN116478530A CN 116478530 A CN116478530 A CN 116478530A CN 202310344901 A CN202310344901 A CN 202310344901A CN 116478530 A CN116478530 A CN 116478530A
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composite material
wear
polyamide composite
ptfe
resistant antistatic
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CN116478530B (en
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陈飒飒
吴长波
黄牧
易新
周华龙
王丰
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Shanghai Kingfa Science and Technology Co Ltd
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Shanghai Kingfa Science and Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a wear-resistant antistatic polyamide composite material and a preparation method thereof. The composite material comprises the following components in parts by weight: 35-65 parts of polyamide resin; 10-20 parts of glass fiber; 10-20 parts of an antiwear agent; 15-25 parts of antistatic agent. The composite material has better wear resistance and antistatic property.

Description

Wear-resistant antistatic polyamide composite material and preparation method thereof
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a wear-resistant antistatic polyamide composite material and a preparation method thereof.
Background
Polyamide commonly called nylon (PA) is crystalline engineering plastic and has the advantages of excellent comprehensive mechanical property, wear resistance, solvent resistance and the likeThe method is widely applied to the fields of automobiles, electronic appliances, machinery, instruments and meters and the like. When used as parts with relative motion such as bearings and gears, the polyamide has certain limitations on wear resistance, mechanical strength and the like, and particularly in occasions with high load, high frequency, high speed and long-term motion, the polyamide is required to be reinforced and wear-resistant modified in practice so as to ensure the service life of the parts and the safety of equipment. As with most high molecular materials, polyamide has good electrical insulation property, and its volume resistivity is generally 10 13 ~10 15 The conductivity of the material is far smaller than that of a metal material, and charges are easier to accumulate in the processing and using processes to generate static electricity. Parts with static electricity are easy to generate dust static adsorption and even generate static breakdown to cause damage to electronic components. Therefore, in some occasions where the antistatic requirement is high, research is required to solve the antistatic or conductive problems of the wear-resistant material.
Fluoropolymers generally have good self-lubricating properties and a low coefficient of friction and are often used as wear resistant materials or wear resistant additives. Chinese patent CN105849182a discloses a sliding material with addition of PTFE (polytetrafluoroethylene) of multimodal molecular weight, optimizing the friction coefficient and wear resistance of a thermoplastic-based sliding material by adding PTFE having at least two different molecular weights; this approach, while improving wear resistance, has limited improvement. Chinese patent CN100458598C discloses a fixing rotor which obtains good abrasion resistance and release effects using PFA (perfluoropropyl perfluorovinyl ether/polytetrafluoroethylene copolymer) and PTFE and a binder composition as coating layers, but PFA is mainly used as an improvement in release effects in the disclosed technology, but the modification is not suitable for injection molding. Furthermore, the above disclosed technology also does not mention the effect of improvement of wear resistance on the antistatic properties of the material itself. In practice, nylon materials are still required to be further improved in terms of wear resistance and antistatic property when used as injection molded fine parts such as precision gears, bearings, sliding parts and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a wear-resistant antistatic polyamide composite material and a preparation method thereof, so as to overcome the defect of poor wear resistance and antistatic property of a polyamide material in the prior art.
The invention provides a wear-resistant antistatic polyamide composite material, which comprises the following components in parts by weight:
the wear-resistant agent comprises 50-80% of polytetrafluoroethylene PTFE and 50-20% of perfluoropropyl perfluorovinyl ether/polytetrafluoroethylene copolymer PFA according to weight ratio, wherein the PTFE has a number average molecular weight of 9 multiplied by 10 3 -7×10 4 g/mol, the PFA number average molecular weight is 5X 10 5 -5×10 6 g/mol。
Preferably, the composite material comprises the following components in parts by weight:
preferably, the polyamide resin is nylon 6.
Preferably, the weight ratio of PTFE in the wear-resistant agent is 55% -75%, and the weight ratio of PFA is 45% -25%.
Preferably, the PTFE has an average particle diameter of 2 μm to 25. Mu.m. The particle size of the wear-resistant PTFE has obvious influence on the friction coefficient, and the reason is probably that if the size of the powder is too small, the coating surface of the micro powder particles by the matrix is small, the holding force is small, and the micro powder particles are easy to fall off in the sliding friction process; when the particle size is too large, the number of PTFE particles distributed on the friction surface is relatively reduced, the total contact area with the friction surface is reduced, and the contact area between the matrix resin and the friction surface is relatively increased, so that the reduction of the friction coefficient is not facilitated.
More preferably, the PTFE has an average particle diameter of 10 μm to 12. Mu.m.
Preferably, the glass fibers are chopped alkali-free glass fibers.
Preferably, the antistatic agent is a conductive whisker comprising conductive potassium titanate whisker and/or conductive calcium sulfate whisker.
Preferably, the preparation method of the conductive calcium sulfate whisker comprises the following steps: pulping calcium sulfate whisker in deionized water, performing ultrasonic treatment to obtain a calcium sulfate suspension, adding hydrochloric acid solution of tin chloride and antimony chloride, stirring and mixing, filtering, washing, drying, grinding, and calcining (calcining can remove crystal water from the calcium sulfate whisker) to obtain the conductive calcium sulfate whisker.
Preferably, the calcium sulfate suspension concentration is 15-25g/mL.
Preferably, the mol ratio of the stannic chloride, the antimonic chloride and the calcium sulfate whisker is 1 (2.5-3.5): 1.5-2.5.
Preferably, the concentration of the hydrochloric acid solution of the stannic chloride and the antimony chloride is 3-10mol/L.
Preferably, the calcination temperature is 700-800 ℃ and the calcination time is 1-5 hours.
Preferably, the composite material further comprises 0-2 parts of other auxiliary agents.
Preferably, the further auxiliary agent comprises an antioxidant and/or a lubricant.
Preferably, the antioxidant is 0.1-0.5 parts by weight.
Preferably, the antioxidant comprises one or more of hindered amine antioxidants, phosphite antioxidants and thioester antioxidants.
Preferably, the lubricant is 0.3 to 1 part by weight.
Preferably, the lubricant comprises one or more of stearate, hyperbranched polyester, aliphatic fatty acid ester, ethylene-acrylic acid copolymer.
The invention also provides a preparation method of the wear-resistant antistatic polyamide composite material, which comprises the following steps:
mixing all components except glass fiber, adding the obtained premix into a double-screw extruder from a main feeding port, feeding the glass fiber into the double-screw extruder from side, and carrying out melt extrusion, water cooling and granulating to obtain the wear-resistant antistatic polyamide composite material.
Preferably, the melt extrusion temperature is 200 to 270 ℃.
Preferably, the length-diameter ratio of the main machine screw of the double-screw extruder is (30-40): 1, and the rotating speed is 250-350r/min.
The invention also provides application of the wear-resistant antistatic polyamide composite material in electronic mechanical equipment, such as sliding bearings, transmission gears and the like.
The invention adopts the combination of the low molecular weight PTFE and the high molecular weight PFA, the high molecular weight PFA particles on the friction interface are uniformly distributed around the low molecular weight PTFE particles, and can disperse and bear partial friction stress, so that the PTFE transfer film delays the damage and the falling off, the composite material matrix can be better protected, and the wear resistance of the composite material is improved while the lower friction coefficient is kept.
Advantageous effects
The invention adopts the combination of low molecular weight PTFE and high molecular weight PFA, can obviously improve the wear resistance of the composite material and simultaneously ensure the antistatic property of the composite material. The dynamic friction coefficient of the composite material is below 0.23, such as 0.17-0.23, the abrasion loss is below 60mg, such as 19-56mg, and the volume resistivity is 7.5X10 9 Omega cm or less, e.g. 2.5X10 8 -7.3×10 9 Ω·cm。
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Reagent source:
polyamide resin: brand PA6 HY2800A, sea-sun chemical fiber group;
glass fiber: trade mark ECS11-03-560A, china boulder Co., ltd;
wear-resistant agent:
wear-resistant agent 1-1: PTFE having a number average molecular weight of 3X 10 4 g/mol, average grain size of 12 μm, brand GR-C0590P, zhejiang Gerui New Material Co., ltd;
wear-resistant agent 1-2: PTFE having a number average molecular weight of 1.2X10 4 g/mol, average particle size of 2.5 μm, brand GR-C525, zhejiang Gerui New Material Co., ltd;
wear-resistant agent 1-3: PTFE having a number average molecular weight of 5X 10 4 g/mol, average particle size of 25 μm, brand RF-225A, zongfang Runfulong technology Co., ltd;
wear-resistant agent 1-4: PTFE having a number average molecular weight of 9X 10 3 g/mol, average grain size of 1.5 μm, brand A01, shenyang Tianyuxiang micro powder materials factory;
wear-resistant agent 1-5: PTFE having a number average molecular weight of 5.5X10 4 g/mol, average particle diameter of 28. Mu.m, trade name M111, japanese Dajin Co.
Wear-resistant agent 1-6: PTFE having a number average molecular weight of 6.5X10 3 g/mol, average grain size of 3.5 μm, brand A02, shenyang Tianyuxiang micro powder materials factory;
wear-resistant agent 1-7: PTFE having a number average molecular weight of 1X 10 5 g/mol, average particle diameter of 20 μm, trade name M112, japanese Dajin Co.
Wear-resistant agent 2-1: PFA having a number average molecular weight of 3.5X10 6 g/mol, trade name AC5600, japanese Dajin company;
2-2 of an antiwear agent: PFA having a number average molecular weight of 5.5X10 5 g/mol, brand ACX-34, japanese Dajin company;
2-3 parts of wear-resistant agent: PFA having a number average molecular weight of 2.3X10 5 g/mol, brand P7010, suwei company, U.S.;
2-4 parts of wear-resistant agent: PFA having a number average molecular weight of 6.5X10 6 g/mol, brand ACX-31, japanese Dajin company;
antistatic agent 1: conductive potassium titanate whisker with the trade name ECP-TF1 and Beijing special security antistatic equipment factory;
antistatic agent 2: the preparation method of the conductive calcium sulfate whisker comprises the following steps: pulping calcium sulfate whisker (NP-M02-I30 of Shanghai Feng Zhu composite New Material science and technology Co., ltd.) in deionized water, and performing ultrasonic treatment to fully disperse to obtain calcium sulfate suspension with the concentration of 20g/mL; adding 6mol/L tin chloride and antimony chloride (molar ratio 1:3) hydrochloric acid solution into the calcium sulfate suspension, and stirring and mixing, wherein the molar ratio of the tin chloride to the calcium sulfate whisker is 1:2; filtering, washing, drying and grinding the suspension into particles; then conducting high-temperature treatment for 3 hours at 750 ℃ to obtain conductive calcium sulfate whisker;
other auxiliaries:
an antioxidant: a mixture of hindered amine antioxidant (N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine) and phosphite antioxidant (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite) in a weight ratio of 1:1, commercially available; and (3) a lubricant: calcium stearate, commercially available;
unless otherwise specified, both the parallel examples and comparative examples of the present invention are commercially available products in which one component (e.g., antioxidant, lubricant) is the same.
The preparation method of the polyamide composite material comprises the following steps: according to the proportions shown in tables 1, 2 and 3, the components except glass fibers are put into a high-speed mixer to be mixed and stirred uniformly, the obtained premix is added into a double-screw extruder from a main feeding port, the glass fibers are fed and added at the side, and the wear-resistant antistatic polyamide composite material is obtained through melt extrusion, water cooling and granulating, wherein the melt extrusion temperature is 200-270 ℃, the length-diameter ratio of the screw is (30-40): 1, and the rotating speed is 250-350r/min.
The prepared polyamide composite material is subjected to injection molding to prepare a test square board for performance test evaluation:
(1) Antistatic performance test: the volume resistivity of the material was tested with reference to GB1410-1989 test method for volume and surface resistivity of solid insulation material.
(2) Abrasion resistance test: the dynamic friction coefficient and the abrasion loss of the material were measured with reference to JIS K7218-1986 Plastic sliding abrasion test method; a method, ring abrasion test conditions: for carbon steel in grinding material S45C, the load was 200N, the speed was 0.5m/S, the test time=100 min, the drying was performed at 80 ℃/10h before the test, and the weight change was measured after the drying at 80 ℃/10h after the test.
Table 1 examples 1-9 proportions (parts by weight)
Table 2 examples 10-15 ratios (parts by weight)
Table 3 comparative example ratio (parts by weight)
As can be seen from tables 1 to 3, the polyamide composite material of the present invention has a dynamic friction coefficient of 0.17 to 0.23, an abrasion loss of 19 to 56mg and a volume resistivity of 2.5X10 8 -7.3×10 9 Omega cm. The average particle diameter of PTFE in example 1 was 12. Mu.m, the average particle diameter of PTFE in example 2 was 2.5. Mu.m, the average particle diameter of PTFE in example 3 was 25. Mu.m, the average particle diameter of PTFE in example 4 was 1.5. Mu.m, the average particle diameter of PTFE in example 5 was 28. Mu.m, the coefficient of dynamic friction and the abrasion amount of example 1 were smaller than those of examples 2 to 5, and the volume resistivity was 10 6 -10 9 An omega cm section belonging to antistatic grade; examples 2-3 had a dynamic coefficient of friction and abrasion loss of less than examples 4-5, and had a volume resistivity of 10 6 -10 9 Omega cm section, belonging to antistatic fieldIt can be seen from the above that the PTFE having a preferable average particle diameter can reduce the coefficient of dynamic friction and the abrasion loss while securing antistatic properties. PTFE in examples 1 and 6 represents 50% and 80% of the total weight of the antiwear agent, PTFE in examples 7 and 8 represents 55% and 75% of the total weight of the antiwear agent, respectively, and the dynamic friction coefficient and abrasion loss in examples 7 and 8 are smaller than those in examples 1 and 6, respectively, while the volume resistivity is 10 6 -10 9 An omega cm section belonging to antistatic grade; it follows that the PTFE ratio is preferred to reduce the coefficient of dynamic friction and the amount of abrasion while ensuring antistatic properties. Examples 13 and 14 are preferred and examples 11 and 12 are not preferred, and examples 13 and 14 have a coefficient of dynamic friction and abrasion less than examples 11 and 12 and a volume resistivity of 10 6 -10 9 An omega cm section belonging to antistatic grade; therefore, the preferable weight parts of the components can reduce the dynamic friction coefficient and the abrasion loss, and ensure the antistatic performance.
The PTFE molecular weights in comparative examples 1 and 2 are not within the scope of the present invention, and the PFA molecular weights in comparative examples 3 and 4 are not within the scope of the present invention, and the dynamic friction coefficients, abrasion amounts, volume resistivities of comparative examples 1 to 4 are significantly inferior to those of example 1. Therefore, the invention adopts the combination of the low molecular weight PTFE and the high molecular weight PFA, can obviously improve the wear resistance of the composite material and simultaneously ensures the antistatic property of the composite material.

Claims (10)

1. The wear-resistant antistatic polyamide composite material is characterized by comprising the following components in parts by weight:
the wear-resistant agent comprises 50-80% of polytetrafluoroethylene PTFE and 50-20% of perfluoropropyl perfluorovinyl ether/polytetrafluoroethylene copolymer PFA according to weight ratio, wherein the PTFE has a number average molecular weight of 9 multiplied by 10 3 -7×10 4 g/mol, the PFA number average molecular weight is 5X 10 5 -5×10 6 g/mol。
2. The wear-resistant antistatic polyamide composite material according to claim 1, wherein the composite material comprises, in parts by weight:
3. the abrasion resistant antistatic polyamide composite material according to claim 1, wherein said polyamide resin is nylon 6; the weight ratio of PTFE in the wear-resistant agent is 55% -75%, and the weight ratio of PFA is 45% -25%.
4. The abrasion-resistant antistatic polyamide composite material according to claim 1, wherein the PTFE has an average particle diameter of 2 μm to 25 μm.
5. The abrasion resistant antistatic polyamide composite material of claim 1 wherein said glass fibers are chopped alkali free glass fibers.
6. The abrasion resistant antistatic polyamide composite material according to claim 1, wherein the antistatic agent is a conductive whisker comprising conductive potassium titanate whisker and/or conductive calcium sulfate whisker.
7. The abrasion resistant antistatic polyamide composite material according to claim 1, wherein said composite material further comprises 0-2 parts of other adjuvants; the other auxiliary agents comprise antioxidants and/or lubricants.
8. A method of preparing the abrasion resistant antistatic polyamide composite material of any one of claims 1-7, comprising:
mixing all components except glass fiber, adding the obtained premix into a double-screw extruder from a main feeding port, feeding the glass fiber into the double-screw extruder from side, and carrying out melt extrusion, water cooling and granulating to obtain the wear-resistant antistatic polyamide composite material.
9. The method of claim 8, wherein the melt extrusion temperature is 200 to 270 ℃.
10. Use of a wear resistant antistatic polyamide composite material according to any one of claims 1 to 7 in an electromechanical device.
CN202310344901.1A 2023-04-03 2023-04-03 Wear-resistant antistatic polyamide composite material and preparation method thereof Active CN116478530B (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351882A (en) * 1981-01-13 1982-09-28 E. I. Du Pont De Nemours And Company Article coated with fluoropolymer finish with improved durability
US5874489A (en) * 1996-10-15 1999-02-23 E. I. Du Pont De Nemours And Company Nonstick finish for molding articles
CN101242912A (en) * 2005-08-12 2008-08-13 纳幕尔杜邦公司 Process for improving the corrosion resistance of a non-stick coating on a substrate
CN101864170A (en) * 2009-04-17 2010-10-20 爱尔铃克铃尔股份公司 Polymer complex and the structural part that under the situation of using this mixture, prepares
CN101932268A (en) * 2008-02-07 2010-12-29 杜邦公司 Article with non-stick finish and improved scratch resistance
CN103173117A (en) * 2011-12-22 2013-06-26 上海鑫氟化工材料有限公司 Coating for piston of compressor of automotive air conditioner and preparation method and application of coating
CN105860524A (en) * 2016-04-29 2016-08-17 四川大学 Thermoplastic low-friction wear-resistant composite material and preparation method thereof
EP3357587A1 (en) * 2017-02-07 2018-08-08 Industrielack AG Non-stick coating
CN111465997A (en) * 2017-12-26 2020-07-28 大金美国股份有限公司 Electric wire, method for producing electric wire, and master batch
CN113121988A (en) * 2019-12-31 2021-07-16 财团法人工业技术研究院 Composite material and foam prepared therefrom

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351882A (en) * 1981-01-13 1982-09-28 E. I. Du Pont De Nemours And Company Article coated with fluoropolymer finish with improved durability
US5874489A (en) * 1996-10-15 1999-02-23 E. I. Du Pont De Nemours And Company Nonstick finish for molding articles
CN101242912A (en) * 2005-08-12 2008-08-13 纳幕尔杜邦公司 Process for improving the corrosion resistance of a non-stick coating on a substrate
CN101932268A (en) * 2008-02-07 2010-12-29 杜邦公司 Article with non-stick finish and improved scratch resistance
CN101864170A (en) * 2009-04-17 2010-10-20 爱尔铃克铃尔股份公司 Polymer complex and the structural part that under the situation of using this mixture, prepares
CN103173117A (en) * 2011-12-22 2013-06-26 上海鑫氟化工材料有限公司 Coating for piston of compressor of automotive air conditioner and preparation method and application of coating
CN105860524A (en) * 2016-04-29 2016-08-17 四川大学 Thermoplastic low-friction wear-resistant composite material and preparation method thereof
EP3357587A1 (en) * 2017-02-07 2018-08-08 Industrielack AG Non-stick coating
CN111465997A (en) * 2017-12-26 2020-07-28 大金美国股份有限公司 Electric wire, method for producing electric wire, and master batch
CN113121988A (en) * 2019-12-31 2021-07-16 财团法人工业技术研究院 Composite material and foam prepared therefrom

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