CN109737159B - Composite salt binder composite friction material and preparation method thereof - Google Patents
Composite salt binder composite friction material and preparation method thereof Download PDFInfo
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- CN109737159B CN109737159B CN201910025160.4A CN201910025160A CN109737159B CN 109737159 B CN109737159 B CN 109737159B CN 201910025160 A CN201910025160 A CN 201910025160A CN 109737159 B CN109737159 B CN 109737159B
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Abstract
The invention discloses a composite salt binder composite friction material and a preparation method thereof, wherein the main components of the composite salt binder composite friction material comprise a silicate binder, a phosphate binder, an auxiliary agent, a curing agent, a toughness regulator, reinforcing fibers, a friction performance regulator and a filler, wherein the silicate binder mainly takes sodium silicate and potassium silicate as raw materials, the phosphate binder mainly takes liquid aluminum dihydrogen phosphate as a raw material, and the phosphate binder is prepared into a composite salt binder as a friction material binder by mixing with a calcium fluoride auxiliary agent. The composite inorganic salt solution mixture is used as the adhesive, and the characteristics of good flame retardance, environmental protection, no toxicity, simple preparation process and high temperature resistance of the inorganic salt adhesive are utilized to replace resin adhesives. The silicate adhesive and phosphate composite has excellent adhesive property to carbon fiber, barite, alumina and other powder materials, effectively improves the friction coefficient stability of medium-temperature and high-temperature regions, solves the problem of heat fading of common resin-based friction materials, and improves the safety of the friction materials in practical use.
Description
Technical Field
The invention relates to a friction material and a preparation method thereof, in particular to a preparation method of the friction material which is suitable for brake pads of motor vehicles, machine tools, brakes of electrodes, clutch linings and friction materials needing to work at high temperature.
Background
The friction material for automobile braking is commonly called as a brake pad, is one of the most important safety parts in an automobile braking system, and is related to the life and property safety of automobile drivers. The brake pad is generally prepared by uniformly mixing a binder, a reinforcing fiber, a friction performance regulator, a filler and the like as raw materials, and then carrying out hot pressing and curing.
The resin-based friction material widely used in the market at present has the advantages of excellent mechanical property, low noise, low cost and the like, but as the binder is mainly composed of organic components such as phenolic resin and the like, the friction coefficient is unstable, the wear resistance is poor, and particularly, the phenomenon of high-temperature heat fading is easy to occur, the braking efficiency is seriously deteriorated, even the brake failure is caused, and the accident is caused. The research on solving the problem of heat fading of friction materials has been a hot spot in the research of friction materials, and the search for adhesives capable of bearing high temperature to replace resin binders is one of the directions of people's efforts.
Inorganic binders such as silicate binders and phosphate binders have the advantages of good flame retardance, environmental protection, no toxicity, low cost, low curing shrinkage, simple use method, good durability and the like. The base material of the silicate binder is sodium silicate, potassium silicate or mixed base material, and can provide good binding action for the composite material in a medium-low temperature range. Phosphate binders generally have good adhesive properties in the medium-high temperature range. Liucheng Lun et al uses the mixture of sodium water glass and potassium water glass as base material, and adds some metal oxides, non-metal oxides and metal powder to prepare adhesive with high adhesive strength, room temperature curing property, easy construction and other features, and can raise the adhesion of composite material in middle and high temperature range. Nora and the like use aluminum dihydrogen phosphate as a base material, magnesium oxide as a curing agent, and silicon dioxide, aluminum oxide and the like as fillers to prepare a refractory material which can be cured at room temperature and has a compact structure and high strength. The sodium fluorosilicate is used as curing agent to prepare sodium silicate adhesive with excellent curing performance. Copper oxide is used as a curing agent of the phosphate adhesive, and polyphosphoric acid molecules can be connected to form a continuously distributed inorganic high polymer by forming-O-Cu-O-ionic bonds, so that the bonding strength is improved. However, bonded composites made with these binders are very brittle in the medium and high temperature range and are not suitable for direct use in making friction materials. Many studies on the performance of inorganic salt adhesives have been reported, but the research on the application of inorganic binders in the preparation of friction materials has been very rare.
The inventor researches and discovers that the dehydration products of the compound prepared from the mixed salt of sodium silicate and potassium silicate and phosphate have a complex crosslinking effect with each other at the temperature of 200-400 ℃, the complex crosslinking generates polymers with complex forms, and the complex crosslinking effect is more complete and severe at higher temperature. The polymer has excellent bonding performance on carbon fibers, barite, alumina and other powder materials. Based on the research result of the inventor, the invention uses the silicate and phosphate compound as the binder and the nitrile rubber as the toughness regulator, and adopts the hot-press molding process to prepare the composite friction material. In the friction braking process of the friction material, the high temperature generated by friction is utilized to promote the compound salt to generate the compound crosslinking effect, so that the adhesive forms good bonding strength, the stability of the friction performance of the friction material in a medium-temperature and high-temperature interval is obviously improved, and the problem of heat fading of the friction material in the medium-temperature and high-temperature areas is solved.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant adhesive with high bonding strength and good mechanical property, which replaces the traditional resin adhesive as a friction material adhesive, so that the stability of the friction coefficient of a medium-temperature and high-temperature area of the friction material is improved, and the problem of heat fading of the material is solved. The invention utilizes the discovery of the inventor that the dehydration products of the compound prepared by the mixed salt of sodium silicate and potassium silicate and phosphate are mutually compounded and crosslinked at the temperature of 200-400 ℃, the compound crosslinking action generates a polymer with a more complex form, the compound crosslinking action is stronger along with the temperature rise, and particularly when a calcium fluoride auxiliary agent exists, the compound crosslinking action product has excellent bonding performance on carbon fibers, barite, alumina and other powder materials. The silicate binder is mainly used for dehydration at a low temperature region (300 ℃) to form polymers and the like, the phosphate binder is used for polymerization and polycondensation at a medium temperature region (250-450 ℃) to form metaphosphate, composite crosslinking is performed at a medium temperature region (200-400 ℃) under the action of a calcium fluoride auxiliary agent, a crosslinked product has good high-temperature binding performance, and the temperature region is the temperature region where resin in the friction material is decomposed and loses efficacy. The research results of the inventor provide a new theoretical basis for designing a novel friction material and provide a technical basis for developing the friction material with good heat fading resistance. The invention designs and prepares the friction material with better performance in a middle and high temperature area by utilizing the characteristic of excellent high-temperature bonding performance of a silicate and phosphate composite crosslinking reaction product; the normal-temperature mechanical property of the friction material is obtained by utilizing the bonding effect of hydration products of the mixed salt of sodium silicate and potassium silicate in the range from normal temperature to medium temperature (less than 300 ℃); the friction heat of the composite salt and the auxiliary agent in the friction braking process is utilized to form high temperature (200-400 ℃) of a friction interface, and a product with a composite crosslinking effect has an excellent bonding effect, so that the friction material has stable tribology performance in a medium-high temperature region.
The invention provides a composite salt binder composite friction material, which comprises the following components in parts by weight:
15-20 parts of silicate binder
10-15 parts of phosphate binder
2.5-5 parts of calcium fluoride auxiliary agent
5-15 parts of curing agent
5-15 parts of reinforcing fiber
2.5-10 parts of toughness regulator
10-60 parts of friction performance regulator and filler
The preparation method of the composite salt binder composite friction material provided by the invention mainly comprises the following steps:
(1) the preparation process of the composite salt binder comprises the following steps: and adding 10-50 parts of potash water glass with the same modulus and baume degree into 100 parts of sodium water glass with the modulus of 2.8 and the baume degree of 45, and uniformly mixing and stirring to obtain silicate binders with different Na/K. Weighing phosphoric acid and aluminum hydroxide with a molar ratio of 10:3, mixing and stirring until the solution is clear and transparent, heating at about 85 ℃ to evaporate water in the solution to proper viscosity, stopping heating, and cooling to obtain the liquid phosphate binder (aluminum dihydrogen phosphate). Adding 15-20 parts of silicate binder and 10-15 parts of phosphate binder into 2.5-5 parts of calcium fluoride auxiliary agent, uniformly stirring, heating at 25-50 ℃ and stirring for 10min to obtain the composite salt binder.
(2) Mixing and stirring a curing agent, reinforcing fibers, a friction performance regulator and a filler for 2 minutes at normal temperature, introducing nitrile rubber serving as a toughness regulator, and mixing and stirring for 1 minute; placing the mixed powder into a forced air drying oven for drying for 1-3 hours, introducing the composite salt binder after drying, and mixing and stirring for 10-15 minutes; and (3) molding the uniformly mixed and stirred composite material at 130 ℃ and under the pressure of 10-20 MPa for 60-90 minutes, and then carrying out heat treatment at 130-190 ℃ for 10-20 hours to obtain the composite salt binder composite friction material.
In the invention, the composite salt binder is an aqueous solution prepared by mixing an aqueous solution mixture of sodium silicate and potassium silicate with liquid aluminum dihydrogen phosphate and calcium fluoride according to different proportions.
The auxiliary agent is calcium fluoride.
The curing agent is a plurality of sodium fluosilicate, magnesium oxide and zinc oxide, and the toughness regulator is nitrile rubber.
The reinforcing fiber can be steel fiber, carbon fiber or the mixture of the steel fiber and the carbon fiber.
The friction performance regulator and the filler can be selected from barite, wollastonite, graphite, copper powder, silicon carbide, boron carbide and alumina.
The invention has the following beneficial effects:
the composite salt binder has the advantages of good flame retardance, environmental protection, no toxicity, low curing shrinkage, low cost, simple use method, good durability and the like, can resist high temperature of 400-500 ℃, can replace the resin binder of the traditional friction material, can ensure that the mechanical property of the friction material meets related industrial standards, can remarkably improve the stability of the friction coefficient of a medium-temperature region and a high-temperature region of the friction material, and effectively solves the problem of heat fading of the friction material in the medium-temperature region and the high-temperature region, thereby improving the safety of the friction material in practical use.
Detailed Description
The present invention is further described below with reference to examples.
Example 1:
adding 10 parts of potash water glass with the same modulus and baume degree into 100 parts of sodium water glass with the modulus of 2.8 and the baume degree of 45, and uniformly mixing and stirring to obtain the silicate binder with the Na/K of 10/1.
Weighing 20 parts of silicate binder with silicate Na/K of 10/1, adding 10 parts of liquid aluminum dihydrogen phosphate and 2.5 parts of calcium fluoride auxiliary agent, uniformly mixing and stirring, heating at 25-50 ℃, and stirring for 10min to obtain the composite salt binder.
Weighing 3 parts of sodium fluosilicate, 2 parts of copper oxide, 12.5 parts of carbon fiber, 12.5 parts of barite, 5 parts of aluminum oxide, 3 parts of silicon carbide, 2 parts of copper powder, 2 parts of graphite and 2 parts of boron carbide, mixing and stirring for 2 minutes, then weighing 12.5 parts of nitrile rubber as a toughness regulator, introducing, mixing and stirring for 1 minute; and (3) placing the mixed powder into a forced air drying oven for drying for 3 hours, and drying to obtain the friction material matrix powder. Adding 65 parts of composite salt binder into 100 parts of matrix powder, and mixing and stirring for 15 minutes; and (3) molding the uniformly mixed and stirred composite material at 130 ℃ and 15MPa for 60 minutes, then preserving heat at 140 ℃ for 3 hours, preserving heat at 160 ℃ for 3 hours, and preserving heat at 180 ℃ for 10 hours to obtain the composite salt binder composite friction material.
Example 2:
adding 30 parts of potash water glass with the same modulus and baume degree into 100 parts of sodium water glass with the modulus of 2.8 and the baume degree of 45, and uniformly mixing and stirring to obtain the silicate binder with the Na/K of 10/3.
Weighing 15 parts of silicate binder with silicate Na/K of 10/3, adding 10 parts of liquid aluminum dihydrogen phosphate and 4 parts of calcium fluoride auxiliary agent, uniformly mixing and stirring, heating at 25-50 ℃, and stirring for 10min to obtain the composite salt binder.
Weighing 3 parts of sodium fluosilicate, 1 part of copper oxide, 1 part of magnesium oxide, 12.5 parts of carbon fiber, 10 parts of barite, 10 parts of wollastonite, 5 parts of aluminum oxide, 3 parts of silicon carbide, 2 parts of copper powder, 2 parts of graphite and 2 parts of boron carbide, mixing and stirring for 2 minutes, then weighing 7.5 parts of nitrile rubber as a toughness regulator, introducing, mixing and stirring for 1 minute; and (3) placing the mixed powder into a forced air drying oven for drying for 3 hours, and drying to obtain the friction material matrix powder. Adding 75 parts of silicate binder into 100 parts of matrix powder, and mixing and stirring for 15 minutes; and (3) molding the uniformly mixed and stirred composite material at 130 ℃ and 20MPa for 90 minutes, then preserving heat at 140 ℃ for 1 hour, preserving heat at 150 ℃ for 1 hour, preserving heat at 160 ℃ for 1 hour, preserving heat at 170 ℃ for 1 hour, and preserving heat at 180 ℃ for 10 hours to obtain the composite salt binder composite friction material.
Example 3:
adding 50 parts of potash water glass with the same modulus and baume degree into 100 parts of sodium water glass with the modulus of 2.8 and the baume degree of 45, and uniformly mixing and stirring to obtain the silicate binder with the Na/K of 10/5.
Weighing 15 parts of silicate binder with silicate Na/K of 10/5, adding 15 parts of liquid aluminum dihydrogen phosphate and 5 parts of calcium fluoride auxiliary agent, uniformly mixing and stirring, heating at 25-50 ℃, and stirring for 10min to obtain the composite salt binder.
Weighing 2 parts of sodium fluosilicate, 2 parts of copper oxide, 1 part of zinc oxide, 12.5 parts of carbon fiber, 10 parts of barite, 5 parts of wollastonite, 5 parts of alumina, 5 parts of silicon carbide, 2 parts of copper powder, 2 parts of graphite and 2 parts of boron carbide, mixing and stirring for 2 minutes, then weighing 10 parts of nitrile rubber as a toughness regulator, introducing, mixing and stirring for 1 minute; and (3) placing the mixed powder into a forced air drying oven for drying for 3 hours, and drying to obtain the friction material matrix powder. Adding 50 parts of silicate binder into 100 parts of matrix powder, and mixing and stirring for 15 minutes; and (3) molding the uniformly mixed and stirred composite material at 130 ℃ and 15MPa for 90 minutes, then preserving heat at 140 ℃ for 3 hours, preserving heat at 160 ℃ for 3 hours, and preserving heat at 180 ℃ for 10 hours to obtain the composite salt binder composite friction material.
Testing the friction coefficient of the prepared friction material on a constant-speed friction tester according to the national standard GB 5763-1998; the impact strength is measured on an XJJ-5 type simply supported beam impact tester according to the national standard GB/T1043-2008 rigid plastic simply supported beam impact test method. The specific test results are shown in the following table:
as can be seen from the table above, the friction coefficient of the product of the invention is stable, especially the high-temperature friction coefficient is obviously improved compared with the traditional resin-based friction material, and the problem of heat fading is effectively solved; the impact toughness is reduced compared with the traditional resin-based friction material, but still higher than the national standard requirement. The invention shows that the composite salt binder replaces the traditional resin binder to improve the high-temperature binding strength, and the special high-temperature resistance of the composite salt binder is utilized to effectively improve the stability of the high-temperature friction coefficient of the friction material and solve the problem of heat fading on the basis of stabilizing the friction coefficient of the friction material and ensuring the composite standard of impact toughness, thereby improving the safety of the friction material in actual use.
Claims (5)
1. The composite salt binder composite friction material is characterized by comprising the following components in parts by weight:
15-20 parts of silicate binder
10-15 parts of phosphate binder
2.5-5 parts of calcium fluoride auxiliary agent
The silicate binder, the phosphate binder and the calcium fluoride auxiliary agent form a composite salt binder;
5-15 parts of curing agent
5-15 parts of reinforcing fiber
2.5-10 parts of toughness regulator
10-60 parts of friction performance regulator and filler
The silicate binder is a mixed aqueous solution of sodium silicate and potassium silicate; the phosphate binder is liquid aluminum dihydrogen phosphate; the curing agent is selected from sodium fluosilicate, magnesium oxide and zinc oxide; the auxiliary agent is calcium fluoride; the reinforced fiber is carbon fiber, steel fiber or the mixture of the carbon fiber and the steel fiber; the toughness regulator is nitrile rubber; the friction performance regulator and the filler are selected from barite, wollastonite, graphite, copper powder, silicon carbide, boron carbide and alumina.
2. The composite salt binder composite friction material of claim 1, wherein said silicate binder is prepared by the process of: and adding 10-50 parts of potash water glass with the same modulus and baume degree into 100 parts of sodium water glass with the modulus of 2.8 and the baume degree of 45, and uniformly mixing and stirring to obtain the silicate binders with different Na/K.
3. The composite salt binder composite friction material of claim 1, wherein said phosphate binder is prepared by the process of: firstly, respectively and accurately measuring phosphoric acid and aluminum hydroxide with a molar ratio of 10:3, mixing and stirring until the solution is clear and transparent, then heating at about 85 ℃ to evaporate the water of the solution to a certain viscosity, stopping heating, and cooling to obtain the liquid aluminum dihydrogen phosphate binder.
4. The composite salt binder composite friction material of claim 1, wherein the composite salt binder is prepared by the following process: adding 15-20 parts of silicate binder and 10-15 parts of phosphate binder into 2.5-5 parts of calcium fluoride auxiliary agent, uniformly stirring, heating at 25-50 ℃ and stirring for 10min to obtain the composite salt binder.
5. The method of making a composite salt binder composite friction material as set forth in any one of claims 1-4, characterized by the steps of: firstly, mixing and stirring a curing agent, reinforcing fibers, a friction performance regulator and a filler for 2 minutes, and then introducing nitrile rubber serving as a toughness regulator, mixing and stirring for 1 minute; placing the mixed powder into a forced air drying oven for drying for 1-3 hours, introducing the composite salt binder after drying, and mixing and stirring for 10-15 minutes; and (3) molding the uniformly mixed and stirred composite material at 130 ℃ under the pressure of 10-20 MPa for 60-90 minutes, and then carrying out heat treatment at 130-190 ℃ for 10-20 hours to obtain the composite salt binder composite friction material.
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| BR102019014855A2 (en) * | 2019-07-18 | 2021-01-26 | Fras Le S A | inorganic resin, inorganic resin manufacturing process, friction material, friction material manufacturing process, use of inorganic resin, use of friction material, brake pad, brake liner and brake shoe |
| CN113816719B (en) * | 2021-10-09 | 2023-01-31 | 航天特种材料及工艺技术研究所 | Phosphate group nano heat-insulating material and preparation method thereof |
| CN114483845B (en) * | 2022-04-01 | 2022-06-28 | 东营睿智友亮石油设备有限公司 | Carbon-ceramic type friction material and preparation method and application thereof |
| WO2024154065A1 (en) * | 2023-01-19 | 2024-07-25 | Raicam Industrie S.R.L. | A friction material for brakes which contains a solid inorganic binder |
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| CN105440744A (en) * | 2015-11-20 | 2016-03-30 | 南京航空航天大学 | Water-based ceramic anticorrosive coating containing aluminum phosphate as well as preparation and curing methods thereof |
| CN107915228A (en) * | 2017-10-20 | 2018-04-17 | 神雾环保技术股份有限公司 | A kind of compound binding agent and preparation method and application |
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| US4171986A (en) * | 1977-04-02 | 1979-10-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Binders based on alkali metal silicates and potassium metaborate |
| CN101161759A (en) * | 2006-10-09 | 2008-04-16 | 陶建新 | Dualistic bonding system high-performance synthetic friction material and preparation method thereof |
| CN101367637A (en) * | 2007-08-13 | 2009-02-18 | 江西铜业集团公司 | Method of preparing composite material |
| CN102093841A (en) * | 2010-11-11 | 2011-06-15 | 咸阳师范学院 | Double-adhesive friction material |
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