CN109929511B - Copper-free and antimony-free environment-friendly friction material, friction plate, preparation method and application - Google Patents
Copper-free and antimony-free environment-friendly friction material, friction plate, preparation method and application Download PDFInfo
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Abstract
The invention discloses a copper-free and antimony-free environment-friendly friction material, a friction plate, a preparation method and application, and belongs to the technical field of brake pads. The copper-free and antimony-free environment-friendly friction material is composed of the following raw material components in parts by mass: 5-12 parts of phenolic resin, 2-9 parts of organic silicon modified resin, 1-3 parts of aramid fiber, 3-8 parts of butyronitrile powder, 5-12 parts of natural graphite, 5-12 parts of artificial graphite, 2-7 parts of carbon fiber, 8-15 parts of mineral fiber, 3-8 parts of silicon micropowder, 15-30 parts of silica fume, 3-8 parts of cashew nut shell oil friction powder, 3-8 parts of tin powder, 7-12 parts of aluminum alloy fiber, 8-12 parts of steel fiber and 5-9 parts of petroleum coke. The friction plate manufactured and formed by using the copper-free and antimony-free environment-friendly friction material disclosed by the invention does not contain pollutants such as copper, antimony sulfide and the like, and has excellent high-temperature resistance, impact resistance, wear resistance and compression performance.
Description
Technical Field
The invention relates to the technical field of automobile friction braking materials, in particular to a copper-free and antimony-free environment-friendly friction material, a friction plate, a preparation method and application.
Background
With the rapid development of the automobile industry, the requirements of people on safety and comfort of braking are higher and higher. Meanwhile, with the enhancement of environmental awareness of people, the requirements on the environmental protection performance of the friction material are more strict, the selection of the raw materials of the friction material is more strictly controlled, and the selection of the raw materials of the friction material is not only considered on economy. Because the raw materials used by the friction material for the cars on the market at present generally contain copper and antimony trisulfide pollutants, copper in the brake disc is discharged into the air in the form of friction particles in the braking process, and is finally enriched in soil or water areas to cause heavy metal pollution to the ecological environment, and the copper-free friction material becomes the development trend of the friction material. With the precedent of california, washington, etc. in the united states, the content of copper in the friction material is not allowed to exceed 5% in 2021 years, and is not allowed to exceed 0.5% in 2025 years, and various car manufacturers have responded to the call and started to develop copper-free friction materials. Antimony trisulfide is documented to be converted to antimony trioxide at high temperatures, and the state of the U.S. sector clearly requires that the friction material be inhibited from containing antimony trioxide. Antimony and copper belong to heavy metal elements, antimony trisulfide is widely used as a high-temperature lubricating material in friction materials, copper has excellent heat conductivity and high-temperature lubricating property, and antimony trisulfide is a high-temperature lubricant with better performance, so the development of copper-free and antimony-free friction materials has great difficulty, and the development of a copper-free and antimony-free environment-friendly friction material is not only a new development trend, but also a difficult problem to be solved urgently.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to provide an environment-friendly friction material, friction plate, brake pad and friction plate preparation method without copper and antimony trisulfide, so as to solve the problem that the copper and antimony trisulfide in the existing friction material pollute the environment, and the friction plate without copper and antimony trisulfide has poor performance.
In order to achieve the above objects or other objects, the present invention is achieved by the following technical solutions:
the copper-free and antimony-free environment-friendly friction material comprises the following raw material components in parts by mass: 5-12 parts of phenolic resin, 2-9 parts of organic silicon modified resin, 1-3 parts of aramid fiber, 3-8 parts of butyronitrile powder, 5-12 parts of natural graphite, 5-12 parts of artificial graphite, 2-7 parts of carbon fiber, 8-15 parts of mineral fiber, 3-8 parts of silicon micropowder, 15-30 parts of silica fume, 3-8 parts of cashew nut shell oil friction powder, 3-8 parts of tin powder, 7-12 parts of aluminum alloy fiber, 8-12 parts of steel fiber and 5-9 parts of petroleum coke.
Preferably, the flow distance of the phenolic resin at 125 ℃ is 40-70mm, the gelation time at 150 ℃ is 75-125s, and the flow distance and the gelation time are measured by referring to the method in the appendix A2 and A4 in GB/T24411-2009 standard.
Preferably, the flow distance of the organosilicon modified resin at 125 ℃ is 10-30mm, the gelation time at 150 ℃ is 60-90s, and the flow distance and the gelation time are measured by referring to the method in the appendix A2 and A4 in GB/T24411-2009 standard.
Preferably, the carbon fibers are surface modified pitch-based carbon fibers.
Preferably, the aluminum alloy fibers are aluminum zinc alloy fibers.
Preferably, the fiber length of the carbon fiber is 2-5mm, the fiber length of the mineral fiber is 100-150 μm, the fiber length of the aluminum alloy fiber is 0.4-0.8mm, the fiber length of the steel fiber is 90-220 μm, and the fiber length of the aramid fiber is 90-135 mm.
Preferably, the butyronitrile powder is 325 meshes, the natural graphite is 325 meshes, the artificial graphite is 30-100 meshes, the silica micropowder is 325-800 meshes, the micro silica powder is 325 meshes, the cashew nut shell oil friction powder is 40-325 meshes, the tin powder is 200 meshes, and the petroleum coke is 14-100 meshes.
The invention also provides a preparation method of the copper-free and antimony-free environment-friendly friction material, which comprises the following steps:
(1) material distribution: weighing all raw materials according to the raw material components and the mass parts in the formula of the copper-free and antimony-free environment-friendly friction material;
(2) mixing materials: firstly, putting aramid fiber, natural graphite, artificial graphite and silica fume into a mixer, stirring for 1-3 minutes, then adding the rest raw materials into the mixer, and stirring for 5-7 minutes to obtain the copper-free and antimony-free environment-friendly friction material.
The invention also provides the application of the copper-free and antimony-free environment-friendly friction material in a brake pad.
The invention further provides a brake pad which comprises a steel back and a friction plate made of the environment-friendly friction material, wherein the friction plate is arranged on the steel back.
The invention also provides a method for preparing a friction plate by adopting any one of the copper-free and antimony-free environment-friendly friction materials, which comprises the following steps:
(1) preparing a copper-free and antimony-free environment-friendly friction material;
(2) preforming: placing the copper-free and antimony-free environment-friendly friction material into a die to be cold-pressed under the pressure of 15-20MPa to form a blank;
(3) hot pressing: putting the blank into a hot-pressing mold, wherein the temperature of the mold is 140-160 ℃, and the pressing pressure is 12-17 MPa; carrying out hot pressing for 5-10s for the first time, carrying out hot pressing for 15s at intervals, exhausting for 5-10s and 4-6 times for each time, and carrying out pressure keeping for 200-300 s;
(5) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3-5 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1-2 h; and (3) raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the heat for 1-3h to obtain the friction plate.
The copper-free and antimony-free environment-friendly friction material disclosed by the invention does not contain pollutants such as copper and antimony sulfide, and is used for manufacturing a formed friction plate, so that the high temperature resistance of the friction plate is improved through the synergistic effect of the phenolic resin and the organic silicon modified resin, the compression performance of the friction plate is improved, and the braking comfort is improved. The micro silicon powder is used as the friction material space filler, so that the overall density of the friction plate is reduced, and the friction plate has excellent impact strength and wear resistance, moderate hardness and low cost due to the small average size of the micro silicon powder and excellent filling effect. The environment-friendly friction material also improves the thermal conductivity of the friction plate under the high-temperature condition, improves the strength of the friction material and reduces the fluctuation of the friction coefficient by selecting the surface modified short-cut asphalt-based carbon fiber and the aluminum alloy fiber.
The method for preparing the friction plate enables all components to be fully polymerized together, plays the synergistic effect among all components, has stable physical performance and is beneficial to improving the comfort of braking.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
The phenolic resin and silicone modified resin in the present invention can employ conventional phenolic resin and silicone modified resin materials well known to those skilled in the art and can be obtained by general commercial means. Preferably, the flow distance (125 ℃) of the phenolic resin is 40-70mm, the gelation time (150 ℃) is 75-125s, the average particle diameter is 75 μm, and the specific surface area is 0.901m in all the following examples3Per g, melting point 94 ℃. The flow distance (125 ℃) of the organic silicon modified resin is 10-30mm, the gelation time (150 ℃) is 60-90s, the average grain diameter is 45 mu m, and the specific surface area is 1.03m3Melting point 105 ℃ in mg. Flow distance and gel time reference GB/T24411 and 2009 by the methods of appendix A2 and A4.
The various fibers of the present invention can be of fiber sizes well known to those skilled in the art and are generally commercially available. Preferably, the carbon fiber in all the following embodiments is a surface modified pitch-based carbon fiber, and the fiber length is 2-5 mm; the fiber length of the mineral fiber is 100-150 mu m; the aluminum alloy fiber is aluminum-zinc alloy fiber, the fiber length is 0.4-0.8mm, the fiber length of the steel fiber is 90-220 mu m, and the fiber length of the aramid fiber is 90-135 mm.
The butyronitrile powder, the artificial graphite, the natural graphite, the silicon micropowder, the silica fume, the cashew nut shell oil friction powder, the tin powder and the petroleum coke in the invention are all selected from conventional raw materials in the field and can be obtained by common commercial approaches. Preferably, the butyronitrile powder selected in all the following examples is 325 meshes, the natural graphite is 325 meshes, the artificial graphite is 30-100 meshes, the silica micropowder is 325-800 meshes, the silica fume is 325 meshes, the cashew nut shell oil friction powder is 40-325 meshes, the tin powder is 200 meshes, and the petroleum coke is 14-100 meshes.
It should be noted that the unpublished conditions in the examples of the present invention are the same except for the numerical values explicitly given.
Example 1
a) The copper-free and antimony-free environment-friendly friction material comprises the following components in parts by mass:
12 parts of phenolic resin, 2 parts of organic silicon modified phenolic resin, 3 parts of aramid fiber, 3 parts of butyronitrile powder, 8 parts of natural graphite, 5 parts of artificial graphite, 4 parts of surface modified asphalt-based carbon fiber, 8 parts of mineral fiber, 8 parts of silicon micropowder, 15 parts of micro silicon powder, 5 parts of cashew nut shell oil friction powder, 3 parts of tin powder, 9 parts of aluminum alloy fiber, 8 parts of steel fiber and 7 parts of petroleum coke.
b) Preparing a copper-free and antimony-free environment-friendly friction material:
(1) weighing: weighing all raw materials according to the components and the mass part formula of the copper-free and antimony-free environment-friendly friction material;
(2) mixing materials: firstly putting aramid fiber, natural graphite, artificial graphite and micro silicon powder into a ploughshare mixer, starting a main paddle to stir for 1-3 minutes, then adding the rest raw materials into the mixer, starting the main paddle and a high-speed reamer to stir for 5-7 minutes, and obtaining the copper-free and antimony-free environment-friendly friction material.
c) Preparation of friction plate
(1) Preforming: placing the prepared copper-free and antimony-free environment-friendly friction material into a die, and cold-pressing at 17MPa to form a blank;
(2) hot pressing: putting the blank into a hot-pressing die, wherein the temperatures of an upper die, a middle die and a lower die are respectively 160 ℃, 150 ℃ and 155 ℃, and the pressing pressure is 15 MPa; starting 5s for the first time of hot pressing and pressure maintaining, then exhausting 5s for each time at an interval of 15s, exhausting 6 times, and maintaining the pressure for 300 s;
(3) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1 h; raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the temperature for 1h to obtain the friction plate A.
Example 2
a) The copper-free and antimony-free environment-friendly friction material comprises the following components in parts by mass:
5 parts of phenolic resin, 9 parts of organic silicon modified phenolic resin, 1 part of aramid fiber, 5 parts of butyronitrile powder, 5 parts of natural graphite, 5 parts of artificial graphite, 2 parts of surface modified asphalt-based carbon fiber, 11 parts of mineral fiber, 3 parts of silicon micropowder, 22 parts of micro silicon powder, 3 parts of cashew nut shell oil friction powder, 5 parts of tin powder, 7 parts of aluminum alloy fiber, 12 parts of steel fiber and 5 parts of petroleum coke.
b) The preparation of the copper-free and antimony-free environment-friendly friction material is the same as that of example 1:
c) preparation of friction plate
(1) Preforming: placing the copper-free and antimony-free environment-friendly friction material into a die, and cold-pressing at 15MPa to form a blank;
(2) hot pressing: putting the blank into a hot-pressing die, wherein the temperatures of an upper die, a middle die and a lower die are respectively 160 ℃, 150 ℃ and 155 ℃, and the pressing pressure is 12 MPa; carrying out hot pressing and pressure maintaining for 10s for the first time, then carrying out air exhaust for 10s every time at intervals of 15s, carrying out air exhaust for 4 times, and carrying out pressure maintaining for 300 s;
(3) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1 h; raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the temperature for 1h to obtain a friction plate B
Example 3
a) The copper-free and antimony-free environment-friendly friction material comprises the following components in parts by mass:
6.5 parts of phenolic resin, 3.5 parts of organic silicon modified phenolic resin, 2 parts of aramid fiber, 8 parts of butyronitrile powder, 12 parts of natural graphite, 5 parts of artificial graphite, 2 parts of surface modified asphalt-based carbon fiber, 8 parts of mineral fiber, 3 parts of silicon micropowder, 15 parts of micro silicon powder, 3 parts of cashew nut shell oil friction powder, 3 parts of tin powder, 12 parts of aluminum alloy fiber, 8 parts of steel fiber and 9 parts of petroleum coke.
b) The preparation of the copper-free and antimony-free environment-friendly friction material is the same as that of example 1:
c) preparation of friction plate
(1) Preforming: placing the copper-free and antimony-free environment-friendly friction material into a die, and cold-pressing at 20MPa to form a blank;
(2) hot pressing: putting the blank into a hot-pressing die, wherein the temperatures of an upper die, a middle die and a lower die are respectively 160 ℃, 150 ℃ and 155 ℃, and the pressing pressure is 17 MPa; carrying out hot pressing and pressure maintaining for 10s for the first time, then carrying out air exhaust for 10s every time at intervals of 15s, carrying out air exhaust for 4 times, and carrying out pressure maintaining for 300 s;
(3) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1 h; and (3) raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the temperature for 1h to obtain the friction plate C.
Example 4
a) The copper-free and antimony-free environment-friendly friction material comprises the following components in parts by mass:
5 parts of phenolic resin, 2 parts of organic silicon modified phenolic resin, 1 part of aramid fiber, 3 parts of butyronitrile powder, 5 parts of natural graphite, 12 parts of artificial graphite, 7 parts of surface modified asphalt-based carbon fiber, 9 parts of mineral fiber, 5 parts of silicon micropowder, 15 parts of micro silicon powder, 8 parts of cashew nut shell oil friction powder, 8 parts of tin powder, 7 parts of aluminum alloy fiber, 8 parts of steel fiber and 5 parts of petroleum coke.
b) The preparation of the copper-free and antimony-free environment-friendly friction material is the same as that of example 1:
c) preparation of friction plate
(1) Preforming: placing the copper-free and antimony-free environment-friendly friction material into a die, and cold-pressing at 20MPa to form a blank;
(2) hot pressing: putting the blank into a hot-pressing die, wherein the temperatures of an upper die, a middle die and a lower die are respectively 160 ℃, 150 ℃ and 155 ℃, and the pressing pressure is 17 MPa; carrying out hot pressing and pressure maintaining for 10s for the first time, then carrying out air exhaust for 10s every time at an interval of 15s, carrying out air exhaust for 4 times, and carrying out pressure maintaining for 200 s;
(3) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1 h; and (3) raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the temperature for 1h to obtain the friction plate D.
Example 5
a) The copper-free and antimony-free environment-friendly friction material comprises the following components in parts by mass:
5 parts of phenolic resin, 2 parts of organic silicon modified phenolic resin, 1 part of aramid fiber, 3 parts of butyronitrile powder, 5 parts of natural graphite, 5 parts of artificial graphite, 3 parts of surface modified asphalt-based carbon fiber, 15 parts of mineral fiber, 3 parts of silicon micropowder, 30 parts of micro silicon powder, 3 parts of cashew nut shell oil friction powder, 3 parts of tin powder, 7 parts of aluminum alloy fiber, 10 parts of steel fiber and 5 parts of petroleum coke.
b) The preparation of the copper-free and antimony-free environment-friendly friction material is the same as that of example 1:
c) preparation of friction plate
(1) Preforming: placing the copper-free and antimony-free environment-friendly friction material into a die, and cold-pressing at 20MPa to form a blank;
(2) hot pressing: putting the blank into a hot-pressing die, wherein the temperatures of an upper die, a middle die and a lower die are respectively 160 ℃, 150 ℃ and 155 ℃, and the pressing pressure is 17 MPa; carrying out hot pressing and pressure maintaining for 10s for the first time, then carrying out air exhaust for 10s every time at intervals of 15s, carrying out air exhaust for 4 times, and carrying out pressure maintaining for 300 s;
(3) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1 h; and (3) raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the temperature for 1h to obtain the friction plate E.
The copper-free and antimony-free environment-friendly friction material disclosed by the invention is subjected to friction wear and compression strain tests by referring to GB5763-2008 and adopting a test method specified in GB5763-2008 'brake lining for an automobile' in comparison with friction plates manufactured by the formulas provided in examples 1 to 5. The friction performance requirements are shown in table 1, the compressive strain requirements are shown in table 2, and the test results are shown in tables 3, 4 and 5.
TABLE 1 GB5763-2008 Friction Performance requirements
TABLE 2 compressive Strain requirement
TABLE 3 Friction Properties test results
TABLE 4 Friction wear test results
TABLE 5 compressive Strain test results
According to the test result, the copper-free antimony-free environment-friendly friction plate prepared by the invention has stable friction performance, low fading, good anti-fading performance and low abrasion loss tested at each stage; the normal temperature compressive strain is close to the high temperature compressive strain, the braking comfort is high, and the development trend of the environment-friendly friction material is met.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The copper-free antimony-free environment-friendly friction material is characterized by comprising the following raw material components in parts by mass: 5-12 parts of phenolic resin, 2-9 parts of organic silicon modified resin, 1-3 parts of aramid fiber, 3-8 parts of butyronitrile powder, 5-12 parts of natural graphite, 5-12 parts of artificial graphite, 2-7 parts of carbon fiber, 8-15 parts of mineral fiber, 3-8 parts of silicon micropowder, 15-30 parts of silica fume, 3-8 parts of cashew nut shell oil friction powder, 3-8 parts of tin powder, 7-12 parts of aluminum alloy fiber, 8-12 parts of steel fiber and 5-9 parts of petroleum coke.
2. The copper-free and antimony-free environment-friendly friction material as recited in claim 1, wherein the phenolic resin has a flow distance of 40-70mm at 125 ℃, a gelation time of 75-125s at 150 ℃, and the flow distance and the gelation time are measured according to the methods of appendix A2 and A4 of GB/T24411-.
3. The copper-free and antimony-free environment-friendly friction material as recited in claim 1, wherein the silicone modified resin has a flow distance of 10-30mm at 125 ℃, a gelation time of 60-90s at 150 ℃, and the flow distance and the gelation time are measured with reference to the methods of appendix A2 and A4 of GB/T24411-2009-one.
4. The copper-free and antimony-free environment-friendly friction material as recited in claim 1, wherein the silica micropowder is 325-800 mesh.
5. The copper-free and antimony-free environment-friendly friction material as recited in claim 1, wherein the carbon fiber is a surface-modified pitch-based carbon fiber.
6. The copper-free and antimony-free environment-friendly friction material as recited in claim 1, wherein the aluminum alloy fiber is an aluminum-zinc alloy fiber.
7. A method for preparing the copper-free and antimony-free environment-friendly friction material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps;
(1) weighing: weighing all raw materials according to the raw material components and the parts by mass of any one of claims 1 to 6;
(2) mixing materials: firstly, putting aramid fiber, natural graphite, artificial graphite and silica fume into a mixer, stirring for 1-3 minutes, then adding the rest raw materials into the mixer, and stirring for 5-7 minutes to obtain the copper-free and antimony-free environment-friendly friction material.
8. Use of the copper-free and antimony-free environment-friendly friction material as defined in any one of claims 1 to 6 in a brake pad.
9. A brake pad comprising a steel backing and a friction plate made of the copper-free and antimony-free environmentally friendly friction material of any one of claims 1 to 6.
10. A method of manufacturing a friction plate using the copper-free and antimony-free environment-friendly friction material as defined in any one of claims 1 to 6, comprising the steps of:
(1) preparing a copper-free and antimony-free environment-friendly friction material;
(2) preforming: placing the copper-free and antimony-free environment-friendly friction material into a die to be cold-pressed under the pressure of 15-20MPa to form a blank;
(3) hot pressing: putting the blank into a hot-pressing mold, wherein the temperature of the mold is 140-160 ℃, and the pressing pressure is 12-17 MPa; carrying out hot pressing for 5-10s for the first time, carrying out hot pressing for 15s at intervals, exhausting for 5-10s and 4-6 times for each time, and carrying out pressure keeping for 200-300 s;
(5) and (3) heat treatment: raising the temperature from room temperature to 180 ℃ at a constant speed, and preserving the temperature for 3-5 h; raising the temperature from 180 ℃ to 200 ℃ at a constant speed, and keeping the temperature for 1-2 h; and (3) raising the temperature from 200 ℃ to 250 ℃ at a constant speed, and preserving the heat for 1-3h to obtain the friction plate.
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