A method for manufacturing a carbon fiber-based disc brake pad material for an automobile

Abstract

The application relates to the field of automobile brake pads, and relates to a preparation method of a carbon fiber-based automobile disc brake pad material.A preparation method of a carbon fiber-based automobile disc brake pad material comprises the following steps: weighing materials according to a formula; stirring aramid pulp and composite mineral fibers to obtain mixture 1; mixing modified phenolic resin powder and modified pipe material by ball milling to obtain mixture 2; mixing and stirring the remaining part of the materials, the mixture 1 and the mixture 2 to obtain compression plastic; heating a hot-pressing mold, then applying release agent, pouring the compression plastic into a mold cavity, combining films, maintaining pressure, and pressure-keeping to make the compression plastic hot-pressing forming to obtain a pre-product; placing the pre-product into a hot air oven to heat, and then lowering the temperature to room temperature to obtain a product.The application has the advantages that the friction material has a stable friction coefficient at high temperature.

Description

TECHNICAL FIELD

[0001] The application relates to the field of automobile brake pads, in particular to a preparation method of a carbon fiber-based disc brake pad material for automobiles. BACKGROUND

[0002] The disc brake pad is currently mainly used on passenger cars, but in recent years, disc brake pads are gradually used on some commercial vehicles, especially on buses and public buses, and the development speed is relatively fast. At present, the disc brake pad materials sold in China are mainly semi-metal, low-metal NAO and carbon fiber, among which the carbon fiber friction material is the best in performance among various types of friction materials.

[0003] The carbon fiber brake pad is a kind of friction material with carbon fiber as the reinforcing material. The carbon fiber has the characteristics of high modulus, good heat conduction and heat resistance. The carbon fiber friction pad has the characteristics of high unit area absorption power and light specific gravity. The carbon fiber brake pad is composed of a high molecular adhesive, carbon fiber and a friction performance filler, and most of them contain metal components. The carbon fiber brake pad is mainly reinforced with carbon fiber. The single carbon fiber reinforced resin-based friction material has insufficient performance in heat recession. The brake pad cannot avoid high-temperature heat recession, and if the stability is poor, the friction coefficient is low or high when the temperature is too high, the friction coefficient is not within the specified friction coefficient and deviation range, which will cause various conditions during braking, and there will be safety hazards. SUMMARY

[0004] In order to make the friction material have stable friction coefficient at high temperature, the application provides a preparation method of a carbon fiber-based disc brake pad material for automobiles.

[0005] The preparation method of the carbon fiber-based disc brake pad material for automobiles provided by the application adopts the following technical scheme: a preparation method of a carbon fiber-based disc brake pad material for automobiles, comprising the following steps:

[0006] Step 1: the materials are weighed according to the formula, and the materials include the following raw material components by weight: 5-10 parts of modified phenolic resin powder, 1-2 parts of potassium hexatitanate whisker, 5-7 parts of calcium hydroxide, 20-30 parts of barium sulfate, 1-3 parts of artificial graphite, 2-6 parts of coke powder, 3-5 parts of cashew nut shell oil friction powder, 1-3 parts of carboxyl nitrile rubber powder, 4-8 parts of antimony sulfide, 4-6 parts of mica, 2-6 parts of zirconium oxide, 9-11 parts of composite fiber, 4-6 parts of nano filler, and 0.06-0.12 parts of modified pipe material; the composite fiber includes chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber;

[0007] Step 2: mix and stir the aramid pulp and the composite mineral fiber in the material evenly for 10-15 min to obtain mixture 1; mix and stir the modified phenolic resin powder and the modified pipe material in the material by ball milling for 5-8 min at a speed of 200-300 rpm to obtain mixture 2; mix and stir the remaining part of the material with mixture 1 and mixture 2 for 25-30 min to obtain the compression molding material;

[0008] Step 3: heat the hot-pressing mold to a preset temperature, the preset temperature is 135-145℃ for the upper mold, 125-135℃ for the middle mold, and 165-175℃ for the lower mold, then apply release agent, pour the compression molding material into the mold cavity, close the mold, maintain the pressure at 12-14 MPa for 4-6 min, and heat-press the compression molding material to form a pre-product, during the pressure maintaining, exhaust every 14-16 s for 9-10 times;

[0009] Step 4: heat the pre-product in the hot air oven to 80-85℃ and maintain the temperature for 2-2.5 h, then heat to 120-125℃ and maintain the temperature for 4-4.5 h, then heat to 160-165℃ and maintain the temperature for 4-4.5 h, then reduce the temperature to room temperature at a rate of 70-90℃ / h to obtain the product.

[0010] By adopting the technical scheme, the carbon fiber has the characteristics of high strength, fatigue resistance, high temperature resistance, wear resistance, self-lubricating property, corrosion resistance, good dimensional stability and the like, and can effectively improve the performance of the material. The ceramic fiber has good thermal stability, good chemical stability, mechanical shock resistance and the like, and can improve the hardness and internal shear strength of the friction material. The aramid pulp can improve the internal shear strength of the friction material. The composite mineral fiber can improve the adhesion between the fiber and the adhesive, improve the heat resistance of the friction material, reduce the thermal recession of the material, and make the friction coefficient more stable. The combination of the four fibers can still have a very stable friction coefficient at high temperature, the change of the friction coefficient is very small, and the wear rate is very low, so that the service life of the friction material is prolonged, and the shear strength and hardness of the friction material are improved, so that the performance of the friction material is comprehensively improved. The potassium hexatitanate whisker is an inorganic compound with needle-shaped crystals. The strong infrared reflection capability can quickly release part of the energy generated during friction, improve the use temperature of the friction material, and the low thermal conductivity can slow down the energy transfer rate during friction, reduce the heating rate of the friction material, and the high-temperature sound absorption performance can reduce the braking noise during friction. The phenolic resin has good heat resistance and bonding performance, and is a good adhesive. The carboxyl nitrile rubber powder can be copolymerized with the phenolic resin to improve the impact strength and friction resistance of the phenolic resin. The modification effect of the carboxyl nitrile rubber powder on the phenolic resin is better than that of other rubbers. The cashew nut shell oil friction powder can form a soft and tough film on the surface of the material, improve the friction stability, and further modify the phenolic resin. The calcium hydroxide, barium sulfate, artificial graphite, coke powder, cashew nut shell oil friction powder, antimony sulfide, mica, vermiculite, zirconium oxide and calcium silicate are added as the filler and friction performance regulator components of the friction material.

[0011] Preferably, the mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is 3-5:1-3:2-4:10-12.

[0012] By adopting the technical scheme, the mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is different, and the performance of the friction material is also different. The application proposes an optimal ratio, so that the performance of the friction material is best improved.

[0013] Preferably, the modified phenolic resin powder comprises phenol, formaldehyde, cashew nut shell oil and melamine, and the molar ratio of the phenol, formaldehyde, cashew nut shell oil and melamine is 2:1.4:0.15-0.35:0.025-0.03.

[0014] By adopting the technical scheme, the melamine and cashew nut shell oil modified phenolic resin can effectively improve the mechanical capability of the friction material, has good heat resistance and thermal stability, and can form a dense friction layer on the friction surface of the material, thereby reducing the high-temperature thermal recession of the friction material, stabilizing the friction coefficient, and reducing wear.

[0015] Preferably, the preparation method of the modified phenolic resin comprises the following steps: accurately measuring phenol and heating to a molten state, then adding into a stirrer and continuously stirring, then adding accurately measured melamine, cashew nut shell oil and formaldehyde, then heating to 70-80 DEG C, adding a catalyst and adjusting the pH value to 2-2.5, stirring for 3-3.5 h, continuously condensing and refluxing, then vacuumizing to a vacuum degree of 0.09 MPa, controlling the temperature to 65-70 DEG C, vacuum distilling for 2-2.5 h, then heating to 180-185 DEG C, stopping heating after maintaining for 3-4 min, and cooling to room temperature to obtain the modified phenolic resin.

[0016] Preferably, the modified tube material comprises carbon nanotubes, anhydrous p-aminobenzenesulfonic acid, sodium nitrite and azobisisobutyronitrile, and the mass ratio of the carbon nanotubes, the anhydrous p-aminobenzenesulfonic acid, the sodium nitrite and the azobisisobutyronitrile is 0.2:5.54:2.21:1.2.

[0017] By adopting the technical scheme, the friction material added with the carbon nanotubes can improve the impact strength, so that it is easier to buffer and absorb the shearing effect of the friction material, and the wear resistance of the friction material is improved, the carbon nanotubes modified by the anhydrous p-aminobenzenesulfonic acid and the sodium nitrite have better compatibility with the phenolic resin, the friction performance of the friction material is further improved, and the friction coefficient is less affected at high temperature, and the heat recession resistance is stronger.

[0018] Preferably, the preparation of the modified tube material comprises the following steps:

[0019] Step 1: accurately measuring the carbon nanotubes, pouring into a concentrated sulfuric acid and ammonium persulfate mixed solution, stirring at room temperature for 1-1.5 h until no obvious particles are present;

[0020] Step 2: adding accurately measured anhydrous p-aminobenzenesulfonic acid, ultrasonic oscillation and stirring until uniform, then adding accurately measured sodium nitrite, cooling to 10-15 DEG C, and stirring for 20-25 min;

[0021] Step 3: adding accurately measured azobisisobutyronitrile, heating to 80-85 DEG C, continuously stirring for 6-6.5 h, centrifuging and ultrasonic cleaning after the reaction is completed, vacuum drying at 80-85 DEG C for 24-26 h after filtration, and obtaining the modified tube material.

[0022] Preferably, the nanofiller includes one or more combinations of nanosilicon carbide and nanoboron carbide.

[0023] By using the above technical solution, the addition of small size and irregular shape nanosilicon carbide and nanoboron carbide can fill the pores between large size particles, prevent interface slip, improve the interface bonding performance of the friction material, and reduce the wear rate of the friction material. Nanosilicon carbide can improve the friction performance at high temperature, reduce the decrease of friction performance caused by thermal recession, and boron carbide has good interface bonding performance with various fibers and other fillers. When the high-temperature resin decomposes, boron carbide can play a role in consolidating the material, thereby maintaining the stability of the friction material at high temperature, reducing the change of the friction coefficient, and reducing thermal recession.

[0024] Preferably, the mass ratio of the nanosilicon carbide and the nanoboron carbide is 0.5:1-2.

[0025] By using the above technical solution, different mass ratios of nanosilicon carbide and nanoboron carbide will have different effects on the performance improvement of the friction material. The present application proposes an optimal mass ratio of nanosilicon carbide and nanoboron carbide, so that the performance of the friction material is best improved.

[0026] Preferably, the material further includes 2-10 parts of lanthanum oxide.

[0027] By using the above technical solution, the addition of a certain amount of lanthanum oxide can effectively improve the hardness, shear strength and wear resistance of the friction material, and the lanthanum oxide can make the friction material maintain a relatively stable friction coefficient at high temperature, effectively alleviate the decrease of the friction coefficient, and thereby inhibit thermal recession.

[0028] In summary, the present application has the following beneficial effects:

[0029] 1. Since the present application uses short carbon fibers, ceramic fibers, aramid pulp and composite mineral fibers, the friction coefficient of the friction material can be maintained within a good range, the friction coefficient can be stabilized at high temperature, the friction coefficient can be improved at high temperature, the wear rate can be maintained at a low wear rate at different temperatures, and the shear strength of the friction material can be significantly improved, thereby improving the overall performance of the product.

[0030] 2. In the present application, the modified tube material mainly uses carbon nanotubes. The carbon nanotubes can improve the impact strength, make it easier to buffer and absorb the shear effect of the friction material, and improve the wear resistance of the friction material. The carbon nanotubes modified by anhydrous p-aminobenzenesulfonic acid and sodium nitrite have better compatibility with phenolic resin, which further improves the friction performance of the friction material and has less effect on the friction coefficient at high temperature. DETAILED DESCRIPTION

[0031] Preparation Example

[0032] Preparation Example 1

[0033] The preparation method of the modified phenolic resin comprises the following steps: 2 kg of phenol is added into a heater and heated to a temperature of 45℃, so that the phenol becomes a molten state, then it is transferred into a stirrer and continuously stirred at a speed of 300 rpm, then 0.15 kg of melamine, 0.025 kg of cashew nut shell oil and 1.4 kg of formaldehyde are added, then the temperature is increased to 75℃, hydrochloric acid is added and the pH value is adjusted to 2, stirring is performed for 3 h, and continuous condensation reflux is performed, then vacuum distillation is performed by a vacuum distillation device to a vacuum degree of 0.09 MPa, the temperature is controlled to be 70℃, and vacuum distillation is performed for 2 h, then the temperature is increased to 180℃, heating is stopped after maintaining for 3 min, and the modified phenolic resin is obtained after cooling to room temperature.

[0034] Preparation Example 2

[0035] Preparation Example 2 is different from Preparation Example 1 in that the 0.15 kg of melamine added is changed to 0.35 kg of melamine.

[0036] Preparation Example 3

[0037] Preparation Example 3 is different from Preparation Example 1 in that the 0.15 kg of melamine added is changed to 0.25 kg of melamine.

[0038] Preparation Example 4

[0039] Preparation Example 4 is different from Preparation Example 1 in that the 0.15 kg of melamine and 0.025 kg of cashew nut shell oil added are changed to 0.25 kg of melamine and 0.03 kg of cashew nut shell oil.

[0040] Preparation Example 5

[0041] Preparation Example 5 is different from Preparation Example 1 in that the 0.15 kg of melamine and 0.025 kg of cashew nut shell oil added are changed to 0.25 kg of melamine and 0.027 kg of cashew nut shell oil.

[0042] Preparation Example 6

[0043] The preparation of the modified pipe material comprises the following steps:

[0044] Step 1: 0.2 kg of carbon nanotubes is weighed and poured into a mixed solution of 150 ml of concentrated sulfuric acid and 100 ml of ammonium persulfate, and stirred at room temperature for 1 h until no obvious particles are present, at a speed of 100 rpm;

[0045] Step 2: Add 5 kg of anhydrous p-aminobenzenesulfonic acid, ultrasonic vibration and stirring until uniform, time 30-40 s, after mixing, add 2 kg of sodium nitrite, cooling to 13 °C, stirring for 23 min;

[0046] Step 3: Add 1.2 kg of azobisisobutyronitrile, heat to 85 °C, then continue stirring for 6 h, speed 150 rpm, after the reaction is completed, centrifugal separation and ultrasonic cleaning, then the modified carbon nanotubes are filtered, and after filtration, vacuum drying at 85 °C for 24 h, to obtain the modified tube material.

[0047] Preparation Example 7

[0048] Preparation Example 7 and Preparation Example 6 differ in that the 5 kg of anhydrous p-aminobenzenesulfonic acid added is changed to 6 kg of anhydrous p-aminobenzenesulfonic acid.

[0049] Preparation Example 8

[0050] Preparation Example 8 and Preparation Example 6 differ in that the 5 kg of anhydrous p-aminobenzenesulfonic acid added is changed to 5.5 kg of anhydrous p-aminobenzenesulfonic acid.

[0051] Preparation Example 9

[0052] Preparation Example 9 and Preparation Example 6 differ in that the 5 kg of anhydrous p-aminobenzenesulfonic acid and 2 kg of sodium nitrite added are changed to 5.5 kg of anhydrous p-aminobenzenesulfonic acid and 2.4 kg of sodium nitrite.

[0053] Preparation Example 10

[0054] Preparation Example 10 and Preparation Example 6 differ in that the 5 kg of anhydrous p-aminobenzenesulfonic acid and 2 kg of sodium nitrite added are changed to 5.5 kg of anhydrous p-aminobenzenesulfonic acid and 2.2 kg of sodium nitrite.

[0055] Example

[0056] Example 1

[0057] Step 1: measure the materials according to the formula, 0.7 kg of modified phenolic resin powder in Preparation Example 1, 0.15 kg of potassium titanate whisker, 0.6 kg of calcium hydroxide, 2.5 kg of barium sulfate, 0.2 kg of artificial graphite, 0.4 kg of coke powder, 0.4 kg of cashew nut shell oil rubbing powder, 0.2 kg of carboxyl nitrile rubber powder, 0.6 kg of antimony sulfide, 0.5 kg of mica, 0.4 kg of zirconia, 1 kg of composite fiber, 0.5 kg of nano filler, 0.006 kg of modified tube material in Preparation Example 6; wherein the mass of each component in the composite fiber is 0.15 kg of chopped carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of composite mineral fiber, and the mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is 3:1:4:12; the mass of each component in the nano filler is 0.16 kg of nano silicon carbide and 0.34 kg of nano boron carbide.

[0058] Step 2: mix and stir the aramid pulp and the composite mineral fiber uniformly for 10 min at a speed of 200 rpm to obtain mixture one; mix and stir the modified phenolic resin powder and the modified tube material by ball milling for 7 min at a speed of 300 rpm to obtain mixture two; mix and stir the remaining materials with the mixture one and the mixture two for 30 min to obtain the compression molding material;

[0059] Step 3: heat the hot-pressing mold to a preset temperature, the preset temperature is an upper mold temperature of 140℃, a middle mold temperature of 130℃ and a lower mold temperature of 170℃, then apply zinc stearate as a release agent, pour the compression molding material into the mold cavity, close the mold, maintain a pressure of 13 MPa for 5 min, heat-press the compression molding material, release the pressure every 14-16 s during the pressure maintaining period, a total of 10 times, to obtain a pre-product; Step 4: place the pre-product into a hot air oven, heat to 80℃, maintain for 2 h, continue to heat to 120℃, maintain for 4 h, continue to heat to 160℃, maintain for 4 h, then reduce the temperature to room temperature at a rate of 80℃ / h to obtain the product.

[0060] Example 2

[0061] The difference between Example 2 and Example 1 is that the measured 0.15 kg of chopped carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of composite mineral fiber are changed to 0.15 kg of chopped carbon fiber, 0.15 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.5 kg of composite mineral fiber, and the mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is 3:3:4:10.

[0062] Example 3

[0063] Example 3 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of composite mineral fiber are changed to 0.15 kg of short-cut carbon fiber, 0.15 kg of aramid pulp, 0.1 kg of ceramic fiber, and 0.6 kg of composite mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and composite mineral fiber is 3:3:2:12.

[0064] Example 4

[0065] Example 4 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of composite mineral fiber are changed to 0.25 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.1 kg of ceramic fiber, and 0.6 kg of composite mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and composite mineral fiber is 5:1:2:12.

[0066] Example 5

[0067] Example 5 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of composite mineral fiber are changed to 0.25 kg of short-cut carbon fiber, 0.15 kg of aramid pulp, 0.1 kg of ceramic fiber, and 0.5 kg of composite mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and composite mineral fiber is 5:3:2:10.

[0068] Example 6

[0069] Example 6 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of composite mineral fiber are changed to 0.25 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.5 kg of composite mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and composite mineral fiber is 5:1:4:10.

[0070] Example 7

[0071] Example 7 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of composite mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.1 kg of ceramic fiber, and 0.6 kg of composite mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and composite mineral fiber is 4:2:2:12.

[0072] Example 8

[0073] Example 8 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.6 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:1:3:12.

[0074] Example 9

[0075] Example 9 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.15 kg of aramid pulp, 0.10 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:3:2:11.

[0076] Example 10

[0077] Example 10 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:2:3:11.

[0078] Example 11

[0079] Example 11 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:2:3:11; and the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 2.

[0080] Example 12

[0081] Example 12 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber is 4:2:3:11; and the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 3.

[0082] Example 13

[0083] Example 13 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber is 4:2:3:11; and the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 4.

[0084] Example 14

[0085] Example 14 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, and the mass ratio of the short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber is 4:2:3:11; and the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 5.

[0086] Example 15

[0087] Example 15 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber being 4:2:3:11; the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 5; and the weighed 0.006 kg of modified tube material in Preparation Example 6 is changed to 0.006 kg of modified tube material in Preparation Example 7.

[0088] Example 16

[0089] Example 16 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber being 4:2:3:11; the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 5; and the weighed 0.006 kg of modified tube material in Preparation Example 6 is changed to 0.006 kg of modified tube material in Preparation Example 8.

[0090] Example 17

[0091] Example 17 differs from Example 1 in that the weighed 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber, and 0.6 kg of complex mineral fiber are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber, and 0.55 kg of complex mineral fiber, the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber, and complex mineral fiber being 4:2:3:11; the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of modified phenolic resin powder in Preparation Example 5; and the weighed 0.006 kg of modified tube material in Preparation Example 6 is changed to 0.006 kg of modified tube material in Preparation Example 9.

[0092] Example 18

[0093] Example 18 differs from example 1 in that 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber weighed out are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:2:3:11; 0.7 kg of modified phenolic resin powder in preparation example 1 weighed out is changed to 0.7 kg of modified phenolic resin powder in preparation example 5; 0.006 kg of modified tube material in preparation example 6 weighed out is changed to 0.006 kg of modified tube material in preparation example 10.

[0094] Example 19

[0095] Example 19 differs from example 1 in that 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber weighed out are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:2:3:11; 0.7 kg of modified phenolic resin powder in preparation example 1 weighed out is changed to 0.7 kg of modified phenolic resin powder in preparation example 5; 0.006 kg of modified tube material in preparation example 6 weighed out is changed to 0.01 kg of modified tube material in preparation example 10.

[0096] Example 20

[0097] Example 20 differs from example 1 in that 0.15 kg of short-cut carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of complex mineral fiber weighed out are changed to 0.2 kg of short-cut carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of complex mineral fiber, and the mass ratio of short-cut carbon fiber, aramid pulp, ceramic fiber and complex mineral fiber is 4:2:3:11; 0.7 kg of modified phenolic resin powder in preparation example 1 weighed out is changed to 0.7 kg of modified phenolic resin powder in preparation example 5; 0.006 kg of modified tube material in preparation example 6 weighed out is changed to 0.008 kg of modified tube material in preparation example 10.

[0098] Example 21

[0099] Example 21 is different from Example 1 in that 0.15 kg of the cut carbon fiber, 0.05 kg of the aramid pulp, 0.2 kg of the ceramic fiber and 0.6 kg of the complex mineral fiber weighed are changed to 0.2 kg of the cut carbon fiber, 0.1 kg of the aramid pulp, 0.15 kg of the ceramic fiber and 0.55 kg of the complex mineral fiber, and the mass ratio of the cut carbon fiber, the aramid pulp, the ceramic fiber and the complex mineral fiber is 4:2:3:11; 0.7 kg of the modified phenolic resin powder in Preparation Example 1 weighed is changed to 0.7 kg of the modified phenolic resin powder in Preparation Example 5; 0.006 kg of the modified tube material in Preparation Example 6 weighed is changed to 0.008 kg of the modified tube material in Preparation Example 10; and 0.16 kg of the nano silicon carbide and 0.34 kg of the nano boron carbide weighed are changed to 0.1 kg of the nano silicon carbide and 0.4 kg of the nano boron carbide.

[0100] Example 22

[0101] Example 22 is different from Example 1 in that 0.15 kg of the cut carbon fiber, 0.05 kg of the aramid pulp, 0.2 kg of the ceramic fiber and 0.6 kg of the complex mineral fiber weighed are changed to 0.2 kg of the cut carbon fiber, 0.1 kg of the aramid pulp, 0.15 kg of the ceramic fiber and 0.55 kg of the complex mineral fiber, and the mass ratio of the cut carbon fiber, the aramid pulp, the ceramic fiber and the complex mineral fiber is 4:2:3:11; 0.7 kg of the modified phenolic resin powder in Preparation Example 1 weighed is changed to 0.7 kg of the modified phenolic resin powder in Preparation Example 5; 0.006 kg of the modified tube material in Preparation Example 6 weighed is changed to 0.008 kg of the modified tube material in Preparation Example 10; and 0.16 kg of the nano silicon carbide and 0.34 kg of the nano boron carbide weighed are changed to 0.125 kg of the nano silicon carbide and 0.375 kg of the nano boron carbide.

[0102] Example 23

[0103] Example 23 is different from Example 1 in that:

[0104] Step 1: ingredients were weighed according to the formula, 0.7 kg of modified phenolic resin powder in Preparation Example 5, 0.15 kg of potassium hexatitanate whisker, 0.6 kg of calcium hydroxide, 2.5 kg of barium sulfate, 0.2 kg of artificial graphite, 0.4 kg of coke powder, 0.4 kg of cashew nut shell oil rubbing powder, 0.2 kg of carboxyl nitrile rubber powder, 0.6 kg of antimony sulfide, 0.5 kg of mica, 0.4 kg of zirconia, 1 kg of composite fiber, 0.5 kg of nano filler, 0.008 kg of modified tube material in Preparation Example 10, 0.6 kg of lanthanum oxide; wherein the mass of each component in the composite fiber is 0.2 kg of chopped carbon fiber, 0.1 kg of aramid pulp, 0.15 kg of ceramic fiber and 0.55 kg of composite mineral fiber, and the mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is 4:2:3:11; the mass of each component in the nano filler is 0.125 kg of nano silicon carbide and 0.375 kg of nano boron carbide.

[0105] Step 2: aramid pulp and composite mineral fiber were mixed and stirred uniformly for 10 min at 200 rpm to obtain mixture one; modified phenolic resin powder and modified tube material were ball-milled and mixed for 7 min at 300 rpm to obtain mixture two; the remaining ingredients were mixed with mixture one and mixture two and stirred for 30 min to obtain compression molding material;

[0106] Step 3: the hot press mold was heated to a preset temperature, the preset temperature was 140℃ for the upper mold, 130℃ for the middle mold and 170℃ for the lower mold, then zinc stearate was applied as a release agent, the compression molding material was poured into the mold cavity, the mold was closed, the pressure was maintained at 13 MPa for 5 min, the compression molding material was hot-pressed to form a pre-product, during the pressure maintaining period, the exhaust was performed every 14-16 s for a total of 10 times, to obtain a pre-product; Step 4: the pre-product was placed in a hot air oven and heated to 80℃, maintained for 2 h, then heated to 120℃, maintained for 4 h, then heated to 160℃, maintained for 4 h, then the temperature was reduced to room temperature at a rate of 80℃ / h, to obtain a product.

[0107] Comparative Example

[0108] Comparative Example 1

[0109] The difference between Comparative Example 1 and Example 1 is that the weighed 0.15 kg of chopped carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of composite mineral fiber are replaced by only 0.125 kg of aramid pulp, 0.1875 kg of ceramic fiber and 0.6875 kg of composite mineral fiber.

[0110] Comparative Example 2

[0111] The difference between Comparative Example 2 and Example 1 is that the weighed 0.15 kg of short carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of composite mineral fiber are changed to only weigh 0.44 kg of short carbon fiber, 0.22 kg of aramid pulp and 0.34 kg of ceramic fiber.

[0112] Comparative Example 3

[0113] The difference between Comparative Example 3 and Example 1 is that the weighed 0.15 kg of short carbon fiber, 0.05 kg of aramid pulp, 0.2 kg of ceramic fiber and 0.6 kg of composite mineral fiber are changed to only weigh 0.235 kg of short carbon fiber, 0.118 kg of aramid pulp and 0.647 kg of composite mineral fiber.

[0114] Comparative Example 4

[0115] The difference between Comparative Example 4 and Example 1 is that the weighed 0.7 kg of modified phenolic resin powder in Preparation Example 1 is changed to 0.7 kg of ordinary phenolic resin powder

[0116] Comparative Example 5

[0117] The difference between Comparative Example 5 and Example 1 is that no modified pipe is added.

[0118] Performance detection test

[0119] Shear strength: According to GB / T26739-2011 “Road vehicle brake pad material internal shear strength test procedure”, the shear strength of Examples 1-23 and Comparative Examples 1-5 is tested.

[0120] Friction coefficient: According to GB5763-2018 “Automobile brake pad”, the friction coefficient of Examples 1-23 and Comparative Examples 1-5 is determined at different temperatures.

[0121] Wear rate: According to GB5763-2018 “Automobile brake pad”, the wear rate of Examples 1-23 and Comparative Examples 1-5 is determined at different temperatures.

[0122] Table 1 Friction coefficient (μ) of Examples 1-10 and Comparative Examples 1-3

[0123]

[0124] Table 2 Wear rate (V / [10 -7 cm 3 / (Nm)])

[0125]

[0126]

[0127] Table 3 Shear strength (MPa) of Examples 1-10 and Comparative Examples 1-3

[0128] Item Shear strength (MPa) Example 1 16.3 Example 2 17.5 Example 3 17.3 Example 4 16.1 Example 5 16.8 Example 6 17.4 Example 7 16.3 Example 8 16.1 Example 9 16.7 Example 10 17.8 Comparative Example 1 8.6 Comparative Example 2 12.5 Comparative Example 3 13.6

[0129] Table 4 Coefficient of friction (μ) of Examples 11-23 and Comparative Examples 4-5

[0130]

[0131]

[0132] Table 5 Wear rate (V / [10 -7 cm 3 / (Nm)])

[0133]

[0134]

[0135] Table 5 Shear strength (MPa) of Examples 11-23 and Comparative Examples 4-5

[0136]

[0137]

[0138] In combination with Examples 1-10 and Comparative Examples 1-4 and in combination with Tables 1-3, it can be seen that using a combination of short-cut carbon fibers, ceramic fibers, aramid pulp and composite mineral fibers, the coefficient of friction can be well stabilized at high temperatures, and the coefficient of friction can also be improved at high temperatures, so that the coefficient of friction at different temperatures is always maintained within the interval of 0.36 (± 15%), the wear rate at different temperatures is also maintained within 0.3, and the shear strength is high. However, due to the different properties of different fibers, such as hardness, flexibility, and the compatibility and connection strength between the fibers and the adhesive, the thermal decay, wear rate and shear strength of the friction material are also affected to varying degrees. In combination with comprehensive consideration, the performance of the friction material in Example 10 is better.

[0139] It can be seen from the combination of examples 11-23 and comparative examples 4-5 and tables 4-6 that the modification effects of the modified phenolic resin are different when the amounts of melamine and cashew nut shell oil added in the modified phenolic resin are different, thereby having different degrees of influence on the thermal decay, wear rate and shear strength of the friction material. The modification effects of the carbon nanotubes are different when the amounts of anhydrous p-aminobenzenesulfonic acid and sodium nitrite added in the modified pipe material are different, and the amounts of the modified pipe material added also have different degrees of influence on the thermal decay, wear rate and shear strength of the friction material. The proportions of the added nano-silicon carbide and nano-boron carbide and whether or not lanthanum oxide is added also have different degrees of influence on the thermal decay, wear rate and shear strength of the friction material, and examples 11-23 all have good performance.

[0140] The specific embodiments are merely illustrative of the present application, and are not intended to limit the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A method for producing a carbon fiber-based automotive disc brake pad material, characterized by, It comprises the following steps: Step 1: weigh the materials according to the formula, the materials comprising the following raw material composition by weight: 5-10 parts of modified phenolic resin powder, 1-2 parts of potassium hexatitanate whisker, 5-7 parts of calcium hydroxide, 20-30 parts of barium sulfate, 1-3 parts of artificial graphite, 2-6 parts of coke powder, 3-5 parts of cashew nut shell oil rubbing powder, 1-3 parts of carboxyl nitrile rubber powder, 4-8 parts of antimony sulfide, 4-6 parts of mica, 2-6 parts of zirconium oxide, 9-11 parts of composite fiber, 4-6 parts of nano filler, 0.06-0.12 parts of modified tube material; the composite fiber comprises chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber; Step 2: mix and stir the aramid pulp and composite mineral fiber in the materials uniformly for 10-15 min to prepare mixture one; mix and stir the modified phenolic resin powder and modified tube material in the materials by ball milling for 5-8 min at a speed of 200-300 rpm to prepare mixture two; mix and stir the remaining part of the materials with mixture one and mixture two for 25-30 min to prepare compression molding material; Step 3: heat the hot-pressing mold to a preset temperature, the preset temperature being 135-145℃ for the upper mold, 125-135℃ for the middle mold and 165-175℃ for the lower mold, then apply release agent, pour the compression molding material into the mold cavity, close the mold, maintain the pressure at 12-14 MPa for 4-6 min, heat-press the compression molding material to form a pre-product, exhaust every 14-16 s during the pressure maintaining period, a total of 9-10 times, to prepare the pre-product; the modified phenolic resin powder comprises phenol, formaldehyde, cashew nut shell oil and melamine, the molar ratio of the phenol, formaldehyde, cashew nut shell oil and melamine being 2:1.4:0.15-0.35:0.025-0.03; the modified tube material comprises carbon nanotube, anhydrous p-aminobenzenesulfonic acid, sodium nitrite and azobisisobutyronitrile, the mass ratio of the carbon nanotube, anhydrous p-aminobenzenesulfonic acid, sodium nitrite and azobisisobutyronitrile being 0.2:5-6:2-2.4:1.2; Step 4: place the pre-product into a hot air oven and heat to 80-85℃, maintain the temperature for 2-2.5 h, continue to heat to 120-125℃, maintain the temperature for 4-4.5 h, continue to heat to 160-165℃, maintain the temperature for 4-4.5 h, then reduce the temperature to room temperature at a rate of 70-90℃ / h to prepare the product.

2. A method of manufacturing a carbon fiber based automotive disc brake pad material as claimed in claim 1, wherein: The mass ratio of the chopped carbon fiber, aramid pulp, ceramic fiber and composite mineral fiber is 3-5:1-3:2-4:10-12.

3. A method of manufacturing a carbon fiber based automotive disc brake pad material as claimed in claim 1, wherein: The preparation method of the modified phenolic resin comprises the following steps: accurately measuring phenol, heating to a molten state, then adding to a stirrer and continuously stirring, then adding accurately measured melamine, cashew nut shell oil and formaldehyde, then heating to 70-80 DEG C, adding a catalyst and adjusting the pH value to 2-2.5, stirring for 3-3.5 h and continuously condensing reflux, then vacuumizing to a vacuum degree of 0.09 MPa, temperature control being 65-70 DEG C, vacuum distillation being 2-2.5 h, then heating to 180-185 DEG C, maintaining for 3-4 min and then stopping heating, cooling to room temperature to obtain the modified phenolic resin.

4. A method of manufacturing a carbon fiber based automotive disc brake pad material as claimed in claim 1, wherein: The preparation of the modified pipe material comprises the following steps: Step 1: accurately measuring carbon nanotubes, pouring into a concentrated sulfuric acid and ammonium persulfate mixed solution, stirring at room temperature for 1-1.5 h until no obvious particles are observed; Step 2: accurately measuring anhydrous p-aminobenzenesulfonic acid, ultrasonic oscillation and stirring until uniform, then accurately measuring sodium nitrite, cooling to 10-15 DEG C and stirring for 20-25 min; Step 3: accurately measuring azobisisobutyronitrile, heating to 80-85 DEG C, continuously stirring for 6-6.5 h, then centrifuging and ultrasonic cleaning after the reaction is completed, filtering and vacuum drying at 80-85 DEG C for 24-26 h to obtain the modified pipe material.

5. A method of manufacturing a carbon fiber based automotive disc brake pad material as claimed in claim 1, wherein: The nano filler comprises one or more combinations of nano silicon carbide and nano boron carbide.

6. A method of making a carbon fiber based automotive disc brake pad material according to claim 5, characterized in that: The mass ratio of the nano silicon carbide and the nano boron carbide is 0.5:1-2.

7. A method of manufacturing a carbon fiber based automotive disc brake pad material as claimed in claim 1, wherein: The material further comprises 2-10 parts of lanthanum oxide.

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