Automobile brake disc Cf/SiC matrix material and preparation method thereof
Technical field
The present invention relates to a kind of automobile brake disc Cf/SiC matrix material and preparation method thereof, be applicable to automobile brake disc production field.
Background technology
The material mainly graphitic cast iron that traditional braking dish uses, China's traditional braking disk material is HT250, is equal to U.S. G3000.The requirement of principal element is respectively C:3.1-3.4%Si:1.9-2.3%Mn:0.6-0.9%.HT200 or HT250 not only has certain intensity and wear resistance, and its material cost is low, manufacturing cost is lower, becomes the material of the main first-selection of retarding disc.But graphitic cast iron cutting ability is poor, thermotolerance and vibration damping bad, density is large.In addition, during braking, easily produce noise, have a strong impact on life-span and the comfort level of automobile; Although powder metallurgy technology comparative maturity, manufacturing cost is comparatively cheap, and their performances are at high temperature not good and be easy to produce thermal etching.
With ceramic particles such as SiC or Al203 for reinforcement, aluminium is the type material of matrix, and the high-wearing feature of existing ceramic particle component, high rigidity (intensity) and low-expansion coefficient, have again heat conductivity and low density that its matrix component aluminium is good.But it is lower that its shortcoming is plasticity, once there is crack initiation, be easy to expansion.
With carbon fiber or its fabric for wild phase, with the C/C matrix material that chemical vapor infiltration RESEARCH OF PYROCARBON or liquid impregnation carbide resin carbon, bitumencarb are matrix, there is the advantages such as density is low, specific heat capacity is high, thermal expansivity is little, but humidity, temperature factor can cause its frictional coefficient unstable.In addition, when temperature is greater than 400 DEG C, it is easily oxidized, and cost is higher.
Cf/SiC matrix material inherits the advantage of above-mentioned materials, have that density is low, intensity is high, hardness is high, wear resistance is high, the feature of high temperature resistant, resistance to ablation, but due to the nature of SiC matrix, its unique not enough place is that its fragility is comparatively large, is further improved.
Cf/SiC matrix material is the optimization to Cf/SiC composite property, which overcomes the deficiency that Cf/SiC matrix material fragility is large, demonstrates excellent frictional behaviour compared with above brake material.Meanwhile, its density is low, the life-span is long, and thermal shock resistance is good, and to residing environment and temperature susceplibility low.
At present, the preparation technology of Cf/SiC matrix material mainly contains following several: chemical vapour deposition (CVD), and precursor infiltration and pyrolysis (PIP), lqiuid phase sintering method (LPS) are also silicon melting method of impregnation (LSI) etc.
1, chemical vapour deposition (CVD)
Reaction principle:
Trichloromethyl silane (MTS) is source material, and argon gas is diluent gas, and hydrogen is carrier gas.The advantage that MTS makes raw material in its molecule Si: C is 1: 1, is decomposed into stoichiometric SiC, thus can prepares high-purity alpha-SiC, all can deposit at 900 DEG C ~ 1600 DEG C.
Processing condition are:
Temperature 1100 DEG C ~ 1300 DEG C, H2 flow 200mL/min ~ 600mL/min, Ar flow 100mL/min ~ 600mL/min; Furnace pressure 2kPa ~ 10kPa, brings reactant into reaction chamber in the mode of bubbling; Sedimentation rate 40 μm/about 24h.
Chemical vapour deposition (CVD) can synthesize reinforcement under lower than body melting temperature, matrix high temperature can be avoided to issue biochemical reaction, thus ensure that the performance of matrix and the integrity of matrix are not destroyed, but it is longer also to there is preparation cycle in the method, there is the deficiency of the defects such as pore in material.
2, precursor infiltration and pyrolysis (PIP)
Technological process:
1. prepare precursor solution.
2. vacuum impregnation: vacuumize after fiber preform being placed in impregnating autoclave, makes pressure be less than 100Pa, closes vacuum pump, the above-mentioned precursor solution configured is added impregnating autoclave, makes fiber preform thorough impregnation 2-10 hour below liquid level.
3. crosslinking curing: the fiber preform after vacuum impregnation is taken out and dries (the air-dry 2-10 hour of general nature), be placed in baking box crosslinking curing again, curing mechanism is warmed up to 150-250 DEG C of solidification 1-5 hour for 1-5 hour again for adopting 80-120 DEG C of insulation.
4. Pintsch process: the Pintsch process fiber preform after crosslinking curing being carried out 800-1800 DEG C, pyrolysis time is 0.5-2 hour, first can be evacuated to low vacuum and pass into rare gas element again or logical nitrogen is protected in 100Pa before carrying out Pintsch process.
5. densification: periodically repeat above-mentioned vacuum impregnation-crosslinking curing-Pintsch process technical process, until obtain the matrix material of densification.
Precursor infiltration and pyrolysis (PIP) is temperature required lower, less to body injury, can prepare the component of complex construction.But this processing disadvantages is to need in densifying materials process to carry out several times dipping-cracking, and the production cycle is longer; In addition, have small molecules during cracking and overflow from matrix, cause cavity in material more.
3, silicon melt impregnation (LSI)
Under vacuum state, manufacture raw material is put into closed unit (the Graphite box of Fig. 1), and the manufacture raw material be communicated with by closed unit in it is incubated 1 hour at 1420-1700 DEG C of temperature, as Fig. 1.After the fusing point (1414 DEG C) of Si, liquid Si is penetrated in the obtained matrix of roughing rapidly by wicking action, reacts and forms SiC, become the wild phase in matrix material with matrix.
It is short that silicon melt impregnation (LSI) has the cycle, and hole is few, and cost is lower, can prepare the advantages such as complex-shaped component, but the silicon of molten state easily and carbon fiber substrate react, cause fibre property to reduce.Meanwhile, a large amount of matrix micro mist can be introduced precast body in advance, Fast Filling macrovoid, improve the density of pickling efficiency and end article.
Summary of the invention
The present invention seeks to: the present invention is in conjunction with the chemical vapour deposition introduced in background technology, precursor infiltration and pyrolysis and silicon melting method of impregnation, and explore the new processing method of a set of production automobile brake disc Cf/SiC matrix material, the Cf/SiC matrix material using the method to obtain makes automobile brake disc, it is high that retarding disc has intensity, quality is light, wear-resistant, corrosion resistance and good, brakeless is decayed, abrasion loss is little and muting feature.
Technical scheme of the present invention is: the preparation method of described automobile brake disc Cf/SiC matrix material, and it is matrix with carbon fiber, take SiC as reinforcement, and adds boron to prepare the Cf/SiC matrix material of automobile brake disc in making raw material.
The present invention, on the basis of technique scheme, also comprises following preferred version:
The method specifically comprises the following steps:
Step one, prepare prefabricated matrix,
To pass in liquid resin as raw-material carbon fiber, certain thickness protective layer is formed at carbon fiber surface after drying, then these surfaces are made without latitude cloth and tire net with the carbon fiber of protective layer, and obtained is replaced together with lay-up without latitude cloth and tire net, afterwards introducing carbon fiber bundle perpendicular to laying direction, obtain three-dimensional preformed matrix;
Step 2, add caking agent,
In the three-dimensional preformed matrix that step one is obtained, infiltrate previously prepared good mud, described mud is made up of furane resin, silicon carbide powder, boron powder and dehydrated alcohol, is and then cured process, thus obtains carbon-fibre composite first product;
Step 3, pyrolysis,
The carbon-fibre composite first product that step 2 obtains is carried out pyrolysis in nitrogen environment, and pyrolysis temperature requires 200 DEG C ~ 850 DEG C, and pyrolysis time is 5 ~ 20 hours, and described carbon-fibre composite first product becomes porous material after this pyrolysis processing;
Step 4, injection liquid-state silicon,
Under nitrogen protection state, porous material step 3 obtained, 1420 ~ 1700 DEG C of scope insulations 1 ~ 2 hour, just obtains automobile brake disc Cf/SiC matrix material to be prepared after cooling.
In described step one, the thickness of described carbon fiber surface protective layer is 1 ~ 5 μm.
In described step one, be the T300-3K long carbon fiber that Japanese Toray company produces as raw-material described carbon fiber.
In described step one, to described without latitude cloth and tire net carry out alternately lay-up time, adopt individual layer to replace the mode of lay-up.
In described step one, to described without latitude cloth and tire net carry out alternately lay-up time, adjacent two layers to stagger certain angle without the lay angle of latitude cloth.
In described step one, to described without latitude cloth and tire net carry out alternately lay-up time, adjacent two layers staggers 45 ° without the lay angle of latitude cloth.
In described step 2, be in prefabricated matrix, infiltrate previously prepared good mud under temperature 65 DEG C, pressure 2.0 ~ 2.2MPa condition.
In described step 2,180 ~ 220 DEG C, process is cured to three-dimensional preformed matrix and slurry mixture under pressure 2.0 ~ 2.2MPa condition, set time is 3 ~ 5 hours.
Automobile brake disc Cf/SiC matrix material obtained by a kind of aforesaid method.
Advantage of the present invention is:
1, take carbon fiber as matrix, SiC is that the obtained composite density of reinforcement is low, the life-span is long, and thermal shock resistance is good, and to residing environment and temperature susceplibility low, overcome the deficiency that Cf/SiC matrix material fragility is larger simultaneously.
2, boron add the resistance of oxidation that can improve carbon fiber in retarding disc, improve the degree of crystallinity of SiC, make carbon, silicon fully reacts, effectively reduce remaining silicone content.
3, liquid-state silicon is flooded environment and become nitrogen protection from vacuum condition, cost reduces greatly.Even if nitrogen and matrix react generate Si3N4, material property also can not be made to decline.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the operation demonstration graph of traditional silicon melt impregnation;
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1
The preparation method of this automobile brake disc Cf/SiC of the present embodiment matrix material, main improvement is that it is when preparing Cf/SiC matrix material, take carbon fiber as matrix, take SiC as reinforcement, and add boron to carry out the preparation of Cf/SiC matrix material making in raw material, and be not conventionally that matrix is prepared with SiC.The method specifically comprises the following steps:
Step one, prepare prefabricated matrix.
To pass in liquid resin as raw-material carbon fiber, just certain thickness protective layer is defined at each carbon fiber surface after drying, the overcoat thickness that general requirement carbon fiber surface is formed is at 1 ~ 5 μm of optimum, and this example ensures that the surfacecti proteon layer thickness of every root carbon fiber is at about 1 μm as far as possible.Then these surfaces are made without latitude cloth and tire net with the carbon fiber of protective layer, and by make without latitude cloth and tire net alternate cycles lay-up, namely according to together with being laid in tire net alternate cycles without latitude cloth without latitude cloth-tire net-without latitude cloth-tire net-without latitude cloth-tire net-without the order of latitude cloth-tire net.Adopt relay-type needling technique introducing carbon fiber bundle perpendicular to laying direction afterwards, thus obtain three-dimensional preformed matrix.
Through contriver's experimental verification, in this step one, when the T300-3K long carbon fiber adopting Japanese Toray company to produce as raw-material above-mentioned carbon fiber, excellent.What this example adopted is exactly this T300-3K long carbon fiber.
In all directions, all there is excellent tension anti-pressure ability in order to make final obtained Cf/SiC matrix material, in this step one, to described without latitude cloth and tire net carry out alternately lay-up time, adopt individual layer to replace the mode of lay-up, namely replace lay-up without latitude cloth-one deck tire net-one deck without the mode of latitude cloth-one deck tire net without latitude cloth-one deck tire net-one deck according to one deck.Ensure that adjacent two layers is different without the lay angle of latitude cloth, such as the first layer is 0 ° without the lay angle of latitude cloth, and so the second layer then elects 30 ° as without the lay angle of latitude cloth, and third layer then elects 60 ° as without the lay angle of latitude cloth, so analogizes simultaneously.Experiment proves, often adjacent two-layer without latitude cloth stagger 45 ° of laies time, best results, namely the first layer is 0 ° without latitude cloth lay angle, the second layer is 45 ° without latitude cloth lay angle, and third layer is 90 ° without latitude cloth lay angle, and the 4th layer is 135 ° without latitude cloth lay angle.
Step 2, add caking agent.
Previously prepared good mud is infiltrated in the three-dimensional preformed matrix that step one is obtained, described mud is made up of furane resin, silicon carbide powder, boron powder and dehydrated alcohol, and then process is cured to the mixture of described three-dimensional preformed matrix and mud, thus obtains carbon-fibre composite first product.
Through experimental verification, when infiltrating described mud in prefabricated matrix under temperature 65 DEG C, pressure 2.0-2.2MPa condition, final obtained Cf/SiC matrix material has preferably physicochemical property.This example infiltrates described mud under temperature 65 DEG C, pressure 2.0-2.2MPa condition.
In this example, described mud obtains particular by the furane resin being added with dehydrated alcohol, boron powder and silicon carbide powder, and wherein the mass ratio of dehydrated alcohol, boron powder, silicon carbide powder, furane resin is 3:7:10:80.
In general, in this step 2,180 ~ 220 DEG C, process is cured to three-dimensional preformed matrix and slurry mixture under pressure 2.0 ~ 2.2MPa condition, and set time is in 3 ~ 5 hours window, and effect is better.The present embodiment 180 DEG C, process is cured to three-dimensional preformed matrix and slurry mixture under pressure 2.0MPa condition, set time is 5 hours.
Step 3, pyrolysis.
The carbon-fibre composite first product that step 2 obtains is carried out pyrolysis in nitrogen environment, and pyrolysis temperature is 200 DEG C ~ 850 DEG C, and pyrolysis time is in 5 ~ 20 hours window, and described carbon-fibre composite first product becomes porous material after this pyrolysis processing.After pyrolysis, carbon-fibre composite first product becomes porous material, and this is main because pyrolysis makes furane resin become resin carbon-point and become a part for matrix material.In pyrolytic process, if resin is in the pyrolysis temperature environment of 200 DEG C ~ 650 DEG C, resin is originally heated gradually between 200 DEG C-650 DEG C, and the part that volatilization is gone bad can be spread out by matrix and not affect the integrity of matrix material.When temperature is higher than 650 DEG C, along with temperature raises, quality is not almost lost.
In this example, pyrolysis temperature is 200 DEG C, and pyrolysis time is 20 hours.
Step 4, injection liquid-state silicon,
Under nitrogen protection state; porous material step 3 obtained is incubated 2 hours at 1420 DEG C of temperature; after the fusing point (1414 DEG C) of Si; liquid Si will penetrate in the obtained matrix of roughing rapidly; react with matrix and form SiC, becoming the wild phase in matrix material.Just automobile brake disc Cf/SiC matrix material to be prepared is obtained after cooling.
The conveniently operation of above-mentioned steps four; the porous material that step 3 obtains need be put into a closed unit (encloses container; with reference to Fig. 1), and then the porous material being communicated with this closed unit and Qi Nei is incubated 2 hours under nitrogen protection state at 1420 DEG C of temperature.
Through measuring and calculating, the Cf/SiC composite density obtained by the present embodiment is about 1.8g/cm3, and dynamic friction coefficient is about 0.4, static friction coefficient is about 0.5, wear rate is about 0.02cm3/MJ, and thermal diffusivity is about 0.22cm2/s, and resistance to impact shock is about 2.9KJ/m2.
Embodiment 2
The preparation method of this automobile brake disc Cf/SiC of the present embodiment matrix material, specifically comprises the following steps:
Step one, prepare prefabricated matrix.
Passed in liquid resin by the T300-3K long carbon fiber that Japanese Toray company produces, just define certain thickness protective layer at each carbon fiber surface after drying, this example ensures that the surfacecti proteon layer thickness of every root carbon fiber is at about 1.5 μm as far as possible.Then these surfaces are made without latitude cloth and tire net with the carbon fiber of protective layer, and by make without latitude cloth and tire net alternate cycles lay-up, namely according to together with being laid in tire net alternate cycles without latitude cloth without latitude cloth-tire net-without latitude cloth-tire net-without latitude cloth-tire net-without the order of latitude cloth-tire net.Adopt relay-type needling technique introducing carbon fiber bundle perpendicular to laying direction afterwards, thus obtain three-dimensional preformed matrix.
In all directions, all there is excellent tension anti-pressure ability in order to make final obtained Cf/SiC matrix material, in this step one, to described without latitude cloth and tire net carry out alternately lay-up time, adopt individual layer to replace the mode of lay-up, and often adjacently two-layerly to stagger 45 ° of laies without latitude cloth.
Step 2, add caking agent.
Previously prepared good mud is infiltrated in the three-dimensional preformed matrix that step one is obtained, described mud is made up of furane resin, silicon carbide powder, boron powder and dehydrated alcohol, and then process is cured to the mixture of described three-dimensional preformed matrix and mud, thus obtains carbon-fibre composite first product.
Through experimental verification, when infiltrating described mud in prefabricated matrix under temperature 65 DEG C, pressure 2.0-2.2MPa condition, final obtained Cf/SiC matrix material has preferably physicochemical property.This example infiltrates described mud under temperature 65 DEG C, pressure 2.0-2.2MPa condition.
In this example, described mud obtains particular by the furane resin being added with dehydrated alcohol, boron powder and silicon carbide powder, and wherein the mass ratio of dehydrated alcohol, boron powder, silicon carbide powder, furane resin is 5:5:15:75.
The present embodiment 200 DEG C, process is cured to three-dimensional preformed matrix and slurry mixture under pressure 2.1MPa condition, set time is 4 hours.
Step 3, pyrolysis.
The carbon-fibre composite first product that step 2 obtains is carried out pyrolysis in nitrogen environment, and pyrolysis temperature is 650 DEG C, and pyrolysis time is 4 hours, and described carbon-fibre composite first product becomes porous material after this pyrolysis processing.
Step 4, injection liquid-state silicon,
Under nitrogen protection state, porous material step 3 obtained by encloses container is incubated 1.5 hours at 1600 DEG C of temperature, just obtains automobile brake disc Cf/SiC matrix material to be prepared after cooling.
After tested, the Cf/SiC composite density obtained by the present embodiment is about 1.85g/cm3, and dynamic friction coefficient is about 0.43, static friction coefficient is about 0.52, wear rate is about 0.018cm3/MJ, and thermal diffusivity is about 0.28cm2/s, and resistance to impact shock is about 2.7KJ/m2.
Embodiment 3
The preparation method of this automobile brake disc Cf/SiC of the present embodiment matrix material, specifically comprises the following steps:
Step one, prepare prefabricated matrix.
Passed in liquid resin by the T300-3K long carbon fiber that Japanese Toray company produces, just define certain thickness protective layer at each carbon fiber surface after drying, this example ensures that the surfacecti proteon layer thickness of every root carbon fiber is at about 2 μm as far as possible.Then these surfaces are made without latitude cloth and tire net with the carbon fiber of protective layer, and by make without latitude cloth and tire net alternate cycles lay-up, namely according to together with being laid in tire net alternate cycles without latitude cloth without latitude cloth-tire net-without latitude cloth-tire net-without latitude cloth-tire net-without the order of latitude cloth-tire net.Adopt relay-type needling technique introducing carbon fiber bundle perpendicular to laying direction afterwards, thus obtain three-dimensional preformed matrix.
In all directions, all there is excellent tension anti-pressure ability in order to make final obtained Cf/SiC matrix material, in this step one, to described without latitude cloth and tire net carry out alternately lay-up time, adopt individual layer to replace the mode of lay-up, and often adjacently two-layerly to stagger 45 ° of laies without latitude cloth.
Step 2, add caking agent.
Previously prepared good mud is infiltrated in the three-dimensional preformed matrix that step one is obtained, described mud is made up of furane resin, silicon carbide powder, boron powder and dehydrated alcohol, and then process is cured to the mixture of described three-dimensional preformed matrix and mud, thus obtains carbon-fibre composite first product.
This example infiltrates described mud under temperature 65 DEG C, pressure 2.2MPa condition.
In this example, described mud obtains particular by the furane resin being added with dehydrated alcohol, boron powder and silicon carbide powder, and wherein the mass ratio of dehydrated alcohol, boron powder, silicon carbide powder, furane resin is for being 7:3:20:70.
The present embodiment 200 DEG C, process is cured to three-dimensional preformed matrix and slurry mixture under pressure 2.2MPa condition, set time is 3 hours.
Step 3, pyrolysis.
The carbon-fibre composite first product that step 2 obtains is carried out pyrolysis in nitrogen environment, and pyrolysis temperature is 850 DEG C, and pyrolysis time is 5 hours, and described carbon-fibre composite first product becomes porous material after this pyrolysis processing.
Step 4, injection liquid-state silicon,
Under nitrogen protection state, porous material step 3 obtained by encloses container is incubated 1 hour at 1700 DEG C of temperature, just obtains automobile brake disc Cf/SiC matrix material to be prepared after cooling.
After tested, the Cf/SiC composite density obtained by the present embodiment is about 1.89g/cm3, and dynamic friction coefficient is about 0.44, static friction coefficient is about 0.54, wear rate is about 0.015cm3/MJ, and thermal diffusivity is about 0.23cm2/s, and resistance to impact shock is about 2.6KJ/m2.
Certainly, above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to people can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to the spirit of main technical schemes of the present invention or modification, all should be encompassed within protection scope of the present invention.