CN103922777A

CN103922777A - Method for preparing carbon/carbon-silicon carbide composite material for bearings

Info

Publication number: CN103922777A
Application number: CN201410141041.2A
Authority: CN
Inventors: 白瑞成; 李波; 李爱军; 周春节; 孙晋良
Original assignee: SHANGHAI UNIVERSITY
Current assignee: SHANGHAI UNIVERSITY
Priority date: 2014-04-09
Filing date: 2014-04-09
Publication date: 2014-07-16

Abstract

The invention discloses a method for preparing a carbon/carbon-silicon carbide composite material for bearings. The preparation method comprises the following steps: making a 0.15-0.30 g/cm ³ carbon fiber integral felt by subjecting polyacrylonitrile pre-oxidized fibers to needle-punched carbonization treatment , or alternately stack the non-weft cloth and the net tire and make the non-weft cloth carbon fiber integral felt of 0.4~0.6g/cm ³ through needle punching carbonization; adopt the comprehensive process of chemical vapor infiltration (CVI) and resin impregnation pyrolysis (PIP) , to prepare a C/C porous preform with a density of 1.35-1.75g/cm ³ , and perform a high-temperature treatment at 2250-2600°C under an Ar gas protective atmosphere; after vacuuming, Ar gas is introduced, and the temperature is raised to 2200-2350°C Carry out fusion siliconizing, and keep warm for 1.5 hours. The invention relates to a method for preparing a carbon/carbon-silicon carbide (C/C-SiC) composite material with less residual silicon and low wear rate for bearings.

Description

A kind of preparation method of charcoal/carbon-silicon carbide matrix material for bearing

Technical field

The present invention relates to a kind of preparation method of charcoal/carbon-silicon carbide (C/C-SiC) matrix material for bearing, be specifically related to that a kind of quality is light, cost is low, intensity is high, the preparation method of the low C/C-SiC matrix material of wear rate.Belong to high performance composite technique technology of preparing.

Background technology

That C/C-SiC matrix material has is high temperature resistant, density is low, wear resistance good, good corrosion resistance, and the advantage such as excellent friction and wear behavior, has therefore been applied to aerospace and high-grade automotive field as brake flange.It also has self-lubricating property, can be used to bearing materials.Solid Self-lubricant Bearing adopts the compound of metal base and solid lubricant at present, can be high temperature, low speed, heavy duty, difficult formation under oil-bound film or the easy severe special conditions losing efficacy of oil film, realize oil-free self lubrication, reach wear and tear slow and high object of life-span, but can not be applied to high speed and have pollution occasion.Charcoal/carbon-silicon carbide matrix material is used for to oil-free lubricatoin, contains the mechanical consumable accessory such as oil lubrication, few oil lubrication, particularly at a high speed and have under the bad working environments such as occasion of pollution, to be conducive to extend the maintenance cycle of machine, reduce the use of lubricating oil, alleviate weight of equipment, improve productivity effect.Preparation C/C-SiC matrix material mainly contains chemical vapor infiltration (CVI), precursor infiltration and pyrolysis (PIP) and reaction infiltration (RMI) technique [Xiao Peng etc. at present, the present Research of C/C-SiC ceramic braking material and application. China YouSe Acta Metallurgica Sinica, 2005.15 (5): 667-674].Compare with PIP technique with CVI, RMI technique is prepared C/C-SiC matrix material, have that preparation cycle is short, cost is low, residual porosity rate is low and advantage [the M ü hlratzer A such as near-net-shape, Production, properties and applications of ceramic matrix composites.C/Fiber DKG, 1999.76 (4): 30-35].Xiao Peng etc. [impact of SiC content on C/C-SiC friction materials friction and wear behavior. Materials Science and Engineering of Powder Metallurgy, 2012 (01): 121-126] adopt reaction infiltration method to prepare C/C-SiC matrix material, and studied the impact of SiC content on material friction wear properties, result shows that the frictional coefficient of C/C-SiC matrix material is along with the increase of SiC content is first risen and declined afterwards.[Effect of pyrolytic carbon content on microstructure and tribological properties of C/C-SiC brake composites fabricated by isothermal chemical vapor infiltration[J] the .Solid State Sciences such as Shi Qilong, 2012,14:26-34] yan] study the microtexture of pyrolysised carbon content on C/C-SiC matrix material and the impact of friction and wear behavior, find that the increase of the friction coefficient pyrolysised carbon content of material is fallen after rising.Pyrolysised carbon content, the degree of graphitization of preparation temperature, siliconising time and C/C porous insert porosity all can exert an influence to the performance of C/C-SiC matrix material.

Summary of the invention

The object of the present invention is to provide the preparation method of charcoal/carbon-silicon carbide that a kind of bearing is few with remaining silicon, wear rate is low (C/C-SiC) matrix material.

For achieving the above object, a kind of preparation method of charcoal/carbon-silicon carbide matrix material for bearing that the present invention proposes, comprises the following steps:

(1) make carbon fabric integer felt with pre-oxidized polyacrylonitrile fiber through acupuncture, or with without latitude cloth and net tire is alternately laminated makes without latitude cloth carbon fabric integer felt through acupuncture;

(2) carbon fabric integer felt step (1) being made and carry out charing processing at 900～1000 DEG C without latitude cloth carbon fabric integer felt, obtaining density is 0.15～0.30gcm ^-3carbon fabric integer felt and density be 0.4～0.6g/cm ³without latitude cloth carbon fabric integer felt;

(3) adopt chemical vapor infiltration to carry out density, put into chemical vapor infiltration poke by the described carbon fabric integer felt making through step (2) or without latitude cloth carbon fabric integer felt, be warming up to 900～1100 DEG C, pass into C ₃h ₆after gas and Ar oxygen mixture, make C/C porous preform;

(4) after each chemical vapor infiltration technique, the C/C porous preform making is carried out to surface treatment repeating step (3), until the density of C/C porous preform is 1.3～1.5g/cm ³;

(5) material of preparation in step (4) is carried out to 2350～2600 DEG C of pyroprocessing under Ar gas protective atmosphere;

(6) adopt resin impregnation cracking technology to carry out density the material of preparation in step (5); flood-solidify-charing processing with furane resin; under Ar gas protective atmosphere, C/C porous preform is carried out to 2250～2600 DEG C of high-temperature heat treatment, and to make density be 1.35～1.75g/cm ³c/C porous preform;

(7) adopt reaction infiltration (RMI) technique to carry out melting siliconising to the C/C porous preform of preparing through step (6), put into plumbago crucible by C/C porous preform, add Si powder, Si Powder Particle Size is 20～30 μ m, passes into Ar gas after vacuumizing under condition in High Temperature Furnaces Heating Apparatus, and furnace temperature rises to 2200～2350 DEG C from room temperature, be incubated 1.5 hours, liquid Si infiltrates C/C porous preform inside under suction function, and reacts generation SiC matrix with matrix C, prepares C/C-SiC matrix material.

Advantage of the present invention is: chemical vapor infiltration of the present invention (CVI) and resin impregnation cracking (PIP) composite technology are prepared the C/C porous preform of different openings porosity, and adopt reaction infiltration (RMI) technique to prepare C/C-SiC matrix material, preparation cycle obviously shortens, cost; The present invention can control content and the degree of graphitization of pyrolytic carbon in matrix as CVI technique pyrolysis temperature, time, airshed and pyroprocessing temperature and time by adjusting process parameter, thereby regulates the frictional coefficient of material; The present invention controls the content of SiC in material and regulates the frictional coefficient of material by choosing the C/C porous preform of different openings porosity; The present invention, by the control to the Theoretical Calculation of Si powder consumption strict control and high-temperature processing technology, effectively reduces the content of remaining Si in material; Melting siliconising temperature of the present invention is more than 2200 DEG C, is conducive to Si and also effectively reduces material internal residual stress with reacting of C; SiC prepared by the present invention is reticulated structure in C/C porous insert inside, is conducive to improve the wear resistance of material.

Brief description of the drawings

The XRD figure spectrum of C/C-SiC matrix material grind into powder prepared by Fig. 1 the present invention, wherein X-coordinate is 2 θ, unit is °; Ordinate zou is diffraction peak intensity, and unit is a.u..

Embodiment

Embodiment mono-

By with without latitude cloth and net tire alternately laminated make through acupuncture put into heat treatment furnace without latitude cloth carbon fabric integer felt, vacuumize, at 900～1000 DEG C of temperature, carry out charing processing, obtaining density is 0.60g/cm ³without latitude cloth carbon fabric integer felt, this is inserted in CVI stove, with C without latitude cloth carbon fabric integer felt ₃h ₆for presoma, at 900～1100 DEG C of temperature, carry out CVI densification, making density is 1.30g/cm ³c/C porous preform; C/C porous preform is carried out under Ar gas protective atmosphere to 2350～2600 DEG C of pyroprocessing; after pyroprocessing, C/C porous preform is placed in to dipping still; vacuumize; flood with furane resin; pressurization; after dipping, put into baking oven and be cured processing; solidify to be placed on and in High Temperature Furnaces Heating Apparatus, vacuumize charing at 900～1000 DEG C of temperature; after charing, material is placed in to High Temperature Furnaces Heating Apparatus; under Ar gas protective atmosphere, temperature is that high-temperature heat treatment is carried out in 2250 DEG C of left and right, and making density is 1.47g/cm ³c/C porous preform; C/C porous preform is put into plumbago crucible, add silica flour according to Theoretical Calculation Si amount/actual amount with Si amount=1:1.5, Si Powder Particle Size is 30 μ m; The plumbago crucible that C/C porous preform and Si powder are housed is put into High Temperature Furnaces Heating Apparatus, pass into Ar gas, melting siliconising temperature is 2200～2350 DEG C, and insulation 1.5h, prepares C/C-SiC matrix material.The C/C-SiC matrix material making is carried out to material phase analysis (Fig. 1) with XRD diffractometer, analytical results shows that material is that SiC is mainly face-centered cubic type SiC(fcc by SiC and two kinds of thing phase composites of C; β).The C/C-SiC density being prepared by this porous insert is 2.0g/cm ³, XY is to flexural strength 208.6MPa, Z-direction flexural strength 182.7MPa, and XY is to compressive strength 187.5Mpa, and line wear rate is 0.009167.

Embodiment bis-

The carbon fabric integer felt that pre-oxidized polyacrylonitrile fiber is made through acupuncture is put into heat treatment furnace, vacuumizes, and at 900～1000 DEG C of temperature, carries out charing processing, and obtaining density is 0.30g/cm ³carbon fabric integer felt, inserts carbon fabric integer felt in CVI stove, with C ₃h ₆for presoma, at 900～1100 DEG C of temperature, carry out CVI densification, making density is 1.30g/cm ³c/C porous preform; C/C porous preform is carried out under Ar gas protective atmosphere to 2350～2600 DEG C of pyroprocessing; after pyroprocessing, C/C porous preform is placed in to dipping still; vacuumize; flood with furane resin; pressurization; after dipping, put into baking oven and be cured processing; solidify to be placed on and in High Temperature Furnaces Heating Apparatus, vacuumize charing at 900～1000 DEG C of temperature; after charing, material is placed in to High Temperature Furnaces Heating Apparatus; under Ar gas protective atmosphere, temperature is that high-temperature heat treatment is carried out in 2250 DEG C of left and right, and making density is 1.45g/cm ³c/C porous preform; C/C porous preform is put into plumbago crucible, add silica flour according to Theoretical Calculation Si amount/actual amount with Si amount=1:1.5, Si Powder Particle Size is 30 μ m; The plumbago crucible that C/C porous preform and Si powder are housed is put into High Temperature Furnaces Heating Apparatus, pass into Ar gas, melting siliconising temperature is 2200～2350 DEG C, is incubated 1.5 hours, prepares C/C-SiC matrix material.The C/C-SiC matrix material making is carried out to material phase analysis (Fig. 1) with XRD diffractometer, analytical results shows that material is that SiC is mainly face-centered cubic type SiC(fcc by SiC, two kinds of thing phase composites of C; β).The C/C-SiC density being prepared by this porous insert is 2.2g/cm ³, XY is to flexural strength 55.81MPa, Z-direction flexural strength 30.78MPa, and XY is to compressive strength 187.12MPa, Z-direction compressive strength 136.36MPa.

Embodiment tri-

The carbon fabric integer felt that pre-oxidized polyacrylonitrile fiber is made through acupuncture is put into heat treatment furnace, vacuumizes, and at 900～1000 DEG C of temperature, carries out charing processing, and obtaining density is 0.30g/cm ³carbon fabric integer felt, inserts carbon fabric integer felt in CVI stove, with C ₃h ₆for presoma, at 900～1100 DEG C of temperature, carry out CVI densification, making density is 1.30g/cm ³c/C porous preform; C/C porous preform is carried out under Ar gas protective atmosphere to 2350～2600 DEG C of pyroprocessing; after pyroprocessing, C/C porous preform is placed in to dipping still; vacuumize; flood with furane resin; pressurization; after dipping, put into baking oven and be cured processing; solidify to be placed on and in High Temperature Furnaces Heating Apparatus, vacuumize charing at 900～1000 DEG C of temperature; after charing, material is placed in to High Temperature Furnaces Heating Apparatus; under Ar gas protective atmosphere, temperature is that high-temperature heat treatment is carried out in 2250 DEG C of left and right, and making density is 1.67g/cm ³c/C porous insert; C/C porous preform is put into plumbago crucible, add silica flour according to Theoretical Calculation Si amount/actual amount with Si amount=1:1.5, Si Powder Particle Size is 30 μ m; The plumbago crucible that C/C porous insert and Si powder are housed is put into High Temperature Furnaces Heating Apparatus, pass into Ar gas, melting siliconising temperature is 2200～2350 DEG C, is incubated 1.5 hours, prepares C/C-SiC matrix material.The C/C-SiC matrix material making is carried out to material phase analysis (Fig. 1) with XRD diffractometer, analytical results shows that material is that SiC is mainly face-centered cubic type SiC(fcc by SiC, two kinds of thing phase composites of C; β).The C/C-SiC density being prepared by this porous insert is 2.0g/cm ³, XY is to flexural strength 58.69MPa, Z-direction flexural strength 29.29MPa, and XY is to compressive strength 184.77MPa, Z-direction compressive strength 166.9MPa

But above-mentioned embodiment is exemplary, be to be the restriction that this patent is comprised to scope in order better to make those skilled in the art can understand this patent, can not to be interpreted as; As long as any being equal to done according to spirit that this patent discloses changes or modify, all fall into the scope that this patent comprises.

Claims

1. a preparation method of carbon/carbon-silicon carbide composite material for bearing, is characterized in that: comprise the following steps:

(1) Use polyacrylonitrile pre-oxidized fibers to make carbon fiber integral felt by needle punching, or alternately stack non-weft cloth and mesh tires to make non-weft cloth carbon fiber integral felt by needle punching;

(2) Carry out carbonization treatment at 900-1000°C for the carbon fiber integral felt and the carbon fiber integral felt without weft cloth prepared in step (1) to obtain a carbon fiber integral felt with a density of 0.15-0.30 g cm ^-3 and a density of 0.4～0.6g/cm ³ non-woven carbon fiber integral felt;

(3) Densify by chemical vapor infiltration method, put the carbon fiber integral mat or non-weft cloth carbon fiber integral felt obtained in step (2) into a chemical vapor infiltration furnace, heat up to 900-1100°C, The C/C porous prefabricated body is prepared by feeding a mixed gas of C ₃ H ₆ gas and Ar gas;

(4) After each chemical vapor infiltration process, perform surface treatment on the prepared C/C porous preform and repeat step (3) until the density of the C/C porous preform is 1.3-1.5 g/cm ³ ;

(5) subjecting the material prepared in step (4) to a high temperature treatment at 2350-2600°C under an Ar gas protective atmosphere;

(6) The material prepared in step (5) is densified by resin impregnation cracking process, that is, impregnation-curing-carbonization treatment is performed with furan resin, and the C/C porous preform is subjected to 2250~ A C/C porous preform with a density of 1.3-1.75g/ ^cm3 was obtained by high-temperature heat treatment at 2600°C;

(7) The reactive infiltration process is used to melt siliconize the C/C porous preform prepared in step (6), that is, put the C/C porous preform into a graphite crucible, add Si powder, and the particle size of Si powder is 20~ 30μm, in the high-temperature furnace under vacuum conditions, Ar gas is introduced, the furnace temperature rises from room temperature to 2200-2350°C, and the temperature is kept for 1.5 hours. The liquid Si penetrates into the interior of the C/C porous preform under negative pressure, and it The matrix C reacts to form a SiC matrix, and a C/C-SiC composite material is prepared.

2. The method according to claim 1, characterized in that: in the step (2), put the carbon fiber integral mat and the non-weft cloth carbon fiber integral felt prepared in the step (1) into a heat treatment furnace, and vacuumize , Carry out carbonization treatment at a temperature of 900-1000°C.

3. The method according to claim 1, characterized in that: the resin impregnation cracking process in the step (6) includes placing the C/C porous preform in an impregnation kettle, vacuuming, impregnating with furan resin, and pressurizing After impregnation, put it into an oven for curing treatment. After curing, put it in a high-temperature furnace to vacuumize and carbonize at a temperature of 900-1000°C. After carbonization, put the material in a high-temperature furnace under an Ar gas protective atmosphere at a temperature of 2250-2600 C/C porous preform with a density of 1.3 to 1.75 g/cm ³ is obtained by performing high temperature heat treatment.