CN1240640C - Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body - Google Patents

Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body Download PDF

Info

Publication number
CN1240640C
CN1240640C CN 200410013684 CN200410013684A CN1240640C CN 1240640 C CN1240640 C CN 1240640C CN 200410013684 CN200410013684 CN 200410013684 CN 200410013684 A CN200410013684 A CN 200410013684A CN 1240640 C CN1240640 C CN 1240640C
Authority
CN
China
Prior art keywords
hours
sintering
under
sio
density
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 200410013684
Other languages
Chinese (zh)
Other versions
CN1562885A (en
Inventor
温广武
王静
宋亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN 200410013684 priority Critical patent/CN1240640C/en
Publication of CN1562885A publication Critical patent/CN1562885A/en
Application granted granted Critical
Publication of CN1240640C publication Critical patent/CN1240640C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Ceramic Products (AREA)

Abstract

The present invention relates to a method for preparing BN/SiO2 composite ceramics by immersing and cracking precursors, which belongs to a method for preparing ceramic material. The existing hot-pressing sintering method has the disadvantages of directional arrangement of tissue, anisotropic performance, etc. The method of the present invention comprises: a) B powder and BN powder are used as raw material to be processed and shaped; b) the shaped material is sintered in the atmosphere of nitrogen with one atmospheric pressure to obtain porous boron nitride ceramics, wherein the sintering temperature is from 1500 DEG C to 1600 DEG C, and the heat preservation time is from 4 hours to 5 hours; c) the porous boron nitride ceramics are immersed in poly carbon silicon alky solution for 32 hours to hours at room temperature under the condition of vacuum; d) the immersed product is oxidized and cracked at the temperature of 800 DEG C; e) the oxidized and cracked product is sintered for 2 hours at the temperature of 1300 under the protection of nitrogen with one atmospheric pressure, and the BN/SiO2 composite material is obtained. The BN/SiO2 composite material prepared by the method of the present invention has the advantages of uniform tissue, dispersive distribution, no directional arrangement and good comprehensive performance; because pressure is not applied in the whole reaction sintering process, the present invention has the advantages that the rate of finished products is improved, the sintering temperature is reduced by 300 DEG C to 500 DEG C than hot-pressed sintering temperature, and the cost is reduced.

Description

Precursor infiltration and pyrolysis prepares BN/SiO 2The method of composite ceramics
Technical field:
The present invention relates to a kind of preparation method of stupalith, particularly a kind of precursor Polycarbosilane dipping porous BN ceramic matrix cracking then prepares BN/SiO 2The method of matrix material.
Background technology:
BN, SiO 2Pottery is owing to their specific inductivity, and dielectric loss is all very little, and thermal conductivity, heat-shock resistance, chemical stability are also very superior, is excellent high temperature wave-transparent material.Prepared BN/SiO in the past 2Matrix material often adopts pressing methods, and typical hot-pressing sintering technique is pressure 10～30Mpa, and temperature is 1600～1800 ℃, and density reaches 95%.But there is following problem in existing hot-pressing sintering method: the tissue behind the hot pressed sintering presents and aligns, performance shows as anisotropy, for the large-scale component material, density high thermal shock stability more is poor more, particularly adopt pressing methods cost when the large-scale complex-shaped member of preparation too high, also have very big difficulty at present.
Summary of the invention:
The object of the present invention is to provide a kind of precursor infiltration and pyrolysis to prepare BN/SiO 2The method of composite ceramics, it is suitable for pressureless sintering, is suitable for the preparation of large complicated member.Operation steps of the present invention is: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, and the mass ratio of B and BN is 5～20: 80～95, carries out batch mixing, granulation, moulding; B. be 1.4～1.6g/cm with density then 3Pressed compact place sintering oven, sintering in an atmospheric nitrogen atmosphere, sintering temperature is 1500～1600 ℃, soaking time 4～5 hours obtains the porous boron nitride ceramics; C. the porous boron nitride ceramics be impregnated in the precursor Polycarbosilane solution, the room temperature dipping is 32～40 hours under the condition of vacuumizing, and gets prefabricated section after the drying; D. density is no more than 1.75g/cm 3Prefabricated section under 800 ℃ of conditions in air furnace oxicracking, soaking time 3～4 hours; E. then under 1300 ℃, one atmospheric nitrogen protection condition in vacuum sintering furnace sintering 2 hours, promptly get BN/SiO 2Matrix material.Effect of the present invention is: with the BN/SiO of method preparation of the present invention 2The omnidirectional arrangement that distributes of microstructure of composite even dispersion, over-all properties is good; Owing to be that the whole process of reaction sintering is not exerted pressure, improved yield rate, sintering temperature reduces by 300～500 ℃ than hot pressing sintering, has reduced cost.
Embodiment:
Embodiment one: the operation steps of present embodiment is: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, and by mass ratio, the mass ratio of B and BN is (5～20): (80～95), technology batch mixing, granulation, moulding routinely; B. be 1.4～1.6g/cm with density then 3Pressed compact place sintering oven, sintering in an atmospheric nitrogen atmosphere, sintering temperature is 1500～1600 ℃, soaking time 4～5 hours obtains the porous boron nitride ceramics; C. with porous boron nitride ceramics dipping precursor Polycarbosilane solution, the room temperature dipping is 32～40 hours under the condition of vacuumizing, and gets prefabricated section after the drying; D. density is no more than 1.75g/cm 3Prefabricated section under 800 ℃ of conditions in air furnace oxicracking, soaking time 3～4 hours; E. then under 1300 ℃, one atmospheric nitrogen protection condition in vacuum sintering furnace sintering 2 hours, promptly get BN/SiO 2Matrix material.
Embodiment two: the operation steps of present embodiment is: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, by mass ratio, the mass ratio of B and BN is 5: 95, pour into then in the 120# gasoline that contains 1% styrene-butadiene rubber(SBR) binding agent, dryness compression moulding behind the thorough mixing, by the stroke of control pressure head, the density of control pressed compact is 1.40g/cm 3B. pressed compact is placed multifunctional vacuum sintering oven sintering, 600 ℃ vacuumized in the past, and vacuum tightness is 3 * 10 -2Pa slowly heats up, and heat-up rate is 200 ℃/h, and insulation is 1 hour under 200 ℃ of conditions, 600 ℃ are incubated 1 hour, feed nitrogen then, and nitrogen pressure is 1.1～1.2 normal atmosphere, speed with 100 ℃/h is warming up to 1500 ℃ of insulations 4 hours, obtains porous BN ceramic matrix, and density is 1.40g/cm 3, void content is 38.4%.C: porous BN cerdip Polycarbosilane/hexane solution, the mass ratio of Polycarbosilane and normal hexane is 50: 100, takes out oven dry after 40 hours at room temperature dipping under the condition that vacuumizes; D. then density is no more than 1.75g/cm 3Prefabricated section place air-heating furnace slowly to be warming up to 800 ℃ of oxicrackings; soaking time 3 hours; e. place further densification under the vacuum sintering furnace nitrogen protection atmosphere again, insulation is 2 hours under 1300 ℃, one atmospheric nitrogen protection condition, promptly prepares BN/SiO 2Pottery.Through experiment, gained BN/SiO 2Ceramic density is 1.52g/cm 3, bending strength is 62Mpa, specific inductivity 3.50, dielectric loss 2.0 * 10 -3
Embodiment three: the operation steps of present embodiment is, a. be that B and the BN powder of 3～5 μ m is raw material with particle diameter, by mass ratio, the mass ratio of B and BN is 10: 90, pour in the 120# gasoline that contains 1% styrene-butadiene rubber(SBR) binding agent, dryness compression moulding behind the thorough mixing, the density that obtains pressed compact by the stroke of controlling pressure head is 1.45g/cm 3B. pressed compact is placed multifunctional vacuum sintering oven sintering, 600 ℃ vacuumized in the past, and vacuum tightness is 3 * 10 -2Pa, slowly heat up, heat-up rate is 200 ℃/h, insulation is 1 hour under 200 ℃ of conditions, and 600 ℃ are incubated 1 hour, feed nitrogen then, nitrogen pressure is 1.1～1.2 normal atmosphere, speed with 100 ℃/h is warming up to 1550 ℃ of insulations 5 hours, obtains porous BN ceramic matrix, and density is 1.42g/cm 3, void content is 37.5%; C. porous BN cerdip Polycarbosilane/hexane solution, the mass ratio of Polycarbosilane and normal hexane is 50: 100, the room temperature dipping takes out oven dry under the condition that vacuumizes after 36 hours; D. then density is no more than 1.75g/cm 3Prefabricated section place air-heating furnace slowly to be warming up to 800 ℃ of oxicrackings, be incubated 3.5 hours, e. places under atmospheric nitrogen protection atmosphere of vacuum sintering furnace further densification again, insulation is 2 hours under 1300 ℃ of conditions, promptly obtains BN/SiO 2Pottery, gained BN/SiO 2The density of pottery is 1.56g/cm 3, bending strength is 64Mpa, specific inductivity 3.56, dielectric loss 4.4 * 10 -3
Embodiment four: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, by mass ratio, the mass ratio of B and BN is 15: 85, pour in the 120# gasoline that contains 1% styrene-butadiene rubber(SBR) binding agent, dryness compression moulding behind the thorough mixing, by the stroke of control pressure head, the density that obtains pressed compact is 1.45g/cm 3, b. places multifunctional vacuum sintering oven sintering to pressed compact, and 600 ℃ vacuumized in the past, and vacuum tightness is 3 * 10 -2Pa slowly heats up, and heat-up rate is 200 ℃/h, and insulation is 1 hour under 200 ℃ of conditions, 600 ℃ are incubated 1 hour, feed nitrogen then, and nitrogen pressure is 1.1～1.2 normal atmosphere, speed with 100 ℃/h is warming up to 1550 ℃ of insulations 5 hours, obtains porous BN ceramic matrix, and density is 1.50g/cm 3, void content is 33.9%; C. porous BN cerdip Polycarbosilane/hexane solution, the mass ratio of Polycarbosilane and normal hexane is 50: 100, vacuumizes that the room temperature dipping takes out oven dry under the condition after 36 hours; D. then density is no more than 1.75g/cm 3Prefabricated section place air-heating furnace slowly to be warming up to 800 ℃ of oxicrackings, soaking time 4 hours, e. places under atmospheric nitrogen protection atmosphere of vacuum sintering furnace further densification again, insulation is 2 hours under 1300 ℃ of conditions, promptly prepares BN/SiO 2Pottery.Through experiment, gained BN/SiO 2The density of pottery is 1.65g/cm 3, bending strength is 78Mpa, specific inductivity 3.78, dielectric loss 3.4 * 10 -3
Embodiment five: the operation steps of present embodiment is, a. be that B and the BN powder of 3～5 μ m is raw material with mean particle size, by mass ratio, the mass ratio of B and BN is 20: 80, pour in the 120# gasoline that contains 1% styrene-butadiene rubber(SBR) binding agent, dryness compression moulding behind the thorough mixing, by the stroke of control pressure head, the density that obtains pressed compact is 1.45g/cm 3B. pressed compact is placed multifunctional vacuum sintering oven sintering, 600 ℃ vacuumized in the past, and vacuum tightness is 3 * 10 -2Pa, slowly heat up, heat-up rate is 200 ℃/h, insulation is 1 hour under 200 ℃ of conditions, and 600 ℃ are incubated 1 hour, feed nitrogen then, nitrogen pressure is 1.1～1.2 normal atmosphere, speed with 100 ℃/h is warming up to 1550 ℃ of insulations 5 hours, obtains porous BN ceramic matrix, and BN ceramic matrix density is 1.54g/cm 3, void content is 32%; C. porous BN cerdip Polycarbosilane/hexane solution, the mass ratio of Polycarbosilane and normal hexane is 50: 100, the room temperature dipping takes out oven dry under the condition that vacuumizes after 32 hours; D. place air-heating furnace slowly to be warming up to 800 ℃ of oxicrackings then; soaking time 4 hours; e. place further densification under atmospheric nitrogen protection atmosphere of vacuum sintering furnace again, soaking time is 2 hours under 1300 ℃ of conditions, promptly prepares BN/SiO 2Pottery, gained BN/SiO 2The density of pottery is 1.69g/cm 3, bending strength is 94Mpa, specific inductivity 3.73, dielectric loss 3.0 * 10 -3
Embodiment six: present embodiment is following result: a. with particle diameter with the concrete parameter optimization in the operating process is that B and the BN powder of 3～5 μ m is raw material, the mass ratio of B and BN is 5: 95 or 10: 90 or 15: 85 or 20: 80, technology batch mixing, granulation, moulding routinely; B. be 1.4～1.6g/cm with density then 3Pressed compact place sintering oven, sintering in an atmospheric nitrogen atmosphere, sintering temperature is 1550 ℃, soaking time 4.5 hours obtains the porous boron nitride ceramics; C. with porous boron nitride ceramics dipping precursor Polycarbosilane solution, the room temperature dipping is 36 hours under the condition that vacuumizes, and gets prefabricated section after the drying; D. density is no more than 1.75g/cm 3Prefabricated section under 800 ℃ of conditions in air furnace oxicracking, soaking time 3～4 hours; E. then under 1300 ℃, one atmospheric nitrogen protection condition in vacuum sintering furnace sintering 2 hours, promptly get BN/SiO 2Matrix material.
In practice; each concrete numerical value can not be controlled definitely consistently with numerical value of the present invention; even so each numerical value and numerical value of the present invention deviation slightly in practice; such as " normal atmosphere "; also can realize purpose of the present invention for " 1.1～1.2 normal atmosphere " in embodiment, this also should be within protection scope of the present invention.

Claims (3)

1, a kind of precursor infiltration and pyrolysis prepares BN/SiO 2The method of composite ceramics is characterized in that its operation steps is: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, and the mass ratio of B and BN is 5～20: 80～95, carries out batch mixing, granulation, moulding; B. be 1.4～1.6g/cm with density then 3Pressed compact place sintering oven, sintering in an atmospheric nitrogen atmosphere, sintering temperature is 1500～1600 ℃, soaking time 4～5 hours obtains the porous boron nitride ceramics; C. the porous boron nitride ceramics be impregnated in the precursor Polycarbosilane solution, the room temperature dipping is 32～40 hours under the condition of vacuumizing, and gets prefabricated section after the drying; D. density is no more than 1.75g/cm 3Prefabricated section under 800 ℃ of conditions in air furnace oxicracking, soaking time 3～4 hours; E. then under 1300 ℃, one atmospheric nitrogen protection condition in vacuum sintering furnace sintering 2 hours, promptly get BN/SiO 2Matrix material.
2, precursor infiltration and pyrolysis according to claim 1 prepares BN/SiO 2The method of composite ceramics is characterized in that precursor Polycarbosilane solution is Polycarbosilane/hexane solution in the c step, and the mass ratio of Polycarbosilane and normal hexane is 50: 100.
3, precursor infiltration and pyrolysis according to claim 1 and 2 prepares BN/SiO 2The method of composite ceramics is characterized in that in the operating process that concrete parameter is: a. is that B and the BN powder of 3～5 μ m is raw material with particle diameter, and the mass ratio of B and BN is 5: 95 or 10: 90 or 15: 85 or 20: 80, carries out batch mixing, granulation, moulding; B. be 1.4～1.6g/cm with density then 3Pressed compact place sintering oven, sintering in an atmospheric nitrogen atmosphere, sintering temperature is 1550 ℃, soaking time 4.5 hours obtains the porous boron nitride ceramics; C. the porous boron nitride ceramics be impregnated in the precursor Polycarbosilane solution, the room temperature dipping is 36 hours under the condition that vacuumizes, and gets prefabricated section after the drying; D. density is no more than 1.75g/cm 3Prefabricated section under 800 ℃ of conditions in air furnace oxicracking, soaking time 3～4 hours; E. then under 1300 ℃, one atmospheric nitrogen protection condition in vacuum sintering furnace sintering 2 hours, promptly get BN/SiO 2Matrix material.
CN 200410013684 2004-04-14 2004-04-14 Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body Expired - Fee Related CN1240640C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410013684 CN1240640C (en) 2004-04-14 2004-04-14 Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200410013684 CN1240640C (en) 2004-04-14 2004-04-14 Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body

Publications (2)

Publication Number Publication Date
CN1562885A CN1562885A (en) 2005-01-12
CN1240640C true CN1240640C (en) 2006-02-08

Family

ID=34478248

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200410013684 Expired - Fee Related CN1240640C (en) 2004-04-14 2004-04-14 Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body

Country Status (1)

Country Link
CN (1) CN1240640C (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100378035C (en) * 2006-01-26 2008-04-02 中国科学院上海硅酸盐研究所 Boride-silicon carbide multiple phase ceramic and its preparation method
CN102617177A (en) * 2012-03-31 2012-08-01 中材高新材料股份有限公司 Manufacture method of boron nitride fabric reinforced silicon-boron-nitrogen ceramic-based composite material
CN102992776B (en) * 2012-12-13 2013-12-04 山东理工大学 Preparation method of h-BN/VC machinable ceramic
CN103145112B (en) * 2013-03-29 2014-11-19 哈尔滨工业大学 BN-Si2N2O composite ceramic and preparation method thereof
CN104446656B (en) * 2014-12-15 2016-10-05 航天特种材料及工艺技术研究所 A kind of preparation method of porous carbon materials ORC
CN109678477B (en) * 2019-01-02 2021-06-01 南方科技大学 Nano-structure Siquartz-cubic boron nitride superhard composite material and preparation method and cutter thereof
CN113614051A (en) * 2019-03-29 2021-11-05 电化株式会社 Method for producing composite

Also Published As

Publication number Publication date
CN1562885A (en) 2005-01-12

Similar Documents

Publication Publication Date Title
CN102424597B (en) Preparation method of C/C-SIC ceramic composite material
CN103086731B (en) Micro-region in-situ reaction preparation method for high strength fiber-reinforced ceramic matrix composite material
CN106927800B (en) Process method for preparing gel-casting fused quartz ceramic
CN106747477B (en) A kind of Cf/SiC-ZrC-ZrB2The preparation method of ultra-temperature ceramic-based composite material
CN106278278B (en) A method of regulating and controlling silicon carbide thermal conductivity by modifying presoma
CN105130474B (en) A kind of refractory material and preparation method thereof
CN108585917B (en) Preparation method of silicon nitride-silicon carbide complex phase porous ceramic
CN1240640C (en) Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body
CN112552063A (en) Preparation method of carbon fiber reinforced silicon carbide composite material
CN106938934A (en) A kind of ultra-temperature ceramic-based aerogel material and preparation method thereof
CN104496484A (en) Method for preparing Si3N4/BAS composite ceramic material
CN107698270A (en) The method that fabricated in situ amorphous Si OC nano wires strengthen ceramic core
CN108101543A (en) A kind of silicon carbide-based carbon ceramic friction material and its molding preparation method
CA2571485C (en) Process for manufacturing high density boron carbide
CN114702328B (en) SiC nanowire network reinforced layered porous SiC ceramic and preparation method thereof
CN101434486A (en) Preparation of SiC wooden ceramic
CN111747748B (en) Ultrahigh-temperature heat-proof/insulation integrated ZrC/Zr 2 C complex phase material and preparation method thereof
CN101054301A (en) Method of preparing composite material of silicon nitride and silicon carbide by reverse reaction sintering
CN108002854B (en) High-thermal-conductivity high-corrosion-resistance electrically calcined coal-based carbon brick and preparation method thereof
CN105859298A (en) Microwave aftertreatment modifying method for polymer precursor-derived ceramics
CN114196019A (en) Preparation method of shape-plastic high-molecular ceramic precursor
CN1245481C (en) Die stamping semi-carbonized formation method for preparing coal materials
CN112573928B (en) Preparation method of boron-containing polymer precursor ceramic
JP2002037682A (en) Porous silicon carbide sintered body and its manufacturing method
CN115385705B (en) Boron nitride fiber mat and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee