CN1887797A - Fast prepn process of machinable high-strength SiN-B4C ceramic - Google Patents

Fast prepn process of machinable high-strength SiN-B4C ceramic Download PDF

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Publication number
CN1887797A
CN1887797A CN 200610088995 CN200610088995A CN1887797A CN 1887797 A CN1887797 A CN 1887797A CN 200610088995 CN200610088995 CN 200610088995 CN 200610088995 A CN200610088995 A CN 200610088995A CN 1887797 A CN1887797 A CN 1887797A
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sintering
ceramic
strength
stove
fast
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CN100432017C (en
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李永利
张久兴
李瑞霞
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The fast preparation process of machinable high-strength Si3N4-BN ceramic belongs to the field of structural ceramic preparing technology. The present invention prepares compact heterogenous Si3N4-BN ceramic through mixing Si3N4 powder, h-BN powder and sintering additive Y2O3-Al2O3, ball mixing, drying, filling in mold, setting the mold in discharging plasma sintering furnace, vacuum pumping, heating to 1600-1700 deg.c, sintering at 30-50 MPa for 3-8 min and cooling in the furnace. The fast preparation process has short sintering time, low sintering temperature and low cost, and the prepared ceramic material has high bending strength and excellent machinability.

Description

The method for preparing fast machinable high-strength SiN-B 4 C ceramic
Technical field
A kind of quick method for preparing machinable high-strength SiN-B 4 C ceramic belongs to the structural ceramics preparing technical field.
Background technology
The Si that contains hexagonal boron nitride (h-BN) disperse phase 3N 4Pottery is the most outstanding class processable ceramic of present combination property.Not only keep and improved Si 3N 4The performances such as ceramic good elevated temperature strength, creep resistant, anti-thermal shock, but also give material outstanding preventing corrosion from molten metals performance, low Young's modulus, and can carry out precision optical machinery processing by enough hard alloy cutters, satisfy complex shaped components to the harsh requirement of forming materials.
Because h-BN bending strength very low (about 100MPa), add in the ceramic matrix and can cause strength deterioration, and the h-BN powder reunites and be difficult for opening, in sintering process, be easy to assemble growth and form big defective, cause material actual strength and Si 3N 4Ceramic phase is more excessive than reduction amplitude, and its mechanics reliability can't satisfy the high-end applications requirement.From the preparation method, work as Si 3N 4When-BN pottery had good machinability (BN>20%), the bending strength that adopts hot-pressing sintering technique to obtain only was 400-500MPa, and the loss of intensity reaches (Si more than 50% 3N 4Pottery is 900-1400MPa), and the Si that adopts pressureless sintering to obtain 3N 4-BN pottery bending strength is then lower.Obtain high strength Si 3N 4-BN processable ceramic, its microscopic structure must satisfy such characteristics, namely with long column shape β-Si 3N 4Crystal grain forms the interlocking frame structure, h-BN crystal grain through may keep tiny and even dispersion at crystal boundary, agglomeration not.The complicated presoma preparation technology of the utilizations such as Japanese Kusunose T is coated to Si with nanoscale BN 3N 4Particle surface eliminate the problem that h-BN crystal grain is reunited with this, and h-BN crystal grain remains in the nanoscale scope behind hot pressed sintering, the Si of their preparation 3N 4Therefore-BN processable ceramic (BN volume content 20%-40%) bending strength reaches about 850-1100MPa (Kusunose T, Sekino T, Choa Y H, Niihara K.J Am Ceram Soc, 2002,85:2678-2688), yet its technology comprises complicated presoma reaction coating process, and adopt hot pressed sintering to need high sintering temperature (1800-1850 ℃) and long-time insulation (2-4h), complex process is tediously long, and the cycle reaches 7 days (even longer), and preparation efficiency is very low, preparation cost is very high, thereby has limited to a great extent the application of materials.
Summary of the invention
For above-mentioned deficiency, the purpose of this invention is to provide the Si that a kind of quick low temperature prepares high strength, easily processes 3N 4The method of-BN complex phase ceramic.This method realizes by following technical though: utilize Si 3N 4With the difference of h-BN sintering diffusion coefficient, adopt suitable sinter additives, utilize fast characteristics of discharge plasma sintering technique low temperature, realize the sintering to this system, make Si 3N 4Full densification forms column β-Si 3N 4Crystal grain interlocking structure, and h-BN does not participate in densification process substantially, crystallite dimension still rest on the primary granule size or the long width of cloth very little; Owing to the effect of Joule heat, the temperature of powder surface raises rapidly, simultaneously the powder in the mould is applied high pressure simultaneously, and the flowability of powder quick can effectively be opened the h-BN powder agglomerates, makes the thin brilliant even dispersion of h-BN at Si 3N 4In the matrix.Form desirable microscopic structure with this, realize the unification of high strength and machinability.
A kind of quick method for preparing machinable high-strength SiN-B 4 C ceramic is characterized in that, comprises the steps:
1) takes by weighing the Si of average grain diameter 0.3-1um 3N 4The h-BN micro mist of micro mist and average grain diameter 0.3-1um, h-BN volume content 20%-40% wherein, all the other are Si 3N 4
2) add additive Y 2O 3-Al 2O 3, its weight is the 6%-10% of material after final the mixing;
3) with material ball milling mixing 12-48 hour in dehydrated alcohol, after drying, in the mould of packing into;
4) mould that material will be housed places the discharge plasma sintering stove, predetermined fixed pressure 30-50MPa is evacuated to below the 10Pa, with the 150-250 degree/minute speed be warmed up to the 1600-1700 degree and carry out sintering, sintering current ratio of pulse length to the total cycle length 12: 1, sintering time 3-8 minute;
5) sample cooled off with stove after sintering finished, and obtained fine and close Si 3N 4-BN complex phase ceramic.
The invention has the advantages that technical process simple (only needing raw meal is carried out mechanical mixture), sintering time short (total process is in 30 minutes) has fast characteristics of efficient energy-saving, for realizing having high strength Si 3N 4Simple, quick, the low-cost preparation of-BN processable ceramic provides a new way.The material that utilizes the inventive method to prepare has high strength, machinable performance characteristics simultaneously.
Description of drawings
Fig. 1 is the prepared Si of embodiment 1-3 3N 4The XRD collection of illustrative plates of-BN complex phase ceramic; Can find out, after sintering, most Si 3N 4Change mutually the β phase into by α, a small amount of α-Si is only arranged 3N 4Remaining, BN content reduces, and phase transformation is more complete.
Fig. 2 is the prepared Si of embodiment 1 3N 4The section SEM photo of-BN complex phase ceramic; Can find out that h-BN behind the sintering (crystal grain that is tabular or sheet among the figure) grows up to some extent, but still remains on about 1um, is evenly distributed.
Fig. 3 is the prepared Si of embodiment 2 3N 4The polishing etch surface SEM photo of-BN complex phase ceramic; Can find out that microscopic structure is meticulous evenly behind the sintering, by the β phase Si of big L/D ratio 3N 4Columnar grain consists of (h-BN is removed) in corrosion process.
Fig. 4 is the prepared Si of embodiment 2 3N 4The section SEM photo of-BN complex phase ceramic; Can find out that h-BN behind the sintering (being tiny bar-shaped or granular crystal grain among the figure) significantly less than 1um, has kept the size of initial h-BN particle substantially, and not have obviously to assemble and big aggregate.
Fig. 5 is the prepared Si of embodiment 3 3N 4The section SEM photo of-BN complex phase ceramic; Can find out that h-BN behind the sintering (among the figure in the form of sheets or granular crystal grain) crystallite dimension is still very little, most of less than 1um, substantially kept the size of initial h-BN particle; Because h-BN content is bigger, some aggregations occurred, a small amount of grain growth surpasses 1um.
Embodiment
Embodiment 1:
Take by weighing the Si of average grain diameter 1 μ m 3N 4The h-BN micro mist of micro mist and average grain diameter 0.5 μ m, wherein the h-BN volume content accounts for 20%, adds Y again 2O 3-Al 2O 3Its weight accounts for final mixture material 6%, ball milling mixed 12 hours in absolute ethyl alcohol, after the drying, in the graphite jig of packing into, place discharge plasma sintering (SPS) stove, fixed pressure 30MPa in advance under the room temperature, be evacuated to 8Pa after, be warmed up to 1600 degree with 250 degrees/mins speed and carry out sintering, sintering current pulse ratio 12: 1, sintering time 3 minutes.Sample cooled off with stove after sintering finished, and obtained Si 3N 4-BN complex phase ceramic.Si after measured 3N 4The relative density of-BN complex phase ceramic is 94.2%, and bending strength is σ f3=1111MPa, can carry out precision optical machinery processing by enough hard alloy cutters.
Embodiment 2:
Take by weighing the Si of average grain diameter 0.5 μ m 3N 4The h-BN micro mist of micro mist and average grain diameter 0.3 μ m makes the h-BN volume content account for 30%, adds Y again 2O 3-Al 2O 3Its weight accounts for final mixture material 8%, ball milling mixed 24 hours in absolute ethyl alcohol, after the drying, in the graphite jig of packing into, place discharge plasma sintering (SPS) stove, fixed pressure 40MPa in advance under the room temperature, be evacuated to 8Pa after, be warmed up to 1650 degree with 150 degrees/mins speed and carry out sintering, sintering current pulse ratio 12: 1, sintering time 5 minutes.Sample cooled off with stove after sintering finished, and obtained Si 3N 4-BN complex phase ceramic.Si after measured 3N 4The relative density of-BN complex phase ceramic is 93.7%, and flexural strength is σ F3=920MPa can carry out precision optical machinery processing by enough inserted tools.
Embodiment 3:
Take by weighing the Si of average grain diameter 0.3 μ m 3N 4The h-BN micro mist of micro mist and average grain diameter 0.3 μ m makes the h-BN volume content account for 40%, adds Y again 2O 3-Al 2O 3Its weight accounts for final mixture material 10%, ball milling mixed 48 hours in absolute ethyl alcohol, after the drying, in the graphite jig of packing into, place discharge plasma sintering (SPS) stove, fixed pressure 50MPa in advance under the room temperature, be evacuated to 6Pa after, be warmed up to 1700 degree with 200 degrees/mins speed and carry out sintering, sintering current pulse ratio 12: 1, sintering time 8 minutes.Sample cooled off with stove after sintering finished, and obtained Si 3N 4-BN complex phase ceramic.Si after measured 3N 4The relative density of-BN complex phase ceramic is 93.8%, and flexural strength is σ F3=702MPa can carry out precision optical machinery processing by enough inserted tools.

Claims (1)

1. a method for preparing machinable high-strength SiN-B 4 C ceramic fast is characterized in that, comprises the steps:
1) takes by weighing the Si of average grain diameter 0.3-1um 3N 4The h-BN micro mist of micro mist and average grain diameter 0.3-1um, h-BN volume content 20%-40% wherein, all the other are Si 3N 4
2) add additive Y 2O 3-Al 2O 3, its weight is the 6%-10% of material after final the mixing;
3) with material ball milling mixing 12-48 hour in dehydrated alcohol, after drying, in the mould of packing into;
4) mould that material will be housed places the discharge plasma sintering stove, predetermined fixed pressure 30-50MPa is evacuated to below the 10Pa, with the 150-250 degree/minute speed be warmed up to the 1600-1700 degree and carry out sintering, sintering current ratio of pulse length to the total cycle length 12: 1, sintering time 3-8 minute;
5) sample cooled off with stove after sintering finished, and obtained fine and close Si 3N 4-BN complex phase ceramic.
CNB2006100889957A 2006-07-28 2006-07-28 Fast prepn process of machinable high-strength SiN-B4C ceramic Expired - Fee Related CN100432017C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817684A (en) * 2010-03-25 2010-09-01 西安交通大学 Method for coating h-BN coating on surface of porous Si3N4 substrate
CN101565308B (en) * 2009-06-04 2012-05-23 山东大学 Silicon nitride ceramics enhanced by boron nitride nanotube and preparation method thereof
CN101456739B (en) * 2008-10-08 2012-10-31 中国科学院上海硅酸盐研究所 Si3N4-BN porous ceramic of super lyophobic metal melt, preparation method and use thereof
CN101955357B (en) * 2008-04-25 2012-11-28 西安交通大学 Processable complex-phase ceramic material and preparation method thereof as well as secondary hardening heat treatment method
CN104284860A (en) * 2012-05-09 2015-01-14 Esk陶瓷有限两合公司 Boron nitride agglomerates, method for the production thereof and usage thereof
CN104529412A (en) * 2014-12-27 2015-04-22 西安交通大学 Preparation method of nano-scale hexagonal boron nitride/silicon dioxide multi-phase ceramic material
CN105036749A (en) * 2015-06-30 2015-11-11 陕西科技大学 Hot-pressing preparation method for hexagonal boron nitride-added silicon nitride
CN105272269A (en) * 2015-10-20 2016-01-27 西安邮电大学 Preparation method of Si3N4/h-BN nano-composite ceramics
CN108117396A (en) * 2017-12-11 2018-06-05 陕西科技大学 The preparation method of biomedical ceramics material based on silicon nitride
CN110105072A (en) * 2019-06-04 2019-08-09 宁波市大工新材料科技有限公司 A kind of preparation method of high hardness silicon nitride material

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JPS61158868A (en) * 1984-12-29 1986-07-18 株式会社東芝 Manufacture of ceramic sintered body
US4883776A (en) * 1988-01-27 1989-11-28 The Dow Chemical Company Self-reinforced silicon nitride ceramic of high fracture toughness and a method of preparing the same
CN1250762A (en) * 1999-09-24 2000-04-19 清华大学 Process for preparing boron nitride compounded conducting ceramic evaporator by non-pressure sinter method
CN1246253C (en) * 2004-05-17 2006-03-22 清华大学 Manufacturing method of high thermoconductivity high trength silicon nitride ceramic
US20060084566A1 (en) * 2004-10-19 2006-04-20 General Electric Company Multiphase ceramic nanocomposites and method of making them
CN1282627C (en) * 2005-01-26 2006-11-01 清华大学 Micro processing process for silicon nitride ceramic parts
CN1793042A (en) * 2006-01-06 2006-06-28 清华大学 In-situ flexible silicon nitride base ceramic and super-speed sintering process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955357B (en) * 2008-04-25 2012-11-28 西安交通大学 Processable complex-phase ceramic material and preparation method thereof as well as secondary hardening heat treatment method
CN101456739B (en) * 2008-10-08 2012-10-31 中国科学院上海硅酸盐研究所 Si3N4-BN porous ceramic of super lyophobic metal melt, preparation method and use thereof
CN101565308B (en) * 2009-06-04 2012-05-23 山东大学 Silicon nitride ceramics enhanced by boron nitride nanotube and preparation method thereof
CN101817684B (en) * 2010-03-25 2012-08-15 西安交通大学 Method for coating h-BN coating on surface of porous Si3N4 substrate
CN101817684A (en) * 2010-03-25 2010-09-01 西安交通大学 Method for coating h-BN coating on surface of porous Si3N4 substrate
CN104284860B (en) * 2012-05-09 2018-02-13 3M创新有限公司 Boron nitride aggregate, Its Preparation Method And Use
CN104284860A (en) * 2012-05-09 2015-01-14 Esk陶瓷有限两合公司 Boron nitride agglomerates, method for the production thereof and usage thereof
CN104529412A (en) * 2014-12-27 2015-04-22 西安交通大学 Preparation method of nano-scale hexagonal boron nitride/silicon dioxide multi-phase ceramic material
CN104529412B (en) * 2014-12-27 2016-06-29 西安交通大学 A kind of preparation method of nanoscale hexagonal boron nitride/silicon dioxide diphase ceramic material
CN105036749A (en) * 2015-06-30 2015-11-11 陕西科技大学 Hot-pressing preparation method for hexagonal boron nitride-added silicon nitride
CN105272269A (en) * 2015-10-20 2016-01-27 西安邮电大学 Preparation method of Si3N4/h-BN nano-composite ceramics
CN108117396A (en) * 2017-12-11 2018-06-05 陕西科技大学 The preparation method of biomedical ceramics material based on silicon nitride
CN110105072A (en) * 2019-06-04 2019-08-09 宁波市大工新材料科技有限公司 A kind of preparation method of high hardness silicon nitride material

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