CN100432016C - Method of manufacturing aluminium nitride/boron nitride multiple phase ceramic - Google Patents
Method of manufacturing aluminium nitride/boron nitride multiple phase ceramic Download PDFInfo
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- CN100432016C CN100432016C CNB2007100634488A CN200710063448A CN100432016C CN 100432016 C CN100432016 C CN 100432016C CN B2007100634488 A CNB2007100634488 A CN B2007100634488A CN 200710063448 A CN200710063448 A CN 200710063448A CN 100432016 C CN100432016 C CN 100432016C
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- boron nitride
- aluminium nitride
- nitride
- oxide
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Abstract
The invention discloses a making method of aluminium nitride/boron nitride multiple phase ceramic in the functional ceramic domain, which comprises the following steps: sintering boron nitride pioneer C3N6H12B2O6 and aluminium nitride particle in the non-oxygen environment; adopting nitrogen or hydrogen as environmental gas; generating pure composite powder of aluminium nitride/boron nitride; dispersing boron nitride in the aluminium nitride base without block; blending the composite powder and one rare earth oxide additive completely; selecting additive from one of yttrium oxide, samarium oxide and dysprosium oxide with yttrium oxide at best; placing in the discharge plasma sintering furnace; extracting into vacuum; heating at 100-200 deg.c/min to 1600-1800 to sinter 5-20 min; insulating at 800-1000 deg.c for 10-30min; closing power; cooling.
Description
Technical field
A kind of method for preparing aluminium nitride/boron nitride multiple phase ceramic has high strength, high heat conduction and is easy to the characteristic of mechanical workout, belongs to the function ceramics preparing technical field.
Background technology
Aluminium nitride ceramics has high a series of premium propertiess such as thermal conductivity, is the packaged material of ideal semiconductor substrate materials and high-power electronic device.Along with the device development constantly advances towards multifunction and miniaturization, correspondingly require material to have high combination property, turn to multifunction from the single high-performance of simple pursuit, can in the environment for use of complexity, require to take into account various performances.Therefore require aluminium nitride ceramics that high thermal conductivity, good processing characteristics are not only arranged, and keep high mechanical strength.
The same with most of ceramic materials, owing to behind sintering, be difficult to the inherent shortcoming of machining, be difficult to prepare the aluminium nitride ceramics parts that some have complicated shape and small size.The diphase ceramic material of hexagonal boron nitride disperse is the most outstanding class processable ceramic of present over-all properties.Have outstanding high temperature corrosion resistance, thermal shock resistance, and low modulus and can enough hard alloy cutters carry out precision optical machinery processing, satisfy complex shaped components to the harsh requirement of forming materials.In addition, hexagonal boron nitride also has outstanding thermal conductivity, though far away from aluminium nitride, also can reach 40-60W/mK.In the aluminium nitride matrix, introduce an amount of boron nitride, can take into account preferably thermal conductance and machinability.At present, though the aluminium nitride/boron nitride pottery with high orientation tissue reaches more than the 200W/mK being parallel to boron nitride crystal c direction of principal axis thermal conductivity, but the vertical direction thermal conductivity is reduced to below the 85W/mK, intensity also presents anisotropy, the c direction of principal axis is below 350MPa, and vertical direction only is about 100MPa or lower; The aluminium nitride/boron nitride processable ceramic of non-oriented growth can reach between the 100-140W/mK, but intensity is usually about 300MPa.With regard to preparation technology, aluminium nitride/boron nitride multiple phase ceramic mostly be with the micron order boron nitride as second phase, form by mechanically mixing, sintering.Because the flexural strength very low (about 100MPa) of hexagonal boron nitride pottery, add in the ceramic matrix and can cause strength deterioration, and the boron nitride powder reunion is difficult for opening, in sintering process, be easy to assemble growth and form big defective, it is excessive to cause the material actual strength to compare the reduction amplitude with aluminium nitride ceramics, and its mechanics reliability can't satisfy the requirement of high-end applications to intensity.
Obtain high strength aluminium nitride/boron nitride processable ceramic, its microstructure must satisfy such characteristics, and promptly the boron nitride grain-size should be far smaller than aluminium nitride matrix grain-size, keep tiny as far as possible and even dispersion at crystal boundary, do not take place to assemble and grow up.Such design feature can increase the contact area between the aluminum nitride grain, is conducive to equally the thermal conductivity that keeps high.From sintering method, in order to keep the thermal conductivity of aluminium nitride/boron nitride multiple phase ceramic as much as possible, often need carry out long-time sintering at the high temperature more than 1800 ℃, guarantee that aluminum nitride grain is fully grown up and closely contact, but boron nitride crystal grain is grown up too and is assembled in this course, and this all is disadvantageous for heat conductivility and mechanical property.Japanese Kusunose T etc. utilizes boric acid, urea is as the boron nitride presoma, the nano level boron nitride is coated to the aluminum nitride particle surface, eliminate the problem that boron nitride crystal grain is reunited with this, and boron nitride crystal grain remains in the nano level scope behind hot pressed sintering, they have obtained flexural strength up to the aluminium nitride/boron nitride multiple phase ceramic more than the 600MPa (boron nitride volume fraction 15%-30%) (Kusunose T, Sekino T, Kim BS, Choa YH, et al.Mater Sci Forum, 2003,439:131-136), taken into account intensity and workability well.Yet boric acid and urea generate the gentle phase oxidation boron of liquid phase with a small amount of oxidized aluminum nitride in reaction process, give in the system and bring extra oxygen into, and oxygen level is increased to 5.6% from 1.1%, thereby the thermal conductivity of material is significantly reduced, and only is 37W/mK.In addition, adopt hot pressed sintering to need high sintering temperature (1800-1850 ℃) and long-time insulation (2-4 hour), manufacturing cycle is long, and efficient is very low, thereby has limited to a great extent the application of materials.
Summary of the invention
At above-mentioned deficiency, the purpose of this invention is to provide the method that a kind of quick low temperature prepares aluminium nitride/boron nitride multiple phase ceramic, prepared material possesses the high strength taken into account, good workability and high thermal conductivity.This method realizes by following technical though: adopt boric acid and melamine to be dissolved at 2: 1 reacting in the hot water with mol ratio and make boron nitride presoma C
3N
6H
12B
2O
6, carry out high-temperature heat treatment then with after aluminium nitride mixes, presoma C
3N
6H
12B
2O
6Generate boron nitride through the pyroreaction original position, obtain the aluminium nitride/boron nitride composite granule of even dispersion, this presoma does not produce liquid phase in the process of reaction generation boron nitride, can obviously not give in the system and bring oxygen impurities into; Select suitable sinter additives, in order to reduce the sintering temperature of aluminium nitride, promote its sintering densification, thereby can cause the difference of aluminium nitride and boron nitride sintered diffusion coefficient; Utilize fast characteristics of discharge plasma sintering technique low temperature, realization is to the sintering of this system, make the aluminium nitride full densification, form the structure of crystal grain close contact, amplitude is littler and boron nitride is grown up in sintering process, make the thin brilliant even dispersion of boron nitride at aluminium nitride matrix crystal boundary, to the big obstruction of the inadequate one-tenth of the direct contact of aluminum nitride grain, realize the unification of high heat conduction, high strength and machinability with this.
A kind of method for preparing aluminium nitride/boron nitride multiple phase ceramic, its feature comprises the steps:
1) takes by weighing AlN micro mist and the BN presoma C of average grain diameter 0.2-2 μ m
3N
6H
12B
2O
6, presoma C wherein
3N
6H
12B
2O
6Weight content 28%-47%, all the other are AlN; BN presoma C
3N
6H
12B
2O
6Fully mix with the AlN powder, at N
2Or H
21300 ℃-1500 ℃ calcinings formed the AlN/BN composite granule in 1-2 hour in the atmosphere;
2) add a kind of rare earth oxide as additive, its weight content accounts for the 3%-10% of final blending material; Rare earth oxide is a kind of in yttrium oxide, Samarium trioxide, the dysprosium oxide; Described rare earth oxide preferably adopts yttrium oxide;
3) with material ball milling mixing 3-12 hour, after the drying, the graphite jig of packing into;
4) mould that material will be housed places the discharge plasma sintering stove, predetermined fixed pressure 30-50MPa, vacuumize furnace chamber air pressure is in below the 6Pa, the energising heating, with the 100-200 degree/minute speed be warmed up to 1600 ℃-1800 ℃ and carry out sintering, sintered heat insulating 5-20 minute, be cooled to 800 ℃-1000 ℃ insulations 10-30 minute powered-down immediately subsequently, furnace cooling obtains fine and close aluminium nitride/boron nitride multiple phase ceramic.
The invention has the advantages that technological process is simple, sintering time short (total sintering process 40-90 minute) has efficient energy-saving characteristics fast.The material that utilizes the inventive method to prepare has the characteristic of property of high strength, high heat conduction, easy processing simultaneously.
Embodiment
Embodiment 1:
Take by weighing aluminium nitride micro mist and the boron nitride presoma C of average grain diameter 0.2 μ m
3N
6H
12B
2O
6, presoma C wherein
3N
6H
12B
2O
6Weight content 28% fully mixes rear at N
2Calcined 2 hours for 1300 ℃ in the atmosphere, measuring oxygen content after the cooling is 1.3%; Add dysprosia, its weight accounts for final mixture material 3% again, and ball milling mixed 3 hours, after the drying, pack in the graphite jig, place discharge plasma sintering (SPS) stove, fixed pressure 30MPa in advance under the room temperature, be evacuated to 6Pa, be warmed up to 1600 degree with 200 degrees/mins speed and carry out sintering, sintering time 20 minutes is cooled to 10 minutes powered-downs immediately of 1000 ℃ of insulations subsequently, with the stove cooling, obtain aluminium nitride/boron nitride multiple phase ceramic.Flexural strength is σ after measured
F3=497MPa, thermal conductivity is 122W/mK, Vickers' hardness 9.6GPa can carry out precision optical machinery processing by enough inserted tools.
Embodiment 2:
Take by weighing aluminium nitride micro mist and the boron nitride presoma C of average grain diameter 0.5 μ m
3N
6H
12B
2O
6, presoma C wherein
3N
6H
12B
2O
6Weight content 37.5% fully mixes rear at N
2Calcined 1 hour for 1400 ℃ in the atmosphere, measuring oxygen content after the cooling is 1.5%; Add samarium oxide, its weight accounts for final mixture material 5% again, and ball milling mixed 5 hours, after the drying, pack in the graphite jig, place discharge plasma sintering (SPS) stove, fixed pressure 40MPa in advance under the room temperature, be evacuated to 5Pa, be warmed up to 1700 degree with 150 degrees/mins speed and carry out sintering, sintering time 105 minutes is cooled to 20 minutes powered-downs immediately of 900 ℃ of insulations subsequently, with the stove cooling, obtain aluminium nitride/boron nitride multiple phase ceramic.Flexural strength is σ after measured
F3=488MPa, thermal conductivity is 109W/mK, Vickers' hardness 7.4GPa can carry out precision optical machinery processing by enough inserted tools.
Embodiment 3:
Take by weighing aluminium nitride micro mist and the boron nitride presoma C of average grain diameter 1.2 μ m
3N
6H
12B
2O
6, presoma C wherein
3N
6H
12B
2O
6Weight content 37.5% fully mixes rear at N
2Calcined 1 hour for 1500 ℃ in the atmosphere, measuring oxygen content after the cooling is 1.6%; Add yittrium oxide, its weight accounts for final mixture material 8% again, and ball milling mixed 8 hours, after the drying, pack in the graphite jig, place discharge plasma sintering (SPS) stove, fixed pressure 40MPa in advance under the room temperature, be evacuated to 5Pa, be warmed up to 1800 degree with 150 degrees/mins speed and carry out sintering, sintering time 5 minutes is cooled to 30 minutes powered-downs immediately of 800 ℃ of insulations subsequently, with the stove cooling, obtain aluminium nitride/boron nitride multiple phase ceramic.Flexural strength is σ after measured
F3=461MPa, thermal conductivity is 106W/mK, Vickers' hardness 6.3GPa can carry out precision optical machinery processing by enough inserted tools.
Embodiment 4:
Take by weighing aluminium nitride micro mist and the boron nitride presoma C of average grain diameter 2 μ m
3N
6H
12B
2O
6, presoma C wherein
3N
6H
12B
2O
6Weight content 47% fully mixes rear at H
2Calcined 2 hours for 1500 ℃ in the atmosphere, measuring oxygen content after the cooling is 2.1%; Add yittrium oxide, its weight accounts for final mixture material 10% again, and ball milling mixed 12 hours, after the drying, pack in the graphite jig, place discharge plasma sintering (SPS) stove, fixed pressure 50MPa in advance under the room temperature, be evacuated to 6Pa, be warmed up to 1800 degree with 200 degrees/mins speed and carry out sintering, sintering time 20 minutes is cooled to 20 minutes powered-downs immediately of 800 ℃ of insulations subsequently, with the stove cooling, obtain aluminium nitride/boron nitride multiple phase ceramic.Flexural strength is σ after measured
F3=54MPa, thermal conductivity is 97W/mK, Vickers' hardness 6.4GPa can carry out precision optical machinery processing by enough inserted tools.
Claims (2)
1. a method for preparing aluminium nitride/boron nitride multiple phase ceramic is characterized in that, comprises the steps:
1) takes by weighing AlN micro mist and the BN presoma C of average grain diameter 0.2-2 μ m
3N
6H
12B
2O
6, presoma weight content 28%-47% wherein, all the other are AlN; BN presoma C
3N
6H
12B
2O
6Fully mix with the AlN powder, at N
2Or H
21300 ℃-1500 ℃ calcinings formed the AlN/BN composite granule in 1-2 hour in the atmosphere;
2) add a kind of rare earth oxide as additive, its weight content accounts for the 3%-10% of final blending material; Rare earth oxide is a kind of in yttrium oxide, Samarium trioxide, the dysprosium oxide;
3) with material ball milling mixing 3-12 hour, after the drying, the graphite jig of packing into;
4) the above-mentioned mould that material is housed is placed the discharge plasma sintering stove, predetermined fixed pressure 30-50MPa, vacuumize furnace chamber air pressure is in below the 6Pa, the energising heating, with the 100-200 degree/minute speed be warmed up to 1600 ℃-1800 ℃ and carry out sintering, sintered heat insulating 5-20 minute, be cooled to 800 ℃-1000 ℃ insulations 10-30 minute powered-down immediately subsequently, furnace cooling obtains fine and close aluminium nitride/boron nitride multiple phase ceramic.
2. the method for preparing aluminium nitride/boron nitride multiple phase ceramic according to claim 1 is characterized in that, described rare earth oxide adopts yttrium oxide.
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| CNB2007100634488A CN100432016C (en) | 2007-02-01 | 2007-02-01 | Method of manufacturing aluminium nitride/boron nitride multiple phase ceramic |
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| CNB2007100634488A CN100432016C (en) | 2007-02-01 | 2007-02-01 | Method of manufacturing aluminium nitride/boron nitride multiple phase ceramic |
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| CN100432016C true CN100432016C (en) | 2008-11-12 |
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|---|---|---|---|---|
| WO2013030714A1 (en) * | 2011-08-29 | 2013-03-07 | Koninklijke Philips Electronics N.V. | A flexible lighting assembly, a luminaire, and a method of manufacturing a flexible layer |
| CN102557646B (en) * | 2011-12-23 | 2013-07-31 | 浙江工业大学 | Preparation method of AlN ceramic substrate |
| CN104402480B (en) * | 2014-10-30 | 2016-09-07 | 青岛橡胶谷知识产权有限公司 | A kind of aluminium nitride ceramics composite and preparation method thereof |
| CN104591735B (en) * | 2015-01-15 | 2016-08-24 | 哈尔滨工业大学 | A kind of preparation method of antioxidation boron nitride graphite block body material |
| CN107746285B (en) * | 2017-10-18 | 2020-09-08 | 武汉科技大学 | Three-dimensional porous nitride nano ceramic and preparation method thereof |
| CN108516836A (en) * | 2018-03-27 | 2018-09-11 | 董小琳 | A kind of preparation method and encapsulating material of aluminum nitride ceramic substrate |
| CN109369191B (en) * | 2019-01-02 | 2021-08-03 | 山东博奥新材料技术有限公司 | Preparation method of yttrium-containing boron nitride-aluminum nitride composite powder |
| CN109384468B (en) * | 2019-01-02 | 2020-11-03 | 山东博奥新材料技术有限公司 | Preparation method of boron nitride-aluminum nitride composite powder |
| CN112582164A (en) * | 2019-09-29 | 2021-03-30 | 京磁材料科技股份有限公司 | Sintered Nd-Fe-B rapid hardening alloy Nd-rich phase grain boundary doping method |
| CN113264778B (en) * | 2021-05-17 | 2022-10-14 | 厦门理工学院 | Boron nitride composite ceramic and preparation method and application thereof |
| CN114605158A (en) * | 2022-03-07 | 2022-06-10 | 华南理工大学 | Nitride composite refractory material for titanium alloy smelting and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093074A (en) * | 1993-03-26 | 1994-10-05 | 高级陶瓷有限公司 | Ceramic composite and method for making |
-
2007
- 2007-02-01 CN CNB2007100634488A patent/CN100432016C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093074A (en) * | 1993-03-26 | 1994-10-05 | 高级陶瓷有限公司 | Ceramic composite and method for making |
Non-Patent Citations (2)
| Title |
|---|
| 原位反应合成AlN-BN复合材料的工艺研究. 贾铁昆等.武汉理工大学学报，第28卷第1期. 2006 * |
| 热压烧结AlN-BN复合陶瓷的制备及介电性能. 李晓云等.电子元件与材料，第22卷第6期. 2003 * |
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