JP4282629B2 - Method for producing a boron nitride fired body - Google Patents
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- JP4282629B2 JP4282629B2 JP2005108285A JP2005108285A JP4282629B2 JP 4282629 B2 JP4282629 B2 JP 4282629B2 JP 2005108285 A JP2005108285 A JP 2005108285A JP 2005108285 A JP2005108285 A JP 2005108285A JP 4282629 B2 JP4282629 B2 JP 4282629B2
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 46
- 229910052582 BN Inorganic materials 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005087 graphitization Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 208000037584 hereditary sensory and autonomic neuropathy Diseases 0.000 description 38
- 238000010304 firing Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、窒化ホウ素焼成体の製造方法に関するものである。
The present invention relates to a method for manufacturing a boron nitride fired body.
窒化ホウ素焼成体は、六方晶窒化ホウ素粉を含む成形体を例えばホットプレス、ホットアイソスタティックプレス（ＨＩＰ）等の加熱加圧焼成法か、又は六方晶窒化ホウ素粉を含む一軸加圧成形体を冷間等方圧加圧処理した後、常圧下で焼成する常圧焼成法で製造されている。いずれの方法にあっても、例えばＢ２Ｏ３、Ｙ２Ｏ３、Ａｌ２Ｏ３、ＣａＦ２、ＭｇＯ、Ｓｉ、ＣａＢ６、ＭｇＢｘ等の焼結助剤が必要に応じて用いられている。 The boron nitride fired body is formed by subjecting a molded body containing hexagonal boron nitride powder to a heating and pressing method such as hot pressing or hot isostatic press (HIP), or a uniaxial pressure molded body containing hexagonal boron nitride powder. It is manufactured by a normal pressure firing method in which a cold isotropic pressure is applied and then fired under normal pressure. In any method, sintering aids such as B 2 O 3 , Y 2 O 3 , Al 2 O 3 , CaF 2 , MgO, Si, CaB 6 , and MgB x are used as necessary. Yes.
窒化ホウ素焼成体の主要な用途の一つに、シリコンウェハ等の半導体製品や、窒化アルミニウム材を焼成する際のセッターがある。近年、これらの大型化にともない、セッターに対してもそれに適応できる大型化と、大型化するに際しての加工端材の発生が少ない窒化ホウ素焼成体の製造法の開発が待たれている。加熱加圧焼成法ではこのような大型化にはもはや対応はできず、常圧焼成法によるしかないと考えられる現状において、常圧焼成法による量産化技術では、密度が１．３〜１．６ｇ／ｃｍ３、相対密度が６０〜７０％程度の六方晶窒化ホウ素焼成体しか得ることができていない。 One of the main uses of the boron nitride fired body is a semiconductor product such as a silicon wafer and a setter for firing an aluminum nitride material. In recent years, with these increases in size, development of a method of manufacturing a boron nitride fired body that can be applied to a setter and that generates less processing scrap when the size is increased is awaited. In the present situation where the heating and pressure firing method can no longer cope with such an increase in size, and it is considered that there is only the atmospheric pressure firing method, the density is 1.3 to 1. Only a hexagonal boron nitride fired body of 6 g / cm 3 and a relative density of about 60 to 70% can be obtained.
特許第２００５９４５号公報には、常圧焼成法によって、曲げ強度が５ｋｇｆ／ｍｍ２（４９ＭＰａ）の六方晶窒化ホウ素焼成体を得られたことが記載されているが、これは５０×５０×１０ｍｍの小片である。容積が３０００ｃｍ３以上の大型品にして２５ＭＰａの曲げ強度を保証したものではなく、多くは１２〜１８ＭＰａである。これを改善するため、例えばアルカリ土類金属や炭化ホウ素等の焼結助剤を用いること（特許文献１）や、常圧焼成条件を最適化すること（特許文献２）などの提案があるが、焼結助剤が残留することの問題の他に、強度改善効果がまだ不十分であった。
本発明の目的は、例えば容積が３０００ｃｍ３以上の大形品にして３０ＭＰａの曲げ強度を有する窒化ホウ素焼結体を、焼結助剤を用いなくても、容易に製造することができる方法を提供することである。 An object of the present invention is to provide a method capable of easily producing a boron nitride sintered body having a bending strength of 30 MPa, for example, having a volume of 3000 cm 3 or more without using a sintering aid. Is to provide.
本発明は、六方晶窒化ホウ素粉を含むセラミックス粉末を、４〜１５ＭＰａの圧力で一軸加圧成形してから、最初に行うＣＩＰ（以下、「第１のＣＩＰ」ともいう。）と、その後に行うＣＩＰ（以下、「第２のＣＩＰ」ともいう。）の少なくとも２回の冷間等方圧加圧処理を行った後、焼成する方法であって、第２のＣＩＰ圧力を第１のＣＩＰ圧力よりも高くすることを特徴とする窒化ホウ素焼成体の製造方法である。 In the present invention, ceramic powder containing hexagonal boron nitride powder is uniaxially pressed at a pressure of 4 to 15 MPa, and then CIP performed first (hereinafter also referred to as “first CIP”), and thereafter. performing CIP (hereinafter, also referred to as "second CIP".) of at least twice after Tsu rows isostatic pressing process cold, a method of baking, the second CIP pressure first a method for producing a boron nitride sintered body, characterized that you higher than CIP pressure.
本発明においては、以下の実施態様から得ばれた少なくとも一つを有していることが好ましい。
（１）第２のＣＩＰ圧力が、第１のＣＩＰ圧力の１．５〜５倍であること。
（２）第１のＣＩＰ圧力が、５０〜１２０ＭＰａであること。
（３）冷間等方圧加圧処理成形体を焼成する前に熱処理を行い、１２０℃における加熱減量分を０．１質量％以下に減じておくこと。
（４）冷間等方圧加圧処理成形体の焼成を、非酸化性雰囲気下、昇温速度を１５０℃／ｈｒ以下、最高温度を１８００〜２２００℃、この温度範囲における保持時間を５時間以上にして行うこと。
（５）一軸加圧成形体のセラミックス原料末中、六方晶窒化ホウ素粉の含有率が２０質量％以上（１００％を含む）であり、しかもその六方晶窒化ホウ素粉中、黒鉛化指数が４以上の低結晶性六方晶窒化ホウ素粉の割合が３０〜８０質量％であること。
In this invention, it is preferable to have at least one obtained from the following embodiments.
(1) The second CIP pressure is 1.5 to 5 times the first CIP pressure.
(2) The first CIP pressure is 50 to 120 MPa.
(3) A heat treatment is performed before firing the cold isostatic pressing molded body, and the heat loss at 120 ° C. is reduced to 0.1% by mass or less.
(4) Calcination of the cold isostatic press treatment molded body is performed in a non-oxidizing atmosphere at a heating rate of 150 ° C./hr or less, a maximum temperature of 1800 to 2200 ° C., and a holding time in this temperature range of 5 hours. Do this.
(5) The content of the hexagonal boron nitride powder is 20% by mass or more (including 100%) in the ceramic raw material powder of the uniaxial pressure formed body, and the graphitization index is 4 in the hexagonal boron nitride powder. The ratio of the above low crystalline hexagonal boron nitride powder is 30 to 80% by mass.
本発明によれば、例えば体積が３０００ｃｍ３以上で厚さが４０ｍｍ以上の大型品にして三点曲げ強度が３０ＭＰａ以上、密度が１．７ｇ／ｃｍ３以上の窒化ホウ素焼成体を常圧焼成で容易に製造することができる。 According to the present invention, for example, a boron nitride fired body having a three-point bending strength of 30 MPa or more and a density of 1.7 g / cm 3 or more in a large product having a volume of 3000 cm 3 or more and a thickness of 40 mm or more is obtained by atmospheric pressure firing. It can be manufactured easily.
本発明で用いるセラミックス原料粉は、六方晶窒化ホウ素粉の含有率が２０質量％以上（１００％を含む）を含むセラミックス粉末であることが好ましい。それを例示すれば、六方晶窒化ホウ素粉単独、又は六方晶窒化ホウ素粉と例えば窒化ケイ素粉、窒化アルミニウム粉、アルミナ粉、炭化ホウ素粉、炭化ケイ素粉等の六方晶窒化ホウ素粉以外のセラミックス粉との混合粉であり、いずれも必要に応じて焼結助剤を存在させたものである。焼結助剤としては、例えばＢ２Ｏ３、Ｙ２Ｏ３、Ａｌ２Ｏ３、ＣａＦ２、ＭｇＯ、Ｓｉ、ＣａＢ６、ＭｇＢｘ等を成分とする粉末を用いることができる。セラミックス原料粉の調整に際しては、混合媒体も含め、不純物の混入には十分注意がいる。鉄をはじめとした重金属やアルカリ金属、ハロゲンの混入は、極力避けなければならない。適切な混合機器を例示すれば、ボールミル、振動ミル、アトライターミル、ヘンシェルミキサー、バンバリミキサー、パワフルミキサーなどである。 The ceramic raw material powder used in the present invention is preferably a ceramic powder containing a hexagonal boron nitride powder content of 20% by mass or more (including 100%). For example, hexagonal boron nitride powder alone or ceramic powder other than hexagonal boron nitride powder such as silicon nitride powder, aluminum nitride powder, alumina powder, boron carbide powder, silicon carbide powder, etc. In any case, a sintering aid is present if necessary. As the sintering aid, for example, powders containing B 2 O 3 , Y 2 O 3 , Al 2 O 3 , CaF 2 , MgO, Si, CaB 6 , MgB x and the like can be used. When preparing the ceramic raw material powder, attention should be paid to the mixing of impurities including the mixed medium. Mixing of heavy metals such as iron, alkali metals and halogens should be avoided as much as possible. Examples of suitable mixing equipment include a ball mill, a vibration mill, an attritor mill, a Henschel mixer, a Banbury mixer, and a powerful mixer.
六方晶窒化ホウ素粉としては、特に制約はないが、低結晶性の窒化ホウ素粉と高結晶性の窒化ホウ素粉を組み合わせて用いることが好ましい。これによって、一方を単独で用いる場合に比べて窒化ホウ素焼成体の曲げ強度が大きくなり、しかも焼成時に発生するガス量が著しく少なくなるので、クラックやラミネーションの欠陥が生じにくい窒化ホウ素焼成体となる。低結晶性の窒化ホウ素粉と高結晶性の窒化ホウ素粉の割合は、両者の合計粉中、低結晶性の窒化ホウ素粉が３０〜８０質量％、特に４０〜７０質量％であることが好ましい。 Although there is no restriction | limiting in particular as a hexagonal boron nitride powder, It is preferable to use combining a low crystalline boron nitride powder and a highly crystalline boron nitride powder. This increases the bending strength of the boron nitride fired body as compared with the case where one of them is used alone, and the amount of gas generated during firing is significantly reduced, resulting in a boron nitride fired body that is less prone to cracks and lamination defects. . The ratio of the low crystalline boron nitride powder and the high crystalline boron nitride powder is preferably 30 to 80% by mass, particularly 40 to 70% by mass of the low crystalline boron nitride powder in the total powder of both. .
本発明において、低結晶性の窒化ホウ素粉とは黒鉛化指数が４以上の窒化ホウ素粉であり、高結晶性の窒化ホウ素粉とは黒鉛化指数が４未満の窒化ホウ素粉であると定義する。黒鉛化指数は、粉末Ｘ線回折で、（１００）、（１０１）、（１０２）の各面の回折線強度Ｉ１００、Ｉ１０１、Ｉ１０２を測定し、式、（黒鉛化指数）＝（Ｉ１００＋Ｉ１０１）／（Ｉ１０２）、によって算出される。 In the present invention, the low crystalline boron nitride powder is a boron nitride powder having a graphitization index of 4 or more, and the high crystalline boron nitride powder is defined as a boron nitride powder having a graphitization index of less than 4. . The graphitization index is measured by powder X-ray diffraction, and the diffraction line intensities I 100 , I 101 , and I 102 of (100), (101), and (102) are measured, and the formula (graphitization index) = ( I 100 + I 101 ) / (I 102 ).
一軸加圧成形体は、セラミックス原料粉を型に詰め、一軸加圧成形をすることによって製造することができる。加圧はエア抜きをしながらゆっくり行うことが好ましい。エア抜きが不十分であると、エアボイドが残留することがあり、エア抜きが早過ぎると、エア抜け時にチャネリングを生じてエアの抜け跡が欠陥になる場合がある。エア抜きをよくするために、セラミックス原料粉の造粒粉を用いるか、脱気をしながら加圧することは好ましいことである。なお、造粒粉を用いたときには、焼成前に造粒バインダーを除いておく。 The uniaxial pressure-formed body can be produced by filling ceramic raw material powder in a mold and performing uniaxial pressure forming. The pressurization is preferably performed slowly while releasing air. If air venting is insufficient, air voids may remain, and if air venting is too early, channeling may occur when air escapes, resulting in defects in air escape. In order to improve air bleeding, it is preferable to use granulated powder of ceramic raw material powder or pressurize while deaeration. When granulated powder is used, the granulated binder is removed before firing.
冷間等方圧加圧処理（以下、「ＣＩＰ」ともいう。）時の変形を小さくするために、一軸加圧成形圧力は高い方が好ましいが、あまり高いとクラックやラミネーションが発生するので、本発明では３〜２０ＭＰａとする。好ましくは４〜１５ＭＰａとする。これによって、セラミックス原料粉はＣＩＰ時のハンドリングが容易となり、またＣＩＰ時の収縮が小さくなるために変形が少なくなりクラックやラミネーションの発生を著しく抑制することができる。一軸加圧成形機としては、特にこれを限定するものではなく、通常の油圧式のプレス機で行うことができる。 In order to reduce deformation during cold isostatic pressing (hereinafter also referred to as “CIP”), it is preferable that the uniaxial pressing pressure is high, but if it is too high, cracks and lamination occur. In the present invention, the pressure is set to 3 to 20 MPa. The pressure is preferably 4 to 15 MPa. As a result, the ceramic raw material powder can be easily handled at the time of CIP, and since the shrinkage at the time of CIP is reduced, the deformation is reduced and the occurrence of cracks and lamination can be remarkably suppressed. The uniaxial pressure molding machine is not particularly limited, and can be performed with a normal hydraulic press.
ついで、一軸加圧成形体は少なくとも２回のＣＩＰが施される。すなわち、本発明においては、最初に行うＣＩＰ（第１のＣＩＰ）と、その後に行うＣＩＰ（第２のＣＩＰ）の少なくとも２回のＣＩＰが施されるが、第２のＣＩＰ圧力は第１のＣＩＰ圧力よりも高めて行われることが特徴である。ＣＩＰは、例えばビニール製、ゴム製等の袋に被処理物を入れてから脱気後密封し、市販のＣＩＰ装置を用い、例えば水、グリセリン等の圧力媒体を用いて行うことができる。 Subsequently, the uniaxial pressure-molded body is subjected to at least two CIPs. That is, in the present invention, the first CIP ( first CIP ) and the subsequent CIP ( second CIP ) are performed at least twice, but the second CIP pressure is the first CIP. It is characterized by being performed at a pressure higher than the CIP pressure. CIP can be performed using a commercially available CIP device, for example, a pressure medium such as water or glycerin, after putting the object to be processed in a bag made of vinyl, rubber or the like and then degassing and sealing.
第１のＣＩＰ圧力は、５０〜１２０ＭＰａ、特に８０〜１２０ＭＰａであることが好ましく、第２のＣＩＰ圧力は第１のＣＩＰ圧力の１．５〜５倍、特に２〜４倍であることが好ましい。第２のＣＩＰ圧力は１５０〜３００ＭＰａであることが好ましい。いずれのＣＩＰにおいても、低圧過ぎると、高密度品が得られ難く、高圧過ぎるとクラックやラミネーションの発生の原因となる。 The first CIP pressure is preferably 50 to 120 MPa, particularly preferably 80 to 120 MPa, and the second CIP pressure is preferably 1.5 to 5 times, particularly 2 to 4 times the first CIP pressure. . The second CIP pressure is preferably 150 to 300 MPa. In any CIP, if the pressure is too low, it is difficult to obtain a high-density product. If the pressure is too high, cracks and lamination may occur.
ＣＩＰ成形体は、次いで焼成される。焼成する前に、ＣＩＰ成形体を熱処理し、１２０℃における加熱減量分を０．１質量％以下、特に０．０５質量％以下に減じておくことが好ましい。これによって、より高密度の窒化ホウ素成形体を製造することが可能となる。熱処理方法の一例を示せば、１２０〜１８０℃の乾燥機中で、数時間から数十時間放置することである。 The CIP compact is then fired. Before firing, it is preferable to heat-treat the CIP compact and reduce the heat loss at 120 ° C. to 0.1% by mass or less, particularly 0.05% by mass or less. This makes it possible to produce a higher density boron nitride molded body. An example of the heat treatment method is to leave it in a dryer at 120 to 180 ° C. for several hours to several tens of hours.
ＣＩＰ成形体の焼成は、非酸化性雰囲気下、昇温速度を１５０℃／ｈｒ以下、最高温度を１８００〜２２００℃、この温度範囲における保持時間を５時間以上にして行うことが好ましい。非酸化性雰囲気としては、例えば窒素、アンモニア等の窒化性ガス雰囲気であることが好ましい。これらの条件にあても、高密度のＣＩＰ成形体ほど昇温速度を遅くすることが好ましいが、あまり遅いと生産性が低下するので、５０〜１３０℃／ｈｒが好ましい。 The CIP molded body is preferably fired in a non-oxidizing atmosphere at a rate of temperature increase of 150 ° C./hr or less, a maximum temperature of 1800 to 2200 ° C., and a holding time in this temperature range of 5 hours or more. The non-oxidizing atmosphere is preferably a nitriding gas atmosphere such as nitrogen or ammonia. Even under these conditions, it is preferable to lower the rate of temperature rise as the density of the CIP compact is increased. However, if it is too slow, the productivity is lowered, so 50 to 130 ° C./hr is preferable.
最高温度と保持時間は、ＣＩＰ成形体の種類、特にセラミックス原料粉によって異なる。窒化ホウ素単独の場合は、最高温度が１９００〜２１００℃、保持時間が５〜１２時間であることが好ましい。また、窒化ホウ素と窒化アルミニウムの複合系では、最高温度が１８５０〜２０５０℃、保持時間が５〜１０時間、窒化ホウ素と窒化ケイ素との複合系では、最高温度が１８００〜１９００℃、保持時間が５〜８時間、更には窒化ホウ素とホウ化チタンの複合系では、最高温度が１９５０〜２２００℃、保持時間が５〜１５時間であることが好ましい。 The maximum temperature and holding time vary depending on the type of CIP compact, particularly the ceramic raw material powder. In the case of boron nitride alone, the maximum temperature is preferably 1900 to 2100 ° C. and the holding time is preferably 5 to 12 hours. Further, in the composite system of boron nitride and aluminum nitride, the maximum temperature is 1850 to 2050 ° C. and the holding time is 5 to 10 hours, and in the composite system of boron nitride and silicon nitride, the maximum temperature is 1800 to 1900 ° C. and the holding time. For a composite system of boron nitride and titanium boride for 5 to 8 hours, the maximum temperature is preferably 1950 to 2200 ° C. and the holding time is preferably 5 to 15 hours.
実施例１〜７ 比較例１〜３
市販の六方晶窒化ホウ素粉末Ａ（黒鉛化指数１．５）、市販の六方晶窒化ホウ素粉末Ｂ（黒鉛化指数５．２）及び市販の窒化アルミニウム粉末（純度９９質量％以上、平均粒径１．５μｍ）を、表１に示す所定の割合に混合した。混合は、アルミナ製のボール混合媒体とするボールミルで８時間行った。得られたセラミックス原料粉を金型に充填し一軸加圧成形体（２００×３００×９０ｍｍ）を製造した。その際、セラミックス原料粉は、まずその１ｋｇを金型に充填してから、約４分かけてエア抜きをしながら０．５ＭＰａまで加圧した後、更に残りの全量（約１ｋｇ）を充填し、４〜５分かけてエア抜きをしながら０表１に示す圧力まで加圧した。
Examples 1-7 Comparative Examples 1-3
Commercial hexagonal boron nitride powder A (graphitization index 1.5), commercial hexagonal boron nitride powder B (graphitization index 5.2) and commercial aluminum nitride powder (purity 99% by mass or more, average particle size 1) 0.5 μm) was mixed in the predetermined proportions shown in Table 1. The mixing was performed for 8 hours by a ball mill using an alumina ball mixing medium. The obtained ceramic raw material powder was filled into a mold to produce a uniaxial pressure-formed body (200 × 300 × 90 mm). At that time, 1 kg of the ceramic raw material powder is first filled in the mold, and after pressurizing to 0.5 MPa while releasing air over about 4 minutes, the remaining whole amount (about 1 kg) is further filled. The pressure was increased to 0 shown in Table 1 while venting air over 4 to 5 minutes.
ついで、一軸加圧成形体をゴム製の袋に入れ、脱気・密封して表１に示す条件で２回又は３回のＣＩＰを施した。ＣＩＰ成形体の外観観察を行った後、外寸と質量を測定してＣＩＰ成形体密度を求めた。その結果を表１に示す。ＣＩＰ成形体は、各２個を製造した。 Subsequently, the uniaxial pressure-molded body was put in a rubber bag, deaerated and sealed, and subjected to CIP twice or three times under the conditions shown in Table 1. After the appearance of the CIP compact was observed, the outer dimensions and mass were measured to determine the CIP compact density. The results are shown in Table 1. Two CIP compacts were produced.
ＣＩＰ成形体を温度１４０℃の乾燥機に入れ、表２に示される時間熱処理をした後、質量変化を測定した。その後、各々１個のＣＩＰ成形体は、温度１２０℃で３６時間放置し、１２０℃における加熱減量分を測定した。ついで、これらの熱処理物を表２に示す条件で焼成して窒化ホウ素焼成体を製造し、サンプルを切り出して、密度、ショア硬度、三点曲げ強度を測定した。それらの結果を表２に示す。 The CIP compact was put into a dryer at a temperature of 140 ° C., subjected to heat treatment for the time shown in Table 2, and then the mass change was measured. Thereafter, each CIP compact was allowed to stand for 36 hours at a temperature of 120 ° C., and the amount of heat loss at 120 ° C. was measured. Subsequently, these heat-treated products were fired under the conditions shown in Table 2 to produce a boron nitride fired body, a sample was cut out, and the density, Shore hardness, and three-point bending strength were measured. The results are shown in Table 2.
表から明らかなように、本発明の実施例では、いずれも体積が３０００ｃｍ３以上で厚さが４０ｍｍ以上の大型品にして、三点曲げ強度が３０ＭＰａ以上、密度が１．７ｇ／ｃｍ３以上で、クラックやラミネーションのない窒化ホウ素焼成体が得られたのに対し、比較例では強度、密度、外観のいずれにも劣った。 As is apparent from the table, in the examples of the present invention, each of the large-sized products having a volume of 3000 cm 3 or more and a thickness of 40 mm or more has a three-point bending strength of 30 MPa or more and a density of 1.7 g / cm 3 or more. Thus, while a boron nitride fired body without cracks or lamination was obtained, the comparative example was inferior in all of strength, density, and appearance.
本発明によって製造された窒化ホウ素焼成体は、半導体用の大型治具をはじめ、従来から知られている各種用途に広く適用することができる。 The boron nitride fired body produced by the present invention can be widely applied to various conventionally known applications including large jigs for semiconductors.
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