JPH0313191B2 - - Google Patents
Info
- Publication number
- JPH0313191B2 JPH0313191B2 JP60201686A JP20168685A JPH0313191B2 JP H0313191 B2 JPH0313191 B2 JP H0313191B2 JP 60201686 A JP60201686 A JP 60201686A JP 20168685 A JP20168685 A JP 20168685A JP H0313191 B2 JPH0313191 B2 JP H0313191B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- boron nitride
- aluminum
- sintered body
- weight
- 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 - Lifetime
Links
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 69
- 229910052582 BN Inorganic materials 0.000 claims description 65
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 40
- 239000011812 mixed powder Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- -1 aluminum compound Chemical class 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 35
- 238000002156 mixing Methods 0.000 description 25
- 239000002245 particle Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 238000005245 sintering Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000005452 bending Methods 0.000 description 12
- 238000005121 nitriding Methods 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
（産業上の利用分野）
本発明は、窒化アルミニウムと窒化ほう素を含
有する複合焼結体の製造方法に関する。
（従来の技術）
従来、窒化アルミニウムを窒化もう素を含有す
る複合焼結体を製造するに際し、窒化アルミニウ
ム粉末と窒化ほう素粉末をそれぞれ個別に合成
し、得られた窒化アルミニウム粉末と窒化ほう素
粉末を公知の手段により混合し、該混合物を焼結
することにより製造する方法が一般的にとられて
いる。
（発明が解決しようとする問題点）
本発明は、窒化アルミニウム焼結体に類似した
諸物性、例えば熱伝導性や機械的強度を有し、且
つ窒化アルミニウム焼結体に乏しい切削加工性を
改善された材質であり、特に曲げ強度等が改良さ
れた窒化アルミニウムと窒化ほう素との複合焼結
体を提供するにある。
しかし、本発明に用いる六方晶窒化ほう素は、
板状粒子であつて、形状異方性が非常に同きい。
また一般的に一次粒子が凝集して大きい凝集粒を
作にやすい性質をもつている。
このため、窒化アルミニウム粉末と窒化ほう素
粉末を単に混合するだけで両者が均一に分散した
混合粉末を得ることは難かしい。従つて、従来法
では均一な組織を有する窒化アルミニウムと窒化
ほう素からなる複合焼結体を得ることは困難であ
つた。
そのために得られた複合焼結体の物性を向上さ
せることが難かしく、特に曲げ強度の向上には従
来法では限界があつた。
（問題点を解決するための手段）
本発明者等は上記事情に鑑み、均一な組織を有
する窒化アルミニウムと窒化ほう素からなる複合
焼結体を得るべく鋭意研究を進めた結果、窒化ア
ルミニウム粉末の合成を窒化ほう素粉末の存在下
に行ない、得られた混合粉末を焼結することによ
り得た複合焼結体は均一な組織を持ち、且つ高い
曲げ強度を有することを見出し、本発明を完成す
るに至つた。
六方晶窒化ほう素粉末(A)と金属アルミニウム又
は窒化可能なアルミニウム化合物(B)とよりなる混
合物であつて、該混合物は前記(B)が窒化アルミニ
ウムとなつたとき、窒化アルミニウム分が全混合
物の60〜97重量％となるように前記(A)と(B)が混合
された混合物を、窒化処理し、窒化ほう素粉末と
窒化アルミニウム粉末との混合粉末を得、次いで
これを焼結することを特徴とする複合焼結体の製
造方法である。
以下、本発明について更に詳しく説明する。
本発明で好適に採用される六方晶の窒化ほう素
粉末は、純度が99.0重量％以上で、平均粒子が
5μm以下のものである。このような、高純度で粒
子径の小さい窒化ほう素粉末を使用することによ
り、得られる複合焼結体の組織がより一層均一に
なり、高い曲げ強度や高い熱伝導性を示す複合焼
結体を合成することができる。
また、該六方晶の窒化ほう素粉末（以下単に窒
化ほう素粉末ともいう）の製法も特に限定されず
公知の方法が採用できる。
窒化ほう素の存在下に於ける窒化アルミニウム
の合成方法としては、下記の方法が採用される。
(a) 金属アルミニウム又は窒素、アンモニア等の
窒素供給雰囲気下又は窒素源物質と共に加熱し
て窒化アルミニウムとなり得るアルミニウム化
合物を窒素、アンモニア等の含窒素ガス雰囲気
下又は窒素源物質の共存下に通常窒化アルミニ
ウムを生成する条件で加熱窒化する方法
(b) ハロゲン化アルミニウムのアンモニア付加物
又は有機アルミニウム化合物のアンモニア付加
物を熱分解する方法
これら(a)及び(b)のいずれの方法も窒化アルミニ
ウムの合成方法として公知の方法である。従つ
て、本発明に於いてこれらの方法を採用する場
合、使用される原料、及び窒化又は熱分解の条件
等は公知のものが特に制限されず採用し得る。
例えば、(a)の方法に於けるアルミニウム化合物
としては、酸化アルミニウム、窒化温度に於いて
酸化アルミニウムになり得る化合物、又はアルミ
ニウム錯イオンのアンモニウム塩等の公知の原料
が何ら制限なく使用し得る。このうち、窒化温度
に於いて酸化アルミニウムになり得る化合物とし
ては、具体的には、水酸化アルミニウム、硫酸ア
ルミニウム、塩基性硫酸アルミニウム、硝酸アル
ミニウム、アルミニウムのアンモニウム炭酸塩や
アンモニウム硫酸塩等を代表的な化合物として挙
げることができる。また、アルミニウム錯イオン
のアンモニウム塩としては、（NH4）3AlF6等を挙
げることぎができる。
また、窒化に用いる窒素源としては、公知のも
のが何ら制限なく使用し得る。代表的な窒素源と
しては、窒素又は含窒素化合物、例えばNH3，
N2O，NO，N2H4，C2N2，HCN，チオシアン酸
塩、チオ尿素等を挙げることができる。
さらに、(b)の方法で使用されるハロゲン化アル
ミニウムのアンモニア付加物及び有機アルミニウ
ム化合物のアンモニア付加物も、窒化アルミニウ
ム合成に使用される公知の化合物が何ら制限され
ずに使用し得る。ハロゲン化アルミニウムのアン
モニア付加物としては、例えば、AlCl3・NH3，
AlBr3・NH3，AlI3・NH3等が好適に用いられ、
また、有機アルミニウムのアンモニア付加物とし
ては、（CH3）3Al・NH3，（C2H5）3Al・NH3等の
アルキルアルミニウムのアンモニア付加物が好適
に用いられる。
前記(a)及び(b)の方法の中でも、本発明に於いて
特に好適に採用し得る方法を示せば、例えば次の
方法が挙げられる。
(1) アルミナ又は窒化反応の温度でアルミナとな
り得るアルミニウム化合物と窒化ほう素との混
合物を還元窒化する方法。
(2) 金属アルミニウムと窒化ほう素との混合物を
窒素又は含窒素化合物で窒化した後粉砕する方
法
(3) アルミニウム錯イオンのアンモニウム塩と窒
化ほう素との混合物を窒素又は含窒素化合物で
窒化する方法
(4) ハロゲン化アルミニウムのアンモニア付加物
又は有機アルミニウム化合物のアンモニア付加
物と窒化ほう素との混合物を熱分解する方法
上記に示した(1)〜(4)の方法の中で、代表例とし
て(1)及び(4)の方法を採用した場合について以下に
詳細に説明する。まず(1)の方法について説明す
る。
(i) 窒化ほう素粉末、アルミナ粉末又はアルミナ
となり得るアルミニウム化合物（以下、これら
を単にアルミナ等と称する）、さらにカーボン
粉末を混合し、
(ii) 得られた混合物を適宜乾燥し窒素または含窒
素化合物の雰囲気下で1400〜1700℃の温度で焼
成し、
(iii) 次いで得られた粉末を酸素を含む雰囲気下で
600〜900℃の温度で加熱して未反応のカーボン
を加熱除去する
工程によつて本発明の中間原料である窒化アルミ
ニウムと窒化ほう素の混合粉末を得ることができ
る。
前記アルミナ等及びカーボン粉末は特に限定さ
れずいかなるものも採用することができるが、得
られる窒化アルミニウム粉末及び複合焼結体の特
性上、純度99.0重量％以上で平均粒子径が2μm以
下、且つ3μm以下の粒子の含有割合が70容量％以
上のアルミナ等と灰分含量0.2重量％以下で平均
粒子径が1μm以下のカーボン粉末が特に好適に使
用される。
またアルミナ等、カーボン粉末及び窒化ほう素
粉末の混合比は一般にアルミナ等（但し、アルミ
ナになり得る化合物の場合はアルミナに換算す
る）とカーボン粉末の混合比が１：0.36〜１：１
（重量比）の範囲が好ましく、且つ窒化ほう素粉
末の混合比は、本発明により製造される複合焼結
体に要求される性状に応じて広い範囲から選択で
きる。一般に前記混合比のアルミナ等及びカーボ
ン粉末から生成する窒化アルミニウム粉末が70〜
90重量％の範囲に対し窒化ほう素粉末が30〜10重
量％の範囲となるように窒化ほう素粉末を混合し
た場合、得られる窒化アルミニウムと窒化ほう素
の混合粉末を焼結することにより、高い機械的強
度をもち、且つ普通工具による切削加工ができる
複合焼結体を得ることができるので好適である。
前記窒化ほう素粉末、アルミナ等及びカーボン
粉末の混合方法は特に限定されず、ドライブレン
ドする乾式混合、液体分散媒体が関与する湿式混
合等の公知の方法を採用すればよい。特に好適な
実施態様は湿式混合である。
前記湿式混合で使用出来る液体分散媒体は特に
限定されず湿式混合溶媒として公知のものが使用
出来る。一般に工業的には水、炭化水素、脂肪族
アルコール、石油エーテル、ヘキサン、ベンゼ
ン、トルエン等であり、脂肪族アルコールは例え
ばメタノール、エタノール、イソプロパノール等
が好適である。
また、混合の条件及び装置は特に限定されず、
不可避的に混入する不純物成分を抑制できるもの
であれば好適である。例えば、混合時に不純物の
混入を避けるため高純度アルミナ、窒化アルミニ
ウム等の材質の装置を使用するか該装置の原料と
接する内面をプラスチツクでコーテイングする等
の手段は適宜実施できる。
このように混合された原料は必要により乾燥を
経て、窒素または含窒素化合物、特にアンモニア
雰囲気下に1400〜1700℃の温度で焼成する。
該焼成する温度が上記温度より低い場合は工業
的に十分な還元窒化反応が進行しないので好まし
くない。また該焼成温度が前記温度より高くなる
と得られる窒化アルミニウムの一部が焼結を起
し、粒子間の凝集が起るため目的の粒子径の窒化
アルミニウムを得難くなるので好ましくない。
焼成により得られた窒化物微粒子は、次いで酸
素を含む雰囲気下で600〜900℃の温度で加熱処理
され、該窒化物微粒子に含まれる未反応のカーボ
ンを酸化して除去される。
次に(4)の方法について説明する。
ハロゲン化アルミニウムのアンモニア付加物又
は有機アルミニウム化合物のアンモニア付加物を
窒化ほう素と混合する。混合方法及び混合比は前
記(1)の方法と同様に行なうことができる。ただ、
上記のアンモニア付加物は、水や酸素と反応する
ため、窒素又は含窒窒素化合物の雰囲気下で混合
するのが好ましい。
得られた混合物を、、窒素又は含窒素化合物特
にアンモニアの雰囲気下で加熱し、熱分解するこ
とによりより窒化アルミニウムと窒化ほう素の混
合粉末が得られる。熱分解に要する加熱温度は、
原料として用いるアンモニア付加物により最適の
温度を選べば良いが一般には800〜1500℃の範囲
が良い。
以上に、(1)及び(4)の方法について具体的に説明
したが、例えば、窒化ほう素粉末と原料との混合
方法及び混合比等については他の方法に於いても
(1)及び(4)と同様に行なうことができる。いずれの
方法で窒化アルミニウムを合成するにしても、得
られる混合粉末中の窒化アルミニウム粉末が前記
したように60〜97重量％、好ましくは60〜95重量
％、更に好ましくは70〜90重量％の範囲であり、
一方、窒化ほう素粉末は、40〜３重量％、好まし
くは40〜５重量％、更に好ましくは30〜10重量％
の範囲となるように混合粉末を合成することが好
ましい。
前記のようにして得られる窒化アルミニウムと
窒化ほう素の混合粉末を焼結することによつて複
合焼結体が得られる。焼結に際しては、上記の混
合粉末をそのまま焼結させることもできるが、焼
結助剤を用いることが好ましい。焼結助剤として
は、窒化アルミニウム又は窒化ほう素の焼結に用
いられる公知の化合物が何ら制限なく使用し得
る。本発明では、周期律表第ａ族金属又は第
ａ族金属の化合物が焼結助剤として好適に採用さ
れる。
特に好適に使用される代表的なものを例示する
と次の通りである。該周期律表第ａ族からなる
金属としては一般にベリリウム、カルシウム、ス
トロンチウム、バリウム等が好適である。また周
期律表第ａ族からなる金属としてはイツトリウ
ム又はランタン族金属が好適に使用され、より具
体的に挙げればイツトリウム、ランタン、セリウ
ム、プラセオジム、ネオジム、プロメシウム、サ
マリウム、ユーロピウム、カドリニウム、テルビ
ウム、ジスプロシウム、ホルミウム、エルビウ
ム、ツリウム、イツテルビウム、ルテチウム等、
特にイツトリウム、ランタン、セリウム、ネオジ
ム等が好適である。これらの周期律表第ａ族又
は第ａ族よりなる金属化合物は特に限定されず
窒化アルミニウム粉末及び／又は窒化ほう素粉末
の焼結助剤として公知の前記金属化合物が使用出
来る。一般には例えば硝酸塩、炭酸塩、ハロゲン
化物、アルミン酸塩、酸化物等の化合物が好適に
使用される。上記金属化合物の硝酸塩を用いる場
合は酸素含有ガス雰囲気下の加熱によつて亜硝酸
塩となるが、炭酸塩、塩化物は酸化物となる。
また前記周期律第ａ族金属又は第ａ族金属
の化合物の使用量は該金属の最高原子価の酸化物
に換算して複合焼結体中に0.01〜５重量％、好ま
しくは0.05〜４重量％となる範囲から選べばよ
い。これらの添加量は複合焼結体中の酸素含有
量、及び不純粉の含有量あるいは複合焼結体に要
求される性状等によつて異なるので予めこれらの
性状に応じて好適な使用量を決定すればよい。
また前記複合焼結体を得るに際し、前記原料以
外に結合剤、解膠剤、可塑剤等の添加混合は必要
に応じて適宜採用して実施することができる。
上記添加物の混合方法は特に限定されず公知の
方法を採用すればよい。例えば、既述の湿式混合
方法が好適に採用出来るし、液体分散媒体を使用
しない乾式混合方法を採用することも出来る。ま
た混合装置についても特に限定されず公知のもの
をそのまま使用すればよい。もちろん前記したよ
うに混合時に不純物の混入を避けるため高純度ア
ルミナ、窒化アルミニウム等の材質の装置を使用
するか該装置の原料と接する内面をプラスチツク
でコーテイングする等の手段は適宜実施出来る。
焼結は真空又は非酸化性雰囲気下、例えば窒素
ガス雰囲気下に加圧下あるいは常圧下で行なわれ
る。加圧下の焼結の場合は、該混合粉末を黒鉛な
どのモールドに充填し、通常20〜500Kg／cm3の圧
力を加えながら、例えば窒素気流中で1500〜2100
℃に加熱し複合焼結体を製造する。
常圧下に焼結させる場合には、該混合粉末をそ
のままか、あるいはパラフインやポリビニルブチ
ラールなどの公知のバインダーを添加して所望の
形状にラバープレスなどの方法で成形した後、焼
成するのが一般的である。該常圧焼結の条件とし
ては、一般に窒素雰気下1500〜2100℃の温度で焼
成すると良い。
（効果）
本発明の中間原料として得られる窒化アルミニ
ウムと窒化ほう素の混合粉末は両者が均一に分散
した混合粉体である。これは、窒化ほう素粉末の
存在下に於て窒化アルミニウムを合成する際、窒
化ほう素粉末を核として窒化アルミニウムが生成
するためであろうと考えられる。
従つて、上記混合粉末を焼結して得られる複合
焼結体は均一な組織を有する。そのため本発明の
製造方法によつて得られる複合焼結体は、従来、
公知の方法、即ち、窒化アルミニウム粉末と窒化
ほう素粉末を単に混合し、得られた混合物を焼結
することによつて得られる複合焼結体にくらべて
高い曲げ強度を有する。
また、本発明により得られる複合焼結体は高熱
伝導性を示し、特定の組成に於いて普通工具によ
り切削加工ができる、、いわゆるマシーナブルセ
ラミクスとしての性状をも発揮する。
本発明により、上記のようなすぐれた特性を有
する窒化アルミニウムと窒化ほう素を含有する複
合焼結体を得ることができるが、本発明の製造方
法はそれだけにとどまらず、本発明に製造方法を
他のセラミクス粉末、例えば窒化ケイ素、炭化ケ
イ素等に応用することにより均一な組織を有する
種々のセラミクスの窒化ほう素系複合焼結体を得
ることができる。
本発明のような簡単な手段で上記のようなすぐ
れた特性を有する窒化アルミニウム及び窒化ほう
素からなる複合焼結体を得ることが出来ることは
驚異的なことであり、かつ上記のように本発明の
製造方法を広い範囲にわたつて応用できることを
考え合わせると本発明が寄与する利点は計り知れ
ないものである。
以下実施例によつて本発明を具体的に例示する
が、本発明はこれらの実施例に限定されるもので
はない。
実施例 １
純度99.99％（不純物分析値は表１に示す）で
平均粒子径が0.52μmで、3μm以下の粒子の含有
割合が95容量％のアルミナ100重量部、灰分0.08
重量％で平均粒子径が0.45μmのカーボンブラツ
ク55重量部、及び平均粒子径2.5μm、粒径5μm以
下の粒子の割合が95容量％で、且つ純度99.5％の
窒化ほう素粉末20重量部とをナイロン製ポツトと
ボールを用い、エタノールを液体分散媒体として
湿式混合で均一にボールミル混合した。
このようにして得られた混合粉末を乾燥後、高
純度黒鉛製平皿に入れ電気炉内に高純度窒素ガス
を３／分で連続的に供給しながら1600℃の温度
で６時間加熱した。
このようにして得られた反応混合物を空気中で
650℃の温度で10時間加熱し、未反応のカーボン
を酸化除去した。
得られた粉末は白色で、Ｘ線回折による分析の
結果、窒化アルミニウムと窒化ほう素による回折
ピークのみで、Al2O3の回折ピークはなかつた。
化学分析の結果該粉末の組成は窒化アルミニウム
78.5重量％、窒化ほう素20重量％であつた。残部
は主にアルミナであると考えられる。該粉末の走
査型電子顕微鏡による観察では平均0.4μm程度の
均一な窒化アルミニウム粒子が窒化ほう素粒度の
均一な窒化アルミニウム粒子が窒化ほう素粒
表１ Al2O3粉末分析値
Al2O2含有量 99.99％
元素 含有量（ppm）
Mg ＜ ５
Cr ＜10
Si 30
Zn ＜ ５
Fe 22
Cu ＜ ５
Ca ＜20
Ni 15
Ti ＜ ５
子を核として生成しており両者が均一に分散した
混合粉末であつた。
上記混合粉末12ｇを、窒化ほう素粉末を内面に
塗布した直径40mmの黒鉛ダイスに入れ高周波誘導
加熱炉を用い、１気圧の窒素ガス中200Kg／cm2の
圧力下、2000℃の温度で３時間加圧焼結した。得
られた焼結体は白色であつた。この焼結体は、
CuK〓線によるＸ線回析により、窒化アルミニウ
ムに起因する2θが33.2゜，37.9゜及び36.0℃と六方晶
窒化ほう素に起因する26.7゜のピークが認められ
たがアルミナを示す43.3゜，35.2゜及び57.6゜のピー
クは全くなかつた。従つて、この焼結体は、窒化
アルミニウムと六方晶窒化ほう素の２相から成つ
ていることがわかつた。アルキメデス法で測定し
た密度は2.96ｇ／cm3であつた。
上記焼結体から約３mm角長さ約40mmの試験片を
切り出し、1500番のサンドペーパーで磨いた後、
曲げ強度を測定した、測定条件は、クロスヘツド
スピード0.5mm／min、スパン20mmの３点曲げと
した。測定値より計算された曲げ強度は47Kg／mm2
であつた。
また上記焼結体の加工性を調べたところ超硬ド
リルによる穿孔、超硬バイトによる切削のいずれ
も容易に行なえ、快削性であることがわかつた。
更に上記と同条件で製造した窒化アルミニウム
と窒化ほう素の混合粉末を同条件で加圧焼結した
直径10mm、厚さ2.5mmの焼結体の室温における熱
伝導率を理学電機製レーザー・フラツシユ法熱定
数測定装置PS−７を用いて測定した。その結果
熱伝導率は74W／ｍ・ｋであることがわかつた。
実施例 ２〜３
実施例１に於いて窒化ほう素粉末の混合割合を
変えそれ以外は実施例１と全く同一にして実験を
行なつた。
結果を表２にまとめて示す。
(Industrial Application Field) The present invention relates to a method for manufacturing a composite sintered body containing aluminum nitride and boron nitride. (Prior art) Conventionally, when producing a composite sintered body containing aluminum nitride and boron nitride, aluminum nitride powder and boron nitride powder were synthesized separately, and the obtained aluminum nitride powder and boron nitride were synthesized separately. A commonly used method is to mix powders by known means and sinter the mixture. (Problems to be Solved by the Invention) The present invention has physical properties similar to aluminum nitride sintered bodies, such as thermal conductivity and mechanical strength, and improves machinability that is poor in aluminum nitride sintered bodies. The object of the present invention is to provide a composite sintered body of aluminum nitride and boron nitride, which is made of an improved material and has particularly improved bending strength. However, the hexagonal boron nitride used in the present invention is
They are plate-like particles and have very similar shape anisotropy.
Additionally, primary particles generally tend to aggregate to form large aggregate particles. For this reason, it is difficult to obtain a mixed powder in which aluminum nitride powder and boron nitride powder are uniformly dispersed simply by mixing them. Therefore, it has been difficult to obtain a composite sintered body of aluminum nitride and boron nitride having a uniform structure using the conventional method. Therefore, it is difficult to improve the physical properties of the obtained composite sintered body, and in particular, conventional methods have had limits in improving the bending strength. (Means for Solving the Problems) In view of the above circumstances, the present inventors conducted intensive research to obtain a composite sintered body consisting of aluminum nitride and boron nitride having a uniform structure, and as a result, aluminum nitride powder was synthesized in the presence of boron nitride powder, and the composite sintered body obtained by sintering the resulting mixed powder had a uniform structure and high bending strength. It was completed. A mixture consisting of hexagonal boron nitride powder (A) and metallic aluminum or a nitridable aluminum compound (B), which when the above (B) becomes aluminum nitride, the aluminum nitride content is the same as that of the entire mixture. A mixture of (A) and (B) is nitrided to give a content of 60 to 97% by weight of boron nitride powder and aluminum nitride powder, which is then sintered. This is a method for manufacturing a composite sintered body characterized by the following. The present invention will be explained in more detail below. The hexagonal boron nitride powder preferably employed in the present invention has a purity of 99.0% by weight or more and an average particle size of
The diameter is 5 μm or less. By using such high-purity boron nitride powder with small particle size, the structure of the resulting composite sintered body becomes even more uniform, resulting in a composite sintered body that exhibits high bending strength and high thermal conductivity. can be synthesized. Further, the method for producing the hexagonal boron nitride powder (hereinafter also simply referred to as boron nitride powder) is not particularly limited, and any known method can be employed. The following method is adopted as a method for synthesizing aluminum nitride in the presence of boron nitride. (a) Normally nitriding metallic aluminum or an aluminum compound that can become aluminum nitride by heating in a nitrogen supply atmosphere such as nitrogen or ammonia or with a nitrogen source substance in a nitrogen-containing gas atmosphere such as nitrogen or ammonia or in the coexistence of a nitrogen source substance. A method of heating nitriding under conditions that produce aluminum (b) A method of thermally decomposing an ammonia adduct of aluminum halide or an ammonia adduct of an organoaluminum compound Both of these methods (a) and (b) are used to synthesize aluminum nitride. This is a known method. Therefore, when these methods are employed in the present invention, known raw materials, nitriding or thermal decomposition conditions, etc. can be employed without any particular restriction. For example, as the aluminum compound in the method (a), known raw materials such as aluminum oxide, a compound that can become aluminum oxide at the nitriding temperature, or an ammonium salt of an aluminum complex ion can be used without any restriction. Among these, typical examples of compounds that can become aluminum oxide at nitriding temperatures include aluminum hydroxide, aluminum sulfate, basic aluminum sulfate, aluminum nitrate, and ammonium carbonate and ammonium sulfate of aluminum. It can be mentioned as a compound. Furthermore, examples of ammonium salts of aluminum complex ions include (NH 4 ) 3 AlF 6 and the like. Further, as the nitrogen source used for nitriding, any known nitrogen source can be used without any restrictions. Typical nitrogen sources include nitrogen or nitrogen-containing compounds, such as NH3 ,
Examples include N 2 O, NO, N 2 H 4 , C 2 N 2 , HCN, thiocyanate, and thiourea. Further, the ammonia adduct of aluminum halide and the ammonia adduct of organoaluminum compound used in the method (b) can also be used without any limitations on the known compounds used in aluminum nitride synthesis. Examples of ammonia adducts of aluminum halide include AlCl 3 .NH 3 ,
AlBr 3 .NH 3 , AlI 3 .NH 3 etc. are preferably used,
Furthermore, as the ammonia adduct of organoaluminum, ammonia adducts of alkyl aluminum such as (CH 3 ) 3 Al·NH 3 and (C 2 H 5 ) 3 Al·NH 3 are suitably used. Among the methods (a) and (b), examples of methods that can be particularly suitably employed in the present invention include the following methods. (1) A method of reducing and nitriding alumina or a mixture of boron nitride and an aluminum compound that can become alumina at the temperature of the nitriding reaction. (2) A method of nitriding a mixture of metal aluminum and boron nitride with nitrogen or a nitrogen-containing compound and then pulverizing it. (3) Nitriding a mixture of an ammonium salt of an aluminum complex ion and boron nitride with nitrogen or a nitrogen-containing compound. Method (4) A method of thermally decomposing a mixture of an ammonia adduct of aluminum halide or an ammonia adduct of an organoaluminum compound and boron nitride Representative examples among methods (1) to (4) shown above The case where methods (1) and (4) are adopted will be explained in detail below. First, method (1) will be explained. (i) Boron nitride powder, alumina powder, or an aluminum compound that can become alumina (hereinafter simply referred to as alumina, etc.), and carbon powder are mixed; (ii) the resulting mixture is appropriately dried to form nitrogen or nitrogen-containing (iii) The resulting powder is then calcined in an oxygen-containing atmosphere at a temperature of 1400-1700°C.
A mixed powder of aluminum nitride and boron nitride, which is an intermediate raw material of the present invention, can be obtained by heating at a temperature of 600 to 900°C to remove unreacted carbon. The alumina etc. and carbon powder are not particularly limited and any powder can be used, but due to the characteristics of the aluminum nitride powder and composite sintered body obtained, the purity is 99.0% by weight or more and the average particle size is 2 μm or less and 3 μm. Particularly preferably used are alumina or the like having a particle content of 70% by volume or more and carbon powder having an ash content of 0.2% by weight or less and an average particle diameter of 1 μm or less. In addition, the mixing ratio of carbon powder such as alumina and boron nitride powder is generally 1:0.36 to 1:1.
(weight ratio), and the mixing ratio of the boron nitride powder can be selected from a wide range depending on the properties required of the composite sintered body produced by the present invention. Generally, aluminum nitride powder produced from alumina etc. and carbon powder with the above mixing ratio is 70~
When boron nitride powder is mixed so that the boron nitride powder is in the range of 30 to 10% by weight compared to the range of 90% by weight, by sintering the resulting mixed powder of aluminum nitride and boron nitride, This is preferable because it is possible to obtain a composite sintered body that has high mechanical strength and can be cut with ordinary tools. The method of mixing the boron nitride powder, alumina, etc., and carbon powder is not particularly limited, and any known method such as dry mixing using dry blending or wet mixing involving a liquid dispersion medium may be employed. A particularly preferred embodiment is wet mixing. The liquid dispersion medium that can be used in the wet mixing is not particularly limited, and any known wet mixed solvent can be used. In general, water, hydrocarbons, aliphatic alcohols, petroleum ether, hexane, benzene, toluene, etc. are used industrially, and suitable aliphatic alcohols include, for example, methanol, ethanol, isopropanol, etc. In addition, the mixing conditions and equipment are not particularly limited,
Any material that can suppress unavoidably mixed impurity components is suitable. For example, in order to avoid contamination with impurities during mixing, it is possible to use a device made of a material such as high-purity alumina or aluminum nitride, or to coat the inner surface of the device in contact with the raw material with plastic. The raw materials mixed in this manner are dried if necessary, and then calcined at a temperature of 1400 to 1700°C in an atmosphere of nitrogen or a nitrogen-containing compound, particularly ammonia. If the firing temperature is lower than the above temperature, the reduction-nitriding reaction will not proceed industrially sufficiently, which is not preferable. Furthermore, if the firing temperature is higher than the above temperature, a part of the aluminum nitride obtained will sinter, causing agglomeration between particles, making it difficult to obtain aluminum nitride having the desired particle size, which is not preferable. The nitride fine particles obtained by firing are then heat-treated at a temperature of 600 to 900° C. in an oxygen-containing atmosphere to oxidize and remove unreacted carbon contained in the nitride fine particles. Next, method (4) will be explained. An ammonia adduct of an aluminum halide or an ammonia adduct of an organoaluminum compound is mixed with boron nitride. The mixing method and mixing ratio can be the same as the method (1) above. just,
Since the above ammonia adduct reacts with water and oxygen, it is preferable to mix it in an atmosphere of nitrogen or a nitrogen-containing nitrogen compound. The resulting mixture is heated and thermally decomposed in an atmosphere of nitrogen or a nitrogen-containing compound, particularly ammonia, to obtain a mixed powder of aluminum nitride and boron nitride. The heating temperature required for pyrolysis is
The optimum temperature may be selected depending on the ammonia adduct used as a raw material, but generally a range of 800 to 1500°C is good. Above, methods (1) and (4) have been specifically explained, but for example, the method of mixing boron nitride powder and raw materials, the mixing ratio, etc. can also be used in other methods.
This can be done in the same way as (1) and (4). Whichever method is used to synthesize aluminum nitride, the aluminum nitride powder in the resulting mixed powder contains 60 to 97% by weight, preferably 60 to 95% by weight, and more preferably 70 to 90% by weight. range,
On the other hand, the boron nitride powder is 40 to 3% by weight, preferably 40 to 5% by weight, more preferably 30 to 10% by weight.
It is preferable to synthesize the mixed powder so as to have the following range. A composite sintered body is obtained by sintering the mixed powder of aluminum nitride and boron nitride obtained as described above. During sintering, the above mixed powder can be sintered as it is, but it is preferable to use a sintering aid. As the sintering aid, known compounds used for sintering aluminum nitride or boron nitride can be used without any limitations. In the present invention, a group a metal of the periodic table or a compound of a group a metal is suitably employed as the sintering aid. Typical examples that are particularly preferably used are as follows. Generally, beryllium, calcium, strontium, barium, etc. are suitable as the metal of Group a of the periodic table. Yttrium or lanthanum group metals are preferably used as metals belonging to group a of the periodic table, and more specifically, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, cadrinium, terbium, and dysprosium. , holmium, erbium, thulium, itterbium, lutetium, etc.
Particularly suitable are yttrium, lanthanum, cerium, neodymium, and the like. These metal compounds belonging to group a or group a of the periodic table are not particularly limited, and the metal compounds known as sintering aids for aluminum nitride powder and/or boron nitride powder can be used. In general, compounds such as nitrates, carbonates, halides, aluminates, and oxides are preferably used. When nitrates of the metal compounds mentioned above are used, they become nitrites by heating in an oxygen-containing gas atmosphere, but carbonates and chlorides become oxides. Further, the amount of the Group A metal of the Periodic Table or the compound of the Group A metal used in the composite sintered body is 0.01 to 5% by weight, preferably 0.05 to 4% by weight in terms of the highest valence oxide of the metal. You can choose from the range of %. The amount of these additives varies depending on the oxygen content in the composite sintered body, the content of impurity powder, the properties required of the composite sintered body, etc., so determine the appropriate usage amount in advance according to these properties. do it. Further, when obtaining the composite sintered body, addition and mixing of a binder, a deflocculant, a plasticizer, etc. in addition to the raw materials may be appropriately employed as necessary. The method of mixing the above additives is not particularly limited, and any known method may be used. For example, the wet mixing method described above can be suitably employed, or a dry mixing method that does not use a liquid dispersion medium can also be employed. Further, the mixing device is not particularly limited, and any known mixing device may be used as is. Of course, as mentioned above, in order to avoid contamination of impurities during mixing, it is possible to take appropriate measures such as using a device made of a material such as high-purity alumina or aluminum nitride, or coating the inner surface of the device in contact with the raw material with plastic. Sintering is carried out under vacuum or a non-oxidizing atmosphere, for example under a nitrogen gas atmosphere under pressure or normal pressure. In the case of sintering under pressure, the mixed powder is filled into a mold made of graphite, etc., and sintered under a pressure of 1500 to 2100 kg/ cm3 in a nitrogen stream while applying a pressure of usually 20 to 500 kg/cm3.
℃ to produce a composite sintered body. When sintering under normal pressure, it is common to use the mixed powder as it is, or add a known binder such as paraffin or polyvinyl butyral, mold it into the desired shape using a method such as a rubber press, and then sinter it. It is true. As conditions for the pressureless sintering, it is generally preferable to sinter at a temperature of 1500 to 2100°C in a nitrogen atmosphere. (Effects) The mixed powder of aluminum nitride and boron nitride obtained as an intermediate raw material of the present invention is a mixed powder in which both are uniformly dispersed. This is thought to be because aluminum nitride is produced using the boron nitride powder as a nucleus when aluminum nitride is synthesized in the presence of boron nitride powder. Therefore, the composite sintered body obtained by sintering the mixed powder has a uniform structure. Therefore, the composite sintered body obtained by the manufacturing method of the present invention has conventionally been
It has higher bending strength than a composite sintered body obtained by a known method, that is, simply mixing aluminum nitride powder and boron nitride powder and sintering the resulting mixture. Further, the composite sintered body obtained by the present invention exhibits high thermal conductivity, and exhibits properties as so-called machinable ceramics, which can be cut with ordinary tools in a specific composition. According to the present invention, it is possible to obtain a composite sintered body containing aluminum nitride and boron nitride having the excellent properties as described above, but the manufacturing method of the present invention is not limited thereto. By applying the present invention to ceramic powders such as silicon nitride, silicon carbide, etc., boron nitride-based composite sintered bodies of various ceramics having uniform structures can be obtained. It is surprising that a composite sintered body made of aluminum nitride and boron nitride having the above-mentioned excellent properties can be obtained by a simple means such as the present invention, and the present invention Considering that the manufacturing method of the invention can be applied over a wide range of areas, the advantages contributed by the present invention are immeasurable. EXAMPLES The present invention will be specifically illustrated below with reference to Examples, but the present invention is not limited to these Examples. Example 1 100 parts by weight of alumina with a purity of 99.99% (impurity analysis values are shown in Table 1), an average particle diameter of 0.52 μm, and a content ratio of particles of 3 μm or less at 95% by volume, ash content 0.08
55 parts by weight of carbon black with an average particle size of 0.45 μm in weight%, and 20 parts by weight of boron nitride powder with an average particle size of 2.5 μm, a proportion of particles with a particle size of 5 μm or less in 95% by volume, and a purity of 99.5%. were uniformly mixed in a ball mill by wet mixing using a nylon pot and ball with ethanol as a liquid dispersion medium. After drying the mixed powder thus obtained, it was placed in a flat plate made of high-purity graphite and heated at a temperature of 1600° C. for 6 hours while continuously supplying high-purity nitrogen gas at a rate of 3/min into an electric furnace. The reaction mixture thus obtained was heated in air.
It was heated at a temperature of 650°C for 10 hours to oxidize and remove unreacted carbon. The obtained powder was white, and analysis by X-ray diffraction revealed only diffraction peaks due to aluminum nitride and boron nitride, and no diffraction peaks due to Al 2 O 3 .
As a result of chemical analysis, the composition of the powder was aluminum nitride.
78.5% by weight, and boron nitride 20% by weight. The remainder is thought to be mainly alumina. When the powder was observed using a scanning electron microscope , uniform aluminum nitride particles with an average size of about 0.4 μm were found to be boron nitride particles . Amount 99.99% Element Content (ppm) Mg < 5 Cr < 10 Si 30 Zn < 5 Fe 22 Cu < 5 Ca < 20 Ni 15 Ti < 5 It is a mixed powder in which both are uniformly dispersed. It was hot. 12 g of the above mixed powder was placed in a graphite die with a diameter of 40 mm coated with boron nitride powder on the inner surface, and heated at a temperature of 2000°C for 3 hours under a pressure of 200 kg/cm 2 in nitrogen gas of 1 atm using a high-frequency induction heating furnace. Pressure sintered. The obtained sintered body was white. This sintered body is
X-ray diffraction using CuK rays revealed peaks at 2θ of 33.2°, 37.9°, and 36.0°C due to aluminum nitride, and peaks at 26.7° due to hexagonal boron nitride, but peaks at 43.3°, 35.2° indicating alumina were observed. There were no peaks at 57.6° or 57.6°. Therefore, it was found that this sintered body was composed of two phases: aluminum nitride and hexagonal boron nitride. The density measured by Archimedes method was 2.96 g/cm 3 . A test piece of about 3 mm square and about 40 mm long was cut out from the above sintered body, and after polishing it with 1500 grit sandpaper,
The bending strength was measured under three-point bending conditions with a crosshead speed of 0.5 mm/min and a span of 20 mm. The bending strength calculated from the measured values is 47Kg/mm 2
It was hot. Further, when the workability of the above-mentioned sintered body was investigated, it was found that both drilling with a carbide drill and cutting with a carbide cutting tool were easily performed, and the material was free-cutting. Furthermore, the thermal conductivity at room temperature of a sintered body with a diameter of 10 mm and a thickness of 2.5 mm obtained by press-sintering a mixed powder of aluminum nitride and boron nitride produced under the same conditions as above was measured using a laser flash manufactured by Rigaku Denki. Measurement was performed using a method for measuring thermal constants, PS-7. As a result, the thermal conductivity was found to be 74W/m・k. Examples 2 to 3 Experiments were conducted in the same manner as in Example 1 except that the mixing ratio of boron nitride powder was changed. The results are summarized in Table 2.
【表】
実施例 ４
実施例１で得たのと同一組成の窒化アルミニウ
ムと窒化ほう素とからなる混合粉末100重量部と
3CaO・Al2O31.6重量部とをナイロン製ポツトと
ナイロンコーテイングしたボールを用い、エタノ
ールを分散媒体として均一にボールミル混合し
た。得られたスラリーを乾燥器内で60℃24時間乾
燥を行なつた。
上記混合粉末を実施例１と同様にして加圧下の
焼結を行なつた。得られた焼結体は白色で密度は
2.98ｇ／cm3であつた。
実施例１と同様にして上記焼結体の物性を測定
した結果、曲げ強度は52Kg／mm2、室温での熱伝導
率は89W／ｍ・ｋであつた。
一方、実施例１と同様に上記焼結体の加工性を
調べた結果、実施例１で得たものと同様に快削性
であることが判つた。
実施例 ５〜９
実施例４に於いて3CaO・Al2O3を表３に示す
ように他の周期表第ａ及び第ａ族金属の化合
物に変え、混合割合はそれぞれの酸化物換算で１
重量部となるようにして、それ以外は実施例４と
同様にして実施した。その結果は表３に示す通り
であつた。[Table] Example 4 100 parts by weight of a mixed powder of aluminum nitride and boron nitride having the same composition as that obtained in Example 1.
1.6 parts by weight of 3CaO.Al 2 O 3 were uniformly mixed in a ball mill using a nylon pot and a nylon-coated ball with ethanol as a dispersion medium. The obtained slurry was dried in a dryer at 60°C for 24 hours. The above mixed powder was sintered under pressure in the same manner as in Example 1. The obtained sintered body is white and has a density of
It was 2.98g/ cm3 . The physical properties of the sintered body were measured in the same manner as in Example 1, and the bending strength was 52 Kg/mm 2 and the thermal conductivity at room temperature was 89 W/m·k. On the other hand, as in Example 1, the workability of the sintered body was examined, and it was found that it had the same free machinability as that obtained in Example 1. Examples 5 to 9 In Example 4, 3CaO・Al 2 O 3 was changed to other compounds of Group a and Group A metals of the periodic table as shown in Table 3, and the mixing ratio was 1 in terms of each oxide.
It was carried out in the same manner as in Example 4 except that the parts by weight were adjusted. The results were as shown in Table 3.
【表】
実施例 10
実施例１で得たのと同一組成の窒化アルミニウ
ムと窒化ほう素とからなる混合粉末100重量部と
酸化イツトリウム３重量部とをナイロン製ポツト
とナイロン・コーテイングしたボールを用いエタ
ノールを分散媒体として均一にボールミル混合し
た。得られたスラリーを乾燥器内で60℃、24時間
乾燥を行なつた。
上記混合粉末約12ｇを内径55mmの金型に入れ
200Kg／cm2の圧力で一軸プレスした後2000Kg／cm2
の圧力で静水圧プレスして円板状の成型体とし
た。
この成型体を窒化ほう素製容器に入れ、１気圧
の窒素中で1900℃、３時間焼成した。得られた焼
結体は白色で、密度は2.92ｇ／cm3であつた。
実施例１と同様にして上記焼結体の物性を測定
した結果、曲げ強度は40Kg／mm2であつた。また室
温における熱伝導率は102W／ｍ・ｋであつた。
一方実施例１と同様に上記焼結体の加工性を調
べた結果実施例１で得たものと同様に快削性であ
ることが判つた。
実施例 11
純度99.99％の金属アルミニウム粉末100重量部
と実施例１で使用したのと同じ性状の窒化ほう素
粉末38重量部を、エタノールを分散媒体として均
一にボールミル混合した。
得られたスラリーを乾燥後、ニツケルボートに
入れ、電気炉内に高純度窒素ガスを１／minで
連続的に供給しながら、850℃の温度までゆつく
り昇温した。窒化反応は820℃付近で白色光を発
し急速に進行した。反応終了後そのまま窒素気流
中で冷却した。
得られた反応生成物を高純度アルミナ製のポツ
トとボールを用い、乾式粉砕した。得られた粉砕
物をアルミナボートに入れ電気炉内に窒素ガスを
１／minで連続的に供給しながら1200℃の温度
で２時間加熱した。
得られた混合粉末は灰白色で、Ｘ線回折による
分析の結果は、窒化アルミニウムと窒化ほう素に
よる回折ピークのみであつた。化学分析の結果、
該混合粉末の組成は、窒化アルミニウム78.2重量
％窒化ほう素20重量％であつた。残部は未反応金
属アルミニウム及び不純物酸素であると考えられ
る。該粉末の走査型電子顕微鏡による観察では、
窒化アルミニウム粒子と窒化ほう素粒子が相互に
均一に分散した混合粉末であつた。
このようにして得られた粉末100重量部と酸化
イツトリウム１重量部とをエタノールを分散媒体
として均一にボールミル混合した。
得られたスラリーを乾燥後、実施例１と同様に
して加圧下の焼結を行なつた。得られた焼結体は
灰色で、密度は2.97ｇ／cm3であつた。
実施例１と同様にして上記焼結体の物性を測定
した結果、曲げ強度は48Kg／mm2であつた。また室
温における熱伝導率は93W／ｍ・ｋであつた。
一方実施例１と同様に上記焼結体の加工性と調
べた結果、実施例１で得たものと同様に快削性で
あることがわかつた。
実施例 12
純度99.999％の高純度金属アルミニウムを15M
HF水溶液に少しずつ加え、金属アルミニウムを
完全に溶解した。得られた溶液をロ過後、ロ液に
6Nアンモニア水をPHが約９になるまで加えた。
得られた（NH4）3AlF6をロ取し、エタノールで
洗浄後、約110℃で12時間乾燥を行なつた。
このようにして得られた（NH4）3AlF6100重量
部と実施例１で使用したのと同じ性状の窒化ほう
素粉末66重量部とをエタノールを分散媒体として
均一にボールミル混合した。
得られた混合物を乾燥後、Pt40Rh製ボートに
入れ、同じくPt40Rh製炉芯管の電気炉内に高純
度アンモニアガスを連続的に供給しながら、600
℃の温度で３分間加熱後、更に温度800℃まで上
げ35時間加熱を行なつた。
得られた粉末は淡褐色で、Ｘ線回折による分析
の結果は、窒化アルミニウムと窒化ほう素による
回折ピークのみであつた。化学分析の結果、該粉
末の組成は窒化アルミニウム79.8重量％、窒化ほ
う素20重量％で残りは不純物酸素であると考えら
れる。該粉末の走査型電子顕微鏡による観察では
窒化アルミニウム粒子と窒化ほう素粒子が相互に
均一に分散した混合粉末であつた。
このようにして得られた粉末100重量部と酸化
イツトリウム１重量部とをエタノールを分散媒体
として均一にボールミル混合した。
得られたスラリーを乾燥後、実施例１と同様に
して加圧下の焼結を行なつた。得られた焼結体は
淡褐色で密度は2.96ｇ／cm3であつた。
実施例１と同様にして上記焼結体の物性を測定
した結果、曲げ強度は47Kg／mm2で室温における熱
伝導率は96W／ｍ・ｋであつた。
一方実施例１と同様に上記焼結体の加工性を調
べた結果、実施例１で得たものと同様に快削性で
あることがわかつた。
実施例 13
無水AlCl3とNH3を等モルずつ封管に仕込み、
該封管を200℃で30時間加熱した。得られた
AlCl3・NH3100重量部と実施例１で使用したの
と同じ性状の窒化ほう素粉末5.5重量部とを窒素
雰囲気下、振動ボールミルを用い乾式で混合し
た。
得られた混合物をアルミナボートに入れ、電気
炉内に窒素ガスを連続的に供給しながら1200℃の
温度で５時間加熱した。
得られた粉末は白色で、Ｘ線回折による分析の
結果は、窒化アルミニウムと窒化ほう素による回
折ピークのみであつた。化学分析の結果、該粉末
の組成は窒化アルミニウム79重量％、窒化ほう素
20重量％で残りは不純物酸素であると考えられ
る。該粉末の走査型電子顕微鏡による観察では窒
化アルミニウム粒子と窒化ほう素粒子が相互に均
一に分散した混合粉末であつた。
このようにして得られた粉末100重量部と酸化
イツトリウム１重量部とをエタノールを分散媒体
として均一にボールミル混合した。
得られたスラリーを乾燥後、実施例１と同様に
加圧下の焼結を行なつた。得られた焼結体は白色
で密度は2.97ｇ／cm3であつた。
実施例１と同様にして上記焼結体の物性を測定
した結果、曲げ強度は49Kg／mm2で、室温における
熱伝導率は94W／ｍ・ｋであつた。
一方実施例１と同様に上記焼結体の加工性を調
べた結果、実施例１で得たものと同様に快削性で
あることがわかつた。[Table] Example 10 100 parts by weight of a mixed powder of aluminum nitride and boron nitride with the same composition as obtained in Example 1 and 3 parts by weight of yttrium oxide were mixed using a nylon pot and a nylon-coated ball. The mixture was uniformly mixed in a ball mill using ethanol as a dispersion medium. The obtained slurry was dried in a dryer at 60°C for 24 hours. Put about 12g of the above mixed powder into a mold with an inner diameter of 55mm.
2000Kg/cm 2 after uniaxial pressing with a pressure of 200Kg/cm 2
It was hydrostatically pressed at a pressure of This molded body was placed in a boron nitride container and fired at 1900° C. for 3 hours in nitrogen at 1 atm. The obtained sintered body was white and had a density of 2.92 g/cm 3 . The physical properties of the sintered body were measured in the same manner as in Example 1, and the bending strength was 40 Kg/mm 2 . The thermal conductivity at room temperature was 102 W/m·k. On the other hand, as in Example 1, the workability of the sintered body was examined, and it was found that it had the same free machinability as that obtained in Example 1. Example 11 100 parts by weight of metallic aluminum powder with a purity of 99.99% and 38 parts by weight of boron nitride powder having the same properties as those used in Example 1 were uniformly mixed in a ball mill using ethanol as a dispersion medium. After drying the obtained slurry, it was placed in a nickel boat, and the temperature was slowly raised to 850° C. while continuously supplying high-purity nitrogen gas at a rate of 1/min into the electric furnace. The nitriding reaction progressed rapidly at around 820°C, emitting white light. After the reaction was completed, the mixture was directly cooled in a nitrogen stream. The obtained reaction product was dry-pulverized using a pot and ball made of high-purity alumina. The obtained pulverized product was placed in an alumina boat and heated at 1200° C. for 2 hours while continuously supplying nitrogen gas at a rate of 1/min into an electric furnace. The obtained mixed powder was grayish white, and the results of X-ray diffraction analysis revealed only diffraction peaks due to aluminum nitride and boron nitride. As a result of chemical analysis,
The composition of the mixed powder was 78.2% by weight of aluminum nitride and 20% by weight of boron nitride. The remainder is considered to be unreacted metal aluminum and impurity oxygen. In observation of the powder using a scanning electron microscope,
It was a mixed powder in which aluminum nitride particles and boron nitride particles were mutually uniformly dispersed. 100 parts by weight of the powder thus obtained and 1 part by weight of yttrium oxide were uniformly mixed in a ball mill using ethanol as a dispersion medium. After drying the obtained slurry, it was sintered under pressure in the same manner as in Example 1. The obtained sintered body was gray in color and had a density of 2.97 g/cm 3 . The physical properties of the sintered body were measured in the same manner as in Example 1, and the bending strength was 48 Kg/mm 2 . The thermal conductivity at room temperature was 93 W/m·k. On the other hand, as in Example 1, the workability of the sintered body was investigated, and it was found that it had the same free machinability as that obtained in Example 1. Example 12 15M high purity metal aluminum with a purity of 99.999%
It was added little by little to the HF aqueous solution to completely dissolve the metallic aluminum. After filtering the obtained solution, it is added to the filtrate.
6N ammonia water was added until the pH was about 9.
The obtained (NH 4 ) 3 AlF 6 was collected by filtration, washed with ethanol, and then dried at about 110° C. for 12 hours. 100 parts by weight of (NH 4 ) 3 AlF 6 thus obtained and 66 parts by weight of boron nitride powder having the same properties as used in Example 1 were uniformly mixed in a ball mill using ethanol as a dispersion medium. After drying the resulting mixture, it was placed in a Pt40Rh boat and heated for 600 minutes while continuously supplying high-purity ammonia gas into an electric furnace with a Pt40Rh furnace core tube.
After heating for 3 minutes at a temperature of .degree. C., the temperature was further raised to 800.degree. C. and heating was continued for 35 hours. The obtained powder was light brown in color, and analysis by X-ray diffraction revealed only diffraction peaks due to aluminum nitride and boron nitride. As a result of chemical analysis, the composition of the powder is considered to be 79.8% by weight of aluminum nitride, 20% by weight of boron nitride, and the remainder is impurity oxygen. Observation of the powder using a scanning electron microscope revealed that it was a mixed powder in which aluminum nitride particles and boron nitride particles were mutually uniformly dispersed. 100 parts by weight of the powder thus obtained and 1 part by weight of yttrium oxide were uniformly mixed in a ball mill using ethanol as a dispersion medium. After drying the obtained slurry, it was sintered under pressure in the same manner as in Example 1. The obtained sintered body was light brown in color and had a density of 2.96 g/cm 3 . The physical properties of the sintered body were measured in the same manner as in Example 1, and the bending strength was 47 Kg/mm 2 and the thermal conductivity at room temperature was 96 W/m·k. On the other hand, as in Example 1, the workability of the sintered body was examined, and it was found that it had the same free machinability as that obtained in Example 1. Example 13 Equimolar amounts of anhydrous AlCl 3 and NH 3 were charged into a sealed tube,
The sealed tube was heated at 200°C for 30 hours. obtained
100 parts by weight of AlCl 3 .NH 3 and 5.5 parts by weight of boron nitride powder having the same properties as those used in Example 1 were dry mixed using a vibrating ball mill in a nitrogen atmosphere. The obtained mixture was placed in an alumina boat and heated at a temperature of 1200° C. for 5 hours while continuously supplying nitrogen gas into an electric furnace. The obtained powder was white, and analysis by X-ray diffraction revealed only diffraction peaks due to aluminum nitride and boron nitride. As a result of chemical analysis, the composition of the powder was 79% by weight of aluminum nitride and boron nitride.
It is thought that the remaining 20% by weight is impurity oxygen. Observation of the powder using a scanning electron microscope revealed that it was a mixed powder in which aluminum nitride particles and boron nitride particles were mutually uniformly dispersed. 100 parts by weight of the powder thus obtained and 1 part by weight of yttrium oxide were uniformly mixed in a ball mill using ethanol as a dispersion medium. After drying the obtained slurry, it was sintered under pressure in the same manner as in Example 1. The obtained sintered body was white and had a density of 2.97 g/cm 3 . The physical properties of the sintered body were measured in the same manner as in Example 1, and the bending strength was 49 Kg/mm 2 and the thermal conductivity at room temperature was 94 W/m·k. On the other hand, as in Example 1, the workability of the sintered body was investigated, and it was found that it had the same free machinability as that obtained in Example 1.
Claims (1)
又は窒化可能なアルミニウム化合物(B)とよりなる
混合物であつて、該混合物は前記(B)が窒化アルミ
ニウムとなつたとき、窒化アルミニウム分が60〜
97重量％となるように前記(A)と(B)が混合された混
合物を窒化処理し、窒化ほう素粉末と窒化アルミ
ニウム粉末との混合粉末を得、次いでこれを焼結
することを特徴とする複合焼結体の製造方法。1 A mixture consisting of hexagonal boron nitride powder (A) and metal aluminum or a nitridable aluminum compound (B), which mixture has an aluminum nitride content of 60% when the above (B) becomes aluminum nitride. ~
A mixture of the above (A) and (B) is nitrided so as to have a concentration of 97% by weight to obtain a mixed powder of boron nitride powder and aluminum nitride powder, which is then sintered. A method for manufacturing a composite sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201686A JPS6265980A (en) | 1985-09-13 | 1985-09-13 | Production of composite sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60201686A JPS6265980A (en) | 1985-09-13 | 1985-09-13 | Production of composite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6265980A JPS6265980A (en) | 1987-03-25 |
| JPH0313191B2 true JPH0313191B2 (en) | 1991-02-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60201686A Granted JPS6265980A (en) | 1985-09-13 | 1985-09-13 | Production of composite sintered body |
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| Country | Link |
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| JP (1) | JPS6265980A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0745344B2 (en) * | 1988-06-03 | 1995-05-17 | 新日本製鐵株式会社 | Anisotropic BN-A 1-N sintered body and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4942710A (en) * | 1972-09-01 | 1974-04-22 |
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1985
- 1985-09-13 JP JP60201686A patent/JPS6265980A/en active Granted
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4942710A (en) * | 1972-09-01 | 1974-04-22 |
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| JPS6265980A (en) | 1987-03-25 |
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