JPS6210954B2 - - Google Patents
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- Publication number
- JPS6210954B2 JPS6210954B2 JP52116337A JP11633777A JPS6210954B2 JP S6210954 B2 JPS6210954 B2 JP S6210954B2 JP 52116337 A JP52116337 A JP 52116337A JP 11633777 A JP11633777 A JP 11633777A JP S6210954 B2 JPS6210954 B2 JP S6210954B2
- Authority
- JP
- Japan
- Prior art keywords
- sialon
- powder
- main component
- refractory
- component material
- 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
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- 239000000843 powder Substances 0.000 claims description 81
- 239000000463 material Substances 0.000 claims description 51
- 239000011159 matrix material Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
- -1 β'-sialon Chemical compound 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 36
- 238000010304 firing Methods 0.000 description 25
- 239000011819 refractory material Substances 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910003564 SiAlON Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009970 fire resistant effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明はβ′−サイアロンを結合マトリツクス
とする耐火物の製造方法に関するものである。
従来より種々の耐火物が提案され、たとえばア
ルミナ耐火物等の酸化物系耐火物、炭化珪素質耐
火物が用いられている。
しかしながら、前者の酸化物系耐火物は強度、
硬度が低く、耐摩耗性に劣り、マトリツクスが脆
弱なために溶融金属に対する耐蝕性は一般的に低
く、しかも荷重軟化、クリープが生じ易い欠点が
ある。一方、後者の炭化珪素質耐火物は耐熱衝撃
性、強度、硬度の点では良好であるが、溶融金属
に対する耐蝕性が低く、耐摩耗性も劣る問題があ
る。
このようなことから、最近、β′−サイアロン
反応焼結体耐火物、緻密質β′−サイアロン焼結
体耐火物が提案されている。
前者のβ′−サイアロン反応焼結体耐火物は従
来の耐火物に比して高強度で、耐熱衝撃性、溶融
金属に対する耐蝕性、耐酸、耐アルカリ性が著し
く優れているが、耐摩耗性、耐酸化性が劣り、と
りわけ製造時に被焼結体内部まで反応N2ガスが
浸透し得ないために大型形状のものが得られない
という致命的な欠点がある。一方、後者の緻密質
β′−サイアロン焼結体耐火物は、従来の耐火物
に比して高強度、高硬度で、耐摩耗性、溶融金属
に対する耐蝕性、耐酸化性、耐酸、耐アルカリ性
が極めて良好であるが、反面焼成時の収縮が大き
く、寸法安定性が劣るばかりか、焼成変形を生じ
易く大型形状物の製造が困難であり、しかも耐熱
衝撃性が劣り、大型形状にすると亀裂、破損し易
い欠点がある。
本発明は上記欠点を解消するためになされたも
ので、高強度で、優れた耐摩耗性、溶融金属に対
する耐蝕性、耐酸化性、耐酸性及び耐アルカリ性
を有することは勿論、従来のβ′−サイアロン焼
結体耐火物の欠点である耐熱衝撃性と寸法安定性
を改良し、大型形状物の製作が可能なβ′−サイ
アロンを結合マトリツクスとする耐火物の製造方
法を提供しようとするものである。
以下、本発明を詳細に説明する。
まず、次の方法にてβ′−サイアロン主成分素
材（通常β′−サイアロン70〜80重量％含有）を
造る。
(1) シリカ粉末70〜40重量％と金属アルミニウム
粉末30〜60重量％とを充分混合して出発原料粉
とし、この出発原料粉を種々の成形法、たとえ
ば金属プレス法、ラバープレス法、スリツプキ
ヤステイング法、押出成形法により肉厚５cm以
下、好ましくは２cm以下の任意形状の圧粉体と
した後、この圧粉体を窒素含有非酸化性ガス雰
囲気中で1400〜1700℃に加熱反応せしめて固溶
状態のβ′−サイアロン主成分素材を造る。
(2) シリカ粉末70〜40重量％と金属アルミニウム
粉末30〜60重量％とを混合した出発原料粉を一
旦粉砕して平均粒径３μ以下、好ましくは1.5
μ以下にし、この微粉末原料を耐熱性容器に深
さ５cm以下、好ましくは２cm以下に充填した
後、該微粉末原料を窒素含有非酸化性ガス雰囲
気中で1400〜1700℃の温度下にて加熱反応せし
めて固溶状態のβ′−サイアロン主成分素材を
造る。
(3) シリカ粉末70〜40重量％と金属アルミニウム
粉末30〜60重量％とからなる混合粉末100重量
部に、鉄粉、銅粉、コバルト粉、マンガン粉等
の金属粉或いはそれらの酸化物粉、もしくはフ
ツ化カルシウム、フツ化アルミニウム、フツ化
マグネシウム粉、フツ化マンガン粉等の弗化物
粉の群から選ばれる１種または２種以上の添加
剤を0.1〜10重量部添加混合して出発原料粉と
し、この出発原料粉を前記(1)の方法に準じて圧
粉体とするか、もしくは前記(2)の方法に準じて
微粉末状原料とするかした後、窒素含有非酸化
性雰囲気中で1200〜1700℃の温度にて加熱せし
めて固溶状態のβ′−サイアロン主成分素材を
造る。
上記(1)〜(3)の方法における加熱中の化学反応、
化学変化の詳細に不明であるが、基本的には次の
反応が起こつていると考えられる。
(i) 1000℃以下では、
3SiO2＋4Al→3Si＋2Al2O3 ………（）
2Al＋N2→2AlN ………（）
(ii) 1000℃以上では、
3Si＋2N2→β−Si3N4 ………（）
β−Si3N4へのAl2O3、AlNの固溶→
β′−サイアロン主成分素材〓………（）
〓 β′−サイアロン主成分素材；β′−サイア
ロンが主成分であるが、他に未固溶の
Al2O3、Ｙ−相サイアロン（AlN構造中に
Si、Ｏが入り、金属：非金属原子比が５：６
になつている化学式（Si、Al）2（Ｏ、Ｎ）６
で表わされるもの）、AlN等が含有する。
上記(1)〜(3)の方法に使用するシリカ粉末として
は、水晶粉末、珪砂粉末、石英ガラス粉末、蒸発
シリカ（volatilized−silica）、化学沈殿法シリ
カ、気相法シリカ等を挙げることができ、とくに
蒸発シリカはβ′−サイアロン主成分素材の生成
収率が最も良好である。この場合、シリカ粉とし
てシラスを用いることも可能であるが、アルカリ
成分の含有率が高いために加熱時に加熱炉の炉芯
管、ライニング耐火物、断熱耐火物、抵抗、発熱
体などを汚染、劣化するため好ましくない。
上記(1)〜(3)の方法に使用するアルミニウム粉末
としては、アルミニウムの涙滴状アトマイズ粉
（噴霧状）、鱗片状搗砕粉のどちらでも効果は同じ
であるが、とくに50メツシユより細かい粉末を用
いることが望ましい。
上記(1)〜(3)の方法におけるシリカ粉末とアルミ
ニウム粉末との比（SiO2粉末／Al粉末）を上記
範囲に限定した理由は、SiO2粉末／Al粉末の比
を40／60（重量割合）より小さくすると、未反応
のAlが残存したりSi、AlNが生成したりしてβ′
−サイアロン主成分素材中のβ′−サイアロン生
成量が減少し、一方その比が70／30より多いと、
未反応のSiO2が残存したり、ムライトが生成し
たりして該主成分素材中のβ′−サイアロン生成
量が減少するからであり、好ましい比はSiO2粉
末／Al粉末が60／40付近である。
また、上記(1)、(3)の方法において圧粉体の厚さ
を限定した理由はその肉厚が５cmを越えると、加
熱時該圧粉体中に窒素ガスが充分浸入せず、β′
−サイアロンの生成率の高いβ′−サイアロン主
成分素材が得られないからである。
上記(2)、(3)の方法において、微粉末状原料の充
填深さを限定した理由は、その充填深さが５cmを
越えると、加熱時該充填原料中に窒素ガスが充分
浸入せず、β′−サイアロンの生成率の高いβ′−
サイアロン主成分素材が得られないからである。
この場合使用される容器としては、通常黒鉛質、
窒化珪素質、アルミナ質のものであるが、とくに
黒鉛質容器を用いるには炭化珪素の生成を防止す
る目的からその内面に窒化アルミニウム粉末或い
は窒化硼素粉末を被覆することが望ましい。
上記(3)の方法においてシリカ粉末とアルミニウ
ム粉末とからなる混合粉末に添加する添加剤の量
を上述した範囲に限定した理由は、添加剤の量を
0.1重量部未満にすると、上記（）〜（）式
の反応を促進する効果が期待できず、一方その量
が10重量部を越えると、得られたβ′−サイアロ
ン主成分素材の純度を阻害するからである。
さらに、上記(1)、(2)の方法において加熱処理温
度を限定した理由は、加熱処理温度を1400℃より
低くすると、未反応Siが残つてβ′−サイアロン
主成分素材中のβ′−サイアロンの生成率が低下
し、一方その温度が1700℃を越えると、Ｙ−相サ
イアロンが増加してβ′−サイアロン主成分素材
中のβ′−サイアロンの生成率が低下するからで
ある。また、上記(3)の方法においては加熱処理温
度を上記(1)、(2)の方法の温度より200℃低い1200
℃の温度下でも可能となる。
望ましい加熱処理方法は、600℃／Hr以下、好
ましくは200℃／Hr以下の昇温速度で1400〜1500
℃、或いは1200〜1500℃の温度まで加熱し、その
保持温度を５時間以上保持する（これを第１段加
熱処理と称す）。これで加熱処理の目的は達せら
れるが、さらにβ′−サイアロンの生成率を向上
させるには、第１段加熱処理後さらに1500〜1700
℃の間の所定温度まで昇温して３時間以上加熱処
理する（これを第２段加熱処理と称す）。
しかるに、前記(1)の方法にあつては、上述した
組成割合の出発原料粉を成形して圧粉体とし、か
つ該圧粉体の厚さを規定することによりシリカ粉
末とアルミニウム粉末との接触状況が良好となる
と共に各粉末に対する窒素ガスの接触度合も改善
するため、上記した（）〜（）式の反応が促
進され、β′−サイアロンの含有率の高いβ′−サ
イアロン主成分素材が得られる。
また、前記(2)の方法にあつては、上述した組成
割合の出発原料粉を粉砕して微粉末状原料とする
と共に該原料の容器への充填深さを規定すること
により、粉砕、混合中に展延性の優れたアルミニ
ウム粉末がシリカ粉末を被覆してアルミニウム被
膜を形成し、アルミニウムとシリカとの接触状況
が良好となり、かつ各原料に対する窒素ガスの接
触度合も向上するため、上述した（）〜（）
の反応が促進され、β′−サイアロンの含有率の
高いβ′−サイアロン主成分素材が得られる。
さらに、前記(3)の方法にあつては、出発原料粉
を成形、もしくは粉砕する他、該原料粉中に鉄、
マグネシア等の添加剤を混入するため、上述した
(1)、(2)の方法よりさらに反応の促進化が助長さ
れ、極めてβ′−サイアロンの含有率の高いβ′−
サイアロン主成分素材が得られる。
なお、β′−サイアロン主成分素材を得るに
は、上述した方法の他に、(4)シリカ粉末と金属ア
ルミニウム粉末とにさらに金属シリコン粉末を添
加混合して出発原料とし、上記(1)〜(3)の方法に準
じて窒化焼成を行なう方法、(5)窒化珪素、窒化ア
ルミニウム、アルミナ、シリカの各粉末のうちの
２種以上を適切な配合割合で混合微粉砕し、成形
して圧粉体とした後、窒素含有非酸化性雰囲気中
で1600〜2000℃に加熱処理し、反応（固溶反応を
含む）せしめてβ′−サイアロン主成分素材を得
る方法、(6)金属シリコン粉末とアルミナ粉末の混
合粉末、或いは更に金属アルミニウム粉末、窒化
アルミニウム粉末を添加混合した粉末を出発原料
とし、その圧粉体を窒素含有非酸化性雰囲気中で
1400〜1700℃に加熱反応せしめてβ′−サイアロ
ン主成分素材を得る方法、等が実施し得る。
次いで、上述した(1)〜(3)の方法により得たβ′
−サイアロン主成分素材が、平均粒径（フイイツ
シヤー・サブシーブサイザーで測定）が1.6μ以
下、好ましくは1.2μ以下になるまで微粉砕して
β′−サイアロン主成分素材粉とする。つづいて
この主成分素材粉を、炭化珪素、アルミナ、ムラ
イト、ジルコン、ジルコニア、β′−サイアロ
ン、窒化アルミニウムポリタイプサイアロン、及
び窒化珪素から選ばれる１種または２種以上の耐
火性骨材粉に配合し、充分混合し、これを種々の
成形法、たとえば金型プレス、ラバープレス、ス
リツプキヤステイング、押出成形などにより成形
した後、この成形体を窒素含有非酸化性ガス雰囲
気中（大気とほぼ同圧）で1600〜2000℃の温度に
て焼成せしめてβ′−サイアロンを結合マトリツ
クスとする耐火物を造る。
本発明におけるβ′−サイアロン主成分素材の
粉砕法としては、湿式粉砕法、乾式粉砕法が採用
されるが、とくにアルコール中でタングステンカ
ーバイト製或いはアルミナ製のボールミルを用い
た湿式粉砕法は短時間で粉砕できるため有効であ
る。
本発明におけるβ′−サイアロン主成分素材粉
末の粉径を限定した理由は、該主成分素材粉の粒
径が1.6μを越えると、マトリツクスのβ′−サイ
アロンが緻密とななず強度、所期目的の特性を有
する耐火物が得られないからである。
本発明に使用する耐火性骨材粉は、最密充填性
を良好にする観点から、粗粒、中粒、微粒として
用いることが望ましく、場合によつては微粒とし
て粘土、その他の結合性耐火物を少量配合しても
よい。なお、耐火性骨材粉として、とくにアルミ
ナ、ムライト、β′−サイアロン、窒化アルミニ
ウムポリタイプサイアロン、窒化珪素を配合した
場合は、β′−サイアロン主成素材と骨材成分と
の間の固溶反応が顕著となり、これに伴ない骨材
とマトリツクスとの結合性が向上し、より特性の
優れた耐火物を得ることができる。また、耐火性
骨材として、炭化珪素を用いる場合は、骨材とマ
トリツクス（β′−サイアロンからなる）との結
合性を向上させる観点から、炭化珪素粉末表面に
予め酸化被膜を形成しておくことが望ましい。
本発明におけるβ′−サイアロン主成分素材粉
と耐火性骨材粉との配合割合は、通常β′−サイ
アロン主成分素材粉20〜40重量％、耐火性骨材粉
80〜60重量％とすればよい。
本発明に使用する窒素含有非酸化性ガスとして
は、たとえば窒素ガス単独、或いは窒素ガスとア
ルゴンガス、ネオンガスなどの不活性ガス、また
は水素ガス、アンモニアガスとの混合ガス等を挙
げることができる。
本発明における焼成温度を上記範囲に限定した
理由は、焼成温度を1600℃未満にすると、成形体
の焼結速度が遅く、所期目的の耐火物を得るのに
長時間要し、一方その温度が2000℃を越えると、
前記主成分素材粉中のβ′−サイアロンの一部が
Ｙ−相サイアロンに変換され骨材のマトリツクス
に充分な量のβ′−サイアロンを生成できず性能
低下をきたすからである。このような焼成温度下
での保持時間は、通常１〜５時間にすることが望
ましい。この理由は保持時間を１時間未満にする
と、成形体を充分焼結できず、一方保持時間が５
時間を越えると、成形体中のβ′−サイアロン主
成分素材の粒子生長が進み過ぎ得られた耐火物の
特性（とくに強度）が劣化するからである。ま
た、焼成時の昇温速度は成形体の急激な焼結収縮
を抑制して亀裂、寸法精度の低下を防止する観点
から、200℃／Hr以下、好ましくは100℃／Hr以
下にすることが望ましい。なお、焼結時に使用す
る焼成炉は通常黒鉛製抵抗ヒータ、高周波誘導加
熱方式の黒鉛製サセプターを内装した黒鉛質ライ
ニングの炉が用いられるが、この焼成炉にあつて
は、焼成時該黒鉛製ヒータ等から多少のCOガス
が発生するため、得られた耐火物のβ′−サイア
ロンからなるマトリツクスが炭化されて表面に炭
化珪素膜を生じ易い。また焼成時、成形体を同一
温度で均一に焼成せしめることは難しく、その結
果耐火物に亀裂を生じる虞れがある。また焼成
中、成形体のSiO2成分やSi3N4成分の揮散が生
じ、亀裂や多孔化の原因となる。しかるに、この
ような問題を解消するには、窒化硼素粉（BN）、
窒化珪素粉（Si3N4）からなる非反応性詰粉を充填
した黒鉛製容器に成形体を埋設して、該容器ごと
に炉内に入れ、均一に焼成すると共に耐火物のマ
トリツクス表面に炭化珪素膜が生成するのを阻止
し、SiO2成分やSi3N4成分の揮散を防止すること
が望ましい。
なお、本発明においては必要に応じて、上記
β′−サイアロン主成分素材粉に、粒径１〜５μ
程度の炭化珪素粉及び窒化アルミニウム粉のうち
のいずれか１種以上を0.5〜40重量％配合混合し
てβ′−サイアロン混合素材粉とし、この混合素
材粉を耐火性骨材粉に配合し、成形、焼成せしめ
てβ′−サイアロンを結合マトリツクスとする耐
火物を造つてもよい。このようなβ′−サイアロ
ン混合素材粉を用いれば、さらに耐火性骨材のマ
トリツクスが改質され、緻密性、寸法安定性に優
れ、しかもとくに耐アルカリ性、耐熱衝撃性、機
械的強度を向上した耐火物を得ることができる。
また、本発明においては必要に応じて、β′−
サイアロン主成分素材粉と耐火性骨材粉とからな
る成形体を窒素含有非酸化性雰囲気中で1600〜
2000℃の温度にて焼成（一次焼成）せしめた後、
さらに同雰囲気中で前記焼成温度より30℃以上低
く、かつ1500〜1750℃の温度範囲にて焼成（二次
焼成）せしめてもよい。このような二次焼成を行
なえば、結合相の固溶反応、焼結が促進され、よ
り緻密で均質なβ′−サイアロンからなるマトリ
ツクスが形成され、とくに耐蝕性、耐酸化性、耐
摩耗性、強度が向上された耐火物を得ることがで
きる。
上記二次焼成の温度範囲を限定した理由は二次
焼成温度が一次焼成温度（1600〜2000℃）より30
℃未満の低い温度にすると、マトリツクスの粒子
生長が進み過ぎて急激な固体拡散が行なわれるた
め、寸法安定性の優れた耐火物が得られないから
である。しかも二次焼成温度を1500℃未満にする
と、固体拡散が十分行なわれず、マトリツクスの
特性向上化が図れず、一方その温度が1750℃を越
えると、粒子生長が進み過ぎて寸法安定性の優れ
た耐火物が得られなくなる。なお二次焼成温度の
保持時間は、１時間以上、好ましくは４時間以上
にすることが適当である。
しかして、本発明は平均粒径を規定した微細な
β′−サイアロン主成分素材粉を、炭化珪素、ア
ルミナ、ムライト、ジルコン、ジルコニア、β′
−サイアロン、窒化アルミニウムポリタイプサイ
アロン及び窒化珪素から選ばれる１種または２種
以上の耐火性骨材粉に配合し、成形し、これを窒
素含有非酸化ガス雰囲気中で所定温度範囲にて焼
成せしめることによつて、微細なβ′−サイアロ
ン主成分素材粉同志の焼結を容易にし亀裂、変形
を生じにくくすると共に、耐火性骨材の配合によ
る焼成収縮の抑制、寸法安定性の向上が図られ
る。また、焼成時に結合相中のβ′−サイアロン
以外の物質の一部がβ′−サイアロンに変換され
て、骨材のマトリツクスの充分な量のβ′−サイ
アロンが生成されると共に、マトリツクス成分と
骨材成分との間に固溶反応が生じて骨材とマトリ
ツクスとの結合が著しく強固となり、かつ、その
β′−サイアロン自体の優れた特性が発揮され
る。その結果、高強度で優れた耐摩耗性、溶融金
属に対する耐蝕性、耐酸化性、耐酸性及び耐アル
カリ性を有するβ′−サイアロンを結合マトリツ
クスとする耐火物を得ることができる。しかも骨
材の配合による焼成収縮の抑制、寸法安定性の向
上化が図られるため、大型形状の耐火物の製造が
可能となる。
したがつて、本発明により得たβ′−サイアロ
ンを結合マトリツクスとする耐火物は、上述した
種々の優れた特性を有するため、次に示すような
多種多様の分野に応用できる。
溶融非鉄金属用耐火物
溶融炉ライニング材、溶融非鉄金属輸送用パ
イプの内張材、溶融非鉄金属測温用熱電対保護
管、低圧鋳造用ストーク、連続鋳造用ノズル、
タツプホール用インサートノズル、溶融非鉄金
属流量調整弁、溶融非鉄金属用ポンプ摺動部材
（ホツトチヤンバーのピストン、シリンダー、
グーズネツク）、ゲルマニウム或いはシリコン
等の半導体溶融用ルツボ。
溶鋼用耐火物
連続鋳造用各種ノズル、スライデイングノズ
ル用プレート、イマージヨンパイプ。
機械部品
熱交換器、ピストンエンジンにおけるピスト
ンヘツド及びシリンダー、ガスタービンエンジ
ンの燃焼室構造材（ロータ、ステータ、シユラ
ウド等）、ロケツトノズル。
耐蝕材料
耐酸、耐アルカリ容器、塩素或いは硫化水素
ガスの輸送用パイプ、塩基ガス吹込管、プラス
チツクなどの焼成炉の内張材。
次に、本発明の実施例を説明する。
実施例 １
蒸発シリカ粉末60重量％とアルミニウムのアト
マイズ粉（250メツシユ以下）40重量％とをＶミ
キサーで乾式混合した出発原料粉を、ラバープレ
ス（1ton／cm2）により肉厚５cmのチツプ状圧粉体
とした後、この圧粉体を窒素雰囲気中で昇温速度
200℃／Hrの条件下にて1500℃まで高め、その温
度下で10時間保持して加熱処理せしめβ′−サイ
アロン主成分素材を造つた。このβ′−サイアロ
ン主成分素材をＸ線粉末回析法で調べたところ、
β′−サイアロンの大きなピークとα−Al2O3及
びＹ−相サイアロンの小さなピークとが確認さ
れ、ほぼβ′−サイアロンからなることが判つ
た。
その後、上記β′−サイアロン主成分素材をジ
ヨークラツシヤーで粗粋し、さらにハンマークラ
ツシヤーで細粉砕した後、この細粉をアルコール
中にアルミナ製ボールを混入した湿式粉砕法にて
70時間粉砕して平均粒径1.2μのβ′−サイアロン
主成分素材粉を造つた。
次いで、上記β′−サイアロン主成分素材粉と
粒度分布をもつ炭化珪素粉とを下記第１表の如き
割合で混合し、水を少量加えて充分混練し、ラバ
ープレス（1ton／cm2）により成形して50〓×200L
mmの大型円柱状の成形体とした後、この成形体を
窒化硼素と炭化珪素の混合粉末中に埋設し、窒素
雰囲気中で昇温速度100℃／Hrの条件下にて1750
℃まで高め、その温度下で３時間保持して焼結せ
しめ、β′−サイアロンを結合マトリツクスとす
る耐火物を得た。
得られた耐火物の物性を調べ、その結果を同第
１表に併記した。
The present invention relates to a method for producing a refractory using β'-sialon as a bonding matrix. Various refractories have been proposed in the past, including oxide refractories such as alumina refractories and silicon carbide refractories. However, the former oxide-based refractories have low strength and
Since the hardness is low, the wear resistance is poor, and the matrix is fragile, the corrosion resistance against molten metal is generally low, and furthermore, it has the disadvantage of being susceptible to softening under load and creep. On the other hand, the latter silicon carbide refractory has good thermal shock resistance, strength, and hardness, but has the problem of low corrosion resistance against molten metal and poor wear resistance. For these reasons, recently, β'-sialon reaction sintered refractories and dense β'-sialon sintered refractories have been proposed. The former β'-Sialon reaction sintered refractories have higher strength than conventional refractories, and are significantly superior in thermal shock resistance, corrosion resistance to molten metal, acid resistance, and alkali resistance. It has a fatal drawback of poor oxidation resistance, and in particular, that it is impossible to obtain a large-sized product because the reactive N 2 gas cannot penetrate into the inside of the sintered body during manufacturing. On the other hand, the latter dense β'-sialon sintered refractory has higher strength and hardness than conventional refractories, and has excellent wear resistance, corrosion resistance to molten metal, oxidation resistance, acid resistance, and alkali resistance. However, on the other hand, the shrinkage during firing is large and the dimensional stability is poor, and it is difficult to manufacture large-sized products due to easy firing deformation.Furthermore, the thermal shock resistance is poor, and cracks occur when large-sized products are made. , it has the disadvantage of being easily damaged. The present invention was made to eliminate the above-mentioned drawbacks, and it has high strength, excellent wear resistance, corrosion resistance to molten metal, oxidation resistance, acid resistance, and alkali resistance, as well as the conventional β' - The aim is to improve the thermal shock resistance and dimensional stability, which are the drawbacks of sialon sintered refractories, and to provide a method for manufacturing refractories using β'-sialon as a bonding matrix, which enables the production of large-sized products. It is. The present invention will be explained in detail below. First, a β'-sialon main component material (usually containing 70 to 80% by weight of β'-sialon) is produced by the following method. (1) 70 to 40% by weight of silica powder and 30 to 60% by weight of metal aluminum powder are thoroughly mixed to obtain a starting material powder, and this starting material powder is processed by various molding methods such as metal press method, rubber press method, slip molding method, etc. After forming a green compact into any shape with a wall thickness of 5 cm or less, preferably 2 cm or less by casting or extrusion, the green compact is heated to 1400 to 1700°C in a nitrogen-containing non-oxidizing gas atmosphere. A β'-Sialon main component material in a solid solution state is produced using the following steps. (2) A starting raw material powder, which is a mixture of 70 to 40% by weight of silica powder and 30 to 60% by weight of metallic aluminum powder, is once pulverized to have an average particle size of 3μ or less, preferably 1.5μ.
After filling the fine powder raw material into a heat-resistant container to a depth of 5 cm or less, preferably 2 cm or less, the fine powder raw material is heated at a temperature of 1400 to 1700 °C in a nitrogen-containing non-oxidizing gas atmosphere. A heating reaction is carried out to produce a β'-SiAlON main component material in a solid solution state. (3) Metal powders such as iron powder, copper powder, cobalt powder, manganese powder, or their oxide powders are added to 100 parts by weight of a mixed powder consisting of 70 to 40% by weight of silica powder and 30 to 60% by weight of metallic aluminum powder. Alternatively, 0.1 to 10 parts by weight of one or more additives selected from the group of fluoride powders such as calcium fluoride, aluminum fluoride, magnesium fluoride powder, manganese fluoride powder, etc. are added and mixed to prepare the starting material. This starting raw material powder is made into a green compact according to the method (1) above, or into a fine powder raw material according to the method (2) above, and then heated in a nitrogen-containing non-oxidizing atmosphere. The material is heated at a temperature of 1,200 to 1,700°C to produce a β'-SiAlON main component material in a solid solution state. Chemical reaction during heating in the methods (1) to (3) above,
Although the details of the chemical change are unknown, it is thought that the following reaction basically occurs. (i) Below 1000℃, 3SiO 2 +4Al→3Si+2Al 2 O 3 ………() 2Al+N 2 →2AlN ………() (ii) Above 1000℃, 3Si+2N 2 →β−Si 3 N 4 ……… () Solid solution of Al 2 O 3 and AlN in β-Si 3 N 4 → β′-sialon main component material 〓……() 〓 β′-sialon main component material; β′-sialon is the main component However, there are other undissolved
Al 2 O 3 , Y-phase sialon (in the AlN structure)
Contains Si and O, metal:nonmetal atomic ratio is 5:6
Chemical formula (Si, Al) 2 (O, N) 6
), AlN, etc. Examples of the silica powder used in methods (1) to (3) above include quartz powder, silica sand powder, quartz glass powder, volatilized-silica, chemically precipitated silica, and vapor-phase silica. In particular, evaporated silica has the best yield of β'-sialon-based material. In this case, it is possible to use Shirasu as the silica powder, but due to its high content of alkaline components, it may contaminate the furnace core tube, lining refractories, insulation refractories, resistors, heating elements, etc. of the heating furnace during heating. This is not desirable because it deteriorates. The aluminum powder used in methods (1) to (3) above has the same effect as either teardrop-shaped atomized aluminum powder (sprayed) or scale-shaped ground powder, but it is especially finer than 50 mesh. It is preferable to use powder. The reason why the ratio of silica powder to aluminum powder (SiO 2 powder/Al powder) in methods (1) to (3) above is limited to the above range is that the ratio of SiO 2 powder/Al powder is 40/60 (by weight). If it is made smaller than the ratio), unreacted Al may remain or Si and AlN may be generated, resulting in β′
- The amount of β'-sialon produced in the sialon-based material decreases, and on the other hand, if the ratio is more than 70/30,
This is because unreacted SiO 2 remains or mullite is generated, which reduces the amount of β'-sialon produced in the main component material, and the preferred ratio is around 60/40 SiO 2 powder/Al powder. It is. In addition, the reason for limiting the thickness of the green compact in methods (1) and (3) above is that if the wall thickness exceeds 5 cm, nitrogen gas will not penetrate sufficiently into the green compact during heating, and β ′
- This is because a β'-sialon main component material with a high sialon production rate cannot be obtained. In methods (2) and (3) above, the reason why the filling depth of the finely powdered raw material is limited is that if the filling depth exceeds 5 cm, nitrogen gas will not penetrate sufficiently into the packed raw material during heating. , β′- with high production rate of β′-sialon
This is because the main component material of Sialon cannot be obtained.
The containers used in this case are usually graphite,
The container is made of silicon nitride or alumina, but especially when using a graphite container, it is desirable to coat the inner surface with aluminum nitride powder or boron nitride powder in order to prevent the formation of silicon carbide. The reason for limiting the amount of additives added to the mixed powder consisting of silica powder and aluminum powder in the method (3) above is to limit the amount of additives to the above range.
If the amount is less than 0.1 part by weight, the effect of promoting the reactions of formulas () to () above cannot be expected, while if the amount exceeds 10 parts by weight, the purity of the obtained β'-Sialon main component material will be inhibited. Because it does. Furthermore, the reason for limiting the heat treatment temperature in methods (1) and (2) above is that if the heat treatment temperature is lower than 1400°C, unreacted Si remains and β'- This is because the production rate of sialon decreases, and on the other hand, if the temperature exceeds 1700°C, Y-phase sialon increases and the production rate of β'-sialon in the β'-sialon-based material decreases. In addition, in method (3) above, the heat treatment temperature is 1200°C, which is 200°C lower than the temperature in methods (1) and (2) above.
This is possible even at temperatures as low as ℃. A desirable heat treatment method is 1400 to 1500 at a heating rate of 600℃/Hr or less, preferably 200℃/Hr or less.
℃ or 1,200 to 1,500℃, and the temperature is maintained for 5 hours or more (this is referred to as the first stage heat treatment). This achieves the purpose of the heat treatment, but in order to further improve the production rate of β'-Sialon, it is necessary to add an additional 1500 to 1700
The temperature is raised to a predetermined temperature between 0.degree. However, in the method (1) above, the starting raw material powder having the above-mentioned composition ratio is molded into a green compact, and the thickness of the green compact is specified, so that the silica powder and the aluminum powder are combined. Since the contact situation becomes good and the degree of contact of nitrogen gas with each powder is also improved, the reactions of formulas () to () described above are promoted, and the β'-sialon main component material with a high content of β'-sialon is obtained. is obtained. In addition, in the method (2) above, by pulverizing the starting raw material powder having the above-mentioned composition ratio to obtain a finely powdered raw material, and by specifying the filling depth of the raw material into the container, the pulverization and mixing The aluminum powder with excellent malleability coats the silica powder to form an aluminum film, which improves the contact between aluminum and silica and improves the degree of contact of nitrogen gas with each raw material. )～()
reaction is promoted, and a β'-sialon-based material with a high content of β'-sialon can be obtained. Furthermore, in the method (3) above, in addition to molding or pulverizing the starting raw material powder, iron is added to the raw material powder.
In order to mix additives such as magnesia, the above-mentioned
The reaction is further promoted than methods (1) and (2), and the β′-sialon content is extremely high.
Sialon-based material is obtained. In addition to the above-mentioned method, in order to obtain the β'-SiAlON main component material, (4) metal silicon powder is further added to and mixed with silica powder and metal aluminum powder as a starting material, and the above-mentioned (1) to A method of performing nitriding firing according to method (3), (5) mixing and finely pulverizing two or more of each powder of silicon nitride, aluminum nitride, alumina, and silica in an appropriate proportion, shaping and pressing. A method of obtaining a β'-Sialon main component material by heating the powder to 1,600 to 2,000°C in a nitrogen-containing non-oxidizing atmosphere and reacting (including solid solution reaction); (6) Metallic silicon powder The starting material is a mixed powder of aluminum powder and alumina powder, or a powder obtained by adding and mixing metal aluminum powder or aluminum nitride powder, and the green compact is heated in a nitrogen-containing non-oxidizing atmosphere.
A method of heating and reacting at 1400 to 1700°C to obtain a β'-sialon main component material can be carried out. Next, β′ obtained by the methods (1) to (3) described above
- Sialon main component material is finely pulverized until the average particle size (measured with a Fishery Subsieve Sizer) is 1.6 μ or less, preferably 1.2 μ or less to obtain β'-Sialon main component material powder. Next, this main component material powder is converted into one or more types of refractory aggregate powder selected from silicon carbide, alumina, mullite, zircon, zirconia, β'-sialon, aluminum nitride polytype sialon, and silicon nitride. After blending and thoroughly mixing, this is molded by various molding methods such as mold pressing, rubber pressing, slip casting, extrusion molding, etc., and then the molded product is placed in a nitrogen-containing non-oxidizing gas atmosphere (nearly the atmosphere). (same pressure) at a temperature of 1,600 to 2,000°C to produce a refractory with β'-sialon as a bonding matrix. In the present invention, a wet pulverization method and a dry pulverization method are adopted as a method for pulverizing the β'-sialon main component material, but a wet pulverization method using a tungsten carbide or alumina ball mill in alcohol is particularly short. It is effective because it can be crushed in a short amount of time. The reason why the particle size of the main component material powder of β'-sialon in the present invention is limited is that if the particle size of the main component material powder exceeds 1.6μ, the β'-sialon in the matrix will not become dense and the strength will decrease. This is because refractories with desired characteristics cannot be obtained. The refractory aggregate powder used in the present invention is desirably used in the form of coarse, medium, or fine particles from the viewpoint of achieving good close-packing properties. A small amount of the substance may be added. In addition, especially when alumina, mullite, β'-sialon, aluminum nitride polytype sialon, or silicon nitride is blended as the refractory aggregate powder, solid solution between the β'-sialon main material and the aggregate components may occur. The reaction becomes remarkable, and as a result, the bond between the aggregate and the matrix improves, making it possible to obtain a refractory with even better properties. In addition, when using silicon carbide as a fire-resistant aggregate, an oxide film is formed on the surface of the silicon carbide powder in advance in order to improve the bond between the aggregate and the matrix (consisting of β'-SiAlON). This is desirable. In the present invention, the blending ratio of the β'-sialon main component material powder and the fire-resistant aggregate powder is usually 20 to 40% by weight of the β'-sialon main component material powder, and the refractory aggregate powder.
It may be 80 to 60% by weight. Examples of the nitrogen-containing non-oxidizing gas used in the present invention include nitrogen gas alone, or a mixture of nitrogen gas and an inert gas such as argon gas or neon gas, or hydrogen gas or ammonia gas. The reason why the firing temperature in the present invention is limited to the above range is that if the firing temperature is lower than 1600°C, the sintering speed of the compact will be slow and it will take a long time to obtain the desired refractory. When the temperature exceeds 2000℃,
This is because a portion of the β'-sialon in the main component material powder is converted to Y-phase sialon, and a sufficient amount of β'-sialon cannot be produced in the aggregate matrix, resulting in a decrease in performance. It is desirable that the holding time under such a firing temperature be usually 1 to 5 hours. The reason for this is that if the holding time is less than 1 hour, the compact cannot be sufficiently sintered;
This is because, if the time is exceeded, the grain growth of the β'-sialon main component material in the molded body will progress too much and the properties (especially strength) of the obtained refractory will deteriorate. In addition, the temperature increase rate during firing should be 200°C/Hr or less, preferably 100°C/Hr or less, from the viewpoint of suppressing rapid sintering shrinkage of the compact to prevent cracks and reduction in dimensional accuracy. desirable. The firing furnace used during sintering is usually a graphite-lined furnace equipped with a graphite resistance heater and a high-frequency induction heating type graphite susceptor. Since a certain amount of CO gas is generated from the heater etc., the matrix made of β'-sialon of the obtained refractory is likely to be carbonized and a silicon carbide film will be formed on the surface. Furthermore, during firing, it is difficult to uniformly fire the molded body at the same temperature, which may result in cracks in the refractory. Further, during firing, the SiO 2 component and Si 3 N 4 component of the molded body are volatilized, causing cracks and porosity. However, to solve this problem, boron nitride powder (BN),
The molded bodies are buried in graphite containers filled with non-reactive filler made of silicon nitride powder (Si 3 N 4 ), and each container is placed in a furnace to be fired uniformly and coated on the surface of the refractory matrix. It is desirable to prevent the formation of a silicon carbide film and to prevent the volatilization of the SiO 2 component and the Si 3 N 4 component. In addition, in the present invention, if necessary, the above-mentioned β'-sialon main component material powder may be added with a particle size of 1 to 5 μm.
0.5 to 40% by weight of any one or more of silicon carbide powder and aluminum nitride powder of about 10% to 40% by weight is mixed to obtain β'-sialon mixed material powder, and this mixed material powder is blended with fire-resistant aggregate powder, A refractory having β'-sialon as a bonding matrix may be produced by molding and firing. If such β'-Sialon mixed material powder is used, the matrix of the refractory aggregate will be further modified, resulting in excellent compactness and dimensional stability, as well as improved alkali resistance, thermal shock resistance, and mechanical strength. Refractories can be obtained. In addition, in the present invention, β'-
A molded body consisting of Sialon main component material powder and refractory aggregate powder is heated to 1600 ~
After firing at a temperature of 2000℃ (primary firing),
Furthermore, firing (secondary firing) may be performed in the same atmosphere at a temperature range of 1500 to 1750°C, which is 30°C or more lower than the firing temperature. If such secondary firing is performed, the solid solution reaction and sintering of the binder phase will be promoted, forming a denser and more homogeneous matrix of β'-sialon, which will have particularly good corrosion resistance, oxidation resistance, and wear resistance. , a refractory with improved strength can be obtained. The reason for limiting the temperature range of the secondary firing above is that the secondary firing temperature is 30° higher than the primary firing temperature (1600-2000℃)
This is because if the temperature is lower than .degree. C., the growth of particles in the matrix will proceed too much and rapid solid diffusion will occur, making it impossible to obtain a refractory with excellent dimensional stability. Moreover, if the secondary firing temperature is lower than 1500°C, solid diffusion will not be sufficient and the properties of the matrix cannot be improved, whereas if the temperature exceeds 1750°C, particle growth will proceed too much, resulting in a matrix with excellent dimensional stability. Refractories cannot be obtained. Note that it is appropriate that the secondary firing temperature be maintained for 1 hour or more, preferably 4 hours or more. Therefore, the present invention uses fine β'-SiAlON main component material powder with a defined average particle size, such as silicon carbide, alumina, mullite, zircon, zirconia, β'
- Blended with one or more types of refractory aggregate powder selected from Sialon, aluminum nitride polytype Sialon and silicon nitride, molded, and fired at a predetermined temperature range in a nitrogen-containing non-oxidizing gas atmosphere. In particular, this makes it easier to sinter the fine β'-Sialon main component material powder, making it less likely to cause cracks and deformation, as well as suppressing firing shrinkage and improving dimensional stability by incorporating refractory aggregate. It will be done. In addition, during calcination, a part of the substances other than β'-sialon in the binder phase is converted to β'-sialon, and a sufficient amount of β'-sialon is generated in the aggregate matrix, and the matrix component A solid solution reaction occurs between the aggregate components and the bond between the aggregate and the matrix becomes extremely strong, and the excellent properties of β'-sialon itself are exhibited. As a result, it is possible to obtain a refractory having β'-sialon as a bonding matrix, which has high strength and excellent wear resistance, corrosion resistance against molten metal, oxidation resistance, acid resistance, and alkali resistance. Furthermore, since shrinkage during firing is suppressed and dimensional stability is improved by blending the aggregate, it becomes possible to manufacture large-sized refractories. Therefore, the refractories having β'-sialon as a bonding matrix obtained according to the present invention have the various excellent properties described above, and can be applied to a wide variety of fields as shown below. Refractories for molten nonferrous metals Melting furnace lining materials, lining materials for pipes for transporting molten nonferrous metals, thermocouple protection tubes for temperature measurement of molten nonferrous metals, stalks for low-pressure casting, nozzles for continuous casting,
Insert nozzles for tapholes, molten nonferrous metal flow rate adjustment valves, pump sliding parts for molten nonferrous metals (hot chamber pistons, cylinders,
crucible for melting semiconductors such as germanium or silicon. Refractories for molten steel Various nozzles for continuous casting, plates for sliding nozzles, and immersion pipes. Mechanical parts Heat exchangers, piston heads and cylinders in piston engines, combustion chamber structural materials (rotors, stators, shrouds, etc.) in gas turbine engines, rocket nozzles. Corrosion-resistant materials Acid- and alkali-resistant containers, pipes for transporting chlorine or hydrogen sulfide gas, base gas injection pipes, and lining materials for firing furnaces such as plastics. Next, examples of the present invention will be described. Example 1 A starting raw material powder obtained by dry mixing 60% by weight of evaporated silica powder and 40% by weight of atomized aluminum powder (250 mesh or less) in a V-mixer was formed into chips with a wall thickness of 5cm using a rubber press (1 ton/cm 2 ). After making a compact, the temperature increase rate of the compact in a nitrogen atmosphere is
The temperature was raised to 1500°C under the conditions of 200°C/Hr, and the temperature was maintained for 10 hours for heat treatment to produce a β'-sialon-based material. When this β'-Sialon main component material was examined using X-ray powder diffraction method, it was found that
A large peak of β'-sialon and small peaks of α-Al 2 O 3 and Y-phase sialon were confirmed, and it was found that the sample consisted almost entirely of β'-sialon. After that, the above-mentioned β'-sialon main component material was coarsely crushed with a geo crusher, further finely crushed with a hammer crusher, and then this fine powder was subjected to a wet crushing method using alumina balls mixed in alcohol.
After 70 hours of pulverization, a β'-Sialon main component material powder with an average particle size of 1.2μ was produced. Next, the above β'-Sialon main component material powder and silicon carbide powder having a particle size distribution were mixed in the proportions shown in Table 1 below, a small amount of water was added, the mixture was thoroughly kneaded, and the mixture was mixed with a rubber press (1 ton/cm 2 ). Molded into 50〓×200 L
After forming a large cylindrical molded body with a diameter of 1.5 mm, this molded body was embedded in a mixed powder of boron nitride and silicon carbide, and heated to 1750°C under a temperature increase rate of 100°C/Hr in a nitrogen atmosphere.
℃ and held at that temperature for 3 hours to sinter, yielding a refractory having β'-sialon as a bonding matrix. The physical properties of the obtained refractories were investigated, and the results are also listed in Table 1.
【表】
上記第１表から明らかな如く、本発明の耐火物
は高強度で、寸法安定性、溶融金属に対する耐蝕
性、耐化学的安定性及び耐酸化性等全ての性質に
おいて著しく優れていることがわかる。また、大
型形状としても耐火物に亀裂を生じず、全体的に
均一性状を示した。
実施例 ２
前記実施例１と同様なβ′−サイアロン主成分
素材粉（平均粒径1.2μ）と粒度分布をもつアル
ミナ粉とを下記第２表に示す如き割合で混合し、
これを前記実施例１と同条件下で成形、窒化焼成
せしめてβ′−サイアロンを結合マトリツクスと
する耐火物を得た。この耐火物の物性を調べ、そ
の結果を同第２表に併記した。[Table] As is clear from Table 1 above, the refractory of the present invention has high strength and is extremely superior in all properties such as dimensional stability, corrosion resistance to molten metal, chemical stability, and oxidation resistance. I understand that. In addition, even in a large-sized refractory, cracks did not occur in the refractory, and the properties were uniform throughout. Example 2 The same β'-sialon main component material powder (average particle size 1.2μ) as in Example 1 and alumina powder having a particle size distribution were mixed in the proportions shown in Table 2 below,
This was molded and nitrided and fired under the same conditions as in Example 1 to obtain a refractory having β'-sialon as a bonding matrix. The physical properties of this refractory were investigated, and the results are also listed in Table 2.
【表】
以上詳述した如く、発明によれば高強度で、優
れた耐摩耗性、溶融金属に対する耐蝕性、耐酸化
性、耐酸性、及び耐アルカリ性を有することは勿
論、従来のβ′−サイアロン焼結体耐火物の欠点
である耐熱衝撃性と寸法安定性を改良し、大型形
状の製作が可能となり、溶融非鉄金属用耐火物、
溶融用耐火物などの広範囲の分野に有効に利用で
きるβ′−サイアロンを結合マトリツクスとする
耐火物を提供できるものである。[Table] As detailed above, the present invention not only has high strength, excellent wear resistance, corrosion resistance to molten metal, oxidation resistance, acid resistance, and alkali resistance, but also has the conventional β'- Thermal shock resistance and dimensional stability, which are disadvantages of Sialon sintered refractories, have been improved, making it possible to manufacture large-sized shapes, making it possible to produce refractories for molten nonferrous metals,
It is possible to provide a refractory having β'-sialon as a bonding matrix, which can be effectively used in a wide range of fields such as refractories for melting.
Claims (1)
以下に粉砕してβ′−サイアロン主成分素材粉と
し、該主成分素材粉を、炭化珪素、アルミナ、ム
ライト、ジルコン、ジルコニア、β′−サイアロ
ン、窒化アルミニウムポリタイプサイアロン、及
び窒化珪素から選ばれる１種または２種以上の耐
火性骨材粉に配合、混合し、これを成形して成形
体とした後、この成形体を窒素含有非酸化性ガス
雰囲気中で1600〜2000℃の温度下にて焼成せしめ
ることを特徴とするβ′−サイアロンを結合マト
リツクスとする耐火物の製造方法。1 β′-Sialon main component material with average particle size of 1.6μ
The main component material powder is selected from silicon carbide, alumina, mullite, zircon, zirconia, β'-sialon, aluminum nitride polytype sialon, and silicon nitride. After blending and mixing with one or more types of refractory aggregate powder and molding this into a molded body, this molded body is heated at a temperature of 1600 to 2000°C in a nitrogen-containing non-oxidizing gas atmosphere. 1. A method for producing a refractory using β'-sialon as a bonding matrix, characterized in that the refractory is fired by heating.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11633777A JPS5450015A (en) | 1977-09-28 | 1977-09-28 | Method of making refractory using betaasialon as binding matrix |
| DE2805292A DE2805292C2 (en) | 1977-09-28 | 1978-02-08 | Method for producing a sintered body |
| US05/878,393 US4243621A (en) | 1977-09-28 | 1978-02-16 | β'-Sialon sintered body and a method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11633777A JPS5450015A (en) | 1977-09-28 | 1977-09-28 | Method of making refractory using betaasialon as binding matrix |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5450015A JPS5450015A (en) | 1979-04-19 |
| JPS6210954B2 true JPS6210954B2 (en) | 1987-03-09 |
Family
ID=14684451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11633777A Granted JPS5450015A (en) | 1977-09-28 | 1977-09-28 | Method of making refractory using betaasialon as binding matrix |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5450015A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5827232B2 (en) * | 1979-08-07 | 1983-06-08 | 川崎製鉄株式会社 | Monolithic refractories with excellent corrosion resistance |
| JPS57129873A (en) * | 1981-01-29 | 1982-08-12 | Toshiba Ceramics Co | Refractories |
| JPS5895646A (en) * | 1981-11-30 | 1983-06-07 | 旭硝子株式会社 | Silicon carbide sintered body and manufacture |
| JPS60145961A (en) * | 1983-12-31 | 1985-08-01 | 工業技術院長 | Manufacture of high strength heat resistant ceramic sinteredbody |
| SE451581B (en) * | 1984-04-06 | 1987-10-19 | Sandvik Ab | CERAMIC MATERIAL MAINLY BASED ON SILICON NITRIDE, ALUMINUM NITRIDE AND ALUMINUM OXIDE |
| JPS6197165A (en) * | 1984-10-17 | 1986-05-15 | 東京高級炉材株式会社 | Beta' sialon bonding silicon carbide material and manufacture |
| JPH0617272B2 (en) * | 1986-02-12 | 1994-03-09 | 株式会社日本自動車部品総合研究所 | Silicon nitride-alumina composite ceramics and method for producing the same |
| JPH02296770A (en) * | 1989-05-12 | 1990-12-07 | Ngk Spark Plug Co Ltd | Nonoxide-oxide-based ceramic composite material |
-
1977
- 1977-09-28 JP JP11633777A patent/JPS5450015A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5450015A (en) | 1979-04-19 |
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