JPH0497942A - Production of mullite-zirconia composite ceramics - Google Patents
Production of mullite-zirconia composite ceramicsInfo
- Publication number
- JPH0497942A JPH0497942A JP2216726A JP21672690A JPH0497942A JP H0497942 A JPH0497942 A JP H0497942A JP 2216726 A JP2216726 A JP 2216726A JP 21672690 A JP21672690 A JP 21672690A JP H0497942 A JPH0497942 A JP H0497942A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- mullite
- zirconia
- stabilizer
- sintering
- 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.)
- Pending
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000919 ceramic Substances 0.000 title claims description 17
- 239000002131 composite material Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 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 abstract description 26
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
本発明は、低温での焼結性に優れ、高強度 高靭性の焼
結体が得られるムライト・ジルコニア複合セラミックス
の製造方法に関するものである。The present invention relates to a method for producing a mullite-zirconia composite ceramic that has excellent sinterability at low temperatures and can yield a sintered body with high strength and toughness.
ムライトは３Ａｆｆｉ□０．・２Ｓ Ｓｏ□の化学組成
を有するケイ酸アルミニウムであり、化学工業磁器、耐
火物中に含まれる結晶相として知られていたが、その高
純度焼結体は裔温強度、耐クリープ抵抗性、低熱膨張率
等の熱的・機械特性に優れ、高温構造材料セラミックス
としての応用が進みつつある。
しかしながら、ムライトは窒化ケイ素（ＳｉｓＮ４）、
炭化ケイ素（Ｓ ｉ Ｃ） 、部分安定化ジルコニア（
ｐｓｚ）等の構造材料用セラミックスに比較して、室温
における抗折強度、破壊靭性が低く、これらの機械的特
性の改善が望まれている。
そして、これらの機械的特性の改善方法として、ＳｉＣ
やＳｉ、Ｎａウィスカー（ひげ状単結晶）などとの複合
化やＺｒＯ□あるいはＡ１．Ｏｈのような粒子を分散複
合強化する方法が提案されている。
尚、これらの技術のうち前者のものは、ムライト粉末と
ウィスカーとの乾式又は湿式混合によることが多く、そ
して後者のものは、乾式又は湿式混合の他、ゾル−ゲル
法とか共沈法などが採用される。Mullite is 3Affi□0.・It is an aluminum silicate with a chemical composition of 2S So□, and was known as a crystalline phase contained in chemical industrial porcelain and refractories, but its high purity sintered body has high temperature strength, creep resistance, It has excellent thermal and mechanical properties such as a low coefficient of thermal expansion, and its application as a high-temperature structural ceramic material is progressing. However, mullite is silicon nitride (SisN4),
Silicon carbide (S i C), partially stabilized zirconia (
Compared to ceramics for structural materials such as PSZ), it has lower bending strength and fracture toughness at room temperature, and improvements in these mechanical properties are desired. As a method for improving these mechanical properties, SiC
, Si, Na whiskers (beard-like single crystals), ZrO□ or A1. A method of dispersing and composite reinforcement of particles such as Oh has been proposed. The former of these techniques is often based on dry or wet mixing of mullite powder and whiskers, and the latter involves dry or wet mixing, as well as the sol-gel method and coprecipitation method. Adopted.
【発明が解決しようとする！題］
ところで、上記のような技術にあっては、次のような問
題点がある。
すなわち、前者の技術では、この系が難焼結性であるこ
とから、高い焼結温度（一般に１６００°Ｃ以上）、特
殊な焼成雰囲気、熱間加圧焼結などの特殊な装置を必要
とする。
後者の技術では、比較的高い焼結温度が必要とされてお
り、特にＺｒｏｚ分散強化系では大きな問題がある。す
なわち、高温度での焼結は、分散されたＺｒ○、の粒成
長を引き起こし、この為正方晶Ｚｒ○２の単斜晶化が起
こってしまい、応力誘起強靭化の寄与が小さくなり（こ
の寄与は正方晶ＺｒＯ□が多い程大きい）、強度向上は
あまり望めない。
−そこで、本発明の第１の目的は、易焼結性（すなわち
、大気中・常圧焼結・焼結温度の低下）を実現すること
である。
本発明の第２の目的は、Ｚｒｏｚ分散強化系における準
安定正方晶Ｚｒ０ｚの比率を向上させ、高強度・高靭性
の焼結体を得ることである。
【課題を解決する為の手段】
上記本発明の目的は、ベーマイトゾルとシリカゾルとを
混合してムライト組成ゾルを調整するムライト組成ゾル
調整工程と、ジルコニアゾルに安定化剤を添加するジル
コニア−安定他剤混合ゾル調整工程と、前記ムライト組
成ゾルと前記ジルコニア−安定他剤混合ゾルとを混合し
てゲル化するゲル化工程と、このゲル化工程で得たもの
を仮焼する仮焼工程と、仮焼工程で得た仮焼物を成形し
て焼結する焼結工程とを具備することを特徴とするムラ
イト・ジルコニア複合セラミックスの製造方法によって
達成される。
尚、このムライト・ジルコニア複合セラミックスの製造
方法において、ムライト組成ゾル調整工程ではベーマイ
トゾルとシリカゾルと焼結助剤とが混合されてムライト
組成ゾルが調整されるものが好ましい。
焼結助剤としてはＭ ｇ Ｏ，、Ｙ２０３ 、Ｔ ｉ
Ｏア、ＦｅｚＯ５の群の中から選ばれる少なくとも一種
のものが用いられる。
又、このムライト・ジルコニア複合セラミックスの製造
方法において、ベーマイトゾルとシリカゾルのＡｊ２ｚ
Ｃｈ ／Ｓ ｉ Ｏ□のモル比は約１．３７〜１．７
６であることが望ましく、そしてＭｇＯ１Ｙｚ Ｏｓ
、Ｔ ｉ Ｏｘ 、Ｆ ｅ ｚ Ｏ３の群の中から選ば
れる少なくとも一種の焼結助剤が用いられる場合には、
ベーマイトゾルとシリカゾルとの合計量１００重量部に
対して焼結助剤は０．０５〜１．５重量部であることが
好ましい。
ベーマイトゾルとしては反応活性の高いベーマイトゾル
を使用することが好ましく、これはガンマ−アルミナ（
Ｔ Ａｌｚ Ｏｓ ）やベーマイト（Ａ！００Ｈ）の
水分散液を８０°Ｃ以上に加熱しながら、硝酸、塩酸等
の無機酸や酢酸、ギ酸等の有ｉ酸を通置加えて、解膠す
ることムこよって得られる。
シリカゾルとしては、シリカ微粒子、例えば湿式法で製
造されるホワイトカーボンや乾式法のヒユームドシリカ
を水中に分散させたコロイド水溶液が好ましい。
又、安定化剤としてはＭｇＯ，Ｙｚ Ｃｈ 、ＣａＯ１
Ｃｅ ０２の群の中から選ばれる少なくとも一種のもの
が用いられる。
尚、このＭｇＯ，Ｙ２０３ 、Ｃａｂ、ＣｅＣＬの群の
中から選ばれる安定化剤は、ムライト１００重量部に対
して０．０５〜２重量部の程度である。これは、安定化
剤の添加量が多くなりすぎると、正方晶ＺｒＯ□の比率
が低下してしまう為である。
そして、ムライト組成ゾルとジルコニア−安定他剤混合
ゾルとの割合は重量比で９０：１０〜６５：３５である
ことが好ましい。
ジルコニアゾルは、例えばオキシ塩化ジルコニウム及び
オキシ硝酸ジルコニウムの群の中から選ばれる少なくと
も一種類のものをジルコニウム源（ジルコニウム源の濃
度は０．３〜２ｅａｏｅ／ｌ）とし、硝酸アンモニウム
、塩化アンモニウム及び硫酸アンモニウムの群の中から
選ばれる少なくとも一種類のアンモニウム塩（後述の尿
素に対してアンモニウム塩の総量は、モル比で０．５倍
以上）及び尿素（ジルコニウム源に対して尿素の量は、
モル比で１〜５倍）が添加され、尿素の分解により製造
される。
尚、ジルコニウムゾルの製造に際して、ジルコニウム源
と尿素の加水分解物との反応時のｐＨは２〜３であるこ
とが好ましい。
又、ジルコニウムゾルの製造に際して、ジルコニウム源
と尿素の加水分解物との反応生成物を濾過、洗浄した後
、酸で解膠することが好ましい。
特に、濾過・水洗時のｐＨは５〜７とすることが好まし
い。又、解膠処理時のＰＨは２．２以下が好ましい。
そして、前記のヘーマイトゾルとシリカゾルをＡ ｐｇ
０３ ／Ｓ ｉ ｏｘのモル比が所定のものとなるよ
う、さらに必要に応してＭｇＯ，Ｙ、Ｏ，、ＴｉＯ□、
Ｆｅ、０３の群の中から選ばれる少なくとも一種の焼結
助剤を加えて、ムライト組成ゾルを調整する。
又、一方、ジルコニアゾルにＭｇＯ１Ｙ７０゜、ＣａＯ
ｌＣｅＯｚＯ群の中から選ばれる少なくとも一種の安定
化剤を添加しジルコニア−安定他剤混合ゾルを調整する
。
次に、上記ムライトｕ成ヅルとノルコニアー安定他剤混
合ゾルとを所定の割合で混合してゲル化させる。
そして、このゲル化物を所定の温度で仮焼し、その後所
定の温度で焼結する。
この焼結温度は、従来のムライト・ジルコニア複合セラ
ミンクスの製造の場合よりも低い温度、例えば１４５０
°Ｃ程度の低い温度でも行え、正方晶１ｒＣ）２の比率
が高く、高強度・高靭性の焼結体が得られる。[Invention tries to solve! [Problem] By the way, the above technology has the following problems. In other words, the former technology requires special equipment such as a high sintering temperature (generally 1600°C or higher), a special firing atmosphere, and hot pressure sintering because this system is difficult to sinter. do. The latter technique requires relatively high sintering temperatures, which is particularly problematic in Zroz dispersion strengthened systems. That is, sintering at high temperatures causes grain growth of dispersed Zr○, which causes monoclinic crystallization of tetragonal Zr○2, reducing the contribution of stress-induced toughening (this The contribution is larger as the amount of tetragonal ZrO□ increases), so it cannot be expected to improve the strength much. - Therefore, the first object of the present invention is to realize easy sinterability (that is, sintering in the atmosphere, normal pressure, and lowering the sintering temperature). A second object of the present invention is to improve the ratio of metastable tetragonal Zr0z in the Zroz dispersion-strengthened system to obtain a sintered body with high strength and high toughness. [Means for Solving the Problems] The object of the present invention is to provide a mullite composition sol adjustment step in which a mullite composition sol is prepared by mixing a boehmite sol and a silica sol, and a zirconia stabilizer in which a stabilizer is added to a zirconia sol. a step of preparing a sol mixed with other agents, a gelling step of mixing and gelling the mullite composition sol and the zirconia-stable mixed sol of other agents, and a calcination step of calcining the product obtained in this gelling step. This is achieved by a method for manufacturing mullite-zirconia composite ceramics, which is characterized by comprising a sintering step of shaping and sintering the calcined product obtained in the calcination step. In this method for producing mullite-zirconia composite ceramics, it is preferable that in the mullite composition sol adjustment step, boehmite sol, silica sol, and sintering aid are mixed to prepare a mullite composition sol. As sintering aids, M g O,, Y203, T i
At least one selected from the group consisting of Oa and FezO5 is used. In addition, in this method for producing mullite-zirconia composite ceramics, Aj2z of boehmite sol and silica sol
The molar ratio of Ch /S i O□ is about 1.37-1.7
6, and MgO1YzOs
When at least one sintering aid selected from the group consisting of , T i Ox , and F ez O3 is used,
The amount of the sintering aid is preferably 0.05 to 1.5 parts by weight based on 100 parts by weight of the total amount of boehmite sol and silica sol. As the boehmite sol, it is preferable to use a boehmite sol with high reaction activity, which is made of gamma-alumina (
While heating an aqueous dispersion of T Alz Os ) or boehmite (A!00H) to 80°C or higher, inorganic acids such as nitric acid or hydrochloric acid or organic acids such as acetic acid or formic acid are added to peptize the aqueous dispersion. You can get it by doing things. The silica sol is preferably a colloidal aqueous solution in which fine silica particles, such as white carbon produced by a wet method or fumed silica produced by a dry method, are dispersed in water. In addition, as stabilizers, MgO, Yz Ch, CaO1
At least one selected from the group of Ce 02 is used. The amount of the stabilizer selected from the group consisting of MgO, Y203, Cab, and CeCL is about 0.05 to 2 parts by weight per 100 parts by weight of mullite. This is because if the amount of stabilizer added is too large, the ratio of tetragonal ZrO□ will decrease. The weight ratio of the mullite composition sol and the zirconia-stabilizing agent mixed sol is preferably 90:10 to 65:35. Zirconia sol uses, for example, at least one kind selected from the group of zirconium oxychloride and zirconium oxynitrate as a zirconium source (the concentration of the zirconium source is 0.3 to 2 eaoe/l), and contains ammonium nitrate, ammonium chloride, and ammonium sulfate. At least one type of ammonium salt selected from the group (total amount of ammonium salt to urea described below is 0.5 times or more in molar ratio) and urea (the amount of urea to zirconium source is
(1 to 5 times the molar ratio) is added and produced by decomposition of urea. In the production of zirconium sol, the pH during the reaction between the zirconium source and the urea hydrolyzate is preferably 2 to 3. Further, in producing the zirconium sol, it is preferable to filter and wash the reaction product of the zirconium source and the urea hydrolyzate, and then peptize it with an acid. In particular, the pH during filtration and washing with water is preferably 5 to 7. Further, the pH during peptization treatment is preferably 2.2 or less. Then, the hemite sol and silica sol were added to A pg
03/S i ox to a predetermined molar ratio, MgO, Y, O, TiO□,
At least one sintering aid selected from the group consisting of Fe and 03 is added to adjust the mullite composition sol. On the other hand, MgO1Y70° and CaO are added to the zirconia sol.
At least one type of stabilizer selected from the group 1CeOzO is added to prepare a zirconia-stabilized and other agent mixed sol. Next, the mullite u-single and Norconia stabilizer mixed sol are mixed in a predetermined ratio to form a gel. Then, this gelled product is calcined at a predetermined temperature, and then sintered at a predetermined temperature. This sintering temperature is lower than that in the production of conventional mullite-zirconia composite ceramics, for example 1450
It can be carried out even at temperatures as low as °C, and a sintered body with a high ratio of tetragonal 1rC)2 and high strength and high toughness can be obtained.
■ １．０ｍｏｆｆｉ／Ｆ！のＺｒ０Ｃｅｚ溶液にモル
比で２．０８倍の尿素、及び尿素の１／１０量（モル比
）のＮＨ，Ｎｏ、を加え、３．５時間ＪＪｌｌｌ熱還流
してジルコニアゾルを得た。
■ このジルコニアゾルを希アンモニア水でゲル化させ
た後、濾過、水洗し、Ｃ１−イオンを除去■ こうして
得られたジルコニアゲルをＩＮの希硝酸中に再懸濁して
ゾル化し、それにムライト相に対して０．０５〜１．５
重量％のＭｇＯとなるＭ ｇ ＮＯ１＋ ６Ｈｚ Ｏ
（又は００７〜２，０重量％のＹ２Ｏ３となるＹ （Ｎ
ＯＩ ）ｚ ６Ｈｚ ｏ）を加えて溶解した。この混
液を３時間加熱還流し、ＺｒＯ，−ＭｇＯ混合ゾルを得
た。
■ ヘーマイトゾルとシリカゾルをＡｉ ２０３ ／Ｓ
ｉｎ、のモル比が３／２となるよう、さらに０．０５〜
１．５重蓋％のＭｇＯとなるＭｇ （ＮＯｌ）２ ・６
Ｈ７０を加えて、ムライト組成ゾルを得た。
■ 前記ＺｒＯ□−Ｍｇ○混合プルに対して上記のムラ
イト組成ゾルを加え、高速分散機で混合攪拌し、反応さ
せた。その後、１２０ ”Ｃで２０時間乾燥する。
■ このようにして得た乾燥ゲルをボールミルで粉砕し
た後、１００メソンユの篩にかけ、これを電気炉（１４
００°Ｃで１５時間）中で仮焼する。
■ 仮焼粉を湿式スラリー粉砕し、平均粒径が１゜３ｔ
Ｉｍのものにする。この後、スラリーは１２０℃で３０
時間乾燥し、乾燥後１５０メツシユの篩にかけてパスし
た粉末を得る。
■ このようにして得た粉末を２ｔｏｎ／ｃｍ”で静水
圧成形した後、３００℃／ｈｒの昇温速度で昇温させ、
所定の温度で焼結した。
このようにして得たムライト・ジルコニア複合セラミッ
クスの特性を調べたので、その結果を表に示す。■ 1.0moffi/F! To the Zr0Cez solution, urea in a molar ratio of 2.08 times and NH, No in a 1/10 amount (molar ratio) of urea were added, and the mixture was heated under reflux for 3.5 hours to obtain a zirconia sol. ■ After gelling this zirconia sol with dilute ammonia water, it is filtered and washed with water to remove C1- ions ■ The zirconia gel thus obtained is resuspended in IN dilute nitric acid to form a sol, and then added to the mullite phase. 0.05 to 1.5
Mg NO1+ 6Hz O to become MgO in weight%
(or Y (N
OI)z 6Hz o) was added and dissolved. This mixed solution was heated under reflux for 3 hours to obtain a ZrO, -MgO mixed sol. ■ Hemite sol and silica sol Ai 203/S
In, further 0.05~ so that the molar ratio of in is 3/2.
Mg (NOl)2 ・6 which becomes 1.5% MgO
H70 was added to obtain a mullite composition sol. (2) The above mullite composition sol was added to the ZrO□-Mg◯ mixed pull, mixed and stirred using a high-speed disperser, and reacted. Thereafter, it is dried at 120"C for 20 hours. ■ The dry gel thus obtained is ground in a ball mill, passed through a 100-Mesonyu sieve, and then heated in an electric furnace (14
00°C for 15 hours). ■ The calcined powder is wet slurry pulverized and the average particle size is 1°3t.
Make it mine. After this, the slurry was heated to 120°C for 30°C.
After drying, pass through a 150-mesh sieve to obtain a powder. ■ The powder thus obtained was subjected to isostatic pressing at a pressure of 2 tons/cm, and then heated at a rate of 300°C/hr.
Sintered at a specified temperature. The properties of the mullite-zirconia composite ceramic thus obtained were investigated, and the results are shown in the table.
本発明に係るムライト・ジルコニア複合セラミックスの
製造方法は、ヘーマイトゾルとシリカゾルとを混合して
ムライト組成ゾルを調整するムライト組成ゾル調整工程
と、ジルコニアゾルに安定化剤を添加するジルコニア−
安定化側混合ゾル調整工程と、前記ムライト組成ゾルと
前記ジルコニア−安定他剤混合ゾルとを混合してゲル化
するゲル化工程と、このゲル化工程で得たものを仮焼す
る仮焼工程と、仮焼工程で得た仮焼物を成形して焼結す
る焼結工程とを具備するので、焼結工程での焼成温度が
例えば１４５０°Ｃといった低い温度でも良く、そして
曲げ強度及び破壊靭性に優れたものであり、畜強度なセ
ラミックスが簡単に得られる特長を有する。
特許出願人 秩父セメント株式会社The method for manufacturing mullite-zirconia composite ceramics according to the present invention includes a mullite composition sol adjustment step of mixing hemite sol and silica sol to prepare a mullite composition sol, and a zirconia composition sol adjustment step of adding a stabilizer to the zirconia sol.
A stabilizing side mixed sol preparation step, a gelling step of mixing and gelling the mullite composition sol and the zirconia-stabilizing agent mixed sol, and a calcination step of calcining the product obtained in this gelling step. and a sintering step of shaping and sintering the calcined product obtained in the calcination step, the firing temperature in the sintering step can be as low as 1450°C, and the bending strength and fracture toughness can be improved. It has the advantage of being able to easily produce durable ceramics. Patent applicant Chichibu Cement Co., Ltd.
Claims (5)
ト組成ゾルを調整するムライト組成ゾル調整工程と、ジ
ルコニアゾルに安定化剤を添加するジルコニア−安定化
剤混合ゾル調整工程と、前記ムライト組成ゾルと前記ジ
ルコニア−安定化剤混合ゾルとを混合してゲル化するゲ
ル化工程と、このゲル化工程で得たものを仮焼する仮焼
工程と、仮焼工程で得た仮焼物を成形して焼結する焼結
工程とを具備することを特徴とするムライト・ジルコニ
ア複合セラミックスの製造方法。(1) A mullite composition sol preparation step of mixing boehmite sol and silica sol to prepare a mullite composition sol, a zirconia-stabilizer mixed sol preparation step of adding a stabilizer to the zirconia sol, and the mullite composition sol. A gelling step of mixing and gelling the zirconia-stabilizer mixed sol, a calcination step of calcining the product obtained in this gelling step, and a molding of the calcined product obtained in the calcination step. 1. A method for producing mullite-zirconia composite ceramics, comprising the step of sintering.
リカゾルと焼結助剤とが混合されてムライト組成ゾルが
調整されるものである特許請求の範囲第１項記載のムラ
イト・ジルコニア複合セラミックスの製造方法。(2) The method for producing a mullite-zirconia composite ceramic according to claim 1, wherein in the mullite composition sol adjustment step, a mullite composition sol is prepared by mixing boehmite sol, silica sol, and a sintering aid. .
、Ｆｅ＿２Ｏ＿３の群の中から選ばれる少なくとも一種
のものである特許請求の範囲第１項記載のムライト・ジ
ルコニア複合セラミックスの製造方法。(3) Sintering aids are MgO, Y_2O_3, TiO_2
The method for producing a mullite-zirconia composite ceramic according to claim 1, wherein the mullite-zirconia composite ceramic is at least one selected from the group of , Fe_2O_3.
ｅＯ＿２の群の中から選ばれる少なくとも一種のもので
ある特許請求の範囲第１項記載のムライト・ジルコニア
複合セラミックスの製造方法。(4) The stabilizer is MgO, Y_2O_3, CaO, C
The method for producing a mullite-zirconia composite ceramic according to claim 1, wherein the ceramic is at least one selected from the group of eO_2.
ルとの割合が重量比で９０：１０〜６５：３５である特
許請求の範囲第１項記載のムライト・ジルコニア複合セ
ラミックスの製造方法。(5) The method for producing a mullite-zirconia composite ceramic according to claim 1, wherein the weight ratio of the mullite composition sol and the zirconia-stabilizer mixed sol is 90:10 to 65:35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2216726A JPH0497942A (en) | 1990-08-17 | 1990-08-17 | Production of mullite-zirconia composite ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2216726A JPH0497942A (en) | 1990-08-17 | 1990-08-17 | Production of mullite-zirconia composite ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0497942A true JPH0497942A (en) | 1992-03-30 |
Family
ID=16692964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2216726A Pending JPH0497942A (en) | 1990-08-17 | 1990-08-17 | Production of mullite-zirconia composite ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0497942A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994007969A1 (en) * | 1992-09-25 | 1994-04-14 | Minnesota Mining And Manufacturing Company | Abrasive grain including rare earth oxide therein |
| US5429647A (en) * | 1992-09-25 | 1995-07-04 | Minnesota Mining And Manufacturing Company | Method for making abrasive grain containing alumina and ceria |
| US5551963A (en) * | 1992-09-25 | 1996-09-03 | Minnesota Mining And Manufacturing Co. | Abrasive grain containing alumina and zirconia |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN116003159A (en) * | 2022-12-15 | 2023-04-25 | 西北工业大学 | Mullite-zirconia porous ceramic and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60204667A (en) * | 1984-03-29 | 1985-10-16 | 京セラ株式会社 | Thermal shock resistant ceramic sintered body and manufacture |
| JPS61132510A (en) * | 1984-11-30 | 1986-06-20 | Agency Of Ind Science & Technol | Production of heat-resistant conjugated oxide powder |
| JPS62202813A (en) * | 1986-02-27 | 1987-09-07 | Chichibu Cement Co Ltd | Production of mullite fine powder containing uniformly dispersed zirconia |
| JPH0274560A (en) * | 1988-09-09 | 1990-03-14 | Chichibu Cement Co Ltd | Mullite-zirconia compound ceramics having high strength and toughness and production thereof |
-
1990
- 1990-08-17 JP JP2216726A patent/JPH0497942A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60204667A (en) * | 1984-03-29 | 1985-10-16 | 京セラ株式会社 | Thermal shock resistant ceramic sintered body and manufacture |
| JPS61132510A (en) * | 1984-11-30 | 1986-06-20 | Agency Of Ind Science & Technol | Production of heat-resistant conjugated oxide powder |
| JPS62202813A (en) * | 1986-02-27 | 1987-09-07 | Chichibu Cement Co Ltd | Production of mullite fine powder containing uniformly dispersed zirconia |
| JPH0274560A (en) * | 1988-09-09 | 1990-03-14 | Chichibu Cement Co Ltd | Mullite-zirconia compound ceramics having high strength and toughness and production thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994007969A1 (en) * | 1992-09-25 | 1994-04-14 | Minnesota Mining And Manufacturing Company | Abrasive grain including rare earth oxide therein |
| US5429647A (en) * | 1992-09-25 | 1995-07-04 | Minnesota Mining And Manufacturing Company | Method for making abrasive grain containing alumina and ceria |
| US5498269A (en) * | 1992-09-25 | 1996-03-12 | Minnesota Mining And Manufacturing Company | Abrasive grain having rare earth oxide therein |
| US5551963A (en) * | 1992-09-25 | 1996-09-03 | Minnesota Mining And Manufacturing Co. | Abrasive grain containing alumina and zirconia |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN116003159A (en) * | 2022-12-15 | 2023-04-25 | 西北工业大学 | Mullite-zirconia porous ceramic and preparation method and application thereof |
| CN116003159B (en) * | 2022-12-15 | 2024-03-12 | 西北工业大学 | Mullite-zirconia porous ceramic and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109704731B (en) | Preparation method of nano yttrium-stabilized zirconia-alumina composite powder | |
| EP0232094B1 (en) | Chemical preparation of zirconium-aluminum-magnesium oxide composites | |
| CN109704403A (en) | A kind of high tenacity oxidation zirconium base composite powder and preparation method thereof | |
| CN109704759A (en) | A kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof | |
| JPH0497942A (en) | Production of mullite-zirconia composite ceramics | |
| JPS627667A (en) | Alumina-containing partially stabilized zirconia sintered body and manufacture | |
| JP2645826B2 (en) | High-strength zirconia-alumina ceramics with heat resistance and method for producing the same | |
| JPH04231374A (en) | Composition for preparation of ceramic | |
| JPH0339967B2 (en) | ||
| JP2533336B2 (en) | Sintered compact made of partially stabilized zirconium oxide and method for producing the same | |
| JP3190060B2 (en) | Method for producing fine ceria solid solution tetragonal zirconia powder | |
| JP3265344B2 (en) | Synthesis method of zircon powder | |
| JPS62202813A (en) | Production of mullite fine powder containing uniformly dispersed zirconia | |
| JPH0230663A (en) | Sintered material of zirconia and production thereof | |
| JPS6357383B2 (en) | ||
| RU2292320C1 (en) | Method for preparing ceramic composition material powder | |
| JPH05124810A (en) | Starting material for mullite sintered compact, mullite sintered compact and its production | |
| JPH05147924A (en) | Production of alumina-silica powder | |
| Zhien et al. | The effects of additives on the properties and structure of hot-pressed aluminium titanate ceramics | |
| JPH06219828A (en) | Production of mullite-silicon carbide combined ceramics | |
| JPH0274560A (en) | Mullite-zirconia compound ceramics having high strength and toughness and production thereof | |
| JP2968608B2 (en) | Method for producing fine ceria solid solution tetragonal zirconia powder | |
| KR960006247B1 (en) | Process for the preparation of aluminium titanate ceramics | |
| HWANG et al. | Preparation and sinterability of zirconia-toughened-alumina composite powder | |
| JPH03265600A (en) | Production of mullite whisker |