JPH0429609B2 - - Google Patents
Info
- Publication number
- JPH0429609B2 JPH0429609B2 JP58240597A JP24059783A JPH0429609B2 JP H0429609 B2 JPH0429609 B2 JP H0429609B2 JP 58240597 A JP58240597 A JP 58240597A JP 24059783 A JP24059783 A JP 24059783A JP H0429609 B2 JPH0429609 B2 JP H0429609B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- fine powder
- stabilizer
- producing
- reaction
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 115
- 239000000843 powder Substances 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 19
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims description 13
- -1 zirconia compound Chemical class 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 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 20
- 239000002245 particle Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001448434 Pirex Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Description
産業上の利用分野：
本発明は、ジルコニア微粉末、特に正方晶ジル
コニア微粉末の製造方法および該正方晶ジルコニ
アを原料とする部分安定化ジルコニア焼結体の製
造方法に関する。
ジルコニア：ZrO2の焼結体は、1000℃以上の
高温下における耐熱特性および耐蝕性に優れ、か
つ、熱伝導率が小さいため、エンジン、ガスター
ビン等の高温部部材としての利用が期待されてい
る。
従来技術：
ジルコニア結晶は、1900℃以上においては立方
晶、1000℃以上においては正方晶、1000℃未満に
おいては、単斜晶となり、1900℃以上に加熱して
一旦立方晶になると、低温域においても立方晶を
維持して安定であるが、正方晶、単斜晶間では可
逆的に変化し、しかもその間での体積変化は約７
％に達する。ジルコニア微粉末の成形体を2000℃
以上の温度に加熱して安定なジルコニア焼結体を
製造することが可能であるが経済的に極めて不利
であるため、1000℃以上の結晶系である正方晶を
低温域においても維持すべく安定化する部分安定
化法が一般に採用される。部分安定化ジルコニア
焼結体は、通常、水酸化ジルコニウムを仮焼する
方法等で得られる単斜晶ジルコニア微粉末と、イ
ツトリア、カルシア、マグネシア等の安定剤とを
混合仮焼して安定化し、成形焼結する方法で製造
される。しかしながら、常法で得られるジルコニ
ア微粉末は粒子径が大きく、かつ、粒度分布が広
いため、部分安定化処理を完全に、すなわち、ジ
ルコニアの単結晶単位で行うことが困難である。
ジルコニア微粉末をボールミル等を用いて、さら
に微粉砕し粒度を揃えることは、不可能ではない
が、経済的な面から工業的に採用するには問題が
ある。
前記、従来法の欠点を改良する方法として、ジ
ルコニウムアルコキシド溶液に安定化剤を混合し
て加水分解し、安定化剤が均一に分布した単斜晶
または正方晶ジルコニアを共沈させ、仮焼してジ
ルコニア微粉末とする方法が提案されている。し
かしながら、該方法においては、原料のジルコニ
ウムアルコキシドが高価であり、かつ、均一な粒
度のジルコニア結晶を得るための反応条件の制御
が困難であり、大量生産には適さない。
また、CERAMURGIA
INTERNATIONAL、vol.3、141〜146（1977）
には、塩化ジルコニウム：ZrCl4と、酸素との高
温気相反応によりジルコニア微粉末を製造する方
法が、報告されている。しかしながら、該方法に
おいては、反応温度が1100℃以上と高いためジル
コニア微粉末の製造方法として採用するには問題
がある。また、得られるジルコニア微粉末は極め
て凝集性の高いものであるため、それを成形して
部分安定化ジルコニア焼結体を製造する際の成形
性特に充填性が悪い欠点がある。
発明が解決しようとする問題点：
本発明は、部分安定化ジルコニア焼結体の製造
原料に適した粒度の均一な正方晶ジルコニア微粉
末の工業的に採用し得る製造方法を提供すること
その目的とし、また、該方法で得られる正方晶ジ
ルコニア微粉末を原料として使用する部分安定化
ジルコニア焼結体の製造方法を提供することを別
の目的とする。
問題点を解決するための手段：
本発明者等は、前記問題点を解決すべく鋭意研
究した結果、昇化性または気化性のジルコニウム
化合物と水蒸気とを反応させることにより、600
℃〜1100℃の比較的低温域において、粒子径が
150〜300Åの分散性の良好な個々に独立した正方
晶ジルコニア微粉末が得られることを見出し、本
発明を完成した。
本発明は、ガス化したジルコニウム化合物と、
水蒸気とを反応させることを特徴とするジルコニ
ア微粉末の製造方法および該方法で得られるジル
コニア微粉末に安定化剤を被着して成形焼結する
ことを特徴とする部分安定化ジルコニア焼結体の
製造方法である。
本発明のジルコニア微粉末の製造方法におい
て、反応原料のジルコニウム化合物として200℃
以上の温度に加熱することにより、昇華または気
化し、ガス化することが可能なジルコニウム化合
物であれば、無機化合物、有機化合物の如何を問
わず使用することができる。たとえば、塩化ジル
コニウム等の無機ジルコニウム化合物、テトラエ
トキシジルコニウム、テトライソプロポキシジル
コニウム、テトラブトキシジルコニウム等のジル
コニウムアルコキシド類、ジルコニウムアルコキ
シドのアルコキシ基の一部または全部をβ−ジケ
トン類、α−またはβ−ケトン酸類、ケトン酸エ
ステル類、α−またはβ−オキシ酸類、オキシ酸
エステル類、α−またはβ−オキシケトン類、α
−またはβ−オキシアルデヒド類、α−アミノ酸
類、α−またはβ−アミノアルコール類等のキレ
ート化剤の残基で置換した化合物類等の有機ジル
コニウム化合物類を使用することができる。
原料ジルコニウム化合物を不活性ガス雰囲気で
加熱してガス化し、ジルコニア化合物の10倍当量
以上の水蒸気と600〜1100℃、好ましくは650〜
950℃の温度下に接触させて反応させる。水蒸気
は100％の過熱水蒸気として反応させてもよく、
また、空気または酸素ガスをキヤリヤーとして希
釈して反応させてもよい。
具体的には、外部加熱により、650〜950℃に加
熱した管状反応管内に、窒素ガスをキヤリヤーと
してガス化したジルコニウム化合物と、空気また
は酸素をキヤリヤーとする水蒸気とを並流供給
し、反応させることにより、目的とする正方晶ジ
ルコニア微粉末を製造することができる。
本発明の部分安定化ジルコニア焼結体の製造方
法において、前記した反応で得られる正方晶ジル
コニア微粉末を原料とする。一方の原料である安
定化剤は、酸化してイツトリア、カルシア、また
はマグネシア生成するものであればよく、溶媒溶
解性のイツトリウム、カルシウムまたはマグネシ
ウムのアルコキシド類、キレート化合物類、有機
酸塩類、硝酸塩類等が好ましく使用される。
本発明の部分安定化ジルコニア焼結体の製造方
法において、原料ジルコニア微粉末を、安定化剤
の溶媒溶液中に分散混合した後乾燥し、原料ジル
コニア微粉末に安定化剤を被着させる。ついで、
安定化剤の被着したジルコニア微粉末を成形し、
通常の焼結条件たとえば1200〜1500℃の温度で２
〜５時間焼結することにより、目的とする部分安
定化ジルコニア焼結体を製造することができる。
作 用：
本発明のジルコニア微粉末の製造方法におい
て、水蒸気はジルコニウム化合物の酸化剤として
作用し、かつ、その反応温度を1000℃以下の温度
に低下させる。しかも驚くべきことには、反応温
度が1000℃以下であるにも拘らず正方晶のジルコ
ニア微粉末として得られる。また、気相反応の採
用は、得られるジルコニアの微細化、粒度の均一
化に作用し、本発明においては、150〜300Åの粒
径の凝集のない個々に独立した正方晶ジルコニア
微粉末が得られる。
得られる正方晶ジルコニア微粉末は、凝集のな
い個々に独立した正方晶ジルコニア微粉末にであ
るため、部分安定化ジルコニア焼結体の製造にあ
たり、単位粒子毎の安定化が可能であり、かつ、
粒子径が小さく揃つているので成形性に優れる。
本発明の部分安定化ジルコニア焼結体の製造方
法において、前記方法で得られた正方晶ジルコニ
ア微粉末を原料とすることにより、焼結密度が
5.95ｇ／cm2以上の極めて高密度の焼結体を得るこ
とができる。
原料ジルコニア微粉末への安定化剤の被着は、
一般に採用されている固相での混合によつて行う
ことができるが、溶液性の安定化剤を用いること
により、原料ジルコニア微粉末の単位粒子レベル
での被着が可能となるので好ましい。安定化剤を
被着したジルコニア微粉末は、成形に先立ち仮焼
して部分安定化した微粉末として成形に供しても
よい。
実施例および比較例
以下に、本発明を実施例により、さらに詳細に
説明する。ただし、本発明の範囲は下記実施例に
より何等限定されるものではない。
(1) ジルコニア微粉末の製造
添付第１図に示す如き、内径が６cm、加熱部
長さ90cmの反応管本体１の内部に、内径４cm、
加熱部長さ30cmの内管２を挿入し、反応管本体
１の外周に独立して温度設定できる内管挿入部
を加熱する電気加熱部３および反応部を加熱す
る電気加熱器４を取付けた反応装置を用いた。
電気加熱器３による加熱部の温度を300℃、
電気加熱器４による加熱部の温度を600〜1200
℃に設定し、内管２の電気加熱部のほぼ中央位
置に、ジルコニウム化合物５ｇを入れたパイレ
ツクスボート５を挿入し、窒素ガスを流通して
気化し、また、反応管本体１に、内管２の外周
より、水蒸気の単独または水蒸気および酸素ま
たは空気の混合ガスを流通させた。水蒸気と酸
素または空気の混合ガスは、水を超音波霧化装
置を用いて酸素ガスまたは空気中にミストとし
て浮游させ、酸素ガスまたは空気中で気化させ
た。
窒素ガス中に気化したジルコニウム化合物と
水蒸気とが反応部において接触し、酸化反応に
よりジルコニア微粒子が生成した。生成したジ
ルコニア微粒子は反応ガスを冷却することによ
り凝縮水中に回収した。
得られたジルコニア微粉末のＸ線回折、
BET法による粒径測定および電子顕微鏡観察
を行つた。
比較として、酸素ガスのみによる反応を行つ
た。
反応条件および反応結果を第１表中に示す。
Industrial Application Field: The present invention relates to a method for producing a fine zirconia powder, particularly a fine tetragonal zirconia powder, and a method for producing a partially stabilized zirconia sintered body using the tetragonal zirconia as a raw material. Zirconia: ZrO 2 sintered bodies have excellent heat resistance and corrosion resistance at high temperatures of 1000℃ or higher, and have low thermal conductivity, so they are expected to be used as high-temperature components in engines, gas turbines, etc. There is. Conventional technology: Zirconia crystals become cubic crystals at temperatures above 1900℃, tetragonal crystals at temperatures above 1000℃, and monoclinic crystals below 1000℃. Although it maintains a cubic crystal structure and is stable, it changes reversibly between tetragonal and monoclinic crystals, and the volume change between them is about 7
reach %. A molded body of zirconia fine powder is heated to 2000℃
Although it is possible to produce a stable zirconia sintered body by heating it to a temperature above 1,000℃, it is economically disadvantageous, so it is possible to produce a stable zirconia sintered body by heating it to a temperature above 1000℃, so it is necessary to maintain the tetragonal crystal system even at low temperatures. A partial stabilization method is generally employed. Partially stabilized zirconia sintered bodies are usually stabilized by mixing and calcining monoclinic zirconia fine powder obtained by calcining zirconium hydroxide with a stabilizer such as ittria, calcia, magnesia, etc. Manufactured using a molding and sintering method. However, since the zirconia fine powder obtained by a conventional method has a large particle size and a wide particle size distribution, it is difficult to perform partial stabilization treatment completely, that is, in single crystal units of zirconia.
Although it is not impossible to further finely pulverize the zirconia fine powder using a ball mill or the like to make the particle size uniform, there are problems in industrially employing it from an economical point of view. As a method to improve the drawbacks of the conventional method, a stabilizer is mixed into a zirconium alkoxide solution and hydrolyzed, monoclinic or tetragonal zirconia in which the stabilizer is uniformly distributed is co-precipitated, and then calcined. A method has been proposed to produce fine zirconia powder. However, in this method, the raw material zirconium alkoxide is expensive, and it is difficult to control the reaction conditions to obtain zirconia crystals of uniform particle size, so it is not suitable for mass production. Also, CERAMURGIA
INTERNATIONAL, vol.3, 141-146 (1977)
reported a method for producing fine zirconia powder through a high-temperature gas-phase reaction between zirconium chloride (ZrCl 4 ) and oxygen. However, in this method, since the reaction temperature is as high as 1100° C. or higher, there is a problem in adopting it as a method for producing fine zirconia powder. In addition, since the obtained zirconia fine powder has extremely high cohesiveness, it has the disadvantage of poor moldability, particularly poor filling properties, when molding it to produce a partially stabilized zirconia sintered body. Problems to be Solved by the Invention: An object of the present invention is to provide an industrially applicable method for producing fine tetragonal zirconia powder with a uniform particle size suitable as a raw material for producing partially stabilized zirconia sintered bodies. Another object of the present invention is to provide a method for producing a partially stabilized zirconia sintered body using the tetragonal zirconia fine powder obtained by the method as a raw material. Means for Solving the Problems: As a result of intensive research to solve the above problems, the inventors of the present invention discovered that 600
In the relatively low temperature range from ℃ to 1100℃, the particle size
The present invention was completed based on the discovery that individually independent tetragonal zirconia fine powder with a diameter of 150 to 300 Å and good dispersibility can be obtained. The present invention provides a gasified zirconium compound;
A method for producing fine zirconia powder, characterized by reacting it with water vapor, and a partially stabilized zirconia sintered body, characterized in that the fine zirconia powder obtained by the method is coated with a stabilizer and then shaped and sintered. This is a manufacturing method. In the method for producing zirconia fine powder of the present invention, the zirconium compound as a reaction raw material is heated at 200°C.
Any zirconium compound, whether inorganic or organic, can be used as long as it can be sublimed or vaporized and gasified by heating to the above temperature. For example, inorganic zirconium compounds such as zirconium chloride, zirconium alkoxides such as tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium, and some or all of the alkoxy groups of zirconium alkoxides are replaced with β-diketones, α- or β-ketones. Acids, ketonic acid esters, α- or β-oxyacids, oxyacid esters, α- or β-oxyketones, α
Organic zirconium compounds, such as compounds substituted with residues of chelating agents such as - or β-oxyaldehydes, α-amino acids, α- or β-amino alcohols, can be used. The raw material zirconium compound is heated in an inert gas atmosphere to gasify it, and then heated to 600 to 1100°C, preferably 650 to 1100°C, with water vapor of more than 10 times the equivalent of the zirconia compound.
React by contacting at a temperature of 950℃. Steam may be reacted as 100% superheated steam,
Alternatively, the reaction may be carried out by diluting air or oxygen gas as a carrier. Specifically, a gasified zirconium compound using nitrogen gas as a carrier and water vapor using air or oxygen as a carrier are supplied in parallel flow into a tubular reaction tube heated to 650 to 950°C by external heating, and the reaction is caused to occur. By doing so, the desired tetragonal zirconia fine powder can be produced. In the method for producing a partially stabilized zirconia sintered body of the present invention, the tetragonal zirconia fine powder obtained by the above-described reaction is used as a raw material. The stabilizer, which is one of the raw materials, may be one that oxidizes to produce yttrium, calcia, or magnesia, such as solvent-soluble yttrium, calcium, or magnesium alkoxides, chelate compounds, organic acid salts, nitrates, etc. etc. are preferably used. In the method for producing a partially stabilized zirconia sintered body of the present invention, raw zirconia fine powder is dispersed and mixed in a solvent solution of a stabilizer, and then dried to coat the raw zirconia fine powder with the stabilizer. Then,
Molding zirconia fine powder coated with a stabilizer,
Normal sintering conditions e.g. 2 at a temperature of 1200-1500℃
By sintering for ~5 hours, the desired partially stabilized zirconia sintered body can be manufactured. Function: In the method for producing zirconia fine powder of the present invention, water vapor acts as an oxidizing agent for the zirconium compound and lowers the reaction temperature to 1000°C or less. Surprisingly, even though the reaction temperature is below 1000°C, a fine tetragonal zirconia powder is obtained. In addition, the use of gas phase reaction works to make the resulting zirconia finer and more uniform in particle size, and in the present invention, individually independent tetragonal zirconia fine powder with a particle size of 150 to 300 Å without agglomeration can be obtained. It will be done. Since the obtained tetragonal zirconia fine powder is individually independent tetragonal zirconia fine powder without agglomeration, it is possible to stabilize each unit particle when producing a partially stabilized zirconia sintered body, and
It has excellent moldability because the particle size is small and uniform. In the method for producing a partially stabilized zirconia sintered body of the present invention, the sintered density can be increased by using the tetragonal zirconia fine powder obtained by the above method as a raw material.
A sintered body with an extremely high density of 5.95 g/cm 2 or more can be obtained. The deposition of the stabilizer on the raw zirconia fine powder is as follows:
This can be carried out by mixing in a solid phase, which is generally employed, but it is preferable to use a solution stabilizer because it allows the raw zirconia fine powder to be deposited at the unit particle level. The zirconia fine powder coated with the stabilizer may be calcined prior to molding to provide partially stabilized fine powder for molding. EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be explained in more detail with reference to Examples. However, the scope of the present invention is not limited in any way by the following examples. (1) Production of zirconia fine powder As shown in the attached Figure 1, inside a reaction tube body 1 with an inner diameter of 6 cm and a heating section length of 90 cm, a tube with an inner diameter of 4 cm,
A reaction in which an inner tube 2 with a heating length of 30 cm is inserted, and an electric heating section 3 that heats the inner tube insertion section and an electric heater 4 that heats the reaction section are attached to the outer periphery of the reaction tube body 1, the temperature of which can be set independently. using the device. The temperature of the heating part by electric heater 3 is set to 300℃,
The temperature of the heated part by electric heater 4 is set to 600 to 1200.
℃, the Pyrex boat 5 containing 5 g of zirconium compound is inserted into the approximately central position of the electric heating part of the inner tube 2, and nitrogen gas is passed through it to vaporize it. From the outer periphery of the tube 2, water vapor alone or a mixed gas of water vapor and oxygen or air was passed. A mixed gas of water vapor and oxygen or air was obtained by suspending water as a mist in oxygen gas or air using an ultrasonic atomizer and vaporizing it in oxygen gas or air. The zirconium compound vaporized in the nitrogen gas and water vapor came into contact with each other in the reaction section, and zirconia fine particles were produced by an oxidation reaction. The generated zirconia fine particles were collected in condensed water by cooling the reaction gas. X-ray diffraction of the obtained zirconia fine powder,
Particle size measurement using the BET method and observation using an electron microscope were performed. For comparison, a reaction using only oxygen gas was performed. The reaction conditions and reaction results are shown in Table 1.
【表】【table】
【表】
(2) 部分安定化ジルコニア焼結体の製造
前記ジルコニア微粉末の製造の実施例番号１
で得られた正方晶ジルコニア微粉末５ｇを、溶
媒10c.c.に安定化剤を溶解した溶液に加えて混合
分散した後過乾燥し、ジルコニア微粉末に安
定化剤を被着した。ついで、安定化剤の被着し
たジルコニウム微粉末を仮焼するか、または仮
焼しないで成形した後、焼結した。
成形は直径１cmの円板に成形できる金型を用
い成形圧2t／cm2を掛けて行つた。また、焼結
は、焼結温度1400℃×3hr、昇温速度および降
温速度200℃／hrの条件で行つた。
得られた焼結体のＸ線回折を行い結晶形を確
認した。
使用した安定化剤の条件、成形密度、焼結体
密度等を第２表に示す。[Table] (2) Production of partially stabilized zirconia sintered body Example number 1 of production of the zirconia fine powder
5 g of the obtained tetragonal zirconia fine powder was added to a solution of a stabilizer dissolved in 10 cc of solvent, mixed and dispersed, and then overdried to coat the stabilizer on the zirconia fine powder. Then, the zirconium fine powder coated with the stabilizer was calcined or molded without calcining, and then sintered. Molding was carried out using a mold capable of forming a disc with a diameter of 1 cm and applying a molding pressure of 2 t/cm 2 . Further, the sintering was performed under the conditions of a sintering temperature of 1400°C x 3 hours, and a temperature increase rate and a temperature decrease rate of 200°C/hr. The obtained sintered body was subjected to X-ray diffraction to confirm the crystal form. Table 2 shows the conditions of the stabilizer used, the molding density, the sintered body density, etc.
【表】
発明の効果：
本発明において、ガス化したジルコニウム化合
物と水蒸気とを気相で反応させることにより、
600〜1100℃の低温で、粒子径の均一な正方晶ジ
ルコニア微粉末を得ることができる。また、得ら
れた正方晶ジルコニア微粉末は、個々に独立した
非凝集性のジルコニア微粉末であるため、その安
定化処理において粒子単位の安定化が可能であ
り、それを用いることにより高密度の部分安定化
ジルコニア焼結体を製造することができる。
また、ジルコニア微粉末の製造方法は、反応温
度が低く、エネルギー的に極めて有利である。
本発明は、部分安定化ジルコニア焼結体製造の
原料に適した均一な粒径の正方晶ジルコニア微粉
末の製造方法および該方法で得られたジルコニア
微粉末を原料とする高密度の部分安定化ジルコニ
ア焼結体の製造方法を提供するものであり、その
産業的意義は極めて大きい。[Table] Effect of the invention: In the present invention, by reacting the gasified zirconium compound and water vapor in the gas phase,
Tetragonal zirconia fine powder with uniform particle size can be obtained at a low temperature of 600 to 1100°C. In addition, since the obtained tetragonal zirconia fine powder is individually independent and non-agglomerated zirconia fine powder, it is possible to stabilize each particle in the stabilization treatment, and by using it, high-density A partially stabilized zirconia sintered body can be produced. Furthermore, the method for producing zirconia fine powder has a low reaction temperature and is extremely advantageous in terms of energy. The present invention provides a method for producing tetragonal zirconia fine powder with a uniform particle size suitable as a raw material for producing partially stabilized zirconia sintered bodies, and a high-density partially stabilized zirconia fine powder obtained by the method as a raw material. The present invention provides a method for producing a zirconia sintered body, and its industrial significance is extremely large.
第１図 実施例で用いた反応装置の説明用図面
〔使用記号〕、１……反応管本体、２……内管、
３，４……電気加熱器、５……パイレツクスボー
ト、Ａ……ジルコニア化合物、Ｂ……窒素ガス、
Ｃ……水蒸気または水蒸気含有ガス、Ｄ……反応
生成物含有ガス。
Fig. 1 Explanatory drawing of the reaction apparatus used in the examples [Symbols used], 1... Reaction tube main body, 2... Inner tube,
3, 4... Electric heater, 5... Pirex boat, A... Zirconia compound, B... Nitrogen gas,
C... Water vapor or water vapor-containing gas, D... Reaction product-containing gas.
Claims (1)
反応させることを特徴とするジルコニア微粉末の
製造方法。 ２ 反応温度が600〜1100℃である特許請求の範
囲第１項記載の方法。 ３ ジルコニア化合物が塩化ジルコニウムである
特許請求の範囲第１項記載の方法。 ４ 水蒸気を酸素ガスまたは空気をキヤリヤーガ
スとして反応させる特許請求の範囲第１項記載の
方法。 ５ ガス化したジルコニウム化合物と水蒸気とを
反応させて得られるジルコニア微粉末に、安定化
剤を被着して成形焼結することを特徴とする部分
安定化ジルコニア焼結体の製造方法。 ６ 安定化剤が溶媒溶解性のイツトリウム化合物
である特許請求の範囲第５項記載の方法。 ７ 安定化剤溶液にジルコニア微粉末を混合分散
させ、乾燥して、ジルコニア微粉末に安定化剤を
被着させる特許請求の範囲第５項記載の方法。[Claims] 1. A method for producing fine zirconia powder, which comprises reacting a gasified zirconium compound with water vapor. 2. The method according to claim 1, wherein the reaction temperature is 600 to 1100°C. 3. The method according to claim 1, wherein the zirconia compound is zirconium chloride. 4. The method according to claim 1, in which water vapor is reacted with oxygen gas or air as a carrier gas. 5. A method for producing a partially stabilized zirconia sintered body, which comprises applying a stabilizer to zirconia fine powder obtained by reacting a gasified zirconium compound with water vapor, and then shaping and sintering the resultant. 6. The method according to claim 5, wherein the stabilizer is a solvent-soluble yttrium compound. 7. The method according to claim 5, wherein fine zirconia powder is mixed and dispersed in a stabilizer solution and dried to coat the stabilizer on the fine zirconia powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58240597A JPS60131826A (en) | 1983-12-20 | 1983-12-20 | Manufacture of zirconia fine powder and partially stabilized zirconia sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58240597A JPS60131826A (en) | 1983-12-20 | 1983-12-20 | Manufacture of zirconia fine powder and partially stabilized zirconia sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60131826A JPS60131826A (en) | 1985-07-13 |
| JPH0429609B2 true JPH0429609B2 (en) | 1992-05-19 |
Family
ID=17061861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58240597A Granted JPS60131826A (en) | 1983-12-20 | 1983-12-20 | Manufacture of zirconia fine powder and partially stabilized zirconia sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60131826A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546118A (en) * | 2018-05-07 | 2018-09-18 | 内蒙古科技大学 | A kind of yttria-stabilized zirconia powder and preparation method thereof and ceramics |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61291417A (en) * | 1985-06-14 | 1986-12-22 | Sumitomo Cement Co Ltd | Production of stabilized or partially stabilized zirconia fine powder |
| DE3611449A1 (en) * | 1986-04-05 | 1987-10-15 | Degussa | BASIC MATERIAL FOR THE PRODUCTION OF CERAMIC MATERIALS |
| FR2615503B1 (en) * | 1987-05-18 | 1991-01-18 | Criceram | PROCESS FOR OBTAINING FINE ZIRCONIA AND / OR HAFNONE POWDER HAVING A SPECIFIC SURFACE OR A PREDETERMINED GRANULOMETRY |
| US4937062A (en) * | 1988-03-07 | 1990-06-26 | Cabot Corporation | High surface area metal oxide foams and method of producing the same |
| US5147630A (en) * | 1989-06-05 | 1992-09-15 | Reznek Steven R | Method of producing alumina foams |
| JP2007103708A (en) * | 2005-10-05 | 2007-04-19 | Sumitomo Osaka Cement Co Ltd | Composition for sealing light emitting element, light emitting element and optical semiconductor device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169927A (en) * | 1983-02-25 | 1984-09-26 | モンテディソン・エッセ・ピ・ア | Method and apparatus for manufacturing single dispersive andnon-aggregative spherical metal oxide smaller than one micron in diameter |
-
1983
- 1983-12-20 JP JP58240597A patent/JPS60131826A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169927A (en) * | 1983-02-25 | 1984-09-26 | モンテディソン・エッセ・ピ・ア | Method and apparatus for manufacturing single dispersive andnon-aggregative spherical metal oxide smaller than one micron in diameter |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546118A (en) * | 2018-05-07 | 2018-09-18 | 内蒙古科技大学 | A kind of yttria-stabilized zirconia powder and preparation method thereof and ceramics |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60131826A (en) | 1985-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5358695A (en) | Process for producing nanoscale ceramic powders | |
| US5055442A (en) | Carrier for catalyst and method for production thereof | |
| US6030914A (en) | Zirconia fine powder and method for its production | |
| JP6596347B2 (en) | Method for producing vanadium dioxide | |
| JPH0329009B2 (en) | ||
| KR100753773B1 (en) | Method for preparing perovskite oxide nanopowders | |
| Znaidi et al. | Batch and semi-continuous synthesis of magnesium oxide powders from hydrolysis and supercritical treatment of Mg (OCH3) 2 | |
| Yasnó et al. | Microwave synthesis of ultra-high temperature ceramic ZrC nanopowders | |
| JPH0429609B2 (en) | ||
| US5523065A (en) | Process for making ultra-fine barium titanate particles | |
| JPH03170332A (en) | Zirconium dioxide powder, its manufacture and use as well as sintered product | |
| Wang et al. | Controllable synthesis of zirconia nano-powders using vapor-phase hydrolysis and theoretical analysis | |
| JP7011133B2 (en) | A method for producing an alumina-based solid solution ceramic powder by combustion synthesis of aluminum and oxygen and water atomization method. | |
| US4532224A (en) | Composite ceramic powders and a method of making the same | |
| CN1111139C (en) | Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder | |
| JP2009023888A (en) | Method for producing spherical alumina particle | |
| Wang et al. | Preparation and characterization of CuO–ZrO 2 nanopowders | |
| JPS59107905A (en) | Manufacture of hyperfine particle of metallic oxide | |
| JPH10338524A (en) | Production of barium titanate powder | |
| JPH01122964A (en) | Zirconia stabilized by yttrium and its production | |
| Khaleel et al. | Ceramics | |
| JP7383327B1 (en) | Acicular alumina particle aggregate and its manufacturing method | |
| JP3102082B2 (en) | Production method of heat-resistant transition alumina | |
| JPS63210001A (en) | Production of spherical piezoelectric ceramic particles | |
| JPH01226724A (en) | Method for synthesizing fine oxide particles as starting material |