JPS60176920A - Sol dispersed with ultra-fine particle of zirconia single crystal, and its production - Google Patents

Sol dispersed with ultra-fine particle of zirconia single crystal, and its production

Info

Publication number
JPS60176920A
JPS60176920A JP59032114A JP3211484A JPS60176920A JP S60176920 A JPS60176920 A JP S60176920A JP 59032114 A JP59032114 A JP 59032114A JP 3211484 A JP3211484 A JP 3211484A JP S60176920 A JPS60176920 A JP S60176920A
Authority
JP
Japan
Prior art keywords
aqueous solution
hydroxide
sol
divalent metal
precipitate
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.)
Granted
Application number
JP59032114A
Other languages
Japanese (ja)
Other versions
JPH0472768B2 (en
Inventor
Etsuro Kato
加藤 悦朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP59032114A priority Critical patent/JPS60176920A/en
Publication of JPS60176920A publication Critical patent/JPS60176920A/en
Publication of JPH0472768B2 publication Critical patent/JPH0472768B2/ja
Granted legal-status Critical Current

Links

Landscapes

  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE:To peoduce the titled sol, by adding a base to an aqueous solution of a zirconium salt, washing the resultant precipitate with water, adding an alkaline earth metal hydroxide to the precipitate to obtain a suspension, and aging the suspension by heating at a specific temperature. CONSTITUTION:A base (e.g. ammonia water) is added to an aqueous solution of a zirconium salt (e.g. an aqueous solution of ZrOCl2, etc.) to produce the precipitate of zirconium hydroxide. The precipitate is washed with water to remove the major part of the soluble components, and is added with an alkaline earth metal (e.g. calcium hydroxide) or its aqueous solution to obtain a suspension or paste of the mixture. The produce is aged by heating at 90-200 deg.C. The obtained sol contains dispersed separate ultra-fine primary particles of the single crystal of ZrO2-CaO solid solution having a tetragonal or cubic crystal lattice and almost uniform particle diameter of <=200Angstrom .

Description

【発明の詳細な説明】 本発明は本発明者によって既に出願された昭和57年特
許願第215208号(以−ド原特許願という)の追加
の発明であり、ジルコニアを基本成分とするジルコニア
系単結晶超微粒子の分散したゾルおよびその製造方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention is an additional invention of Patent Application No. 215208 filed in 1982 (hereinafter referred to as the original patent application) already filed by the present inventor. The present invention relates to a sol in which single-crystal ultrafine particles are dispersed and a method for producing the same.

ZrO2と、 Y2O3,CaO、MgO、CeO2,
その他、 Sc。
ZrO2, Y2O3, CaO, MgO, CeO2,
Others, Sc.

Yl) 、 La 、 Nd 、 Gd などの酸化物
の一つあるいはそ−のい(つかを含む固溶体は、高温材
料、イオン導電材料、圧電体など各種の応用があり、そ
の出発原料としてこれらの固溶体超微粒子の分散したゾ
ルが極めて有用であることはすでに原特許願に詳細に記
述した。
Solid solutions containing one or more of oxides such as Yl), La, Nd, and Gd have various applications such as high-temperature materials, ion conductive materials, and piezoelectric materials, and these solid solutions are used as starting materials. It has already been described in detail in the original patent application that a sol in which ultrafine particles are dispersed is extremely useful.

しかしながら原特許出願の時点では、Zr02−CaO
系固溶体等Z rO2と2価金属イオンとの固溶体の単
結晶超微粒子の分散したゾルは特許願記載の方法によっ
ては必ずしも得ることができなかった。このことは原特
許願の実施例2において少し述へたが、その後の研究の
結果、方法を若干改良することによってZrO2CaO
系等についても同様の固溶体11結晶超微粒子の分散し
たゾルを製造することがriJ能となったので、追加の
出願として以下にこれを説明する。
However, at the time of the original patent application, Zr02-CaO
A sol in which single-crystal ultrafine particles of a solid solution of ZrO2 and divalent metal ions are dispersed cannot necessarily be obtained by the method described in the patent application. This was briefly mentioned in Example 2 of the original patent application, but as a result of subsequent research, by slightly improving the method, ZrO2CaO
As for systems, etc., it has become possible to produce a sol in which similar solid solution 11 crystalline ultrafine particles are dispersed, so this will be explained below as an additional application.

すなわち原特許願の時点では、 Zr(OH)4と2価
金属水酸化物の共沈物の溶解分離と塩化アンモニウムな
との妨害効果に対し考慮が払われていなかったことによ
る欠陥があった。その後の詳細な研究の結果、水酸化物
または共沈水酸化物をできるだけ1−分に洗滌し、沈澱
生成時の不要の生成物。
In other words, at the time of the original patent application, there was a defect in that no consideration was given to the dissolution and separation of the coprecipitate of Zr(OH)4 and divalent metal hydroxide and the interfering effect of ammonium chloride. . As a result of subsequent detailed research, we found that hydroxide or co-precipitated hydroxide was washed away as much as possible in 1-min, and unnecessary products during precipitation formation.

すなわち塩化アンモニウム、食塩、塩化カリ、硝酸ソー
タ、硝酸カリ等をできるだけ水洗除去することが、 Z
rO2と2価金属イオンの固溶体の生成には必要であり
、同時に6に滌による2価金属イオンの溶解消失を防く
ためその飽和水溶液で洗滌して始めて成功できることが
判明した。8成温度は90(:以1・では生成速度が遅
すきて実用的でなく、200゛(゛以1゛、では生成粒
子が和犬化し、 rIHに凝集連結し始め411 X’
を化が悪くなり、さらにカルシウム分の溶出が増大する
。最後に生成物は]50A程度の超微粒子てあり、これ
は綜特許願のように強酸を加えて分離操作を行うと溶解
消失するので、目的とするCaOなどの固溶量に応じ、
稀酢酸やアンモニア水等で洗滌する必要がある。
In other words, ammonium chloride, common salt, potassium chloride, nitric acid sorter, potassium nitrate, etc. should be removed by washing with water as much as possible.
It was found that rO2 is necessary for the production of a solid solution of divalent metal ions, and that success can only be achieved by washing with a saturated aqueous solution of rO2 to prevent the divalent metal ions from dissolving and disappearing due to oxidation. 8 The formation temperature is 90° (1), the formation rate is too slow and is not practical, and at 200° (1), the formed particles become wavy and begin to aggregate and connect to rIH.
oxidation becomes worse, and elution of calcium content increases. Finally, the product is ultrafine particles of about 50A, which dissolve and disappear when a strong acid is added and separated as in the patent application, so depending on the target amount of solid solution such as CaO,
It is necessary to wash with dilute acetic acid or aqueous ammonia.

また発明者は含水状態の水酸化ジルコニウム沈澱を水洗
後、水酸化カルシウム水溶液を加えて混合した懸濁液ま
たは糊状物のみの加熱熟成によって、 CaOの含有量
の少い重力型、または立方型のジルコニア単結晶超微粒
子か生成することを新たに発見した。共沈させずに行う
この方法は水酸化イツトリウムでは成功せず、水酸化カ
ルシウムのように比1咬的塩基に1の強い場合に増して
いる1、以1−の方法は原特許願の方法を僅かに改良す
るものであるが、その効果は絶大であり、従来全く得ら
れていなかったZrO2−CaO固溶体中結晶微粒子の
分散したゾルの生成を可能にするものであり。
In addition, the inventors washed the zirconium hydroxide precipitate in a water-containing state with water, added an aqueous calcium hydroxide solution, and heat-aged only the mixed suspension or paste-like material to produce a gravity type or cubic type with a low CaO content. We have newly discovered that zirconia single crystal ultrafine particles can be produced. This method without co-precipitation is not successful with yttrium hydroxide, and is increasing in cases where yttrium hydroxide is a strong base such as calcium hydroxide. Although this is a slight improvement, the effect is enormous, and it enables the production of a sol in which crystalline fine particles are dispersed in a ZrO2-CaO solid solution, which has not been previously possible.

その他車J+’; Hの強い2価金属イオン、例えはB
、1゜Srなどにも適用fir能である。この結果、稀
−1類几素に比らへ安価な2価金属酸化物をZr(’)
2の安定化剤または牢安定化剤とするジルコニア糸超徹
Kt了がセラミック原料として人I11に使用可能とな
り、また微粒子であることは2611i金属イオンを添
加するセラミックス用原料としても価値の高いものであ
る。
Other cars J+'; Strong divalent metal ion of H, for example B
, 1°Sr, etc. As a result, Zr(') is a divalent metal oxide that is cheaper than rare class 1 phosphorus.
The zirconia thread used as a stabilizer or a stabilizing agent in No. 2 can now be used as a raw material for ceramics, and its fine particles make it highly valuable as a raw material for ceramics to which 2611i metal ions are added. It is.

実施例1 試薬塩化ジルコニル(ZrOCl2・8H20)87y
を水約500 mlに溶解し、これに1:1アンモニア
水を1−分1d加えて水酸化ジルコニウムの白色性、澱
を生成させた1、これを水酸化カルシウムの飽和水溶液
でデカンテーションを繰返して洗滌した。このようにし
て111られる水酸化ジルコニウム沈澱と水酸化カルシ
ウム水溶液との混合懸濁液を約500 mlに調製し、
これを密封テフロン容訝中で120°Cに30時間保持
熟成したところ、粘性の少い懸濁液を得た。これを1N
稀塩酸で注意深<6IC滌と分離を繰返し、最後にアル
コールで2回デカンテーションした後、60°Cで乾燥
して固体塊を得j:。この固体塊は水に容易に分散して
任意の濃度のツルをりえる。このツルは電子顕微鏡によ
れば原特許の実施例(Z ro2− Y203系固溶体
)の場合と殆んど同一の一辺約10OAの9一方体に近
い形状の単結晶で、Ll:に孤t’/: L分1PIb
た超微粒子であることが確かめられた。
Example 1 Reagent zirconyl chloride (ZrOCl2.8H20) 87y
was dissolved in about 500 ml of water, and 1:1 ammonia water was added thereto for 1 minute to form a white sludge of zirconium hydroxide. 1. This was repeatedly decanted with a saturated aqueous solution of calcium hydroxide. I washed it. A mixed suspension of the zirconium hydroxide precipitate obtained in this way and an aqueous calcium hydroxide solution was prepared to a volume of about 500 ml,
When this was aged in a sealed Teflon container at 120°C for 30 hours, a suspension with low viscosity was obtained. This is 1N
The separation was carefully repeated with dilute hydrochloric acid for <6 IC, and finally, after decantation twice with alcohol, a solid mass was obtained after drying at 60°C. This solid mass can be easily dispersed in water to form any desired concentration. According to an electron microscope, this vine is a single crystal with a shape close to a 9-sided solid with approximately 10 OA on each side, which is almost the same as that of the example of the original patent (Z ro2- Y203 solid solution), and there is an isolated t' in Ll: /: L minute 1PIb
It was confirmed that the particles were ultrafine particles.

実施例2 試薬塩化ジルコニル(ZrOCl 2 ’ 8 H2O
)8711を塩化カルシウム(CaC12) 8.49
 (ZrO2に対しCaO約10mo1%に相当する)
を水約500 mlに溶解し、これを6N苛性ソーダ溶
液中に滴下し、ジルコニウムとカルシウムの共沈水酸化
物を得た。これを水酸化カルシウムの飽和水溶液でデカ
ンテーションを繰返して洗滌した。このようにして得ら
れる共沈水酸化物と水酸化カルシウム飽和水溶液との混
合懸濁液を約500 ml調製し、これを97”Cで1
週間熟成したところ、粘性の少い懸濁液を得た。これを
IN酢酸で注意深く洗滌と分離を繰返し、最後にアルコ
ールで2回デカンテーションした後、60°Cに乾燥し
て固体塊を得た。この固体塊は水に容易に分1枚して任
意の濃度のゾルを与える。電子顕微鏡によれは立方体状
の頂点が丸味を帯びる以外は実施例1とほぼ保様の形状
の単結晶で、5に孤%’1し分1孜した超微粒子である
ことが確かめられた。
Example 2 Reagent Zirconyl chloride (ZrOCl 2' 8 H2O
)8711 as calcium chloride (CaC12) 8.49
(Equivalent to about 10 mo1% of CaO with respect to ZrO2)
was dissolved in about 500 ml of water, and this was added dropwise to a 6N caustic soda solution to obtain a co-precipitated hydroxide of zirconium and calcium. This was washed by repeated decantation with a saturated aqueous solution of calcium hydroxide. Approximately 500 ml of a mixed suspension of the coprecipitated hydroxide thus obtained and a saturated aqueous calcium hydroxide solution was prepared, and this was heated at 97"C for 1 hour.
After aging for a week, a suspension with low viscosity was obtained. This was carefully washed and separated repeatedly with IN acetic acid, finally decanted twice with alcohol, and dried at 60°C to obtain a solid mass. This solid mass can be easily dissolved in water to give a sol of any concentration. By electron microscopy, it was confirmed that the crystal was a single crystal with a shape almost identical to that of Example 1 except that the cube-shaped apex was rounded, and that it was an ultrafine particle with an arc ratio of 1 to 5.

実施例3 試桑硝酸ジルコニルと硝酸バリウムの等モル混合水溶液
を3N・苛性カリ水溶液中に滴下し、水酸化ジルコニウ
ムと水酸化バリウムの共沈物を得た。これを水酸化バリ
ウム飽和水溶液で十分洗滌した乳液状混合懸濁液を97
°Cで1週間熟成したところ粘P1の少い懸濁液を得た
。これはIN・アンモニア水て注意深く洗滌した後、加
熱によりアンモニアを除去した。電子顕微鏡によれば約
300 Aの超微1l11ンr・の分1汐したゾルであ
り、乾燥物のX線回折はBaZrO3の結晶格子を示し
た。
Example 3 An equimolar mixed aqueous solution of test mulberry zirconyl nitrate and barium nitrate was dropped into a 3N caustic potassium aqueous solution to obtain a coprecipitate of zirconium hydroxide and barium hydroxide. This was thoroughly washed with a saturated aqueous solution of barium hydroxide to obtain a milky mixed suspension of 97%
After aging at °C for one week, a suspension with low viscosity P1 was obtained. After carefully washing with IN/ammonia water, the ammonia was removed by heating. According to an electron microscope, it was an ultrafine sol of about 300 A, and X-ray diffraction of the dry product showed a crystal lattice of BaZrO3.

Claims (3)

【特許請求の範囲】[Claims] (1) iF方またはSy方型の結晶格子を持ち、 2
00λ以下のほぼ均一粒径の孤立したZr02− Ca
O系固溶固溶体1ド結微粒子の分散したゾル。
(1) It has an iF or Sy crystal lattice, and 2
Isolated Zr02-Ca with almost uniform particle size of less than 00λ
A sol in which fine particles of an O-based solid solution are dispersed.
(2) ジルコニウム塩水溶液に塩基を加えて沈澱を生
成させ、可溶部分の大半を水洗除去した後、。 アルカリ土類金属の水酸化物又はその水溶液を加え、t
;1られる混合懸濁液または糊状物を90°C〜200
°Cの温度に加熱熟成することを特徴とする。 11一方またはX7方型のZrO,、系単結晶超微粒子
の分散したゾルの製造方法。
(2) After adding a base to an aqueous zirconium salt solution to form a precipitate and removing most of the soluble portion by washing with water. Add alkaline earth metal hydroxide or its aqueous solution, t
;1 Mixed suspension or paste-like material is heated to 90°C to 200°C.
It is characterized by heating and aging at a temperature of °C. 11 A method for producing a sol in which one-sided or X7-gonal ZrO, single-crystal ultrafine particles are dispersed.
(3)ジルコニウムとカルシウム等2価の金属イオンの
共沈水酸化物を共沈物から2価の金属水酸化物が溶11
冒ッない程度にπ′J)”i’、 jc 2価金属水酸
化物水溶液で洗滌し、得られる共沈水酸化物と2価金属
水酸化物飽和水溶液との混合懸濁液または糊状物を90
 ”Cへ200°Cの温度に加熱熟成することを特徴と
する2価金属イオンを含むジルコニア系単結晶超微粒子
の分散したゾルの製造方法。
(3) Co-precipitated hydroxide of divalent metal ions such as zirconium and calcium. Divalent metal hydroxide is dissolved from the coprecipitate 11
π'J)"i', jc Wash with a divalent metal hydroxide aqueous solution to the extent that it does not cause damage, and a mixed suspension or paste-like substance of the obtained coprecipitated hydroxide and a divalent metal hydroxide saturated aqueous solution 90
A method for producing a sol in which zirconia-based single crystal ultrafine particles containing divalent metal ions are dispersed, the method comprising heating and aging at a temperature of 200°C.
JP59032114A 1984-02-21 1984-02-21 Sol dispersed with ultra-fine particle of zirconia single crystal, and its production Granted JPS60176920A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59032114A JPS60176920A (en) 1984-02-21 1984-02-21 Sol dispersed with ultra-fine particle of zirconia single crystal, and its production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59032114A JPS60176920A (en) 1984-02-21 1984-02-21 Sol dispersed with ultra-fine particle of zirconia single crystal, and its production

Publications (2)

Publication Number Publication Date
JPS60176920A true JPS60176920A (en) 1985-09-11
JPH0472768B2 JPH0472768B2 (en) 1992-11-19

Family

ID=12349870

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59032114A Granted JPS60176920A (en) 1984-02-21 1984-02-21 Sol dispersed with ultra-fine particle of zirconia single crystal, and its production

Country Status (1)

Country Link
JP (1) JPS60176920A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927622A (en) * 1987-06-19 1990-05-22 Manville Corporation Process for producing zirconium based granules
US5053214A (en) * 1987-06-19 1991-10-01 Manville Corporation Process for producing zirconium based granules
US5112781A (en) * 1987-06-19 1992-05-12 Manville Corporation Process for producing zirconium based granules and zirconium oxide fibers
JPH04329153A (en) * 1991-04-30 1992-11-17 Victor Co Of Japan Ltd Controlling method for current supply of thermal head
US5223176A (en) * 1988-09-30 1993-06-29 Nissan Chemical Industries, Ltd. Zirconia sol and method for making the same
WO2006115043A1 (en) 2005-04-18 2006-11-02 Nissan Chemical Industries, Ltd. Acidic zirconia sol and method for producing same
US7241437B2 (en) 2004-12-30 2007-07-10 3M Innovative Properties Company Zirconia particles
WO2008023612A1 (en) 2006-08-25 2008-02-28 National University Corporation The University Of Electro-Communications Photosensitive composition comprising organic-zirconia composite microparticle
US7553474B2 (en) 2004-08-17 2009-06-30 Nissan Chemical Industries, Ltd. Method for producing metal oxide sol
US7629389B2 (en) 2005-06-29 2009-12-08 Nissan Chemical Industries, Ltd. Production method of alkaline zirconia sol
US7833621B2 (en) 2005-03-11 2010-11-16 3M Innovative Properties Company Light management films with zirconia particles
JP2011057531A (en) * 2009-09-14 2011-03-24 Sumitomo Osaka Cement Co Ltd Alkaline earth metal oxide-doped zirconia nanoparticle and method for producing the same
JP2011057532A (en) * 2009-09-14 2011-03-24 Sumitomo Osaka Cement Co Ltd Transparent dispersion liquid of alkaline earth metal oxide-doped zirconia nanoparticle, and transparent composite

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927622A (en) * 1987-06-19 1990-05-22 Manville Corporation Process for producing zirconium based granules
US5053214A (en) * 1987-06-19 1991-10-01 Manville Corporation Process for producing zirconium based granules
US5112781A (en) * 1987-06-19 1992-05-12 Manville Corporation Process for producing zirconium based granules and zirconium oxide fibers
US5223176A (en) * 1988-09-30 1993-06-29 Nissan Chemical Industries, Ltd. Zirconia sol and method for making the same
JPH04329153A (en) * 1991-04-30 1992-11-17 Victor Co Of Japan Ltd Controlling method for current supply of thermal head
EP2468682A1 (en) 2004-08-17 2012-06-27 Nissan Chemical Industries, Ltd. Method for producing zirconia sol
US7553474B2 (en) 2004-08-17 2009-06-30 Nissan Chemical Industries, Ltd. Method for producing metal oxide sol
US7429422B2 (en) 2004-12-30 2008-09-30 3M Innovative Properties Company Zirconia particles
US7241437B2 (en) 2004-12-30 2007-07-10 3M Innovative Properties Company Zirconia particles
US7674523B2 (en) 2004-12-30 2010-03-09 3M Innovative Properties Company Zirconia particles
US7833621B2 (en) 2005-03-11 2010-11-16 3M Innovative Properties Company Light management films with zirconia particles
US7691910B2 (en) 2005-04-18 2010-04-06 Nissan Chemical Industries, Ltd. Acidic zirconia sol and production method of the same
US8058318B2 (en) 2005-04-18 2011-11-15 Nissan Chemical Industries, Ltd. Acidic zirconia sol and production method of the same
WO2006115043A1 (en) 2005-04-18 2006-11-02 Nissan Chemical Industries, Ltd. Acidic zirconia sol and method for producing same
US7629389B2 (en) 2005-06-29 2009-12-08 Nissan Chemical Industries, Ltd. Production method of alkaline zirconia sol
WO2008023612A1 (en) 2006-08-25 2008-02-28 National University Corporation The University Of Electro-Communications Photosensitive composition comprising organic-zirconia composite microparticle
JP2011057531A (en) * 2009-09-14 2011-03-24 Sumitomo Osaka Cement Co Ltd Alkaline earth metal oxide-doped zirconia nanoparticle and method for producing the same
JP2011057532A (en) * 2009-09-14 2011-03-24 Sumitomo Osaka Cement Co Ltd Transparent dispersion liquid of alkaline earth metal oxide-doped zirconia nanoparticle, and transparent composite

Also Published As

Publication number Publication date
JPH0472768B2 (en) 1992-11-19

Similar Documents

Publication Publication Date Title
JPS60176920A (en) Sol dispersed with ultra-fine particle of zirconia single crystal, and its production
JP3284413B2 (en) Method for producing hydrated zirconia sol and zirconia powder
JPS63274663A (en) Composition for zirconia ceramic material
IE913935A1 (en) Process for the manufacture of ammonium rare-earth double¹oxalates and their uses for the manufacture of rare-earth¹oxides
US20090215614A1 (en) Colloidal dispersions of compounds of cerium and at least one of zirconium, rare earths, titanium and/or tin and preparation/applications thereof
JPH01153530A (en) Crystalline zirconium oxide powder, method for its manufacture and method for manufacturing sintered ceramic
KR930001257B1 (en) Fine coagulated paticles of ultrafine monoclinic zirconia crystals oriented in a fiber bundle-like form and method of
JP3250243B2 (en) Method for producing zirconia-based sol
JPH0346407B2 (en)
JP2868176B2 (en) Method for producing rare earth element oxide powder
GB2250735A (en) Zirconia coated with hydrous cerium oxide and at least one hydrous oxide of lanthanum,neodymium or praseodymium.
JPH01294521A (en) Production of aqueous colloid dispersion of rare earth element compound and product
JP2000239019A (en) Production of rare earth compound
JPS61141619A (en) Production of zirconia fine powder
JP2021098643A5 (en)
JPH11189469A (en) Oxide sintered compact of fluorite type or its derivative structure and its production
JPH07118016A (en) Uniform-composition zirconia solid solution monodisperse fine globular powder and its production
JPH0611404B2 (en) How to make catalyst-related materials
JPS61106456A (en) Manufacture of high density pzt base piezoelectric ceramics
JPS61122121A (en) Production of rare earth metal oxide powder
JP3254693B2 (en) Preparation of hydrated zirconia sol and zirconia powder
JPH0472773B2 (en)
JPS6183627A (en) Production of powdery zirconium oxide
JPS61106457A (en) Manufacture of plzt light permeable ceramics
JPH07109118A (en) Production of rare earth element oxide