JPH0346407B2 - - Google Patents
Info
- Publication number
- JPH0346407B2 JPH0346407B2 JP57215208A JP21520882A JPH0346407B2 JP H0346407 B2 JPH0346407 B2 JP H0346407B2 JP 57215208 A JP57215208 A JP 57215208A JP 21520882 A JP21520882 A JP 21520882A JP H0346407 B2 JPH0346407 B2 JP H0346407B2
- Authority
- JP
- Japan
- Prior art keywords
- solid solution
- sol
- zirconia
- dispersed
- hydroxide
- 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 24
- 239000013078 crystal Substances 0.000 claims description 23
- 239000006104 solid solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 239000011882 ultra-fine particle Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- -1 basic metal ions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【発明の詳細な説明】
ジルコニアに酸化イツトリウムを３〜10mol／
％固溶させた多結晶体セラミツクスが、最近フ
アインセラミツクス、特に自動車排ガス用や溶鋼
用の酸素センサー並びにエンジン内張等の高強靭
性などとして使用され始めている。これらはジル
コニアの正方または立方型固溶体結晶の特性を利
用するもので、Y2O3の他、Ca、Mg、およびSc
やYb、La、Nd、Gdなどの稀土類元素の酸化物
が同様な効果を持つことが知られている。[Detailed description of the invention] Adding 3 to 10 mol/yttrium oxide to zirconia
% solid solution polycrystalline ceramics have recently begun to be used as fine ceramics, especially oxygen sensors for automobile exhaust gas and molten steel, and high strength and toughness for engine linings. These utilize the properties of square or cubic solid solution crystals of zirconia, and in addition to Y 2 O 3 , Ca, Mg, and Sc
It is known that oxides of rare earth elements such as Yb, La, Nd, and Gd have similar effects.
これらの固溶体フアインセラミツクスの製造、
特に強靭性や耐熱衝撃性のジルコニアセラミツク
スでは均一な立方型または正方型固溶体微粒子の
調製が最重要課題であり、出発原料が300Å以下
の超微結晶でかつ強固な２次凝集粒子を形成して
いないことが特に望まれているが、従来このよう
な固溶体単結晶超微粒子の分散したゾルは生成さ
れていない。 Production of these solid solution fine ceramics,
In particular, for zirconia ceramics with strong toughness and thermal shock resistance, the most important issue is the preparation of uniform cubic or square solid solution fine particles, and the starting materials are ultrafine crystals of 300 Å or less and form strong secondary agglomerated particles. Although it is particularly desired that there be no solid solution single crystal ultrafine particles, such a sol in which solid solution single crystal ultrafine particles are dispersed has not been produced so far.
現在ジルコニア系固溶体微粒子の一般的製造方
法はジルコニウムと他の金属の混合塩または混合
水酸化物を数百℃で仮焼熱分解するものである。
しかしこの方法では出発塩や水酸化物の形骸が残
り、粗大な２次凝集粒子しか得られず、機械的摩
砕が不可欠であり、また純度を保つて500Å以下
に分散した状態にすることはほとんど不可能であ
る。現在知られている最も優れた固溶体微粒子は
混合アルコキシドの加水分解によつて生成する非
晶質ゾルを乾燥、仮焼するものであるが若干の粒
子凝集は不可避である。また結晶性の微粒子を溶
液中に生成させる方法として水溶性ジルコニウム
塩の常圧下での加熱加水分解および水熱加圧下で
の加水分解が知られており、何れも結晶性の微粒
子の分散したゾルを与えるが、生成結晶は単斜型
であり、価または価の塩基性金属イオンを共
存させて加水分解しても析出物はそれらを固溶し
た正方型もしくは立方型結晶とならず、単斜型結
晶しか得られていなかつた。最近に到り、この方
法を改良して、共沈水酸化物をPH10の塩基性領域
で190℃に水熱処理することによつて固溶体結晶
微粒子を調製可能であることが報告された
（Trans.J.Brit.Ceram.Soc.，79 105（1980））。 Currently, the general method for producing zirconia-based solid solution fine particles is to calcinate and thermally decompose a mixed salt or mixed hydroxide of zirconium and other metals at several hundred degrees Celsius.
However, with this method, traces of the starting salt and hydroxide remain, and only coarse secondary agglomerated particles are obtained. Mechanical grinding is essential, and it is difficult to maintain purity and obtain a dispersed state of less than 500 Å. Almost impossible. The best solid solution fine particles currently known are those produced by drying and calcining an amorphous sol produced by hydrolysis of mixed alkoxides, but some particle aggregation is unavoidable. In addition, as methods for producing crystalline fine particles in a solution, heating hydrolysis of water-soluble zirconium salts under normal pressure and hydrothermal hydrolysis under pressure are known, and both methods produce a sol in which crystalline fine particles are dispersed. However, the formed crystals are monoclinic, and even if hydrolyzed in the coexistence of valent or valent basic metal ions, the precipitates do not form square or cubic crystals with these metals dissolved in solid solution, but are monoclinic. Only type crystals were obtained. Recently, it has been reported that solid solution crystalline particles can be prepared by improving this method and hydrothermally treating coprecipitated hydroxide at 190°C in the basic range of PH10 (Trans.J .Brit.Ceram.Soc., 79 105 (1980)).
しかし反応生成物は1500±35Åとかなり粗粒で
あり、しかも共沈水酸化物の形骸が残り、組成は
必ずしも均一でなく、孤立した単結晶微粒子とな
らないことは上記の報告の記載からも明らかであ
る。 However, it is clear from the description in the above report that the reaction product is quite coarse grained at 1500±35 Å, and remains of coprecipitated hydroxide, and the composition is not necessarily uniform and does not form isolated single-crystal fine particles. be.
本発明は上述したジルコニウム塩の加熱加水分
解法（100℃附近でかつPH３以下の低PH領域）と
共沈水酸化物の高温水熱反応法（190℃でかつPH
10の高PH領域）の中間領域に、正方型または立方
型の固溶体単結晶超微粒子の生成領域のあること
を発見し、300Å以下のほぼ均一粒径の孤立した
ジルコニア系固溶体単結晶超微粒子の分散したゾ
ルを始めて生成したものである。すなわち、含水
状態の水酸化ジルコニウムおよびイツトリウム、
スカンジウム、稀土類元素の少くとも１種を含む
水酸化物の共沈物を合量で0.2mol／以上の割
合で含有し、そのPH値が７〜11の範囲にある混合
懸濁液または糊状物を80〜180℃の温度に加熱し、
十分な時間保持した後これに十分量の強酸を加え
て可溶性の非晶質部分を溶解分離除去することを
特徴とするものである。この方法によつて生成す
るゾルは従来如何なる方法によつても生成されな
かつた種類のものであり、後述するように極めて
優れた特性と応用を持つものである。なお上述に
おいて、水酸化ジルコニウム、ジルコニア等の言
葉は、普通に含有される10％以下のHfO2および
その他の微量不純物を含有する一般的な意味のも
のを含めて意味することは勿論である。 The present invention is based on the above-mentioned thermal hydrolysis method of zirconium salt (nearly 100℃ and low PH region of 3 or less) and high-temperature hydrothermal reaction method of coprecipitated hydroxide (at 190℃ and PH 3 or less).
We discovered that there is a region in which square or cubic solid solution single crystal ultrafine particles are generated in the middle region of the high pH region of This was the first time a dispersed sol was produced. That is, zirconium hydroxide and yttrium in a hydrous state,
A mixed suspension or glue containing a coprecipitate of hydroxide containing at least one of scandium and rare earth elements in a total ratio of 0.2 mol or more, and whose PH value is in the range of 7 to 11. Heat the material to a temperature of 80 to 180℃,
After holding for a sufficient period of time, a sufficient amount of strong acid is added to dissolve and separate the soluble amorphous portion. The sol produced by this method is of a type that has not been produced by any conventional method, and has extremely excellent properties and applications as will be described later. In the above description, the words zirconium hydroxide, zirconia, etc. are of course meant to include those containing 10% or less of HfO 2 and other trace impurities that are normally contained.
詳細は明らかではないが、PH７〜11の領域では
非晶質の含水状態共沈水酸化物の各所で局部的な
溶解・析出過程もしくは局部的な微小結晶化過程
が起るものと考えられ、強酸処理は残余の非晶質
部分を溶解することによつて完全に孤立した超微
結晶粒子のみを分散状態で残すものと思われる。 Although the details are not clear, it is thought that in the pH range of 7 to 11, local dissolution/precipitation processes or local microcrystalization processes occur at various locations in the amorphous water-containing co-precipitated hydroxide. The treatment appears to dissolve the remaining amorphous portion, leaving only completely isolated ultrafine crystalline particles in a dispersed state.
加熱処理温度は80℃以下では生成に長大な時間
が要し経済的にも実際的でない。一方180℃以上
では反応時間は短縮されるが、装置および処理費
が高価となるばかりでなく生成結晶が粗大とな
り、生成物は組成、粒度ともに不均一となる。本
発明方法における実際的温度範囲は80℃〜180℃
であり、最も効率的経済的な温度範囲は90℃〜
120℃である。 If the heat treatment temperature is 80° C. or lower, it will take a long time to form and is not economically practical. On the other hand, at 180° C. or higher, the reaction time is shortened, but not only do the equipment and processing costs become expensive, but the crystals formed become coarse and the product becomes non-uniform in both composition and particle size. The practical temperature range for the method of the present invention is 80°C to 180°C
The most efficient and economical temperature range is 90℃~
The temperature is 120℃.
本発明の最大の特徴はジルコニア系の正方型ま
たは立方型の固溶体が、完全に孤立した単結晶の
超微粒子として分散状態で得られることである。
この様なものは従来全く得られていないし、報告
もない。しかしながら孤立化超微粒子であること
は以下に述べるように極めて優れた特徴を持つの
である。 The greatest feature of the present invention is that a zirconia-based square or cubic solid solution can be obtained in a dispersed state as completely isolated single-crystal ultrafine particles.
Nothing like this has ever been obtained or reported. However, the fact that they are isolated ultrafine particles has extremely excellent characteristics as described below.
本発明によつて得られるジルコニア系固溶体単
結晶超微粒子ゾルは完全に孤立化した超微粒子か
ら成るので、凝集、解膠が容易であり、簡単に水
系あるいは有機溶媒系の濃厚ゾルを得ることがで
きる特徴を持つ。例えば生成する水系ゾルに塩酸
を加え軟凝集沈降させ、過脱水し、アルコール
で洗滌後、乾燥したゲル状物は水または水系の調
合物中に容易に分散する特性を持つ。従つて従来
得られなかつた50％以上の高濃度ゾルが容易に調
製でき、また例えば水性の有機高分子溶液中に分
散させて繊維状もしくは薄膜状に成形し、乾燥、
脱脂、焼成すれば、正方型または立方型のジルコ
ニア系固溶体の緻密な多結晶繊維や多結晶膜また
は薄板を得ることが可能である。しかも成形時、
従来得られた如何なるジルコニア系固溶体多結晶
繊維やフイルムよりも緻密であり、微粒子組織で
あり、均一であるので、焼成温度は700〜1300℃
と極めて低温で済み、焼結体の組織も0.2μ以下と
極めて超微粒子が可能等の優れた特徴を持つ。本
発明ゾルは完全孤立化超微粒子から成るので、電
気泳動電着などによる皮膜形成にも極めて適して
いる。またゾル・ゲル法や凍結乾燥法などによる
造粒装作により極めて優れた焼結体用微粉末が得
られ、乾式プレス用の原料粉末の調製も容易であ
り、しかも１次超微粒子がそれぞれ固溶体である
から粉末粒子の組成変動は全く生じない極めて均
質な易焼結性粉末となる。 Since the zirconia-based solid solution single crystal ultrafine particle sol obtained by the present invention is composed of completely isolated ultrafine particles, it is easy to flocculate and deflocculate, and it is possible to easily obtain a concentrated aqueous or organic solvent-based sol. have the characteristics of being able to For example, hydrochloric acid is added to the resulting aqueous sol to cause soft coagulation and sedimentation, excessive dehydration is performed, and after washing with alcohol, the dried gel-like material has the property of being easily dispersed in water or an aqueous formulation. Therefore, it is possible to easily prepare a high concentration sol of 50% or more, which could not be obtained conventionally, and for example, it can be dispersed in an aqueous organic polymer solution, formed into a fiber or thin film, dried,
By degreasing and firing, it is possible to obtain dense polycrystalline fibers, polycrystalline films, or thin plates of square or cubic zirconia solid solution. Moreover, during molding,
It is denser than any conventionally obtained zirconia solid solution polycrystalline fiber or film, has a fine grain structure, and is uniform, so the firing temperature is 700 to 1300℃.
It has excellent features such as requiring extremely low temperatures, and the structure of the sintered body is 0.2μ or less, making it possible to form extremely ultrafine particles. Since the sol of the present invention is composed of completely isolated ultrafine particles, it is extremely suitable for film formation by electrophoretic electrodeposition. In addition, extremely excellent fine powder for sintered bodies can be obtained by granulation using the sol-gel method or freeze-drying method, and raw material powder for dry pressing can be easily prepared, and the primary ultrafine particles are each formed in a solid solution. Therefore, the composition of the powder particles does not change at all, resulting in an extremely homogeneous and easily sinterable powder.
本発明方法では従来全く得られていなかつた、
分散性、混合性に優れた完全に孤立した正方乃至
立方型の結晶格子を持つジルコニア系固溶体単結
晶の超微粒子が得られるが、なお次に述べるよう
に、製造が高効率であり工業的大量生産が可能な
点で極めて経済的価値の高いものである。すなわ
ち本発明ではジルコニウム及び添加金属の出発原
料をそれらの水酸化物の懸濁状態で処理するため
取扱いが容易であり、また1mol／以上の濃厚
液に相当する量が簡単に処理可能となり、同一容
量の容器で大量の処理が可能である。 The method of the present invention has not previously been able to obtain
Ultrafine particles of zirconia-based solid solution single crystals with completely isolated square or cubic crystal lattices with excellent dispersibility and mixability can be obtained, but as described below, production is highly efficient and it is not possible to produce large quantities for industrial production. It has extremely high economic value in that it can be produced. In other words, in the present invention, the starting materials of zirconium and additive metals are processed in a suspended state of their hydroxides, so handling is easy, and an amount equivalent to 1 mol/or more of a concentrated liquid can be easily processed, and the same It is possible to process a large amount with a large capacity container.
実施例 １
試薬塩化ジルコニル（ZrOCl2・8H2O）87ｇお
よび酸化イツトリウム（Y2O3）6.8ｇ（ZrO2に対
しY2O310mol％に相当する）を水約500mlに溶解
し、これに１：１アンモニア水を十分量加えて水
酸化ジルコニウムと水酸化イツトリウムの共沈を
生成させた。これを吸引過して得られる含水状
態のケーキに試薬塩化ジルコニルを1.0ｇおよび
10mlの蒸留水を加えて糊状スラリーとした。この
状態でPH約８である。この混合物を97℃で10日間
保持したところ、粘性の少い乳濁液を得た。これ
に12N塩酸約30mlを加えて放置すると、透明液部
分と沈澱に分離してくるのでこれを過し、稀塩
酸で洗滌後、アルコール中に分散し２回デカンテ
ーシヨンした後60℃で半乾燥して固体塊を得た。
この固体塊は水に容易に分散して任意の濃度のゾ
ルを与える。このゾルは稀薄の場合はほとんど透
明であるが、塩酸によつて軟凝集し沈降する。半
乾燥固体塊はＸ線回析によれば立方型の結晶格子
を持つジルコニア固溶体結晶超微粒子の集合物で
あり、その回析ピークの半価幅から結晶粒径は約
100Å、（111）および（220）の回析角から格子定
数はａ＝5.16Åであつた。これからY2O3の固溶
量は10mol／以上であることが計算される。ま
たゾル分散状態の電子顕微鏡写真は第１図に示す
ようで、これから各粒子は１辺約100Åのきれい
な立方体をした単結晶で互に孤立、分散している
ことが確められた。Example 1 Reagents 87 g of zirconyl chloride (ZrOCl 2 .8H 2 O) and 6.8 g of yttrium oxide (Y 2 O 3 ) (corresponding to 10 mol % of Y 2 O 3 based on ZrO 2 ) were dissolved in about 500 ml of water. A sufficient amount of 1:1 ammonia water was added to produce a coprecipitate of zirconium hydroxide and yttrium hydroxide. 1.0g of reagent zirconyl chloride and
10 ml of distilled water was added to form a pasty slurry. In this state, the pH is about 8. When this mixture was kept at 97°C for 10 days, a less viscous emulsion was obtained. When about 30ml of 12N hydrochloric acid is added to this and left to stand, it will separate into a clear liquid and a precipitate, which will be filtered, washed with diluted hydrochloric acid, dispersed in alcohol, decanted twice, and then heated at 60°C for half a time. Drying yielded a solid mass.
This solid mass is easily dispersed in water to give a sol of any concentration. This sol is almost transparent when diluted, but it softens and precipitates when exposed to hydrochloric acid. According to X-ray diffraction, the semi-dry solid mass is an aggregate of ultrafine particles of zirconia solid solution crystals with a cubic crystal lattice, and the crystal grain size is approximately
From the diffraction angles of 100 Å, (111) and (220), the lattice constant was a=5.16 Å. From this, it is calculated that the solid solution amount of Y 2 O 3 is 10 mol/or more. Furthermore, an electron micrograph of the sol dispersion state is shown in Figure 1, and it was confirmed from this that each particle was isolated and dispersed as a neat cubic single crystal with a side of approximately 100 Å.
実施例 ２
実施例１と同様な実験において、共沈物の含水
状態ケーキに対し塩化ジルコニルの代りに塩化イ
ツトリウム、硝酸イツトリウムまたは塩酸を加え
て実験し、ほぼ類似の結果を得た。しかし共沈物
として水酸化イツトリウムの代りに水酸化カルシ
ウムまたは水酸化マグネシウムを用いた場合には
PH値は９以下とならず、正方型または立方型の結
晶は析出しなかつた。Example 2 In an experiment similar to Example 1, yttrium chloride, yttrium nitrate, or hydrochloric acid was added instead of zirconyl chloride to the water-containing coprecipitate cake, and almost similar results were obtained. However, when calcium hydroxide or magnesium hydroxide is used instead of yttrium hydroxide as a coprecipitate,
The pH value did not fall below 9, and no square or cubic crystals were precipitated.
第１図は本発明方法によつて得られたジルコニ
ア・イツトリア系固溶体単結晶超微粒子の分散し
たゾルの乾燥物の電子顕微鏡写真である。
FIG. 1 is an electron micrograph of a dried sol in which zirconia-yttoria solid solution single crystal ultrafine particles obtained by the method of the present invention are dispersed.
Claims (1)
以下のほぼ均一粒径の孤立したジルコニア系固溶
体単結晶超微粒子の分散したゾル。 ２ 含水状態の水酸化ジルコニウムおよびイツト
リウム、スカンジウム、稀土類元素の少くとも１
種を含む水酸化物の共沈物を合量で0.2mol／
以上の割合で含有し、そのPH値が７〜11の範囲に
ある混合懸濁液または糊状物を80〜180℃の温度
に加熱し、十分な時間保持した後これに十分量の
強酸を加えて可溶性の非晶質部分を溶解分離除去
することを特徴とするジルコニア系固溶体単結晶
超微粒子の分散したゾルの製造方法。[Claims] 1. Having a square or cubic crystal lattice, 300 Å
A sol in which isolated zirconia-based solid solution single crystal ultrafine particles of approximately uniform particle size are dispersed. 2 At least one of zirconium hydroxide and yttrium, scandium, and rare earth elements in a hydrated state
The total amount of hydroxide coprecipitate containing seeds is 0.2 mol/
A mixed suspension or paste containing the above proportions and a pH value in the range of 7 to 11 is heated to a temperature of 80 to 180°C, held for a sufficient period of time, and then a sufficient amount of strong acid is added to it. A method for producing a sol in which zirconia-based solid solution single-crystal ultrafine particles are dispersed, the method further comprising dissolving and separating a soluble amorphous portion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57215208A JPS59107969A (en) | 1982-12-08 | 1982-12-08 | Zirconia solid solution single crystal super fine particle-dispersed sol and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57215208A JPS59107969A (en) | 1982-12-08 | 1982-12-08 | Zirconia solid solution single crystal super fine particle-dispersed sol and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59107969A JPS59107969A (en) | 1984-06-22 |
| JPH0346407B2 true JPH0346407B2 (en) | 1991-07-16 |
Family
ID=16668478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57215208A Granted JPS59107969A (en) | 1982-12-08 | 1982-12-08 | Zirconia solid solution single crystal super fine particle-dispersed sol and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59107969A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031023A (en) * | 2006-07-28 | 2008-02-14 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconia sol and method for producing the same |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1262813A (en) * | 1986-06-26 | 1989-11-14 | Corning Glass Works | Preparation of high purity, homogeneous zirconia mixtures |
| US4719091A (en) * | 1986-07-01 | 1988-01-12 | Corning Glass Works | Preparation of mono-sized zirconia powders by forced hydrolysis |
| JP2560490B2 (en) * | 1988-09-30 | 1996-12-04 | 日産化学工業株式会社 | Method for producing zirconia sol |
| US5223176A (en) * | 1988-09-30 | 1993-06-29 | Nissan Chemical Industries, Ltd. | Zirconia sol and method for making the same |
| US7241437B2 (en) | 2004-12-30 | 2007-07-10 | 3M Innovative Properties Company | Zirconia particles |
| WO2006098899A2 (en) | 2005-03-11 | 2006-09-21 | 3M Innovative Properties Company | Light management films with zirconia particles |
| JP4963820B2 (en) * | 2005-09-02 | 2012-06-27 | 第一稀元素化学工業株式会社 | Method for producing sol using Zr-O-based particles as dispersoid |
| JP5362416B2 (en) * | 2009-04-15 | 2013-12-11 | 旭化成ケミカルズ株式会社 | Organic / inorganic composite composition |
| JP2012086104A (en) * | 2010-10-15 | 2012-05-10 | Asahi Kasei Chemicals Corp | Photocatalyst composition |
| JP5494746B2 (en) * | 2012-07-17 | 2014-05-21 | 住友大阪セメント株式会社 | Method for producing particle aggregate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6143286A (en) * | 1984-08-08 | 1986-03-01 | Matsushita Refrig Co | Sealed type compressor |
-
1982
- 1982-12-08 JP JP57215208A patent/JPS59107969A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6143286A (en) * | 1984-08-08 | 1986-03-01 | Matsushita Refrig Co | Sealed type compressor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031023A (en) * | 2006-07-28 | 2008-02-14 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconia sol and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59107969A (en) | 1984-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4619817A (en) | Hydrothermal method for producing stabilized zirconia | |
| JP2523776B2 (en) | Composition for zirconia ceramic material | |
| US4810680A (en) | Preparation of high purity, homogeneous zirconia mixtures | |
| JP3284413B2 (en) | Method for producing hydrated zirconia sol and zirconia powder | |
| US4873064A (en) | Powder of coagulated spherical zirconia particles and process for producing them | |
| JPH0346407B2 (en) | ||
| AU609280B2 (en) | Process for preparing submicronic powders of zirconium oxide stabilized with yttrium oxide | |
| JP2004517020A (en) | Zirconia in the form of fine powder, zirconia hydroxycarbonate and methods for producing them | |
| JPH04295014A (en) | Stabilized metal oxide composition and method of preparing same | |
| JPH02258624A (en) | Rare earth element oxide with new morphological feature and preparation thereof | |
| JPH0472772B2 (en) | ||
| JPH06305726A (en) | Production of powdery oxide of rare earth element | |
| US4786486A (en) | Stabilized zirconia particulates | |
| JPS60210508A (en) | Manufacture of sinterable ceramic fine powder | |
| RU2600636C2 (en) | Method of producing nanocrystalline powder of zirconium dioxide | |
| JPS61141619A (en) | Production of zirconia fine powder | |
| JPH0230663A (en) | Sintered material of zirconia and production thereof | |
| JPH0420851B2 (en) | ||
| KR100473399B1 (en) | Process for the preparation of fine ceramic powders | |
| JPS6172626A (en) | Production of zirconia fine powder | |
| JPH06171944A (en) | Production of zirconium oxide powder | |
| JP2882040B2 (en) | Method for producing hydrated zirconia sol | |
| JP2607519B2 (en) | Manufacturing method of optical ceramics | |
| JPS62212224A (en) | Production of zirconia solid solution crystal fine powder | |
| JP3394071B2 (en) | Method for producing rare earth oxide fine powder |