JPH042657A - High-strenght colored zirconia sintered material and production thereof - Google Patents
High-strenght colored zirconia sintered material and production thereofInfo
- Publication number
- JPH042657A JPH042657A JP2099288A JP9928890A JPH042657A JP H042657 A JPH042657 A JP H042657A JP 2099288 A JP2099288 A JP 2099288A JP 9928890 A JP9928890 A JP 9928890A JP H042657 A JPH042657 A JP H042657A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- mol
- stabilizer
- burning
- powder
- 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
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000463 material Substances 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract 2
- 238000010304 firing Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 6
- 239000011787 zinc oxide Substances 0.000 claims 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 1
- 150000003114 praseodymium compounds Chemical class 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 15
- 239000003086 colorant Substances 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 230000002706 hydrostatic effect Effects 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 229910002637 Pr6O11 Inorganic materials 0.000 abstract 2
- 229910019328 PrCl3 Inorganic materials 0.000 abstract 1
- 229910009523 YCl3 Inorganic materials 0.000 abstract 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 abstract 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 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 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカラージルコニアセラミックスに関し、特に、
黄色で低温焼結性のジルコニアセラミックスに関するも
のである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to colored zirconia ceramics, and in particular,
It relates to yellow, low-temperature sinterable zirconia ceramics.
〔従来の技術と発明が解決しようとする課題〕ジルコニ
ア焼結体、特に正方晶ジルコニア焼結体はその高い強度
と鏡面研磨後の表面光沢の美しさから刃物等の家庭用品
やゴルフシューズスパイク等のスポーツ用品への応用が
進んでいるが、時計ケースやアクセサリ−等の装飾部材
への応用も広がりをみせている。こうした広がる用途に
対応するためには、各種のカラーを持ったカラージルコ
ニアが要望されている。[Prior art and problems to be solved by the invention] Zirconia sintered bodies, especially tetragonal zirconia sintered bodies, are used for household items such as cutlery, golf shoe spikes, etc. due to their high strength and beautiful surface gloss after mirror polishing. Although its application to sporting goods is progressing, its application to decorative parts such as watch cases and accessories is also expanding. In order to meet these expanding uses, colored zirconia with various colors is required.
カラージルコニアの製造方法としては、安定化したジル
コニアに顔料（主に酸化物）を添加混合して焼結する方
法（特開昭５９−１０５０５５）や、安定化剤とともに
少量の着色剤（主に稀土類）を共沈法等で固溶させる方
法（特開昭６２５９５７１）等が粉末の製造方法として
知られている。Colored zirconia can be produced by adding and mixing pigments (mainly oxides) to stabilized zirconia and sintering the mixture (Japanese Patent Application Laid-open No. 59-105055), or by adding a small amount of coloring agent (mainly A method of solid dissolving rare earth elements (rare earths) by a coprecipitation method (Japanese Patent Application Laid-Open No. 6259571) is known as a method for producing powder.
しかし、上記の着色顔料を混合する方法には、添加量が
比較的子いため焼結しにくく焼結体の特性、特に機械的
強度が低下するという大きな問題や、アルミナに較べて
顔料が固溶しにくいため鮮明な色が出にくいといった問
題が残っていた。また、少量の着色剤を共沈法で固溶さ
せる方法には、色の濃度が薄くカラージルコニアとして
は色が不鮮明で用途が限定されるという欠点があった。However, the above method of mixing color pigments has the major problem that the addition amount is relatively small, making it difficult to sinter and reducing the properties of the sintered body, especially the mechanical strength. There remained the problem that it was difficult to produce clear colors because it was difficult to apply. In addition, the method of dissolving a small amount of coloring agent into solid solution by coprecipitation has the disadvantage that the color density is low and the color is unclear as colored zirconia, which limits its uses.
また、これら両方法は焼結性の面では特に改良された点
はなく、顔料添加法にいたってはむしろ焼結性が低下し
強度も低下するという大きな問題点があった。従って、
含量添加法では高温高圧焼結（ＨＩ Ｐ処理）が常用さ
れるなど焼結が容易ではなかった。In addition, both of these methods have no particular improvement in terms of sinterability, and the pigment addition method has the major problem of decreasing sinterability and strength. Therefore,
In the content addition method, sintering is not easy, as high-temperature, high-pressure sintering (HIP treatment) is commonly used.
本発明の目的はかかる従来の着色ジルコニアの欠点を解
消するもので、特に黄色のカラージルコニアを強度を低
下させず、かつ明瞭なカラーで得ることにある。The object of the present invention is to eliminate the drawbacks of conventional colored zirconia, and in particular to obtain yellow colored zirconia with clear color without reducing strength.
〔課題を解決するための手段〕
本発明に係わるカラージルコニア焼結体は、安定化剤と
少量の着色剤並びに焼結助剤とを含む７、 ｒ Ｏ２か
ら成るもので、焼結温度が低く、色調が明瞭で機械的強
度の高い黄色ジルコニア焼結体である。[Means for Solving the Problems] The colored zirconia sintered body according to the present invention is made of 7, r O2 containing a stabilizer, a small amount of coloring agent, and a sintering aid, and has a low sintering temperature. , a yellow zirconia sintered body with a clear color tone and high mechanical strength.
着色剤としてはプラセオジウム（Ｐｒ）化合物を用いる
が、ジルコニア中に安定化剤と共に共沈法、蓚酸塩法、
蒸発乾固法、加水分解法等で添加・固溶する場合には水
溶性化合物、具体的には塩化物、硝酸塩等が使用でき、
また安定化剤を既に含むＺｒＯ２粉に添加する場合には
前記の水溶性化合物の他に酸化物、酢酸塩、炭酸塩など
も使用でき、焼結体中における酸化物としての量が安定
化剤を含むＺｒＯ２に対して０．Ｏ１〜Ｏ，１モル％に
なるように添加するが好ましくは０．０３モル％〜０゜
０７モル％程度である。A praseodymium (Pr) compound is used as a coloring agent, but it can be mixed with a stabilizer in zirconia by coprecipitation method, oxalate method,
Water-soluble compounds, specifically chlorides, nitrates, etc., can be used when adding/dissolving by evaporation to dryness method, hydrolysis method, etc.
In addition, when adding to ZrO2 powder that already contains a stabilizer, oxides, acetates, carbonates, etc. can be used in addition to the water-soluble compounds mentioned above, and the amount of the oxide in the sintered body is the stabilizer. 0.0 for ZrO2 containing O1 to O is added in an amount of 1 mol %, preferably about 0.03 mol % to 0.07 mol %.
焼結助剤としてはＺｎ化合物を用いるが、酸化物や炭酸
塩等の不溶性化合物をはじめ酢酸塩、塩化物等の可溶性
化合物等、焼成後に酸化物となる化合物であれば特に種
類を限定する必要はなく、焼結体中における酸化物とし
ての量が安定化剤を含むＺｒＯ２に対して０．１〜０．
６モル％になるよう添加する。A Zn compound is used as a sintering aid, but the type must be particularly limited if it is a compound that becomes an oxide after sintering, such as insoluble compounds such as oxides and carbonates, as well as soluble compounds such as acetates and chlorides. However, the amount of oxide in the sintered body is 0.1 to 0.0% relative to ZrO2 containing the stabilizer.
Add so that the amount becomes 6 mol%.
安定化剤としては、得られる黄色ジルコニア焼結体が高
強度を必要とする場合には、焼成後Ｙ２０、となるＹ化
合物が最も好ましく （添加量としては１．５モル％〜
７．０モル％） 次いでＣｅ０２（添加量：１０％〜１
６モル％）が好ましいが、高強度を余り必要としない場
合にはＣａ化合物（焼成後ＣａＯとなるもの：８〜１２
モル％）やＭｇ化合物（焼成後Ｍｇとなるもの＝１６〜
２６モル％）も安定化剤として使用できる。As a stabilizer, when the obtained yellow zirconia sintered body requires high strength, a Y compound that gives Y20 after firing is most preferable (the amount added is 1.5 mol % to
7.0 mol%) Then Ce02 (addition amount: 10% to 1
6 mol%) is preferred, but if high strength is not required, Ca compounds (which become CaO after firing: 8 to 12
mol%) and Mg compounds (things that become Mg after firing = 16~
26 mol %) can also be used as a stabilizer.
本発明において着色剤の含有量を、安定化剤を含むＺｒ
Ｏ２に対して０．０１〜０．１モル％に限定した理由は
、着色剤が０．０１モル％未満では着色の効果が得難く
、また、０月モル％を超えてももはや着色効果が変わら
ないためである。In the present invention, the content of the colorant is changed to Zr containing a stabilizer.
The reason for limiting the amount to 0.01 to 0.1 mol % based on O2 is that if the colorant is less than 0.01 mol %, it is difficult to obtain a coloring effect, and even if it exceeds 0 mol %, the coloring effect is no longer obtained. This is because it does not change.
本発明において焼結助剤の添加量を、安定化剤を含むＺ
ｒ（Ｌに対して０．１〜０．６モル％に限定した理由は
、焼結助剤が０．１モル％未満では助剤の効果が出難く
、また、０．６モル％を超えると焼結体特性に悪影響が
でるためである。In the present invention, the amount of the sintering aid added is changed to Z containing the stabilizer.
r (The reason for limiting the amount to 0.1 to 0.6 mol% relative to L is that if the sintering aid is less than 0.1 mol%, the effect of the auxiliary is difficult to be produced, and if it exceeds 0.6 mol% This is because the properties of the sintered body are adversely affected.
本発明に於ける仮焼温度は８００〜１１００℃であるか
、得られる仮焼粉の比表面積は低温仮焼はど大きく、ま
た高温仮焼はど低（なるので好ましい仮焼温度は目的と
する粉末の比表面積により選へばよい。従って、比表面
積１５〜２０ｍの粉末を得たい場合は９００℃前後、６
〜１０Ｍの粉末を得たい場合は１０００〜１０５０℃ぐ
らいの仮焼温度が好ましい。The calcination temperature in the present invention is 800 to 1100°C, or the specific surface area of the resulting calcined powder is large in low-temperature calcinations, and low in high-temperature calcinations. Therefore, if you want to obtain a powder with a specific surface area of 15 to 20 m, the powder should be selected according to the specific surface area of the powder.
When it is desired to obtain a powder of ~10M, a calcination temperature of about 1000 to 1050°C is preferable.
本発明に於ける黄色ジルコニアの焼結温度は、粉末の比
表面積や成形圧力により異なるが、通常比表面積６Ｍの
粉末では成形圧が静水圧２ｔ／ｃｉの場合で１３００〜
１４００℃で、比表面積１５ｒｒｒの粉末で１２００〜
１３００℃の焼結温度で理論密度の９８％以上の焼結体
が得られる。この焼結温度は通常市販されているジルコ
ニア粉末（比表面積ＩＯ〜１５Ｍ）の焼結温度（１４５
０〜１５００°Ｃ）に比べて２００〜３００℃低い温度
である。また、得られる黄色ジルコニア焼結体の曲げ強
度は、ＪＩＳ規格の３点曲げ法で比較した場合、市販さ
れているジルコニア焼結体（Ｙ２Ｏ，含量３モル％品）
と同等かそれ以上の強度を示す。The sintering temperature of yellow zirconia in the present invention varies depending on the specific surface area of the powder and the compacting pressure, but normally for powder with a specific surface area of 6M, when the compacting pressure is hydrostatic pressure 2t/ci, it is 1300~
At 1400℃, powder with a specific surface area of 15rrr has a temperature of 1200~
A sintered body having a theoretical density of 98% or more can be obtained at a sintering temperature of 1300°C. This sintering temperature is the sintering temperature (145
The temperature is 200 to 300 degrees Celsius lower than the average temperature (0 to 1500 degrees Celsius). In addition, the bending strength of the obtained yellow zirconia sintered body was compared using the three-point bending method of the JIS standard.
Shows strength equal to or greater than.
以下に実施例を挙げて本発明をさらに具体的に説明する
。The present invention will be explained in more detail with reference to Examples below.
実施例１
高強度黄色ジルコニア焼結体を製造するに際し、オキシ
塩化ジルコニウムＺｒ０ＣＩ、２００ｇ（１，１２３−
Ｅ−ル） 、ＹＣ１、９，１６４ｇ （０，０４６９％
ル）及びＰ ｒ Ｃｌ ｓ ０．８７０ｇ （０，０
３５２モル）を溶解した酸性水溶液をアンモニア水に滴
下して生成した共沈物をろ過、水洗、アルコール洗浄し
た後１１０℃で減圧乾燥した。得られた乾燥粉を１００
０℃で３時間仮焼して、比表面積的６−の粉末を得た。Example 1 When producing a high-strength yellow zirconia sintered body, 200 g (1,123-
E-ru), YC1, 9,164g (0,0469%
) and P r Cl s 0.870 g (0,0
A coprecipitate produced by dropping an acidic aqueous solution containing 352 mol) dissolved in aqueous ammonia was filtered, washed with water, washed with alcohol, and then dried under reduced pressure at 110°C. 100% of the obtained dry powder
It was calcined at 0°C for 3 hours to obtain a powder with a specific surface area of 6-.
この仮焼粉末１００ｇ （０，８１２モル）に酢酸亜鉛
・２水和物０．５３６ ｇ （０，００２４４モル）と
エタノール２５０−を加え、ジルコニアボールで約２４
時間ボールミルをおこなった後、スラリーを蒸発乾固し
て原料粉末を得た。To 100 g (0,812 moles) of this calcined powder, 0.536 g (0,00244 moles) of zinc acetate dihydrate and 250 g of ethanol were added, and about 24
After ball milling for an hour, the slurry was evaporated to dryness to obtain a raw material powder.
この粉末を静水圧２ｔ／ｃＪでプレス成形して得た成形
体を１３００℃で３時間焼成して黄色ジルコニア焼結体
を得た。得られた焼結体の密度と曲げ強度（ＪＩＳ規格
３点曲げ試験）、Ｋｌｃ値（ビッカースインデンテーシ
ョン法）は表１に示したように高い値が得られた。This powder was press-molded at a hydrostatic pressure of 2 t/cJ, and the resulting compact was fired at 1300°C for 3 hours to obtain a yellow zirconia sintered body. The density, bending strength (JIS standard 3-point bending test), and Klc value (Vickers indentation method) of the obtained sintered body had high values as shown in Table 1.
実施例２
オキシ塩化ジルコニウムＺｒ０Ｃ１□ ２００ ｇ（１
，１２３モル） 、ＹＣｌ ｓ ９．１６４ｇ （０
，４６９モル） 、Ｐ ｒ Ｃｌ ｓ ０．８７０ｇ
（０，０３５２モル）を溶解した酸性水溶液にこれら
化合物の倍モル量以上の蓚酸を溶解した水溶液を滴下撹
拌し、得られた蓚酸塩沈澱物をろ過、水洗、エタノール
洗浄後減圧乾燥し、ついで９００℃で３時間仮焼して比
表面積１５ｒｄの粉末を得た。この仮焼粉末１００ ｇ
（０，８１２モル）に炭酸亜鉛０．３０６ ｇ（０，
００２４４モル）とエタノール２５０−を加えジルコニ
アボールを用いて約２４時間ボールミルした後スラリー
を蒸発乾固して原料粉末を得た。Example 2 Zirconium oxychloride Zr0C1□ 200 g (1
, 123 mol), YCl s 9.164 g (0
, 469 mol), P r Cl s 0.870 g
(0,0352 mol) was added dropwise to an aqueous solution of oxalic acid dissolved in an amount equal to or more than double the mole of these compounds and stirred, and the obtained oxalate precipitate was filtered, washed with water, washed with ethanol, dried under reduced pressure, and then The powder was calcined at 900°C for 3 hours to obtain a powder with a specific surface area of 15rd. 100 g of this calcined powder
(0,812 mol) to 0.306 g (0,812 mol) of zinc carbonate
After adding 250 moles of ethanol and ball milling for about 24 hours using zirconia balls, the slurry was evaporated to dryness to obtain a raw material powder.
この粉末を実施例１と同様に静水圧プレスで成形Ｌ １
２００℃−３時間焼成して黄色ジルコニア焼結体を得た
。得られた焼結体の密度と機械的特性を表１に示した。This powder was molded using a hydrostatic press in the same manner as in Example 1.
A yellow zirconia sintered body was obtained by firing at 200°C for 3 hours. Table 1 shows the density and mechanical properties of the obtained sintered body.
実施例３
Ｙ、Ｏ，を２モル％含有する比表面積１５ｍＦのジルコ
ニア粉末１００ｇ （０，８１２モル）をＰｒＣＪ 、
０．６０４ ｇ （０，００２４４モル）を含む酸
性水溶液２５０−にボールミル等でよく分散させた後Ｐ
ｒ化合物の倍モル量以上の蓚酸を含む水溶液２５０−を
滴下して得られるＰｒ蓚酸塩とジルコニア粉末の混合沈
澱をろ過水洗、エタノール洗浄後減圧乾燥し、ついで１
０００’Ｃで３時間仮焼して比表面積６耐の粉末を得た
。この仮焼粉末１００ｇに酢酸亜鉛・２水和物０．５３
６ ｇ （０，００２４４モル）トエタノール２５０−
を加えジルコニアボールテ２４時間ボールミルした後、
スラリーを蒸発乾固して原料粉末を得た。得られた粉末
を実施例１と同様に成形し、１３００ ℃で３時間焼成
して黄色ジルコニア焼結体を得た。得られた焼結体の特
性を表１に示した。Example 3 100 g (0,812 mol) of zirconia powder containing 2 mol % of Y, O, and a specific surface area of 15 mF was mixed with PrCJ,
After dispersing well in an acidic aqueous solution containing 0.604 g (0,00244 mol) using a ball mill etc., P
A mixed precipitate of Pr oxalate and zirconia powder obtained by dropping an aqueous solution containing oxalic acid in an amount more than double the molar amount of the r compound was filtered, washed with water, washed with ethanol, dried under reduced pressure, and then dried under reduced pressure.
The powder was calcined at 000'C for 3 hours to obtain a powder with a specific surface area of 6. 0.53 zinc acetate dihydrate per 100 g of this calcined powder
6 g (0,00244 mol) toethanol 250-
After adding zirconia and ball milling for 24 hours,
The slurry was evaporated to dryness to obtain a raw material powder. The obtained powder was molded in the same manner as in Example 1 and fired at 1300° C. for 3 hours to obtain a yellow zirconia sintered body. Table 1 shows the properties of the obtained sintered body.
比較例１
Ｙ２０− を３モル％含有する市販のジルコニア粉末（
比表面積１５ ｒｒｒ） １００ｇ（０，８１１３モル
）に色材として酸化プラセオジウムＰｒ５ＯＯ，４１５
ｇ（０，４０６ミリモル）を加えジルコニアボールで２
４時間ボールミルした後、スラリーを蒸発乾固して原料
粉末を得た。得られた粉末を実施例１と同様の方法で成
形し１２００ ’Ｃで焼成した。Comparative Example 1 Commercially available zirconia powder containing 3 mol% of Y20- (
Specific surface area 15 rrr) 100g (0,8113 mol) of praseodymium oxide Pr5OO,415 as a coloring material
g (0,406 mmol) and diluted with a zirconia ball.
After ball milling for 4 hours, the slurry was evaporated to dryness to obtain a raw material powder. The obtained powder was molded in the same manner as in Example 1 and calcined at 1200'C.
得られた焼結体の結果を表１に示した。Table 1 shows the results of the obtained sintered body.
比較例２
オキシ塩化ジルコニウムＺ ｒ ＱＣ１２２００ｇ（１
１２３モル） 、ＹＣＩ 、 ９．１６４ｇ （０，
０４６９３モル） 、Ｐ ｒ Ｃｌ 、 ０．８７０
ｇ （０，００３５２モ／Ｌ、）を溶解した酸性水溶液
をアンモニア水に滴下して生成した共沈物をろ過、水洗
、アルコール洗浄した後、１１０℃で減圧乾燥した。得
られた乾燥粉を１０００℃で３時間仮焼して、比表面積
６耐の粉末を得た。この仮焼粉末をエタノールとともに
ジルコニアボールを用いて２４時間ボールミル、得られ
たスラリーを蒸発乾固して原料粉末を得た。得られた粉
末を実施例１と同様に成形し、１３００℃で３時間焼成
した。Comparative Example 2 Zirconium oxychloride Zr QC12200g (1
123 mol), YCI, 9.164 g (0,
04693 mol), P r Cl , 0.870
A coprecipitate produced by dropping an acidic aqueous solution containing g (0,00352 mo/L) dissolved in aqueous ammonia was filtered, washed with water, washed with alcohol, and then dried under reduced pressure at 110°C. The obtained dry powder was calcined at 1000°C for 3 hours to obtain a powder with a specific surface area of 6. This calcined powder was ball milled with ethanol using zirconia balls for 24 hours, and the resulting slurry was evaporated to dryness to obtain a raw material powder. The obtained powder was molded in the same manner as in Example 1 and calcined at 1300°C for 3 hours.
得られた焼結体の特性を表１に示した。Table 1 shows the properties of the obtained sintered body.
上記の実施例には安定化剤にＹ２Ｏ３を使用した場合を
示したが、他の安定化剤（ＣｅＯｚ、ＣａＯ，Ｍｇ０）
を使用した場合でも、同様の低温焼結特性を示し比較例
に比べて低温で高密度・高強度の焼結体が得られる。The above example shows the case where Y2O3 was used as the stabilizer, but other stabilizers (CeOz, CaO, Mg0)
Even when using , the same low-temperature sintering characteristics can be obtained, and a sintered body with higher density and higher strength can be obtained at a lower temperature than the comparative example.
焼結温度が低く、色調が鮮明で、機械的強度の高い黄色
ジルコニア焼結体が得られる。A yellow zirconia sintered body with a low sintering temperature, clear color, and high mechanical strength can be obtained.
出願人 （４３０）日本曹達株式会社
代理人 （７１２５）横 山 吉 美（９６４８
）東 海 裕 作Applicant (430) Nippon Soda Co., Ltd. Agent (7125) Yoshimi Yokoyama (9648)
) Written by Hiroshi Tokai
Claims (3)
＿１を０．０１〜０．１モル％、ＺｎＯを０．１〜０．
６モル％含有することを特徴とする黄色ジルコニア焼結
体。1. For ZrO_2 with stabilizer, Pr_6O_1
0.01 to 0.1 mol% of _1 and 0.1 to 0.1 mol% of ZnO.
A yellow zirconia sintered body characterized by containing 6 mol%.
合物、並びに焼成後Ｐｒ＿６Ｏ＿１＿１となるプラセオ
ジウム化合物を含む溶液から得た混合物を仮焼した後、
焼成により酸化亜鉛を生成する化合物を均一に添加混合
して、成形・焼成することを特徴とする黄色ジルコニア
焼結体の製造方法。2. After calcining a mixture obtained from a solution containing a stabilizer, a zirconium compound that becomes ZrO_2 after calcination, and a praseodymium compound that becomes Pr_6O_1_1 after calcination,
A method for producing a yellow zirconia sintered body, which comprises uniformly adding and mixing a compound that produces zinc oxide upon firing, forming and firing the mixture.
後仮焼し、さらに焼成により酸化亜鉛を生成する亜鉛化
合物を添加混合して、成形後焼成することを特徴とする
黄色ジルコニア焼結体の製造方法。3. A method for producing a yellow zirconia sintered body, which comprises adding a Pr compound to zirconia powder containing a stabilizer, then calcining it, adding and mixing a zinc compound that produces zinc oxide when fired, and firing it after molding. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099288A JP2946342B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099288A JP2946342B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH042657A true JPH042657A (en) | 1992-01-07 |
| JP2946342B2 JP2946342B2 (en) | 1999-09-06 |
Family
ID=14243460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2099288A Expired - Lifetime JP2946342B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2946342B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007053084A1 (en) * | 2005-11-03 | 2007-05-10 | Nobel Biocare Services Ag | Device designed for a dental prosthetic or prosthetic component |
-
1990
- 1990-04-17 JP JP2099288A patent/JP2946342B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007053084A1 (en) * | 2005-11-03 | 2007-05-10 | Nobel Biocare Services Ag | Device designed for a dental prosthetic or prosthetic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2946342B2 (en) | 1999-09-06 |
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