JPH04260615A - Hydrated zirconia dried powder - Google Patents
Hydrated zirconia dried powderInfo
- Publication number
- JPH04260615A JPH04260615A JP4231391A JP4231391A JPH04260615A JP H04260615 A JPH04260615 A JP H04260615A JP 4231391 A JP4231391 A JP 4231391A JP 4231391 A JP4231391 A JP 4231391A JP H04260615 A JPH04260615 A JP H04260615A
- Authority
- JP
- Japan
- Prior art keywords
- hydrated zirconia
- bulk density
- zirconium oxide
- powder
- dried 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 108
- 239000000843 powder Substances 0.000 title claims abstract description 53
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 29
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 29
- 239000000725 suspension Substances 0.000 abstract description 20
- 238000001354 calcination Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 8
- 150000002894 organic compounds Chemical class 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 34
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003754 zirconium Chemical class 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は水和ジルコニア粉末に関
する。水和ジルコニア粉末は加熱処理（仮焼）すること
により酸化ジルコニウム粉末とすることができる。酸化
ジルコニウム粉末は、通常他の粉末と混合され、成形し
、焼結することによって、各種の材料が製造される。
たとえば、固体電解質、圧電体、耐摩耗材、研磨材等の
製造に多量に使用されている。また、これにイットリア
、マグネシア、カルシア等の安定化剤を添加したものは
、安定化あるいは部分安定化ジルコニア焼結体からなる
構造材料等の製造に使用される。FIELD OF THE INVENTION This invention relates to hydrated zirconia powder. The hydrated zirconia powder can be made into zirconium oxide powder by heat treatment (calcination). Zirconium oxide powder is usually mixed with other powders, molded, and sintered to produce various materials. For example, it is used in large quantities in the production of solid electrolytes, piezoelectric bodies, wear-resistant materials, abrasive materials, and the like. Moreover, the product to which a stabilizer such as yttria, magnesia, or calcia is added is used for producing structural materials made of stabilized or partially stabilized zirconia sintered bodies.
【０００２】本明細書中『水和ジルコニア』とは、水酸
化ジルコニウム、結晶性水和ジルコニア、非晶質水和ジ
ルコニアなどと称されるものをいう。[0002] In this specification, the term "hydrated zirconia" refers to zirconium hydroxide, crystalline hydrated zirconia, amorphous hydrated zirconia, and the like.
【０００３】0003
【従来の技術】従来、酸化ジルコニウム粉末は、ジルコ
ニウム塩の水溶液から中和法、加水分解法などによって
生成させ、反応液から脱水し、または該反応液に有機溶
媒を添加して共沸蒸留し脱水して分離することによって
水和ジルコニア粉末をえ、これを仮焼して製造されてい
る。このうちこの共沸蒸留によらずに製造された酸化ジ
ルコニウム粉末の軽装嵩密度は、０．４〜０．５ｇ／ｃ
ｍ３であり、また、共沸蒸留によるものの軽装嵩密度は
、０．９ｇ／ｃｍ３程度である。[Prior Art] Zirconium oxide powder has conventionally been produced from an aqueous solution of zirconium salt by a neutralization method, a hydrolysis method, etc., dehydrated from a reaction solution, or azeotropically distilled by adding an organic solvent to the reaction solution. It is produced by dehydrating and separating to obtain hydrated zirconia powder, which is then calcined. Of these, the light bulk density of zirconium oxide powder produced without this azeotropic distillation is 0.4 to 0.5 g/c.
m3, and the light bulk density of the product obtained by azeotropic distillation is about 0.9 g/cm3.
【０００４】0004
【発明が解決しようとする課題】しかし、このように嵩
密度の低い酸化ジルコニウム粉末を使用すると、それに
よって製造される焼結体の密度も低くなり、かつ該焼結
体の強度が低下する原因となる。[Problems to be Solved by the Invention] However, when zirconium oxide powder with such a low bulk density is used, the density of the sintered body produced using it also becomes low, and the strength of the sintered body decreases. becomes.
【０００５】本発明の目的は、仮焼することにより得ら
れた酸化ジルコニウム粉末を成形した後、焼結すること
により高密度、高強度等の高性能の酸化ジルコニウム焼
結体を製造することのできる水和ジルコニア粉末を提供
することにある。An object of the present invention is to produce a high-performance zirconium oxide sintered body with high density and high strength by shaping and sintering zirconium oxide powder obtained by calcining. Our objective is to provide hydrated zirconia powder that can
【０００６】[0006]
【課題を解決するための手段】本発明者らは鋭意検討し
た結果、軽装嵩密度１．０〜２．０ｇ／ｃｍ３の水和ジ
ルコニア乾燥粉末が上記目的を達成できることを見出だ
し本発明を完成した。[Means for Solving the Problems] As a result of intensive studies, the present inventors discovered that a hydrated zirconia dry powder with a light bulk density of 1.0 to 2.0 g/cm3 could achieve the above object, and completed the present invention. did.
【０００７】以下その詳細について説明する。本発明の
水和ジルコニア乾燥粉末は軽装嵩密度１．０〜２．０ｇ
／ｃｍ３であることが必須である。該嵩密度は１．２〜
１．８ｇ／ｃｍ３であることが好ましく、１．３〜１．
５ｇ／ｃｍ３であることがより好ましい。[0007] The details will be explained below. The hydrated zirconia dry powder of the present invention has a light bulk density of 1.0 to 2.0 g.
/cm3 is essential. The bulk density is 1.2~
It is preferably 1.8 g/cm3, and 1.3 to 1.
More preferably, it is 5 g/cm3.
【０００８】該嵩密度がこの範囲より小さいと、該乾燥
粉末を焼成して得られる酸化ジルコニウム粉末も嵩密度
が小さくなり、したがってこれを成形する場合には大き
な金型が必要となり、かつ成形圧力を高くしなければな
らず、さらには、焼結時にの収縮率が大きい、焼結体の
密度および強度が低くなるなどの問題が生じやすい。い
っぽう、該嵩密度が上記の範囲より大きいと、仮焼後に
得られる酸化ジルコニウム粉末は高密度ではあるが粒径
も大きくなり、それからえられる成形体は空隙が大きく
なって該粉末をそのまま使用して焼結体を作成した場合
には高密度の焼結体を得ることが難しく、高密度の焼結
体をうるために仮焼後粉砕すると当然そのために大きい
エネルギーを必要とすることになる。[0008] If the bulk density is smaller than this range, the bulk density of the zirconium oxide powder obtained by firing the dry powder will also be small, and therefore, when molding this, a large mold is required, and the molding pressure is high. Furthermore, problems such as a high shrinkage rate during sintering and a decrease in the density and strength of the sintered body tend to occur. On the other hand, if the bulk density is larger than the above range, the zirconium oxide powder obtained after calcination will have a high density but a large particle size, and the molded body obtained from it will have large voids, making it difficult to use the powder as is. If a sintered body is prepared by using the sintered body, it is difficult to obtain a high-density sintered body, and if the sintered body is pulverized after calcination in order to obtain a high-density sintered body, a large amount of energy is naturally required.
【０００９】本発明の水和ジルコニア乾燥粉末は乾燥後
の含有水分量が１５％以下であることが好ましく、乾燥
方法は噴霧乾燥が好ましい。本発明における水和ジルコ
ニア粉末は、水溶性ジルコニウム塩の加水分解法、中和
沈澱法等その製造方法に限定はない。さらには、イット
リア、マグネシア、カルシア等の安定化剤を添加させた
もの、すなわち仮焼後に安定化あるいは部分安定化ジル
コニア粒子粉末を生成するようにしたものであってもよ
く、その添加方法に制限はない。The hydrated zirconia dry powder of the present invention preferably has a water content of 15% or less after drying, and the drying method is preferably spray drying. The method for producing the hydrated zirconia powder in the present invention is not limited, such as a hydrolysis method of a water-soluble zirconium salt or a neutralization precipitation method. Furthermore, stabilizers such as yttria, magnesia, calcia, etc. may be added, that is, stabilized or partially stabilized zirconia particles may be produced after calcination, but there are no restrictions on the method of addition. There isn't.
【００１０】本発明における水和ジルコニア粉末の平均
一次粒子径は、１０〜５００ｎｍが好ましく、５０〜５
００ｎｍのものがより好ましい。該範囲より平均一次粒
子径が小さいと、粒子間の凝集が強く、軽装嵩密度１．
０ｇ／ｃｍ３以上の水和ジルコニア乾燥粉末とすること
が難しく；いっぽう、該範囲より平均一次粒子径が大き
いと、高密度の焼結体を得ることが難しく、いずれの場
合も高性能のジルコニア焼結体を得ることのできる粉末
とすることが難しいからである。[0010] The average primary particle diameter of the hydrated zirconia powder in the present invention is preferably 10 to 500 nm, preferably 50 to 5 nm.
00 nm is more preferable. If the average primary particle diameter is smaller than this range, agglomeration between particles will be strong, resulting in a light bulk density of 1.
It is difficult to obtain a hydrated zirconia dry powder with a particle size of 0 g/cm3 or more; on the other hand, if the average primary particle size is larger than this range, it is difficult to obtain a high-density sintered body, and in either case, it is difficult to obtain a high-performance zirconia sintered body. This is because it is difficult to form a powder that can form solid bodies.
【００１１】本発明における水和ジルコニア乾燥粒子の
製造方法としては、例えば、水和ジルコニア粒子懸濁液
の濃度を、前記水和ジルコニア粒子懸濁液中の水和ジル
コニア粒子をＺｒＯ２に換算して約１０〜約２０００ｇ
／リットル、好ましくは該換算値で１００〜１０００ｇ
／リットルの範囲としたものを準備する。この水和ジル
コニア粒子懸濁液の濃度は、乾燥の方式や条件等により
この範囲内で決定すればよい。[0011] As a method for producing hydrated zirconia dry particles in the present invention, for example, the concentration of the hydrated zirconia particle suspension is determined by converting the hydrated zirconia particles in the hydrated zirconia particle suspension into ZrO2. Approximately 10 to 2000g
/liter, preferably 100 to 1000g in the converted value
/ liter range. The concentration of this hydrated zirconia particle suspension may be determined within this range depending on the drying method and conditions.
【００１２】該水和ジルコニア粒子懸濁液に有機化合物
を添加する。添加する有機化合物は特に制限はないが、
好ましくはアルコール類，エステル類，界面活性剤など
が用いられる。とくに、炭素数１〜１０のアルコール類
がよい。その添加量は、前記水和ジルコニア粒子懸濁液
に有機化合物を含有Ｚｒに対して０．０１〜１０ｍｏｌ
％、好ましくは０．１〜１ｍｏｌ％とすればよい。該添
加量より多いと経済的でなく、乾燥工程での爆発・火災
の原因となる。もっとも、この範囲をある程度こえても
軽装嵩密度１．０〜２．０ｇ／ｃｍ３のものをうること
ができるが、その量があまり大きすぎると、軽装嵩密度
が１．０ｇ／ｃｍ３に達しないものとなる。いっぽう、
該添加量上記範囲より小さいと、前記水和ジルコニア粒
子の嵩密度をコントロールすることが難しくなる。An organic compound is added to the hydrated zirconia particle suspension. There are no particular restrictions on the organic compounds to be added, but
Preferably, alcohols, esters, surfactants, etc. are used. In particular, alcohols having 1 to 10 carbon atoms are preferred. The amount added is 0.01 to 10 mol based on Zr containing the organic compound in the hydrated zirconia particle suspension.
%, preferably 0.1 to 1 mol%. If the amount added is more than this, it is not economical and may cause an explosion or fire during the drying process. However, even if this range is exceeded to some extent, a light bulk density of 1.0 to 2.0 g/cm3 can be obtained, but if the amount is too large, the light bulk density will not reach 1.0 g/cm3. Become something. On the other hand,
If the amount added is smaller than the above range, it becomes difficult to control the bulk density of the hydrated zirconia particles.
【００１３】前記有機化合物添加後、該懸濁液を乾燥す
る。乾燥温度は通常用いられる温度でよく、たとえば５
０〜２５０℃で乾燥すればよい。乾燥方法は通常の方法
でよいが、とくに噴霧乾燥がよい。これは生産性がよく
、乾燥後に造粒体であるため後工程でのハンドリングが
よいからである。本発明の水和ジルコニア乾燥粉末を仮
焼して得られた酸化ジルコニウム粉末を成形した後、焼
結することにより高密度、高強度等の高性能の酸化ジル
コニウム焼結体を製造することのできる。After adding the organic compound, the suspension is dried. The drying temperature may be a commonly used temperature, for example 5
What is necessary is just to dry at 0-250 degreeC. The drying method may be any conventional method, but spray drying is particularly preferred. This is because it has good productivity and is easy to handle in subsequent steps since it is a granulated product after drying. The zirconium oxide powder obtained by calcining the hydrated zirconia dry powder of the present invention is molded and then sintered to produce a high-performance zirconium oxide sintered body with high density and high strength. .
【００１４】[0014]
【作用】なぜ、本発明の水和ジルコニア乾燥粉末を仮焼
することにより得られた酸化ジルコニウム粉末を成形し
た後、焼結することにより高密度、高強度等の高性能の
酸化ジルコニウム焼結体を製造することのできるかとい
うことについては必ずしも明らかではないが、以下の理
由によるものと推定される。すなわち、本発明の水和ジ
ルコニア乾燥粉末の軽装嵩密度が２．０ｇ／ｃｍ３以下
であるということは、その粒子表面の水の表面張力が小
さく、粒子間の凝集性が低いことを意味し、それによっ
て仮焼の際焼結特性の低下の原因となる粗大な粒子が存
在せず、仮焼してえられる酸化ジルコニウム粉末も凝集
が少なくよい焼結特性を示すものと認められる。いっぽ
う、軽装嵩密度が１．０ｇ／ｃｍ３以上であるので、橋
かけ構造をもたず、かつ凝集性も適度であって、これか
らえられる酸化ジルコニウム粉末の嵩密度も高くなり、
成形体の密度も高くすることができ、ひいては密度の高
い焼結体がえられることとなるものと考えられる。たと
えば、シリカを一次粒子またはそれに近い状態で分散さ
せたヒュームドシリカは、分散性がよく、すなわち凝集
性が乏しすぎて成形性がわるい。それに対し、本発明の
水和ジルコニア乾燥粉末は、上記のように凝集性をほど
よく備えているものと考えられる。[Operation] Why is it possible to mold the zirconium oxide powder obtained by calcining the hydrated zirconia dry powder of the present invention and then sinter it to produce a high-performance zirconium oxide sintered body with high density and high strength? Although it is not necessarily clear whether it is possible to produce the same, it is presumed that this is due to the following reasons. That is, the fact that the light bulk density of the hydrated zirconia dry powder of the present invention is 2.0 g/cm or less means that the surface tension of water on the particle surface is low and the cohesiveness between particles is low. As a result, there are no coarse particles that cause deterioration of sintering properties during calcination, and the zirconium oxide powder obtained by calcination is recognized to exhibit good sintering properties with little agglomeration. On the other hand, since the light bulk density is 1.0 g/cm3 or more, it does not have a crosslinked structure and has moderate cohesiveness, and the bulk density of the zirconium oxide powder obtained from it is also high.
It is believed that the density of the molded body can also be increased, and as a result, a sintered body with high density can be obtained. For example, fumed silica in which silica is dispersed as primary particles or in a state close to primary particles has good dispersibility, that is, has poor cohesiveness and poor moldability. In contrast, the hydrated zirconia dry powder of the present invention is considered to have moderate cohesiveness as described above.
【００１５】[0015]
【発明の効果】本発明の水和ジルコニア乾燥粒子は、こ
れを仮焼することにより得られた酸化ジルコニウム粉末
を成形した後、焼結することにより密度、強度等の点で
従来のものよりも高性能の酸化ジルコニウム焼結体を製
造することのできる。Effects of the Invention: The hydrated zirconia dry particles of the present invention are obtained by calcining the zirconium oxide powder, which is then molded, and then sintered. A high-performance zirconium oxide sintered body can be manufactured.
【００１６】[0016]
【実施例】実施例１
３ｍｏｌ％（Ｙ２Ｏ３換算値とＺｒＯ２換算値との合計
に対する。以下、同じ）のＹ２Ｏ３を含む、ＺｒＯ２換
算濃度３００ｇ／リットルのオキシ塩化ジルコニウム水
溶液を煮沸して加水分解した。えられた懸濁液中の水和
ジルコニア粒子の平均１次粒子径は約１００ｎｍであっ
た（光子相関法による粒度分布測定器による）。該水和
ジルコニア粒子懸濁液にヘキサノールをＺｒＯ２１ｋｇ
に対して２５ｍｌの割合で添加し、常温で攪拌した後、
噴霧乾燥した。得られた乾燥粒子の軽装嵩密度は１．１
５ｇ／ｃｍ３であった。該乾燥粉末を８５０℃で仮焼し
て酸化ジルコニウム粉末を得た。得られた酸化ジルコニ
ウム粉末の軽装嵩密度は、１．０３ｇ／ｃｍ３であった
。Examples Example 1 A zirconium oxychloride aqueous solution containing 3 mol % (based on the sum of Y2O3 equivalent value and ZrO2 equivalent value; the same applies hereinafter) and having a ZrO2 equivalent concentration of 300 g/liter was boiled and hydrolyzed. The average primary particle diameter of the hydrated zirconia particles in the resulting suspension was about 100 nm (as measured by a particle size distribution analyzer using a photon correlation method). 21 kg of ZrO was added to hexanol to the hydrated zirconia particle suspension.
After stirring at room temperature,
Spray dried. The light bulk density of the obtained dry particles is 1.1
It was 5g/cm3. The dry powder was calcined at 850°C to obtain zirconium oxide powder. The light bulk density of the obtained zirconium oxide powder was 1.03 g/cm3.
【００１７】実施例２
水和ジルコニア粒子懸濁液に添加するヘキサノール量を
ＺｒＯ２１ｋｇに対して５ｍｌの割合とする以外は実施
例１と同じ条件で実施した。得られた乾燥水和ジルコニ
ウム粒子の軽装嵩密度は１．４８ｇ／ｃｍ３であった。
また、仮焼後の酸化ジルコニウム粉末の軽装嵩密度は１
．３２ｇ／ｃｍ３であった。Example 2 A test was carried out under the same conditions as in Example 1 except that the amount of hexanol added to the hydrated zirconia particle suspension was changed to 5 ml per 1 kg of ZrO. The light bulk density of the obtained dried hydrated zirconium particles was 1.48 g/cm3. In addition, the light bulk density of zirconium oxide powder after calcination is 1
．． It was 32g/cm3.
【００１８】実施例３
水和ジルコニア粒子懸濁液に添加するヘキサノール量を
ＺｒＯ２１ｋｇに対して１ｍｌの割合とする以外は実施
例１と同じ条件で実施した。得られた乾燥水和ジルコニ
ア粒子の軽装嵩密度は１．８０ｇ／ｃｍ３であった。ま
た、仮焼後の酸化ジルコニウム粉末の軽装嵩密度は１．
４８ｇ／ｃｍ３であった。Example 3 A test was carried out under the same conditions as in Example 1, except that the amount of hexanol added to the hydrated zirconia particle suspension was 1 ml per 21 kg of ZrO. The dry hydrated zirconia particles obtained had a light bulk density of 1.80 g/cm3. Furthermore, the light bulk density of the zirconium oxide powder after calcination is 1.
It was 48g/cm3.
【００１９】実施例４
ＺｒＯ２換算濃度３００ｇ／リットルのオキシ塩化ジル
コニウム水溶液を煮沸して加水分解した。えられた懸濁
液中の水和ジルコニア粒子の平均１次粒子径は約９５ｎ
ｍであった。該懸濁液中に６ｍｏｌ％のＹＣｌ３を添加
した。さらに、前記水和ジルコニア粒子懸濁液にオクタ
ノールをＺｒＯ２１ｋｇに対して５ｍｌの割合で添加し
、常温で攪拌した後、噴霧乾燥した。該乾燥粒子の軽装
嵩密度は１．４３ｇ／ｃｍ３であった。該乾燥粉末を８
５０℃で仮焼して酸化ジルコニウム粉末を得た。得られ
た酸化ジルコニウム粉末の軽装嵩密度は１．２９ｇ／ｃ
ｍ３であった。Example 4 A zirconium oxychloride aqueous solution having a ZrO2 equivalent concentration of 300 g/liter was boiled and hydrolyzed. The average primary particle size of the hydrated zirconia particles in the resulting suspension was approximately 95n.
It was m. 6 mol% YCl3 was added to the suspension. Furthermore, octanol was added to the hydrated zirconia particle suspension at a ratio of 5 ml per 21 kg of ZrO, stirred at room temperature, and then spray-dried. The light bulk density of the dry particles was 1.43 g/cm3. 8 of the dry powder
Calcination was performed at 50°C to obtain zirconium oxide powder. The light bulk density of the obtained zirconium oxide powder is 1.29 g/c
It was m3.
【００２０】実施例５
３ｍｏｌ％のＹ２Ｏ３を含む、ＺｒＯ２換算濃度３００
ｇ／リットルのオキシ塩化ジルコニウム水溶液をアンモ
ニア水により中和した。該懸濁液中の水和ジルコニア粒
子の平均１次粒子径は約９０ｎｍであった。この水和ジ
ルコニア粒子懸濁液にヘキサノールをＺｒＯ２１ｋｇに
対して２５ｍｌの割合で添加し、常温で攪拌した後、噴
霧乾燥した。該乾燥粒子の軽装嵩密度は１．３８ｇ／ｃ
ｍ３であった。該乾燥粉末を８５０℃で仮焼して酸化ジ
ルコニウム粉末を得た。得られた酸化ジルコニウム粉末
の軽装嵩密度は１．１８ｇ／ｃｍ３であった。Example 5 Containing 3 mol% Y2O3, ZrO2 equivalent concentration 300
g/liter aqueous zirconium oxychloride solution was neutralized with aqueous ammonia. The average primary particle diameter of the hydrated zirconia particles in the suspension was about 90 nm. Hexanol was added to this hydrated zirconia particle suspension at a ratio of 25 ml per 21 kg of ZrO, stirred at room temperature, and then spray-dried. The light bulk density of the dry particles is 1.38 g/c
It was m3. The dry powder was calcined at 850°C to obtain zirconium oxide powder. The light bulk density of the obtained zirconium oxide powder was 1.18 g/cm3.
【００２１】実施例６
ヘキサノールのかわりにブタノールを使用するほかは実
施例１と同じ条件にして水和ジルコニア乾燥粉末をえた
。えられた乾燥粒子の軽装嵩密度は、１．２８ｇ／ｃｍ
３であった。それを１１００℃で仮焼して酸化ジルコニ
ウム粉末をえた。その軽装嵩密度は１．３０ｇ／ｃｍ３
であった。Example 6 A hydrated zirconia dry powder was obtained under the same conditions as in Example 1 except that butanol was used instead of hexanol. The light bulk density of the obtained dry particles is 1.28 g/cm
It was 3. It was calcined at 1100°C to obtain zirconium oxide powder. Its light bulk density is 1.30g/cm3
Met.
【００２２】実施例７
ＺｒＯ２１ｋｇに対するブタノールの添加割合を５ｍｌ
とするほかは、実施例６と同じ条件で実施した。えられ
た乾燥粒子の軽装嵩密度は、１．１９ｇ／ｃｍ３であっ
た。酸化ジルコニウム粉末の軽装嵩密度は、１．２０ｇ
／ｃｍ３であった。Example 7 The addition ratio of butanol to 21 kg of ZrO was 5 ml.
The experiment was carried out under the same conditions as in Example 6, except for the following. The light bulk density of the obtained dry particles was 1.19 g/cm3. The light bulk density of zirconium oxide powder is 1.20g
/cm3.
【００２３】比較例
水和ジルコニア粒子懸濁液を共沸蒸留する以外は実施例
１と同じ条件で行った。共沸蒸留は水和ジルコニア粒子
懸濁液にブタノールをＺｒＯ２１ｋｇに対して、３０リ
ットルの割合で加え、常温で攪拌した後、加熱蒸留した
。加熱蒸留終了後、冷却、溶剤分離、乾燥及び加熱を行
った。得られた乾燥水和ジルコニア粒子の軽装嵩密度は
、０．９３ｇ／ｃｍ３であった。また、仮焼後の酸化ジ
ルコニウム粉末の軽装嵩密度は、０．８５ｇ／ｃｍ３で
あった。Comparative Example The same conditions as in Example 1 were followed except that the hydrated zirconia particle suspension was subjected to azeotropic distillation. In the azeotropic distillation, butanol was added to the hydrated zirconia particle suspension at a ratio of 30 liters per 21 kg of ZrO, stirred at room temperature, and then heated and distilled. After the heating distillation was completed, cooling, solvent separation, drying, and heating were performed. The light bulk density of the obtained dried hydrated zirconia particles was 0.93 g/cm3. Further, the light bulk density of the zirconium oxide powder after calcination was 0.85 g/cm3.
【００２４】実施例及び比較例で得られた酸化ジルコニ
ア粉末を同一条件で粉砕した後、成形圧力７００ｋｇ／
ｃｍ２で５７ｍｍ×３４ｍｍ×約５ｍｍに成形し、１５
００℃で２時間焼成することにより、焼結体を得た。得
られた焼結体から、３ｍｍ×４ｍｍ×約４０ｍｍの試験
片を切り出し、ＪＩＳ １６０１に規定された方法に
より常温３点曲げ強度を測定した。３０試料の平均の結
果を表１に示す。After pulverizing the zirconia oxide powders obtained in the examples and comparative examples under the same conditions, the molding pressure was 700 kg/
Form into 57mm x 34mm x approx. 5mm with cm2, 15
A sintered body was obtained by firing at 00°C for 2 hours. A test piece measuring 3 mm x 4 mm x about 40 mm was cut out from the obtained sintered body, and its three-point bending strength at room temperature was measured by the method specified in JIS 1601. The average results of 30 samples are shown in Table 1.
【００２５】 表１[0025] Table 1
Claims (1)
和ジルコニア乾燥粉末。Claims: 1. Dry hydrated zirconia powder having a light bulk density of 1.0 to 2.0 g/cm3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042313A JP3008517B2 (en) | 1991-02-15 | 1991-02-15 | Hydrated zirconia dry powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042313A JP3008517B2 (en) | 1991-02-15 | 1991-02-15 | Hydrated zirconia dry powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04260615A true JPH04260615A (en) | 1992-09-16 |
| JP3008517B2 JP3008517B2 (en) | 2000-02-14 |
Family
ID=12632535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3042313A Expired - Fee Related JP3008517B2 (en) | 1991-02-15 | 1991-02-15 | Hydrated zirconia dry powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3008517B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008019926A1 (en) * | 2006-08-17 | 2008-02-21 | H.C. Starck Gmbh | Zirconium oxide and method for the production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008019926A1 (en) * | 2006-08-17 | 2008-02-21 | H.C. Starck Gmbh | Zirconium oxide and method for the production thereof |
| JP2010500957A (en) * | 2006-08-17 | 2010-01-14 | ハー．ツェー．スタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング | Zirconium oxide and method for producing the same |
| US8383266B2 (en) | 2006-08-17 | 2013-02-26 | H.C. Starck Gmbh | Zirconium oxide and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3008517B2 (en) | 2000-02-14 |
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