JPH04187519A - Production of hydrated zirconia sol - Google Patents
Production of hydrated zirconia solInfo
- Publication number
- JPH04187519A JPH04187519A JP31439990A JP31439990A JPH04187519A JP H04187519 A JPH04187519 A JP H04187519A JP 31439990 A JP31439990 A JP 31439990A JP 31439990 A JP31439990 A JP 31439990A JP H04187519 A JPH04187519 A JP H04187519A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- solution
- hydrated zirconia
- zirconia sol
- less
- 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 106
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 19
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000725 suspension Substances 0.000 abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract 2
- 238000002050 diffraction method Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 150000003754 zirconium Chemical class 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 sodium chloride dicalcium chloride Chemical compound 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ジルコニア系セラミックス原料粉末製造中間
体である水和ジルコニアゾルの製造方法、とくに、上記
原料粉末を成形性、安定化剤との固溶性のよいものとす
ることかできろ水和ジルコニアゾルの製造方法に関する
ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a hydrated zirconia sol, which is an intermediate for producing a zirconia-based ceramic raw material powder, and in particular, a method for producing a hydrated zirconia sol, which is an intermediate for producing a zirconia-based ceramic raw material powder, and in particular, a method for producing a hydrated zirconia sol, which is an intermediate for producing a raw material powder for zirconia-based ceramics, and in particular, a method for producing a hydrated zirconia sol, which is an intermediate for producing a raw material powder for zirconia ceramics. The present invention relates to a method for producing a hydrated zirconia sol that can have good solid solubility.
［従来の技術］
従来、ジルコニウム塩水溶液の加水分解による水和ジル
コニアゾルの製造方法としては、■水溶性ジルコニウム
塩を含む水溶液を１２０〜３００℃で水熱処理する方法
（米国特許第２９８４６２８号明細＠）
■水溶性ジルコニウム塩を含む水溶液を煮沸加水分解処
理する方法（Ｉｎｏｒｇ、Ｃｈｅｍ、３゜■水溶性ジル
コニウム塩を含む水溶液に過酸化水素または過酸化水素
を生成する化合物を加え、８０〜３００℃で加熱処理す
る方法（’Ｆｉ公昭６１−４３２８６号公報）
■ジルコニウム塩水溶液を加水分解処理したあと、０．
１〜０．３μｍのものを沈降法などで分離する方法（特
開昭５８−２１７４３０号公報）等が知られている。[Prior Art] Conventionally, methods for producing hydrated zirconia sol by hydrolyzing an aqueous zirconium salt solution include: (1) a method of hydrothermally treating an aqueous solution containing a water-soluble zirconium salt at 120 to 300°C (U.S. Pat. No. 2,984,628 @ ) ■ Method of boiling and hydrolyzing an aqueous solution containing a water-soluble zirconium salt (Inorg, Chem, 3° ■ Adding hydrogen peroxide or a compound that generates hydrogen peroxide to an aqueous solution containing a water-soluble zirconium salt, and heating at 80 to 300°C ('Fi Publication No. 61-43286) ■ After hydrolyzing a zirconium salt aqueous solution, 0.
A method is known in which particles of 1 to 0.3 μm are separated by a sedimentation method (Japanese Unexamined Patent Publication No. 58-217430).
［発明か解決しようとする課題：
本発明者らか検討したところによれば、水和ジルコニア
ゾルの結晶子か小さいほど、該ゾルとジルコニア系セラ
ミックスの製造に常用されるイツトリア、カルンア、マ
グネンア、セリアなどの安定化剤とを混合し、仮焼して
ジルコニア粉末を得るときに、固溶反応が促進していく
ことか推察され、とくに塩化ジルコニルの濃度かＱ、４
ｍｏｌ／ρ未満であり、かつ塩素イオン濃度か０．８以
上２．０ｍｏ ］／ρ以下の条件で加水分解処理して得
られた水和ジルコニアゾルの結晶子は４０Ａ以下のもの
が得られ、水和ジルコニアゾルの結晶子が４０Ａ以下に
なると、その効果がか顕著に現れることか期待される。[Problem to be solved by the invention: According to studies conducted by the present inventors, the smaller the crystallites of the hydrated zirconia sol, the smaller the crystallites of the hydrated zirconia sol. It is speculated that the solid solution reaction is accelerated when mixing with a stabilizer such as ceria and calcining to obtain zirconia powder.
The crystallites of the hydrated zirconia sol obtained by hydrolysis treatment under conditions where the chloride ion concentration is 0.8 or more and 2.0 mo]/ρ or less are 40A or less, It is expected that this effect will become more noticeable when the crystallite size of the hydrated zirconia sol becomes 40A or less.
また、水和ジルコニアゾルの粒子径は、平均粒径で０．
１μｍ以上、粒径範囲で０．０５〜０，５μｍのものか
好ましく、平均粒径か０１μｍより小さくなると、該ゾ
ルを仮焼してジルコニア粉末を得るときに、強固な凝集
塊か生成し、成形性および焼結体特性の悪いジルコニア
粉末か得られる。The average particle size of the hydrated zirconia sol is 0.
1 μm or more, preferably 0.05 to 0.5 μm in particle size range, and if the average particle size is smaller than 0.1 μm, strong aggregates will be formed when the sol is calcined to obtain zirconia powder, Zirconia powder with poor formability and sintered properties is obtained.
ところで、■および■の方法によって得られる水和ジル
コニアゾルは、粒子径か５００Ａよりも小さいものであ
り、上記のとおり、仮焼の際強固な凝集が起こり、得ら
れるジルコニア粉末が成形しに＜＜、セラミックス原料
粉末に適さないものとなる。さらに■の方法は水熱合成
法であるため、工業的な大量生産に適さず実用的でない
。■および■の方法で得られる水和ジルコニアゾルは、
結晶子が４０Ａよりも大きいものであり、上記のとおり
、安定化剤と固溶しにくいものと考えられる。By the way, the hydrated zirconia sol obtained by the methods ① and ② has a particle size smaller than 500A, and as mentioned above, strong agglomeration occurs during calcination, and the resulting zirconia powder is difficult to mold. <, it becomes unsuitable for ceramic raw material powder. Furthermore, since method (2) is a hydrothermal synthesis method, it is not suitable for industrial mass production and is not practical. The hydrated zirconia sol obtained by methods ■ and ■ is
The crystallites are larger than 40A, and as mentioned above, it is thought that it is difficult to form a solid solution with the stabilizer.
さらに■の方法は、粒径０．〕〜０．３μｍのものを遠
心分離しなければならず、工業化は困難であり実用的で
はない。Furthermore, the method (■) has a particle size of 0. ] to 0.3 μm must be centrifuged, making industrialization difficult and impractical.
本発明は、このような従来方法における欠点を鮮消した
、即ち、粒子径の大きい、且つ結晶子の小さい、したか
つて成形性のよい、さらにイツトリア等の安定化剤と°
よく固溶しているジルコニア粉末の製造に適した水和ジ
ルコニアゾル、を簡易なプロセスにより製造することか
できる方法の提供を目的とするものである。The present invention eliminates the drawbacks of the conventional methods, namely, the particle size is large, the crystallites are small, and the moldability is good.
The object of the present invention is to provide a method for producing, by a simple process, a hydrated zirconia sol suitable for producing zirconia powder that is well dissolved in solid solution.
［課題を解決するための手段］
本発明は、塩化ジルコニル水溶液の加水分解により水和
ジルコニアゾルを製造する方法において、０．４ｍｏｌ
／Ω未満の塩化ジルコニル濃度で、塩素イオン濃度を０
，８以上２．０ｍｏｌ／Ω未以下にし、かつ、加水分解
反応終了時の反応液のｐＨか０．４以上１以下の範囲と
なるように調整された塩化ジルコニル水溶液を８０℃以
上煮沸温度以下で加水分解処理することによる水和ジル
コニアゾルの製造方法、を要旨とするものである。[Means for Solving the Problems] The present invention provides a method for producing a hydrated zirconia sol by hydrolysis of an aqueous zirconyl chloride solution.
At a zirconyl chloride concentration of less than /Ω, the chloride ion concentration can be reduced to 0.
, 8 or more and less than 2.0 mol/Ω, and the pH of the reaction solution at the end of the hydrolysis reaction is adjusted to be in the range of 0.4 or more and 1 or less. The gist of this invention is a method for producing hydrated zirconia sol by hydrolysis treatment.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明で得られる水和ジルコニアゾルの粒径は、電子顕
微鏡による粒径観察または粒度分布測定器による粒径ａ
＋す定、例えば光子相関法等で得られる。The particle size of the hydrated zirconia sol obtained in the present invention can be determined by particle size observation using an electron microscope or particle size a measured using a particle size distribution analyzer.
For example, it can be obtained by the photon correlation method.
塩化ジルコニル水溶液を加水分解すると、水和ンルコニ
アゾルと酸か生成し、反応の進行につれて反応系のｐＨ
か低下していく。これらの塩化ジルコニルのジルコニア
換算濃度０．１ｍ○】７９未満の水溶液をなんらの処理
をもすることもなく加熱して加水分解を完了させると、
反応系のｐＨは１よりも大きくなり、さらに塩素イオン
濃度か０．８ｍｏｌ／、Ｑ未満になる。したがって、本
発明を実施するにあたり、前もって塩化ジルコニル水溶
液に酸を添加してｐＨを低くし、さらにｐＨにあまり影
響のない塩素化合物を添加して塩素イオン濃度を高くし
て、加水分解反応終了時の系のｐＨが０．４以上１以下
、かつ塩素イオン濃度か０．８以上２ｍｏｌ／Ｎ以下と
なるようにしなければならない。添加する酸としては、
塩酸、硝酸。When an aqueous zirconyl chloride solution is hydrolyzed, a hydrated luconia sol and an acid are produced, and as the reaction progresses, the pH of the reaction system increases.
or decrease. When these aqueous solutions of zirconyl chloride with a zirconia equivalent concentration of less than 0.1 m○]79 are heated to complete hydrolysis without any treatment,
The pH of the reaction system becomes greater than 1, and the chlorine ion concentration becomes less than 0.8 mol/Q. Therefore, in carrying out the present invention, an acid is added to the zirconyl chloride aqueous solution in advance to lower the pH, and a chlorine compound that has little effect on the pH is added to increase the chlorine ion concentration. The pH of the system must be 0.4 or more and 1 or less, and the chlorine ion concentration must be 0.8 or more and 2 mol/N or less. The acid to be added is
Hydrochloric acid, nitric acid.
硫酸等の無機酸を挙げることかできるが、これらの他に
酢酸、クエン酸等の有機酸でもよい。好ましくは塩酸で
ある。ま１こ、塩素化合物としては、塩化アンモニウム
、金属塩化物、例えば塩化ナトリウム２塩化カルシウム
等のアルカリ金属またはアルカリ土類金属、塩化アルミ
ニウム等を挙げることかでき、好ましくは塩化アンモニ
ウム、塩化ナトリウムである。Inorganic acids such as sulfuric acid can be mentioned, but in addition to these, organic acids such as acetic acid and citric acid may also be used. Hydrochloric acid is preferred. As the chlorine compound, mention may be made of ammonium chloride, metal chlorides, such as alkali metals or alkaline earth metals such as sodium chloride dicalcium chloride, aluminum chloride, etc., and ammonium chloride and sodium chloride are preferred. .
また塩化ジルコニルのジルコニア換算濃度か０１以上０
．４ｍｏｌ／、ｐ未満の水溶液を加熱して加水分解を完
了させると、反応系のｐＨは０．４以上丁以下の範囲に
入るか、塩素イオン濃度は０．８ｍｏｌ／、Ｑ未満であ
る。このときは、ｐＨにあまり影響のない塩素化合物の
みを添加して塩素イオン濃度を高くして、加水分解反応
終了時の系の塩素イオン濃度が０．８以上２ｍｏ ｌ／
１以下となるようにしなければならない。添加する塩素
化合物としては、上記に記述したものでよい。Also, the zirconia equivalent concentration of zirconyl chloride is 01 or more.
．． When an aqueous solution with a concentration of less than 4 mol/p is heated to complete hydrolysis, the pH of the reaction system is in the range of 0.4 or more and 1 or less, or the chlorine ion concentration is less than 0.8 mol/p. At this time, increase the chlorine ion concentration by adding only chlorine compounds that have little effect on pH, so that the chlorine ion concentration in the system at the end of the hydrolysis reaction is 0.8 or more 2 mol/
It must be set to 1 or less. As the chlorine compound to be added, those described above may be used.
この加水分解反応終了時のｐＨが１よりも大きいと０．
１μｍ以上の平均粒径および４０Ａ以下の結晶子をもつ
水和ジルコニアゾルを製造できす、またｐＨが０，４未
満になると水和ジルコニアゾルの平均粒径がＯ２１μｍ
よりも小さくなるとともに反応率が低下し、さらに反応
時間が長くなる。If the pH at the end of this hydrolysis reaction is greater than 1, the pH is 0.
It is possible to produce hydrated zirconia sol with an average particle size of 1 μm or more and crystallites of 40 A or less, and when the pH becomes less than 0.4, the average particle size of the hydrated zirconia sol becomes 0.21 μm.
As the reaction rate becomes smaller, the reaction rate decreases and the reaction time becomes longer.
さらに、塩素イオン濃度が０．８ｍｏｌ／Ｆ未満になる
と４０Ａ以下の結晶子をもつ水和ジルコニアが得られず
、また塩素イオン濃度が２ｍｏｌ／ｇより大きくなると
水和ジルコニアの結晶性か低下するとともに反応率が低
下し、反応時間か長くなる。Furthermore, if the chlorine ion concentration is less than 0.8 mol/F, hydrated zirconia with crystallites of 40 A or less cannot be obtained, and if the chlorine ion concentration is greater than 2 mol/g, the crystallinity of the hydrated zirconia decreases and The reaction rate will decrease and the reaction time will increase.
上記で調製した原料液の加水分解反応、すなわち反応温
度は、８０℃以上煮沸温度以下に設定しなければならな
い。反応温度か煮沸温度よりも高くなると、水和ジルコ
ニアの結晶子が４０Ａよりも大きくなるとともに平均粒
径か０．１μｍよりも小さくなり、目的とする水和ジル
コニアゾルか製造できず、さらに水熱合成であることか
ら工業的な大量生産か困難になるため実用的でなくなる
。The hydrolysis reaction of the raw material liquid prepared above, that is, the reaction temperature, must be set at 80° C. or higher and lower than the boiling temperature. When the reaction temperature is higher than the boiling temperature, the crystallites of hydrated zirconia become larger than 40A and the average particle size becomes smaller than 0.1 μm, making it impossible to produce the desired hydrated zirconia sol, and furthermore, the hydrothermal Since it is a synthetic method, it is difficult to mass produce it industrially, making it impractical.
反応温度が８０℃未満になると加水分解反応の冗語に長
い時間を要するため、生産効率が低下する。When the reaction temperature is less than 80° C., the hydrolysis reaction takes a long time, resulting in a decrease in production efficiency.
また、反応時間は反応温度にもよるが、約５０〜１５０
時間である。In addition, the reaction time depends on the reaction temperature, but is approximately 50 to 150 minutes.
It's time.
［作用コ
水和ジルコニアゾルの結晶子および粒径か、反応系の塩
素イオン濃度およびｐＨ，特に反応終了時の塩素イオン
濃度およびｐＨに依存する理由は明らかではないか、得
られる水和ジルコニアゾルは、結晶性のよい１次粒子か
凝集した２次粒子からなることか知られており（特公昭
６１−４３２８６号公報）、塩素イオンは加７ｙ（分解
反応のときに生成する水和ジルコニアの結晶核に吸着し
て結晶成長を阻害し１次粒子（結晶子）を小さくする因
子とて考えられる。またｐＨは２次粒子に作用する因子
と考えられ、加水分解反応により生成する１次粒子の粒
径に関する粒子間相互作用と、反応系のｐＨとの相乗作
用により、１次粒子間の凝集結合が促進され、生成２次
粒子の粒径に影響することによるものと推察される。[It is not clear why the effect depends on the crystallite and particle size of the hydrated zirconia sol, the chloride ion concentration and pH of the reaction system, especially the chloride ion concentration and pH at the end of the reaction, or the resulting hydrated zirconia sol is known to be composed of primary particles with good crystallinity or agglomerated secondary particles (Japanese Patent Publication No. 61-43286), and chloride ions are It is thought to be a factor that adsorbs to crystal nuclei, inhibits crystal growth, and reduces the size of primary particles (crystallite).Also, pH is considered to be a factor that acts on secondary particles, and the primary particles generated by hydrolysis reaction. This is presumed to be due to the synergistic effect of interparticle interaction regarding the particle size and the pH of the reaction system, which promotes cohesive bonding between primary particles and influences the particle size of the produced secondary particles.
［発明の効果］
以上説明したとおり、本発明によれば、粒子径の大きい
、且つ結晶子の小さい、したがって成形性のよい、さら
にイツトリア等の安定化剤とよく固溶しているジルコニ
ア粉末の製造に適した水和ジルコニアゾルを製造するこ
とができる。[Effects of the Invention] As explained above, according to the present invention, a zirconia powder having a large particle size and small crystallites, which has good moldability, and which is well dissolved in a solid solution with a stabilizer such as yttria, etc. A hydrated zirconia sol suitable for production can be produced.
本発明で得られる平均粒径が０．１μｍ以上であり、か
つ４０Ａ以下の結晶子の水和ジルコニアゾルは、ジルコ
ニウム塩濃度、陰イオン濃度、酸またはアルカリの添加
量などに依存するので、これらの条件を加水分解反応終
了時の懸濁液のｐＨを本発明で限定した範囲に制御でき
るように適宜設定することによって、ゾル粒径および結
晶子を制御することかできる。The hydrated zirconia sol with an average particle diameter of 0.1 μm or more and crystallites of 40 A or less obtained in the present invention depends on the zirconium salt concentration, anion concentration, the amount of acid or alkali added, etc. The sol particle size and crystallites can be controlled by appropriately setting the conditions so that the pH of the suspension at the end of the hydrolysis reaction can be controlled within the range defined by the present invention.
［実施例コ 以下、実施例により本発明を具体的に説明する。[Example code] Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
２ｍｏｌ／Ωのオキン塩化ジルコニウム１００ｄに塩化
アンモニウムを３０ｇ１加して蒸留水を加え、ジルコニ
ア換算０．２ｍｏｌ／Ωの水溶液にした。このときの塩
素イオン濃度は、０．９６ｍｏ Ｉ／βであった。この
調整した原料液を攪拌しながら１００時間煮沸し、加水
分解反応を行った。反応終了後の懸濁液のｐＨは、０．
７であった。Example 1 30 g of ammonium chloride was added to 100 d of zirconium chloride of 2 mol/Ω, and distilled water was added to make an aqueous solution of 0.2 mol/Ω in terms of zirconia. The chloride ion concentration at this time was 0.96 mo I/β. This prepared raw material liquid was boiled for 100 hours while stirring to perform a hydrolysis reaction. The pH of the suspension after the reaction is 0.
It was 7.
得られた水和ジルコニアの光子相関法による平均粒径は
０．２４μｍであり、粉末Ｘ線回折による結晶子径は約
３６Ａであった。The average particle diameter of the obtained hydrated zirconia was 0.24 μm as determined by photon correlation method, and the crystallite diameter was approximately 36 A as determined by powder X-ray diffraction.
実施例２
塩化アンモニウムを塩化ナトリウムに代えた以外は実施
例１の条件と同様に行なった。反応終了後の懸濁液のｐ
Ｈは、０．６５であり、塩素イオン濃度は１．、Ｏｍｏ
ｌ／Ωてあった。Example 2 The same conditions as in Example 1 were repeated except that ammonium chloride was replaced with sodium chloride. p of suspension after completion of reaction
H is 0.65, and the chlorine ion concentration is 1. , Omo
It was l/Ω.
得られた水和ジルコニアの光子相関法による平均粒径は
０．２６μｍであり、粉末Ｘ線回折による結晶子径は約
３４Ａであった。The average particle diameter of the obtained hydrated zirconia was 0.26 μm as determined by photon correlation method, and the crystallite diameter was approximately 34 A as determined by powder X-ray diffraction.
実施例３
２ｍｏｌ／ρのオキシ塩化ジルコニウム２５戴に１ｍｏ
ｌ／ρの塩酸を３００ｍ１および塩化ナトリウムを３０
ｇ添加して蒸留水を加え、ジルコニア換算０．０５ｍｏ
ｌ／ρの水溶液にし、た。このときの塩素イオン濃度は
、０．９ｍｏｌ／Ｎであった。この調整した原料液を攪
拌しながら８０時間煮沸し、加水分解反応を行った。反
応終了後の懸濁液のｐＨは、０．６８であった。Example 3 2 mol/ρ of zirconium oxychloride 25 to 1 mol
300 ml of l/ρ hydrochloric acid and 30 ml of sodium chloride
g and added distilled water, 0.05 mo in terms of zirconia
It was made into an aqueous solution of l/ρ. The chlorine ion concentration at this time was 0.9 mol/N. The prepared raw material solution was boiled for 80 hours while stirring to perform a hydrolysis reaction. The pH of the suspension after the completion of the reaction was 0.68.
得られた水和ジルコニアの光子相関法による平均粒径は
０，２５μｍであり、粉末Ｘ線回折による結晶子径は約
３８Ａであった。The average particle diameter of the obtained hydrated zirconia was 0.25 μm as determined by photon correlation method, and the crystallite diameter as determined by powder X-ray diffraction was approximately 38A.
実施例４
塩化アンモニウムを塩化ナトリウムに代えた以外は実施
例３の条件と同様に行なった。反応終了後の懸濁液のｐ
Ｈは、０．７１であり、塩素イオン濃度は１ｍｏｌ／Ω
であった。Example 4 The same conditions as in Example 3 were repeated except that ammonium chloride was replaced with sodium chloride. p of suspension after completion of reaction
H is 0.71, and the chlorine ion concentration is 1 mol/Ω
Met.
得られた水和ジルコニアの光子相関法による平均粒径は
０．２８μｍであり、粉末Ｘ線回折による結晶子径は約
３２Ａてあった。The average particle diameter of the obtained hydrated zirconia was 0.28 μm as determined by photon correlation method, and the crystallite diameter as determined by powder X-ray diffraction was approximately 32 Å.
比較例１
２ｍｏ ｌ／Ωのオキシ塩化ジルコニウム１００ｍ１に
蒸留水を加え、ジルコニア換算０．２ｍｏｌ／ｇの水溶
液にして１００時間煮沸し、加水分解反応を行った。反
応終了後の懸濁液のｐＨは、０．６９であった。Comparative Example 1 Distilled water was added to 100 ml of 2 mol/Ω of zirconium oxychloride to form an aqueous solution of 0.2 mol/g in terms of zirconia, and the solution was boiled for 100 hours to perform a hydrolysis reaction. The pH of the suspension after the completion of the reaction was 0.69.
得られた水和ジルコニアの光子相関法による平均粒径は
０．２５μｍであり、粉末Ｘ線回折による結晶子径は５
３Ａであった。The average particle size of the obtained hydrated zirconia by photon correlation method is 0.25 μm, and the crystallite size by powder X-ray diffraction is 5.
It was 3A.
比較例２
２ｍｏ １／ρのオキシ塩化ジルコニウム２５ｍＮに蒸
留水を加え、ジルコニア換算０．０５ｍｏｌ／Ωの水溶
液にして８０時間煮沸し、加水分解反応を行った。反応
終了後の懸濁液のｐＨは、１．２であった。Comparative Example 2 Distilled water was added to 25 mN of zirconium oxychloride of 2 mo 1/ρ to make an aqueous solution of 0.05 mol/Ω in terms of zirconia, and the solution was boiled for 80 hours to perform a hydrolysis reaction. The pH of the suspension after the completion of the reaction was 1.2.
得られた水和ジルコニアの光子相関法による平均粒径は
０．０７μｍであり、粉末Ｘ線回折による結晶子径は７
５Ａであった。The average particle size of the obtained hydrated zirconia by photon correlation method is 0.07 μm, and the crystallite size by powder X-ray diffraction is 7.
It was 5A.
Claims (1)
コニアゾルを製造する方法において、０．４ｍｏｌ／ｌ
未満の塩化ジルコニル濃度で、塩素イオン濃度を０．８
以上２．０ｍｏｌ／ｇ以下にし、かつ、加水分解反応終
了時の反応液のｐＨが０．４以上１以下の範囲となるよ
うに調整された塩化ジルコニル水溶液を８０℃以上煮沸
温度以下で加水分解処理することを特徴とする、水和ジ
ルコニアゾルの製造方法(1) In a method for producing a hydrated zirconia sol by hydrolysis of an aqueous zirconyl chloride solution, 0.4 mol/l
With a zirconyl chloride concentration of less than 0.8, the chloride ion concentration is
Hydrolyze an aqueous zirconyl chloride solution adjusted to 2.0 mol/g or less and the pH of the reaction solution at the end of the hydrolysis reaction to be in the range of 0.4 to 1 at temperatures above 80°C and below the boiling temperature. A method for producing a hydrated zirconia sol, which is characterized by processing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31439990A JP2882040B2 (en) | 1990-11-21 | 1990-11-21 | Method for producing hydrated zirconia sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31439990A JP2882040B2 (en) | 1990-11-21 | 1990-11-21 | Method for producing hydrated zirconia sol |
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| Publication Number | Publication Date |
|---|---|
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| JP2882040B2 JP2882040B2 (en) | 1999-04-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP5758037B1 (en) | 2014-09-29 | 2015-08-05 | 第一稀元素化学工業株式会社 | Sol comprising amorphous Zr-O-based particles as dispersoid and method for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008526669A (en) * | 2004-12-30 | 2008-07-24 | スリーエム イノベイティブ プロパティズ カンパニー | Zirconia particles |
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