JPH04104910A - Production of hydrated zirconium sol - Google Patents
Production of hydrated zirconium solInfo
- Publication number
- JPH04104910A JPH04104910A JP21672790A JP21672790A JPH04104910A JP H04104910 A JPH04104910 A JP H04104910A JP 21672790 A JP21672790 A JP 21672790A JP 21672790 A JP21672790 A JP 21672790A JP H04104910 A JPH04104910 A JP H04104910A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium
- urea
- sol
- ammonium
- hydrated
- 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.)
- Pending
Links
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- -1 zirconium alkoxide Chemical class 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、例えば高強度・高靭性のジルコニア系酸化物
構造セラミック微粉末の合成用原料として用いられたり
、ジルコニア固体電解質セラミッり微粉末の合成用原料
として用いられる水和ジルコニウムゾルの製造方法に関
するものである。The present invention relates to a method for producing a hydrated zirconium sol, which is used, for example, as a raw material for the synthesis of high-strength and high-toughness zirconia-based oxide structured ceramic fine powder, or as a raw material for the synthesis of zirconia solid electrolyte ceramic fine powder. It is something.
近年、ジルコニアセラミンクは、高強度・高靭性を有す
る構造材料として、又、電気伝導性を有する固体電解質
材料として注目を集めている。
ところで、これらのものは、いずれもＺｒＯ。
成分のみから成るのではなく、ＭｇＯ，ＣａＯ１Ｙ２０
３あるいはＣｅ０ｚ 、Ｇｄ、Ｏｓといった添加物を均
−固溶させることによって機能が発現するものである。
又、Ｚｒ０ｚを他のセラミックス（Ａｌ２Ｏ２，３Ａｊ
！２０３ ・２ＳｉＯ□、５ｉｓＮｎ等）中に適当量分
散複合化させることによって、それらのセラミックスの
機能向上を図ることが提案されている。
このようにＺｒ０ｚは、単成分としてではなく、他の成
分と併用するといった利用形態が主流となっている。
この為、すなわち他成分との固相反応性を良好にさせる
為に、微細で、均一な粒径、形状を有し、分散性に冨ん
だ結晶質あるいは非晶質のジルコニア粒子（粉末）が求
められている。
ところで、このようなＺｒｏｔ粒子を得るには湿式法が
有利であり、従来技術としては次の技術がある。
■ ジルコニウム塩水溶液（ＺｒＯＣｆｆｉｚ 、 Ｚ
ｒＣｊ！ｚ ）の中和共沈法
■ ジルコニウム塩水溶液の加水分解法■ ジルコニウ
ムアルコキシドの加水分解法In recent years, zirconia ceramic has attracted attention as a structural material with high strength and high toughness, and as a solid electrolyte material with electrical conductivity. By the way, all of these materials are ZrO. It is not only composed of components, but also MgO, CaO1Y20
The function is expressed by uniformly dissolving additives such as 3, Ce0z, Gd, and Os. In addition, Zr0z can be replaced with other ceramics (Al2O2,3Aj
! It has been proposed to improve the functionality of these ceramics by dispersing and compounding them in appropriate amounts in 203 .2SiO□, 5isNn, etc.). As described above, Zr0z is mainly used not as a single component but in combination with other components. For this reason, in order to improve solid phase reactivity with other components, crystalline or amorphous zirconia particles (powder) have fine, uniform particle size and shape, and are highly dispersible. is required. By the way, a wet method is advantageous for obtaining such Zrot particles, and the following techniques are available as conventional techniques. ■ Zirconium salt aqueous solution (ZrOCffiz, Z
rCj! z) Neutralization coprecipitation method ■ Hydrolysis method of zirconium salt aqueous solution ■ Hydrolysis method of zirconium alkoxide
ところで、上記の技術には、各々以下のような問題点が
ある。
すなわち、■の中和共沈法は、生産性に優れているもの
の、比較的大きな粒子あるいはゲルとなってしまい、微
細な粒子を得る為には、生成物を分離、乾燥後、粉砕し
なければならない。
しかしながら、粉砕しても０．１μｍ程度までで、それ
以下の大きさの微粒子を得るのは困難である。
又、中和反応時の溶液のｐＨ変化速度が重要であり、単
位操作的には溶液の攪拌速度、沈澱剤の滴下速度などの
制御も必要とし、工程管理が難しい。
■の加水分解法は、超微粒子を得る為の方法として合成
化学的には好ましいが、以下の理由により工業的には問
題が有る。
先ず、第１に、−船釣に数十〜数百時間という長い反応
時間を必要とする。
第２に、１０−”〜１０−’ｍａｉｌ ／ １といった
希薄な水溶液を出発点とするので、バッチ式で合成を行
う場合、単位反応容積当たりの収量はかなり低い。
第３に、反応後の微粒子は遠心分離などにより容易に水
と分離できるが、分離後も原料塩中のアニ、ｔ７ （Ｃ
／ｌ！−、Ｎｏｗ −、Ｓｏ、 トなど）が吸着あるい
は含有されている為、これらを除去するにはコロイド濾
過、限外濾過などの特殊な洗浄法を要する。
又、■の加水分解法は、原料のＺｒアルコキシドが無機
Ｚｒ塩類に比べ高価であり、工業的な面では問題がある
。
そこで、本発明の第１の目的は、微細で、均一な粒径の
ジルコニア粒子を提供できる水和ジルコニウムゾルの製
造方法を提供することにある。
本発明の第２の目的は、生産性に優れている水和ジルコ
ニウムゾルの製造方法を提供することにある。
本発明の第３の目的は、ジルコニア粒子を低廉に提供で
きる水和ジルコニウムゾルの製造方法を提供することに
ある。By the way, each of the above techniques has the following problems. In other words, although the neutralization coprecipitation method (2) has excellent productivity, it results in relatively large particles or gel, and in order to obtain fine particles, the product must be separated, dried, and then pulverized. Must be. However, even if it is crushed, it is difficult to obtain fine particles with a size smaller than 0.1 μm. Furthermore, the rate of change in pH of the solution during the neutralization reaction is important, and it is also necessary to control the stirring rate of the solution, the dropping rate of the precipitant, etc. in terms of unit operations, making process control difficult. Although the hydrolysis method (2) is preferable from a synthetic chemical perspective as a method for obtaining ultrafine particles, it is problematic from an industrial perspective for the following reasons. First, - Boat fishing requires a long reaction time of several tens to hundreds of hours. Second, since a dilute aqueous solution of 10-" to 10-'mail/1 is used as the starting point, the yield per unit reaction volume is quite low when performing the synthesis batchwise. Third, the yield per unit reaction volume is quite low after the reaction. Fine particles can be easily separated from water by centrifugation, but even after separation, ani, t7 (C
/l! -, Now -, So, etc.) are adsorbed or contained, so special cleaning methods such as colloid filtration and ultrafiltration are required to remove them. Furthermore, in the hydrolysis method (2), the raw material Zr alkoxide is more expensive than inorganic Zr salts, and there is a problem from an industrial perspective. Therefore, a first object of the present invention is to provide a method for producing a hydrated zirconium sol that can provide fine zirconia particles with a uniform particle size. A second object of the present invention is to provide a method for producing a hydrated zirconium sol with excellent productivity. A third object of the present invention is to provide a method for producing a hydrated zirconium sol that can provide zirconia particles at low cost.
上記本発明の目的は、オキシ塩化ジルコニウム及びオキ
シ硝酸ジルコニウムの群の中から選ばれる少なくとも一
種類のものをジルコニウム源とし、尿素の分解により水
和ジルコニウムゾルが製造される方法であって、上記尿
素の分解に際して硝酸アンモニウム、塩化アンモニウム
及び硫酸アンモニウムの群の中から選ばれる少なくとも
一種類のアンモニウム塩が添加されてなることを特徴と
する水和ジルコニウムゾルの製造方法によって達成され
る。
尚、この水和ジルコニウムゾルの製造方法において、オ
キシ塩化ジルコニウム及びオキシ硝酸ジルコニウムの群
の中から選ばれるジルコニウム源の濃度は０．３〜２ｍ
ｏｌ／ｊ２のものであることが好ましい。すなわち、例
えばＺｒ０Ｃｊ！、水溶液の濃度が０．３ｔｎｏｌ／ｌ
より小さすぎる濃度では反応完了まで非常に長い時間を
要する傾向があり、逆に２ｗｒｏｌ！／ｌより大きすぎ
る濃度では粒子が大きくなる傾向があり、微細なゾル粒
子が得られにくく、ジルコニウム源は０．３〜２ｍｏｆ
／Ａの濃度である；とが好ましい。
又、この水和ジルコニウムゾルの製造方法において、オ
キシ塩化ジルコニウム及びオキシ硝酸ジルコニウムの群
の中から選ばれるジルコニウム源に対して尿素の量は、
モル比で１〜５倍であることが好ましい。すなわち、モ
ル比で１より小さすぎる場合では、加水分解反応が当量
的に起こらず、未反応のＺ ｒ ＯＣ４２Ｋが残ってし
まい、逆に５を越えて大きすぎる場合では、反応終了時
のＰＨが高くなり過ぎ、ＺｒＯ□粒子が成長し過ぎてし
まい、それ故ジルコニウム源に対して尿素の量はモル比
で１〜５倍であることが好ましい。
又、この水和ジルコニウムゾルの製造方法において、尿
素に対して硝酸アンモニウム、塩化アンモニウム及び硫
酸アンモニウムの群の中から選ばれるアンモニウム塩の
総量は、モル比で０．５倍以上であることが好ましい。
すなわち、ＮＩＩＪＯ８、ＮＨ，Ｃｆ、（ＮＨａ） ｚ
ＳＯ４等の添加量が尿素に対してモル比で０．５より小
さすぎる場合には、反応時間短縮効果が小さく、そして
３倍を越えて多すぎても効果向上は少ないことから、モ
ル比で０．５〜３倍程度であることが好ましい。
又、この水和ジルコニウムゾルの製造方法において、ジ
ルコニウム源と尿素の加水分解物との反応時のｐＨは２
〜３であることが好ましい。すなわち、ジルコニウム源
と尿素の加水分解物との反応時（ゲル生成時）のｐＨが
２より小さすぎる場合には、未反応のＺｒ０Ｃ１ｚが残
り、逆にｐＨが３より大きすぎる場合には、ＺｒＯ□粒
子が成長し過ぎてしまい、微細なゾルを得ることが困難
となるから、ゲル生成時のｐＨは２〜３であることが好
ましい。
又、この水和ジルコニウムゾルの製造方法において、ジ
ルコニウム源と尿素の加水分解物との反応生成物を濾過
、洗浄した後、酸で解膠することが好ましい、特に、濾
過・水洗時のｐＨは５〜７とすることが好ましい、特に
、ｐ）（が５未満の低すぎる場合には、濾過性の良いゲ
ルが得られず、濾過にかなりの時間を要し、ＰＨが７を
越えて高すぎる場合には、凝結が強くなり過ぎ、その後
の解膠処理に悪影響を及ぼし、短時間で分散性の良好な
ゾルは得られにくい。
又、濾過物に加える水の量は反応開始時の溶液の１／２
倍以上が好ましい、すなわち、これ以下では分散性の良
いゾルが得られにくい。
又、解膠処理時のｐＨは２．２以下が好ましい。
すなわち、これより高すぎる場合には分散性のよいゾル
が得られにくい。
ところで、本発明者は、例えばオキシ塩化ジルコニウム
を加水分解して水和ジルコニウムとするに際して、これ
まで沈澱剤としてアンモニアが用いられていたのである
が、アンモニアの代わりに尿素も使用できることを知る
に至った。
つまり、尿素は分解して
（ＮＯり ｚｃｏ ＋ ３ Ｈｚ Ｏ→ ２ＮＨｎＯＨ
＋ＣＯ□ ・・・■となり、アンモニアを生ずる。こ
の分解は溶液中で徐々に、そして均一に進むので、微細
な粒径、形状の均一な水和Ｚｒ０ｚ粒子を生成させるの
に最適である。
上記の式で生成したアンモニアにより
Ｚｒ０Ｃ１，ｔ ＋ ２ＮＨ４０Ｈ→Ｚｒ０（ＯＨ）ｔ
＋ ２ＮＨａＣｆ −■Ｚｒ０（ＯＨ）ｚ →Ｚｒ
Ｏ２＋ ＨｔＯ−■となって、水和ＺｒＯ□を生成す
る。
尚、尿素を用いず、アンモニアを直接加えた場合には、
■や■の反応が局部的に起こり、その部分で急激な水和
ＺｒＯ，の生成、成長が起き、粗雑で不均質な生成物と
なってしまうのである。
ところで、上記０式で示される分解は非常に遅い為、こ
れを速やかに進める必要がある。すなわち、上記０式で
示される分解を速やかに進め、水和ジルコニウムの生成
を速やかに行う為にＮ１（ＪＯ，、Ｎ）１．ＣＩ！、、
（Ｎ）＋４） ２Ｓ０４を加えるようにしたのである。
つまり、これらのアンモニウム塩が■の反応に対して触
媒として作用し、尿素の分解が速やかに行われ、前記し
た本発明の目的が達成されるようになったのである。The object of the present invention is to provide a method for producing a hydrated zirconium sol by decomposing urea using at least one selected from the group of zirconium oxychloride and zirconium oxynitrate as a zirconium source, the method comprising: This is achieved by a method for producing a hydrated zirconium sol, which is characterized in that at least one ammonium salt selected from the group of ammonium nitrate, ammonium chloride, and ammonium sulfate is added during the decomposition of the sol. In addition, in this method for producing hydrated zirconium sol, the concentration of the zirconium source selected from the group of zirconium oxychloride and zirconium oxynitrate is 0.3 to 2 m
ol/j2 is preferred. That is, for example, Zr0Cj! , the concentration of the aqueous solution is 0.3 tnol/l
If the concentration is too small, the reaction tends to take a very long time to complete, and conversely, 2wroll! If the concentration is too large than /l, particles tend to become large and it is difficult to obtain fine sol particles, and the zirconium source is 0.3 to 2 mof
It is preferable that the concentration is /A. In addition, in this method for producing hydrated zirconium sol, the amount of urea with respect to the zirconium source selected from the group of zirconium oxychloride and zirconium oxynitrate is as follows:
It is preferable that the molar ratio is 1 to 5 times. In other words, if the molar ratio is too small than 1, the hydrolysis reaction will not occur equivalence and unreacted ZrOC42K will remain; on the other hand, if the molar ratio is too large, exceeding 5, the pH at the end of the reaction will be Therefore, it is preferable that the amount of urea is 1 to 5 times the molar ratio of the zirconium source. Further, in this method for producing a hydrated zirconium sol, the total amount of ammonium salt selected from the group of ammonium nitrate, ammonium chloride, and ammonium sulfate is preferably 0.5 times or more based on urea. That is, NIIJO8, NH, Cf, (NHa) z
If the molar ratio of SO4, etc. to urea is less than 0.5, the reaction time shortening effect will be small, and if it is too large, exceeding 3 times, there will be little improvement in the effect. It is preferable that it is about 0.5 to 3 times. In addition, in this method for producing hydrated zirconium sol, the pH during the reaction between the zirconium source and the urea hydrolyzate is 2.
It is preferable that it is 3. That is, if the pH at the time of reaction between the zirconium source and the urea hydrolyzate (during gel formation) is less than 2, unreacted Zr0C1z remains, and conversely, if the pH is more than 3, ZrO □ The pH during gel formation is preferably 2 to 3, since the particles will grow too much and it will be difficult to obtain a fine sol. In addition, in this method for producing a hydrated zirconium sol, it is preferable to filter and wash the reaction product of the zirconium source and the urea hydrolyzate, and then peptize it with an acid. In particular, the pH at the time of filtration and water washing is It is preferable that the pH is between 5 and 7. In particular, if p) is too low (less than 5), a gel with good filterability will not be obtained, and filtration will take a considerable amount of time, and if the pH is higher than 7, the pH will be too high. If it is too much, the flocculation will be too strong, which will have a negative effect on the subsequent peptization process, making it difficult to obtain a sol with good dispersibility in a short time.Also, the amount of water added to the filtrate should be adjusted to the level of the solution at the start of the reaction. 1/2 of
It is preferable that the amount is more than double that, that is, if it is less than this, it is difficult to obtain a sol with good dispersibility. Further, the pH during peptization treatment is preferably 2.2 or less. That is, if it is higher than this, it is difficult to obtain a sol with good dispersibility. By the way, the present inventor has come to know that, although ammonia has hitherto been used as a precipitant when, for example, zirconium oxychloride is hydrolyzed to produce hydrated zirconium, urea can also be used instead of ammonia. Ta. In other words, urea decomposes (NOri zco + 3 Hz O → 2NHnOH
+CO□...■, producing ammonia. Since this decomposition proceeds gradually and uniformly in the solution, it is optimal for producing hydrated Zr0z particles with fine particle size and uniform shape. Zr0C1,t + 2NH40H → Zr0(OH)t by the ammonia generated by the above formula
+ 2NHaCf −■Zr0(OH)z →Zr
It becomes O2+ HtO-■ to produce hydrated ZrO□. In addition, if ammonia is added directly without using urea,
Reactions (1) and (2) occur locally, and hydrated ZrO rapidly forms and grows in those areas, resulting in a coarse and heterogeneous product. By the way, since the decomposition shown by the above equation 0 is very slow, it is necessary to proceed with it quickly. That is, in order to quickly proceed with the decomposition shown by the above formula 0 and quickly generate hydrated zirconium, N1(JO,,N)1. CI! ,,
(N)+4) 2S04 was added. In other words, these ammonium salts act as catalysts for the reaction (2), and urea is rapidly decomposed, thereby achieving the above-mentioned object of the present invention.
■ １ｓ＋ｏｊ！／ｆのＺｒ０Ｃｌ ｚ水溶液に、２．
０８倍（モル比）の尿素及びその尿素ムこ対して０．１
倍（モル比）のＮＨ４ＮＯ３を加えて溶解した。
■ ■の混液を三角フラスコにとり、還流冷却管を取り
つけて沸点で加熱した。
■ 加熱により溶液はゲル化するが、このゲルのｐＨが
２．０〜３． Ｏになった時点で加熱を停止し、放冷
した。尚、本実施例では所望のＰＨ値になるまで３．５
ｈｒを要した。
■ 放冷後、得られたゲルに対して反応開始時の溶液と
等容の純水を加え、攪拌した。そして、撹拌しつつ、０
．１〜２ＮのＮＨ，ＯＨを加え、ｐＨを５．０〜７．０
に調節した。
■ ■で得られたものを吸引濾過し、残留物を純水で水
洗濾過した。
■ 濾過後の残留物をビーカーにとり、さらに反応開始
時の溶液と等容ないしは１／２容の純水を加えて攪拌し
た。
■ ■で得られたものに濃硝酸を懸ｉ％液のｐＨが１．
０〜２．２になるまで加えた。
■ これを三角フラスコにとり、再び２〜３ｈｒ加熱還
流し、透光性のある水和ジルコニウムゾルを得た。
このようにして得られたゾルの電子顕微鏡写真を第１図
に示すが、これによれば形状は角板状で０．３μｍ以下
の微細な１次粒子が分散した均一な水性コロイドである
ことが判る。
又、上記の方法は、出発のジルコニウム源として比較的
濃い濃度のものを用いることができるから、経済収支が
高いものであり、又、反応時間もＮＨ，ＮＯ３を用いな
い場合に比べて１／２〜１／４と大幅に短縮できている
。
そして、このようにして得られたものは、Ｙ−ＴＺＰ、
Ｍｇ−ＰＳＺ、各種ジルコニア強靭化酸化物セラミック
やジルコニア質固体電解質の焼結用微粉末を製造する際
の原料として用いられるものである。■ 1s+oj! /f Zr0Cl z aqueous solution, 2.
0.8 times (molar ratio) of urea and its urea content: 0.1
Double (molar ratio) NH4NO3 was added and dissolved. The mixed solution of (2) and (2) was placed in an Erlenmeyer flask, fitted with a reflux condenser, and heated to boiling point. (2) The solution gels when heated, but the pH of this gel is 2.0-3. When the temperature reached 0, heating was stopped and the mixture was allowed to cool. In this example, the pH was adjusted to 3.5 until the desired pH value was reached.
It took hours. (2) After cooling, pure water of the same volume as the solution at the start of the reaction was added to the obtained gel and stirred. Then, while stirring,
．． Add 1-2N NH, OH to adjust pH to 5.0-7.0
It was adjusted to (2) The product obtained in (2) was filtered with suction, and the residue was washed and filtered with pure water. (2) The residue after filtration was placed in a beaker, and pure water in an amount equal to or 1/2 volume of the solution at the start of the reaction was added and stirred. ■ Add concentrated nitric acid to the product obtained in step ■ until the pH of the i% solution is 1.
It was added until it became 0-2.2. (2) This was placed in an Erlenmeyer flask and heated under reflux again for 2 to 3 hours to obtain a translucent hydrated zirconium sol. An electron micrograph of the sol obtained in this way is shown in Figure 1, which shows that it is a uniform aqueous colloid with a rectangular plate shape and fine primary particles of 0.3 μm or less dispersed therein. I understand. In addition, the above method has a high economic balance because a relatively high concentration of zirconium can be used as the starting zirconium source, and the reaction time is also 1/1 compared to the case where NH and NO3 are not used. This is a significant reduction of 2 to 1/4. And what was obtained in this way was Y-TZP,
It is used as a raw material for producing fine powder for sintering Mg-PSZ, various zirconia toughened oxide ceramics, and zirconia solid electrolytes.
本発明に係る水和ジルコニウムゾルの製造方法は、オキ
シ塩化ジルコニウム及びオキシ硝酸ジルコニウムの群の
中から選ばれる少なくとも一種類のものをジルコニウム
源とし、尿素の分解により水和ジルコニウムゾルが製造
される方法であって、上記尿素の分解に際して硝酸アン
モニウム、塩化アンモニウム及び硫酸アンモニウムの群
の中から選ばれる少な（とも一種類のアンモニウム塩が
添加されてなるので、尿素の分解によりアンモニアが生
じ、しかもこの尿素の分解は溶液中で徐々に、そして均
一に進むので、微細な粒径、形状の均一な水和Ｚｒ０．
粒子が生成するようになり、そしてこの時に硝酸アンモ
ニウム、塩化アンモニウム及び硫酸アンモニウムの群の
中から選ばれる少なくとも一種類のアンモニウム塩が添
加されているから尿素の分解反応が速やかに進み、微細
で、均一な粒径のＺｒＯ２粒子のゾルが低廉に、かつ、
生産性良く、スピーデイに得られる等の特長を有する。The method for producing a hydrated zirconium sol according to the present invention is a method in which a zirconium source is at least one selected from the group of zirconium oxychloride and zirconium oxynitrate, and a hydrated zirconium sol is produced by decomposition of urea. During the decomposition of urea, one ammonium salt selected from the group of ammonium nitrate, ammonium chloride, and ammonium sulfate is added, so ammonia is produced by the decomposition of urea, and furthermore, the decomposition of this urea proceeds gradually and uniformly in the solution, resulting in hydrated Zr0.
At this time, at least one ammonium salt selected from the group of ammonium nitrate, ammonium chloride, and ammonium sulfate is added, so that the decomposition reaction of urea proceeds rapidly, resulting in fine and uniform particles. A sol of ZrO2 particles with a particle size is inexpensive and
It has features such as high productivity and quick production.
第１図は、Ｚｒｏｔ粒子の形状を説明する電子顕微鏡写
真である。
特許出願人 秩父セメント株式会社FIG. 1 is an electron micrograph illustrating the shape of Zrot particles. Patent applicant Chichibu Cement Co., Ltd.
Claims (6)
ウムの群の中から選ばれる少なくとも一種類のものをジ
ルコニウム源とし、尿素の分解により水和ジルコニウム
ゾルが製造される方法であって、上記尿素の分解に際し
て硝酸アンモニウム、塩化アンモニウム及び硫酸アンモ
ニウムの群の中から選ばれる少なくとも一種類のアンモ
ニウム塩が添加されてなることを特徴とする水和ジルコ
ニウムゾルの製造方法。(1) A method in which a hydrated zirconium sol is produced by decomposing urea, using at least one kind selected from the group of zirconium oxychloride and zirconium oxynitrate as a zirconium source, wherein ammonium nitrate is , ammonium chloride, and ammonium sulfate.
ウムの群の中から選ばれるジルコニウム源の濃度が０．
３〜２ｍｏｌ／ｌのものである特許請求の範囲第１項記
載の水和ジルコニウムゾルの製造方法。(2) The concentration of the zirconium source selected from the group of zirconium oxychloride and zirconium oxynitrate is 0.
The method for producing a hydrated zirconium sol according to claim 1, wherein the hydrated zirconium sol has a concentration of 3 to 2 mol/l.
ウムの群の中から選ばれるジルコニウム源に対して尿素
の量がモル比で１〜５倍である特許請求の範囲第１項記
載の水和ジルコニウムゾルの製造方法。(3) Production of a hydrated zirconium sol according to claim 1, wherein the amount of urea is 1 to 5 times the molar ratio of the zirconium source selected from the group of zirconium oxychloride and zirconium oxynitrate. Method.
ム及び硫酸アンモニウムの群の中から選ばれるアンモニ
ウム塩の総量がモル比で０．５倍以上である特許請求の
範囲第１項記載の水和ジルコニウムゾルの製造方法。(4) Production of the hydrated zirconium sol according to claim 1, wherein the total amount of ammonium salt selected from the group of ammonium nitrate, ammonium chloride, and ammonium sulfate is 0.5 times or more in molar ratio to urea. Method.
が２〜３である特許請求の範囲第１項記載の水和ジルコ
ニウムゾルの製造方法。(5) pH during reaction of zirconium source and urea decomposition product
The method for producing a hydrated zirconium sol according to claim 1, wherein the sol is 2 to 3.
濾過、洗浄した後、酸で解膠する特許請求の範囲第１項
記載の水和ジルコニウムゾルの製造方法。(6) The method for producing a hydrated zirconium sol according to claim 1, wherein the reaction product of the zirconium source and the decomposed product of urea is filtered and washed, and then peptized with an acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21672790A JPH04104910A (en) | 1990-08-17 | 1990-08-17 | Production of hydrated zirconium sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21672790A JPH04104910A (en) | 1990-08-17 | 1990-08-17 | Production of hydrated zirconium sol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04104910A true JPH04104910A (en) | 1992-04-07 |
Family
ID=16692980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21672790A Pending JPH04104910A (en) | 1990-08-17 | 1990-08-17 | Production of hydrated zirconium sol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04104910A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834613A (en) * | 1994-04-05 | 1996-02-06 | Natl Inst For Res In Inorg Mater | Production of high homogeneity and high purity yttrium-containing zirconia powder |
| JPH0834612A (en) * | 1994-04-05 | 1996-02-06 | Natl Inst For Res In Inorg Mater | Production of high homogeneity yttrium-containing zirconia powder |
| WO2006115043A1 (en) * | 2005-04-18 | 2006-11-02 | Nissan Chemical Industries, Ltd. | Acidic zirconia sol and method for producing same |
| JP2007238422A (en) * | 2006-03-10 | 2007-09-20 | Daiichi Kigensokagaku Kogyo Co Ltd | Organic solvent-dispersed zirconia sol and its production method |
-
1990
- 1990-08-17 JP JP21672790A patent/JPH04104910A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834613A (en) * | 1994-04-05 | 1996-02-06 | Natl Inst For Res In Inorg Mater | Production of high homogeneity and high purity yttrium-containing zirconia powder |
| JPH0834612A (en) * | 1994-04-05 | 1996-02-06 | Natl Inst For Res In Inorg Mater | Production of high homogeneity yttrium-containing zirconia powder |
| WO2006115043A1 (en) * | 2005-04-18 | 2006-11-02 | Nissan Chemical Industries, Ltd. | Acidic zirconia sol and method for producing same |
| JPWO2006115043A1 (en) * | 2005-04-18 | 2008-12-18 | 日産化学工業株式会社 | Acid zirconia sol and method for producing the same |
| US7691910B2 (en) | 2005-04-18 | 2010-04-06 | Nissan Chemical Industries, Ltd. | Acidic zirconia sol and production method of the same |
| US8058318B2 (en) | 2005-04-18 | 2011-11-15 | Nissan Chemical Industries, Ltd. | Acidic zirconia sol and production method of the same |
| JP4968475B2 (en) * | 2005-04-18 | 2012-07-04 | 日産化学工業株式会社 | Acid zirconia sol and method for producing the same |
| KR101308118B1 (en) * | 2005-04-18 | 2013-09-12 | 닛산 가가쿠 고교 가부시키 가이샤 | Acidic zirconia sol and method for producing same |
| JP2007238422A (en) * | 2006-03-10 | 2007-09-20 | Daiichi Kigensokagaku Kogyo Co Ltd | Organic solvent-dispersed zirconia sol and its production method |
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