JP3646818B2 - Bismuth oxycarbonate powder and method for producing the same - Google Patents
Bismuth oxycarbonate powder and method for producing the same Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明は、オキシ炭酸ビスマス粉末の製造方法に関する。さらに詳しくは、エレクトロ・セラミックス材料、光学材料等に用いられ、分散性の優れた微細なオキシ炭酸ビスマス粉末の製造方法に関する。
【０００２】
【従来の技術】
オキシ炭酸ビスマスの製法としては、硝酸ビスマス（III ）溶液を炭酸ナトリウム溶液または炭酸水素ナトリウム溶液に加え、得られた沈殿を乾燥する方法が知られている。しかしこのような従来の技術には、得られるオキシ炭酸ビスマスが凝集の激しいものとなっていたため、次のような欠点があった。
【０００３】
すなわち、エレクトロ・セラミックス材料、光学材料等の製造に用いる場合、製品中のＢｉ分布のばらつきが大きくなるため、特性の再現性が乏しい、製品の収率が低いなどの問題があった。
【０００４】
また、一般的には酸化ビスマスをこれら用途に用いるが、同様の問題があった。
【０００５】
【発明が解決しようとする課題】
本発明は、上記の問題点を解決し、分散性に優れた微細なオキシ炭酸ビスマス粉末およびその製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者等は斯かる課題を解決するため鋭意研究したところ、分散性の良いオキシ炭酸ビスマスの製造方法を見出し、本発明を提出することができた。
【０００７】
すなわち本発明は、第１に粒度分布の５０％累積粒径が０．１〜３．０μｍの範囲内にあり、９０％累積粒径が１０．０μｍ以下であることを特徴とするオキシ炭酸ビスマス粉末、第２に比表面積が１０ｍ2／ｇ以上であることを特徴とする第１記載のオキシ炭酸ビスマス粉末、第３にビスマス塩の水溶液をアルカリにて中和し、ｐＨ９以上、液温２５〜４０℃の条件下で水酸化ビスマスを含む沈殿物を生成したのち、この沈殿物を含む溶液に炭酸塩を加えて撹拌し、得られた沈殿物を濾過、乾燥することからなるオキシ炭酸ビスマス粉末の製造方法である。
【０００８】
【作用】
まず、ビスマス塩の水溶液をアンモニア水に添加して、水酸化ビスマスの沈殿を生成させる。この際の水溶液の温度は２５℃〜４０℃、好ましくは２５℃〜３０℃に制御される。液温４０℃以上では、このあと添加する炭酸塩が分解し、反応寄与分が減少してしまい、２５℃以下では冷却の必要が生じ操作上好ましくない。
【０００９】
アンモニア水とビスマス塩水溶液の濃度には特に制限はなく、例えばアンモニア濃度２０〜２５％のアンモニア水およびビスマス濃度（Ｂｉとして）１００〜２００g/l のビスマス塩水溶液が用いられる。
【００１０】
アンモニア水の量はビスマス塩添加後のｐＨが９以上になるように添加することが好ましい。
【００１１】
ビスマス塩としては水に可溶なビスマス塩であればよく、特に制限はない。具体的には硝酸ビスマス、硫酸ビスマス、塩化ビスマス等を用いることができる。
【００１２】
反応系は反応前後を通じて攪拌される。
【００１３】
次に生成した水酸化ビスマスの沈殿を含む反応液に炭酸塩を添加する。炭酸塩としては、炭酸アンモニウム、炭酸水素アンモニウムが好適に用いられる。炭酸塩の添加量はビスマスに対して当量である。炭酸塩添加後のｐＨは９以上となる。
【００１４】
次いで濾過、脱水、水洗、乾燥、解砕を行う。これらの工程には従来の方法を適用できる。乾燥温度は１００〜１５０℃であり、好ましくはオキシ炭酸ビスマスの分解温度を考慮すると１２０℃前後が好ましい。
【００１５】
【実施例１】
アンモニア濃度２５％のアンモニア水８０mlにビスマス濃度（Ｂｉとして）１４０g/l の硝酸ビスマス１６０mlを攪拌しながら添加し、沈殿を生成させた。反応後の溶液のｐＨは９．５程度となる。次いで炭酸水素アンモニウム５ｇを５０mlの水に溶解した水溶液を加えて約１５分間攪拌したのち濾過、水洗した。沈殿物を１２０℃で２０時間乾燥したのち解砕し、オキシ炭酸ビスマス粉を得た。
【００１６】
得られたオキシ炭酸ビスマス粉の粒度分布をレーザー回折・散乱法で測定した。測定には島津製作所製ＳＡＬＤ−１０００を使用し、試料を０．２％ヘキサメタリン酸ソーダ水溶液中に超音波分散（３０秒間）させて測定を行い、その結果を図１に示した。５０％累積粒径（Ｄ50）は１．０４μｍであり、９０％累積粒径（Ｄ90）は２．４９μｍであった。比表面積（ＢＥＴ １点法）は１３．７m2/gであった。粒子構造を示すＳＥＭ写真は図５に示す通りであった。
【００１７】
【実施例２】
アンモニア濃度２５％のアンモニア水２００mlにビスマス濃度（Ｂｉとして）１４０g/l の硝酸ビスマス水溶液２００mlを攪拌しながら添加し、沈殿を生成させた。反応後の溶液のｐＨは１０程度となる。次いで炭酸水素アンモニウム５ｇを５０mlの水に溶解した水溶液を加えて約１５分間攪拌したのち濾過、水洗した。沈殿物を１２０℃で２０時間乾燥したのち解砕し、オキシ炭酸ビスマス粉を得た。
【００１８】
得られたオキシ炭酸ビスマス粉の粒度分布を実施例１と同じ方法で測定したところ、その結果は図１とほぼ同じであって、５０％累積粒径（Ｄ50）は１．３５μｍであり、９０％累積粒径（Ｄ90）は３．１５μｍであった。ＳＥＭ写真も実施例１に示したものと実質的に同じであった。比表面積（ＢＥＴ １点法）は１２．９m2/gであった。
【００１９】
【実施例３】
実施例１で得られたオキシ炭酸ビスマス粉を電気炉にて４００℃、空気中で５時間焼成し、酸化ビスマスを得た。得られた酸化ビスマスの粒度分布を実施例１と同じ方法で測定し、得られた粒度分布図を図２に、粉末の粒子構造を示すＳＥＭ写真を図６に示した。５０％累積粒径（Ｄ50）は１．５９μｍであり、９０％累積粒径（Ｄ90）は７．０４μｍであった。比表面積（ＢＥＴ １点法）は４．１０m2/gであった。
【００２０】
【比較例１】
オキシ炭酸ビスマスの市販品として、和光純薬工業製炭酸酸化ビスマス（ロット番号 ＴＷＦ３４２８）について、実施例１と同じ方法で粒度分布を測定しその結果を図３に示した。５０％累積粒径（Ｄ50）は７．８６μｍであり、９０％累積粒径（Ｄ90）は１９．２８μｍであった。比表面積（ＢＥＴ １点法）は５．３７m2/gであった。粉末の粒子構造を示すＳＥＭ写真を図７に示す。
【００２１】
【比較例２】
硝酸ビスマス溶液を炭酸ナトリウム溶液に加える従来法により得たオキシ炭酸ビスマスを乾燥、解砕した場合の粒度分布およびＳＥＭ写真は比較例１の場合と同様であった。平均粒径（Ｄ50）は１２．９５μｍ、（Ｄ90）は３１．１５μｍであった。この粒径は、ＳＥＭ粒径に比べて極端に大きな粒径であり、これは、得られたオキシ炭酸ビスマスが著しく凝集していることを示している。比表面積は１０．２m2/gであった。
【００２２】
【比較例３】
比較例１のオキシ炭酸ビスマスを電気炉にて４００℃、空気中で５時間焼成し、酸化ビスマスを得た。実施例と同じ方法で粒度分布を測定した結果は図４に示す通りであって、５０％累積粒径（Ｄ50）は７．０１μｍであり、９０％累積粒径（Ｄ90）は１８．１８μｍであった。比表面積（ＢＥＴ １点法）は４．３４m2/gであった。粉末の粒子構造を示すＳＥＭ写真を図８に示す。
【００２３】
上記実施例１〜３および比較例１〜３の結果をまとめて対比すると表１の通りである。
【００２４】
【表１】
【発明の効果】
従来法では得られたオキシ炭酸ビスマスは凝集の激しいものであったが、本発明により、市販品粉末に比べてはるかに微細な、分散性に優れたオキシ炭酸ビスマスの粉末を得ることができた。
【００２６】
また、焼成によって酸化ビスマスを製造する際、通常焼結防止剤の添加が必要であるが、本発明のオキシ炭酸ビスマスを原料として用いることによって、焼結防止剤を使用せずに分散性に優れた微細な酸化ビスマス粉をつくることができる。
【図面の簡単な説明】
【図１】実施例１で得られたオキシ炭酸ビスマスの粒度分布図である。
【図２】実施例３で得られた酸化ビスマスの粒度分布図である。
【図３】比較例１で得られたオキシ炭酸ビスマスの粒度分布図である。
【図４】比較例３で得られた酸化ビスマスの粒度分布図である。
【図５】実施例１で得られたオキシ炭酸ビスマスの粒子構造を示すＳＥＭ写真である。
【図６】実施例３で得られた酸化ビスマスの粒子構造を示すＳＥＭ写真である。
【図７】市販品オキシ炭酸ビスマス（和光純薬工業製炭酸酸化ビスマス）の粒子構造を示すＳＥＭ写真である。
【図８】市販品オキシ炭酸ビスマス（和光純薬工業製炭酸酸化ビスマス）を焼成して得られた酸化ビスマスの粒子構造を示すＳＥＭ写真である。[0001]
[Industrial application fields]
The present invention relates to a method for producing bismuth oxycarbonate powder. More specifically, the present invention relates to a method for producing a fine bismuth oxycarbonate powder that is used in electro-ceramic materials, optical materials, etc. and has excellent dispersibility.
[0002]
[Prior art]
As a method for producing bismuth oxycarbonate, a method is known in which a bismuth (III) nitrate solution is added to a sodium carbonate solution or a sodium hydrogen carbonate solution, and the resulting precipitate is dried. However, such a conventional technique has the following drawbacks because the obtained bismuth oxycarbonate is agglomerated.
[0003]
That is, when used for the production of electro-ceramic materials, optical materials, etc., there are problems such as poor product reproducibility and low product yield because of the large variation in Bi distribution in the product.
[0004]
In general, bismuth oxide is used for these applications, but there are similar problems.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to solve the above problems and to provide a fine bismuth oxycarbonate powder excellent in dispersibility and a method for producing the same.
[0006]
[Means for Solving the Problems]
The inventors of the present invention have intensively studied to solve such a problem. As a result, they have found a method for producing bismuth oxycarbonate having good dispersibility, and have been able to submit the present invention.
[0007]
That is, the present invention provides a bismuth oxycarbonate characterized by firstly having a 50% cumulative particle size distribution in the range of 0.1 to 3.0 μm and a 90% cumulative particle size of 10.0 μm or less. Powder, second specific surface area of 10 m 2 / g or more, neutralized bismuth oxycarbonate powder according to the first, third bismuth salt aqueous solution with alkali, pH 9 or more, liquid temperature 25 Bismuth oxycarbonate comprising forming a precipitate containing bismuth hydroxide under a condition of ˜40 ° C., adding carbonate to the solution containing the precipitate and stirring, and filtering and drying the resulting precipitate. It is a manufacturing method of powder.
[0008]
[Action]
First, an aqueous solution of bismuth salt is added to aqueous ammonia to form a precipitate of bismuth hydroxide. The temperature of the aqueous solution at this time is controlled to 25 ° C to 40 ° C, preferably 25 ° C to 30 ° C. When the liquid temperature is 40 ° C. or higher, the carbonate to be added thereafter is decomposed and the contribution of the reaction is reduced.
[0009]
The concentration of the aqueous ammonia and the aqueous bismuth salt solution is not particularly limited. For example, aqueous ammonia having an ammonia concentration of 20 to 25% and an aqueous bismuth salt solution having a bismuth concentration (as Bi) of 100 to 200 g / l are used.
[0010]
The amount of aqueous ammonia is preferably added so that the pH after addition of the bismuth salt is 9 or more.
[0011]
The bismuth salt is not particularly limited as long as it is soluble in water. Specifically, bismuth nitrate, bismuth sulfate, bismuth chloride, or the like can be used.
[0012]
The reaction system is stirred throughout the reaction.
[0013]
Next, carbonate is added to the reaction solution containing the precipitate of bismuth hydroxide formed. As the carbonate, ammonium carbonate and ammonium hydrogen carbonate are preferably used. The amount of carbonate added is equivalent to bismuth. The pH after the carbonate addition is 9 or more.
[0014]
Next, filtration, dehydration, washing with water, drying and crushing are performed. Conventional methods can be applied to these steps. The drying temperature is 100 to 150 ° C., and preferably around 120 ° C. in consideration of the decomposition temperature of bismuth oxycarbonate.
[0015]
[Example 1]
160 ml of bismuth nitrate having a bismuth concentration (as Bi) of 140 g / l was added to 80 ml of ammonia water having an ammonia concentration of 25% with stirring to form a precipitate. The pH of the solution after the reaction is about 9.5. Next, an aqueous solution in which 5 g of ammonium hydrogen carbonate was dissolved in 50 ml of water was added and stirred for about 15 minutes, followed by filtration and washing with water. The precipitate was dried at 120 ° C. for 20 hours and then crushed to obtain bismuth oxycarbonate powder.
[0016]
The particle size distribution of the obtained bismuth oxycarbonate powder was measured by a laser diffraction / scattering method. For the measurement, SALD-1000 manufactured by Shimadzu Corporation was used, and the sample was subjected to ultrasonic dispersion (30 seconds) in a 0.2% sodium hexametaphosphate aqueous solution, and the result is shown in FIG. The 50% cumulative particle size (D50) was 1.04 μm and the 90% cumulative particle size (D90) was 2.49 μm. The specific surface area (BET 1-point method) was 13.7 m 2 / g. The SEM photograph showing the particle structure is as shown in FIG.
[0017]
[Example 2]
A 200 g aqueous solution of bismuth nitrate having a bismuth concentration (as Bi) of 140 g / l was added to 200 ml of ammonia water having an ammonia concentration of 25% with stirring to form a precipitate. The pH of the solution after the reaction is about 10. Next, an aqueous solution in which 5 g of ammonium hydrogen carbonate was dissolved in 50 ml of water was added and stirred for about 15 minutes, followed by filtration and washing with water. The precipitate was dried at 120 ° C. for 20 hours and then crushed to obtain bismuth oxycarbonate powder.
[0018]
When the particle size distribution of the obtained bismuth oxycarbonate powder was measured by the same method as in Example 1, the result was almost the same as in FIG. 1, and the 50% cumulative particle size (D50) was 1.35 μm. % Cumulative particle size (D90) was 3.15 μm. The SEM photograph was substantially the same as that shown in Example 1. The specific surface area (BET 1-point method) was 12.9 m 2 / g.
[0019]
[Example 3]
The bismuth oxycarbonate powder obtained in Example 1 was baked in an electric furnace at 400 ° C. in air for 5 hours to obtain bismuth oxide. The particle size distribution of the obtained bismuth oxide was measured by the same method as in Example 1. The obtained particle size distribution diagram is shown in FIG. 2, and the SEM photograph showing the particle structure of the powder is shown in FIG. The 50% cumulative particle size (D50) was 1.59 μm, and the 90% cumulative particle size (D90) was 7.04 μm. The specific surface area (BET 1-point method) was 4.10 m 2 / g.
[0020]
[Comparative Example 1]
As a commercial product of bismuth oxycarbonate, particle size distribution was measured for bismuth carbonate carbonate (lot number TWF3428) manufactured by Wako Pure Chemical Industries, Ltd. in the same manner as in Example 1, and the results are shown in FIG. The 50% cumulative particle size (D50) was 7.86 μm and the 90% cumulative particle size (D90) was 19.28 μm. The specific surface area (BET 1-point method) was 5.37 m 2 / g. An SEM photograph showing the particle structure of the powder is shown in FIG.
[0021]
[Comparative Example 2]
When bismuth oxycarbonate obtained by the conventional method of adding a bismuth nitrate solution to a sodium carbonate solution was dried and crushed, the particle size distribution and SEM photograph were the same as in Comparative Example 1. The average particle diameter (D50) was 12.95 μm, and (D90) was 31.15 μm. This particle size is extremely large compared to the SEM particle size, which indicates that the obtained bismuth oxycarbonate is significantly aggregated. The specific surface area was 10.2 m 2 / g.
[0022]
[Comparative Example 3]
The bismuth oxycarbonate of Comparative Example 1 was baked in an electric furnace at 400 ° C. in air for 5 hours to obtain bismuth oxide. The result of measuring the particle size distribution by the same method as in the example is as shown in FIG. 4. The 50% cumulative particle size (D50) is 7.01 μm and the 90% cumulative particle size (D90) is 18.18 μm. there were. The specific surface area (BET 1-point method) was 4.34 m 2 / g. An SEM photograph showing the particle structure of the powder is shown in FIG.
[0023]
Table 1 summarizes the results of Examples 1 to 3 and Comparative Examples 1 to 3 collectively.
[0024]
[Table 1]
【The invention's effect】
Although the bismuth oxycarbonate obtained by the conventional method was intensively aggregated, according to the present invention, it was possible to obtain a powder of bismuth oxycarbonate excellent in dispersibility and much finer than the commercially available powder. .
[0026]
In addition, when producing bismuth oxide by firing, it is usually necessary to add a sintering inhibitor, but by using the bismuth oxycarbonate of the present invention as a raw material, it is excellent in dispersibility without using a sintering inhibitor. Can make fine bismuth oxide powder.
[Brief description of the drawings]
1 is a particle size distribution diagram of bismuth oxycarbonate obtained in Example 1. FIG.
2 is a particle size distribution diagram of bismuth oxide obtained in Example 3. FIG.
3 is a particle size distribution diagram of bismuth oxycarbonate obtained in Comparative Example 1. FIG.
4 is a particle size distribution diagram of bismuth oxide obtained in Comparative Example 3. FIG.
5 is a SEM photograph showing the particle structure of bismuth oxycarbonate obtained in Example 1. FIG.
6 is a SEM photograph showing the particle structure of bismuth oxide obtained in Example 3. FIG.
FIG. 7 is an SEM photograph showing the particle structure of a commercially available bismuth oxycarbonate (bismuth carbonate carbonate manufactured by Wako Pure Chemical Industries, Ltd.).
FIG. 8 is an SEM photograph showing the particle structure of bismuth oxide obtained by firing commercially available bismuth oxycarbonate (bismuth carbonate carbonate manufactured by Wako Pure Chemical Industries, Ltd.).
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-
1995
- 1995-12-27 JP JP35264795A patent/JP3646818B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH09183620A (en) | 1997-07-15 |
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