JPH05294624A - Oriented sulfuric acid-containing zinc hydroxide powder and its production - Google Patents
Oriented sulfuric acid-containing zinc hydroxide powder and its productionInfo
- Publication number
- JPH05294624A JPH05294624A JP12288191A JP12288191A JPH05294624A JP H05294624 A JPH05294624 A JP H05294624A JP 12288191 A JP12288191 A JP 12288191A JP 12288191 A JP12288191 A JP 12288191A JP H05294624 A JPH05294624 A JP H05294624A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- zinc
- oriented
- hydroxide
- sulfuric acid
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、配向性含硫酸水酸化亜
鉛粉末及びその製造方法に関するものである。更に詳し
くは、高度に配向した（００１）配向性含硫酸水酸化亜
鉛粉末及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to oriented sulfuric acid-containing zinc hydroxide powder and a method for producing the same. More specifically, the present invention relates to a highly oriented (001) oriented zinc oxide sulfate-containing powder and a method for producing the same.
【０００２】[0002]
【従来の技術】含硫酸水酸化亜鉛の製造方法としては、
硫酸亜鉛水溶液を尿素の存在下において沸騰させ、ゆっ
くり加水分解し得る方法、硫酸亜鉛水溶液と酸化亜鉛を
反応させ得る方法等が知られている。しかしながら、こ
れらの方法は、特に工業的製造方法として必ずしも適当
な方法ではない。又、これらの方法で（００１）が高度
に配向した（００１）配向性含硫酸水酸化亜鉛粉末が得
られた例は未だ存在しない。2. Description of the Related Art As a method for producing sulfuric acid-containing zinc hydroxide,
Known methods include a method of boiling an aqueous solution of zinc sulfate in the presence of urea to slowly hydrolyze it, a method of reacting an aqueous solution of zinc sulfate with zinc oxide, and the like. However, these methods are not always suitable as industrial manufacturing methods. In addition, there is no example in which a (001) -oriented sulfated zinc hydroxide powder in which (001) is highly oriented is obtained by these methods.
【０００３】ところで、例えば機能性セラミックスの利
用において、焼結体中の結晶粒子の結晶軸を配向させる
ことにより、その優れた特性を更に発揮させることが出
来、従来から配向性セセラミックスに関し種々の方法が
試みられている。焼 この焼結体は、原料粉末を成形
し、得られた成形体を焼成することにより得られ、配向
向性セラミックスの原料粉末としては、配向性の粉末が
必要である。しかしながら、一般的には高度に配向した
原料粉末は入手困難な場合が多い。By the way, in the use of functional ceramics, for example, by orienting the crystal axes of the crystal grains in the sintered body, it is possible to further exhibit its excellent characteristics. The method is being tried. Firing This sintered body is obtained by molding a raw material powder and firing the resulting molded body, and an orienting powder is required as the raw material powder of the oriented ceramics. However, in general, highly oriented raw material powder is often difficult to obtain.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、高度
に配向した（００１）配向性含硫酸水酸化亜鉛粉末及び
それを簡単な方法でかつ容易に製造し得る方法を提供す
ることにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a highly oriented (001) -oriented zinc sulfate hydroxide powder and a method by which it can be produced easily and easily. ..
【０００５】[0005]
【課題を解決するための手段】本発明者等は、配向性含
硫酸水酸化亜鉛粉末及びその製造方法に関し鋭意検討し
た結果、硫酸亜鉛水溶液から含硫酸水酸化亜鉛を製造す
るに当たり、該亜鉛イオンに対し１．３〜２．０倍のモ
ル比の水酸イオンを生じる塩基を加え、その後得られた
含硫酸水酸化亜鉛粉末スラリーを熟成し、これを濾過、
洗浄の後乾燥することにより、Ｘ線回析による（００
１）回析線強度／（００２）回析線強度比が５以上であ
る、（００１）配向性含硫酸水酸化亜鉛粉末が得られる
ことを見出し本発明を完成した。Means for Solving the Problems The inventors of the present invention have made diligent studies on an oriented zinc sulfate-containing hydroxide powder and a method for producing the same. To 1.3 to 2.0 times the molar ratio of a base that produces hydroxide ions, and then the obtained sulfuric acid-containing zinc hydroxide powder slurry is aged and filtered,
After washing and drying, X-ray diffraction (00
The present invention was completed by finding that 1) a (001) oriented zinc sulfate-containing powder having a diffraction line strength / (002) diffraction line strength ratio of 5 or more can be obtained.
【０００６】以下本発明を詳細に説明する。The present invention will be described in detail below.
【０００７】[0007]
【作用】本発明の配向性は、通常の粉末法のＸ線回析装
置によるＸ線回析図形を用いて各々の回析線強度の比か
ら求めたものである。The orientation of the present invention is obtained from the ratio of the respective diffraction line intensities using an X-ray diffraction pattern obtained by an X-ray diffraction apparatus of a usual powder method.
【０００８】結晶の配向性は、Ｘ線回析法により評価す
ることが可能である。すなわち、結晶が材料中に３次元
的に規則的に配列している場合、そのＸ線回析図形は単
結晶の場合と同等な異方性を生じるはずであり、一方、
結晶が材料中にランダムに配列している場合、その得ら
れるＸ線回析図形は粉末Ｘ線と同等である。The crystal orientation can be evaluated by an X-ray diffraction method. That is, when crystals are three-dimensionally regularly arranged in the material, the X-ray diffraction pattern should produce anisotropy equivalent to that of a single crystal, while
When the crystals are randomly arranged in the material, the obtained X-ray diffraction pattern is equivalent to the powder X-ray.
【０００９】本発明で言う含硫酸水酸化亜鉛とは、基本
構造Ｚｎ４ ＳＯ４ （ＯＨ）６で表される化合物であ
る。従来の方法による得られた含硫酸水酸化亜鉛粉末の
（００１）配向比は、Ｘ線回析による（００１）回析線
強度／（００２）回析線強度比にして１〜２程度のもの
である。The sulfuric acid-containing zinc hydroxide referred to in the present invention is a compound represented by a basic structure Zn 4 SO 4 (OH) 6 . The (001) orientation ratio of the sulfated zinc hydroxide powder obtained by the conventional method is about 1 to 2 in terms of (001) diffraction line strength / (002) diffraction line strength ratio by X-ray diffraction. Is.
【００１０】本発明に用いる硫酸亜鉛水溶液に加える水
溶液系で水酸イオン（ＯＨ￣）を与える塩基としては、
水酸化ナトリウム、水酸化カリウム、アンモニア等使用
することが出来るが、不純物の混入がないことから、ア
ンモニアの使用が好ましい。As a base which gives a hydroxide ion (OH) in an aqueous solution system to be added to the zinc sulfate aqueous solution used in the present invention,
Although sodium hydroxide, potassium hydroxide, ammonia and the like can be used, it is preferable to use ammonia because impurities are not mixed.
【００１１】本発明に於いては、硫酸亜鉛水溶液から含
硫酸水酸化亜鉛を製造するに当たり、該亜鉛イオンに対
し１．０〜２．０倍のモル比の水酸イオンを生じる塩基
を加える必要がある。In the present invention, when producing sulfuric acid-containing zinc hydroxide from an aqueous solution of zinc sulfate, it is necessary to add a base which produces a hydroxide ion in a molar ratio of 1.0 to 2.0 times the zinc ion. There is.
【００１２】該モル比が１．０未満の場合、得られる薄
板状粒子がランダムに凝集し高度に配向した含硫酸水酸
化亜鉛粉末を得ることが困難となる。又、２．０を越え
る場合は、含硫酸水酸化亜鉛の溶解度が大きくなり、含
硫酸水酸化亜鉛粉末を得ることが困難となる。If the molar ratio is less than 1.0, it will be difficult to obtain highly sulphated zinc hydroxide-containing powder in which the resulting thin plate-like particles are randomly aggregated. On the other hand, when it exceeds 2.0, the solubility of the zinc sulfate-containing hydroxide increases, and it becomes difficult to obtain the zinc sulfate-containing hydroxide powder.
【００１３】また、反応系の濃度は特に制限されるもの
ではないが、出来るだけ希薄はものが好ましく、反応系
中の亜鉛濃度として０．２モル／リットル程度以下が好
ましい。The concentration of the reaction system is not particularly limited, but is preferably as dilute as possible, and the zinc concentration in the reaction system is preferably about 0.2 mol / liter or less.
【００１４】０．２モル／リットルを越える場合、粒子
の分散性が低下し高配向な含硫酸水酸化亜鉛粉末が得難
い。When it exceeds 0.2 mol / liter, the dispersibility of the particles is lowered and it is difficult to obtain a highly oriented zinc oxide hydroxide powder.
【００１５】本発明に於いては、上記方法により得られ
た含硫酸水酸化亜鉛スラリーを熟成することが必要であ
る。In the present invention, it is necessary to age the sulfuric acid-containing zinc hydroxide slurry obtained by the above method.
【００１６】熟成のない場合、粒子の凝集が激しく高配
向な含硫酸水酸化亜鉛粉末を得ることは困難である。Without aging, it is difficult to obtain highly sulphated zinc oxide hydroxide powder in which particles agglomerate strongly.
【００１７】又、本発明の方法に於ける熟成には配向比
の増加、粒径の増大の作用があり、適性な時間を選定す
ることにより、用途に適した配向度及び粒度の含硫酸水
酸化亜鉛粉末を容易に製造し得ることが可能である。特
に熟成時間に制限はない。Further, the ripening in the method of the present invention has the effect of increasing the orientation ratio and the particle size, and by selecting an appropriate time, the sulfuric acid-containing water having the orientation degree and particle size suitable for the application can be obtained. It is possible to easily produce zinc oxide powder. There is no particular limitation on the aging time.
【００１８】次に、上記本発明の含硫酸水酸化亜鉛スラ
リーを濾過、水洗後乾燥することにより、本発明の条件
を満足する（００１）配向性含硫酸水酸化亜鉛粉末を得
ることが出来る。乾燥温度は３００℃以下であれば特に
制限はないが、温度により得られる含硫酸水酸化亜鉛
（Ｚｎ４ ＳＯ４ （ＯＨ）６ ・ｎＨ２ Ｏ）の水和
量ｎが異なり、本発明では１００〜２００℃で行った。
３００℃を越える場合、得られる含硫酸水酸化亜鉛の分
解が起こり易く好ましくない。Next, the above-mentioned sulfuric acid-containing zinc hydroxide hydroxide slurry of the present invention is filtered, washed with water, and dried to obtain a (001) oriented zinc oxide sulfate-containing powder satisfying the conditions of the present invention. The drying temperature is not particularly limited as long as it is 300 ° C. or lower, but the hydrated amount n of sulfuric acid-containing zinc hydroxide (Zn 4 SO 4 (OH) 6 · nH 2 O) obtained differs depending on the temperature, and in the present invention, it is 100. Performed at ~ 200 ° C.
If the temperature exceeds 300 ° C., the obtained sulfuric acid-containing zinc hydroxide is likely to decompose, which is not preferable.
【００１９】[0019]
【実施例】以下実施例を述べるが、本発明はこれに限定
されるものではない。Ｘ線回析の測定は自動Ｘ線粉末回
析装置（ＰｈｉｌｉｐｓＰＷ１７２９）を使用した。測
定条件は、ＣｕＫα線、Ｘ線管電圧４０ＫＶ、電流５０
ｍＡ、走査速度２°／ｍｉｎで行った。 実施例１ ０．５モルの硫酸亜鉛を３０℃純水１０ｋｇに溶解さ
せ、この硫酸亜鉛水溶液に１．４７モル／リットルのア
ンモニア水５１０ｇを２時間で添加し、その後撹拌下７
２時間３０℃で熟成した。得られたスラリーのＰＨは
８．１であった。この系における水酸イオン（ＯＨ−）
／亜鉛イオンのモル比は１．５であり本発明の条件を満
足するものである。EXAMPLES Examples will be described below, but the present invention is not limited thereto. For the measurement of X-ray diffraction, an automatic X-ray powder diffraction apparatus (Philips PW1729) was used. The measurement conditions are CuKα ray, X-ray tube voltage 40KV, current 50
It was performed at mA and a scanning speed of 2 ° / min. Example 1 0.5 mol of zinc sulfate was dissolved in 10 kg of pure water at 30 ° C., 510 g of 1.47 mol / l ammonia water was added to this zinc sulfate aqueous solution over 2 hours, and then the mixture was stirred under stirring.
Aged for 2 hours at 30 ° C. The pH of the obtained slurry was 8.1. Hydroxide ion (OH − ) in this system
The molar ratio of / zinc ion is 1.5, which satisfies the conditions of the present invention.
【００２０】次に、得られたスラリーを濾過し、純水２
０ｋｇで洗浄した。つづいて、得られたケーキを空気中
１１０℃で２４時間乾燥させ、５９ｇの粉末を得た。得
られた粉末は、ＳＥＭ観察により非常に分散性の良い平
均粒子径７μｍ程度で平均粒子厚さ０．０５μｍ程度の
薄板状の結晶であった。Next, the obtained slurry is filtered to obtain pure water 2
It was washed with 0 kg. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours to obtain 59 g of powder. The obtained powder was a thin plate crystal having an average particle size of about 7 μm and an average particle thickness of about 0.05 μm with excellent dispersibility by SEM observation.
【００２１】この粉末は、Ｘ線回析で調べたところ基本
構造Ｚｎ４ ＳＯ４ （ＯＨ）６で表される含硫酸水酸
化亜鉛であり、（００１）回析線強度／（００２）回析
線強度比にして１５である非常に（００１）が高度に配
向した配向性含硫酸水酸化亜鉛であり、本発明の要件を
満足するものであった。この粉末のＸ線回析図形を図１
に示した。 実施例２ ０．５モルの硫酸亜鉛を３０℃純水１０ｋｇに溶解さ
せ、この硫酸亜鉛水溶液に１．４７モル／リットルのア
ンモニア水５１０ｇを２時間で添加し、その後撹槇下１
０時間３０℃で熟成した。得られたスラリーのＰＨは
８．１であった。この系における水酸イオン（ＯＨ−）
／亜鉛イオンのモル比は１．５であり本発明の要件を満
足するものである。This powder is a sulfuric acid-containing zinc hydroxide having a basic structure of Zn 4 SO 4 (OH) 6 as determined by X-ray diffraction, and has (001) diffraction line intensity / (002) diffraction. Very (001) having a linear strength ratio of 15 was highly oriented oriented sulfated zinc hydroxide, which satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in Fig. 1.
It was shown to. Example 2 0.5 mol of zinc sulfate was dissolved in 10 kg of pure water at 30 ° C., 510 g of 1.47 mol / l ammonia water was added to this zinc sulfate aqueous solution over 2 hours, and then the mixture was stirred under agitation 1
Aged at 30 ° C. for 0 hours. The pH of the obtained slurry was 8.1. Hydroxide ion (OH − ) in this system
The molar ratio of / zinc ion is 1.5, which satisfies the requirements of the present invention.
【００２２】次に、得られたスラリーを濾過し、純水２
０ｋｇで洗浄した。つづいて、得られたケーキを空気中
１１０℃で２４時間乾燥させ、５８．５ｇの粉末を得
た。得られた粉末は、ＳＥＭ観察により分散性の良い平
均粒子径２〜３μｍ程度で平均粒子厚さ０．０５μｍ程
度の薄板状の結晶であった。Next, the obtained slurry is filtered to obtain pure water 2
It was washed with 0 kg. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours to obtain 58.5 g of powder. The obtained powder was a thin plate crystal having an average particle size of about 2 to 3 μm and an average particle thickness of about 0.05 μm with good dispersibility by SEM observation.
【００２３】この粉末は、Ｘ線回析で調べたところ基本
構造Ｚｎ４ ＳＯ４ （ＯＨ）６で表される含硫酸水酸
化亜鉛であり、（００１）回析線強度／（００２）回析
線強度比にして８．５であり、（００１）が高度に配向
した配向性含硫酸水酸化亜鉛であり、本発明の要件を満
足するものであった。この粉末のＸ線回析図形を図２に
示した。 比較例．１ 水酸イオン（ＯＨ−）／亜鉛イオンのモル比を２．２と
大きくする以外は、実施例１と同様の条件下で、含硫酸
水酸化亜鉛粉末を得た。This powder is zinc sulfate-containing hydroxide having a basic structure of Zn 4 SO 4 (OH) 6 as determined by X-ray diffraction, and has (001) diffraction line intensity / (002) diffraction. The linear strength ratio was 8.5, and (001) was highly oriented oriented zinc sulfate-containing hydroxide, which satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG. Comparative example. 1 Sulfate-containing zinc hydroxide powder was obtained under the same conditions as in Example 1 except that the molar ratio of hydroxide ion (OH − ) / zinc ion was increased to 2.2.
【００２４】得られた粉末は、ＳＥＭで観察したとこ
ろ、薄板状粒子が強固に凝集した固いものであり、又、
（００１）回析線強度／（００２）回析線強度比にして
２．０であり、本発明の要件を満足する（００１）配向
性含硫酸水酸化亜鉛は得られなかった。 比較例．２ 水酸イオン（ＯＨ−）／亜鉛イオンのモル比を０．９と
小さくする以外は、実施例１と同様の条件下で、含硫酸
水酸化亜鉛粉末を得た。The obtained powder was a solid material in which thin plate-like particles were strongly aggregated, as observed by SEM, and
The (001) diffraction line strength / (002) diffraction line strength ratio was 2.0, and no (001) -oriented zinc sulfate-containing hydroxide satisfying the requirements of the present invention was obtained. Comparative example. Sulfate-containing zinc hydroxide powder was obtained under the same conditions as in Example 1 except that the molar ratio of dihydroxy ion (OH − ) / zinc ion was reduced to 0.9.
【００２５】得られた粉末は、ＳＥＭで観察したところ
粒子の凝集が強く大きな凝集体からなるものであり、
又、（００１）回析線強度／（００２）回析線強度比に
して２．０であり、本発明の要件を満足する（００１）
配向性含硫酸水酸化亜鉛は得られなかった。 比較例３ 熟成処理がないことを除き実施例１と同様に以下の方法
で行った例である。０．５モルの硫酸亜鉛を３０℃純水
１０ｋｇに溶解させ、この硫酸亜鉛水溶液に１．４７モ
ル／リットルのアンモニア水５１０ｇを２時間で添加
し、ＰＨ８．０のスラリーを得た。次に、得られたスラ
リーを濾過し、純水２０ｋｇで洗浄した。つづいて、得
られたケーキを空気中１１０℃で２４時間乾燥させた。The obtained powder is composed of large agglomerates with strong agglomeration of particles as observed by SEM.
Further, the ratio of (001) diffraction line intensity / (002) diffraction line intensity is 2.0, which satisfies the requirements of the present invention (001).
No oriented sulfuric acid-containing zinc hydroxide was obtained. Comparative Example 3 This is an example of carrying out by the following method as in Example 1 except that no aging treatment was carried out. 0.5 mol of zinc sulfate was dissolved in 10 kg of pure water at 30 ° C., and 510 g of 1.47 mol / liter ammonia water was added to this zinc sulfate aqueous solution for 2 hours to obtain a slurry of PH 8.0. Next, the obtained slurry was filtered and washed with 20 kg of pure water. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours.
【００２６】得られた粉末は、ＳＥＭ観察により０．８
μｍ程度で比較的凝集性の高いものであった。The obtained powder is 0.8 by SEM observation.
It had a relatively high cohesiveness at about μm.
【００２７】この粉末は、（００１）回析線強度／（０
０２）回析線強度比にして３程度と小さく、本発明の要
件を満足するものではなかった。この粉末のＸ線回析図
形を図３に示した。This powder has a (001) diffraction line strength / (0
02) The diffraction line strength ratio was as small as about 3 and did not satisfy the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００２８】[0028]
【発明の効果】本発明は、高度に配向した（００１）配
向性含硫酸水酸化亜鉛粉末を提供するものであり、本発
明により高度に配向した（００１）配向性含硫酸水酸化
亜鉛粉末を簡単な方法でかつ容易に得ることが可能とな
る。EFFECTS OF THE INVENTION The present invention provides highly oriented (001) -oriented zinc sulfate-containing hydroxide powder, which is highly oriented (001) -oriented zinc sulfate-containing powder. It can be obtained easily and easily.
【００２９】例えば、本発明の配向性含硫酸水酸化亜鉛
粉末を原料とし仮焼することにより、高度に配向した酸
化亜鉛が得られ、この酸化亜鉛を原料とし高度に配向し
た酸化亜鉛焼結体を得ることが出来る。For example, highly oriented zinc oxide is obtained by calcining the oriented sulfated zinc oxide hydroxide powder of the present invention as a raw material, and a highly oriented zinc oxide sintered body is obtained from this zinc oxide as a raw material. Can be obtained.
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例１の方法で得られたＸ線回析図形であ
る。1 is an X-ray diffraction pattern obtained by the method of Example 1. FIG.
【図２】実施例２の方法で得られたＸ線回析図形であ
る。2 is an X-ray diffraction pattern obtained by the method of Example 2. FIG.
【図３】比較例３の方法で得られたＸ線回析図形であ
る。3 is an X-ray diffraction pattern obtained by the method of Comparative Example 3. FIG.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年５月２７日[Submission date] May 27, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Name of item to be corrected] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 配向性含硫酸水酸化亜鉛粉末及びそ
の製造方法Title: Oriented sulfuric acid-containing zinc hydroxide powder and method for producing the same
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、配向性含硫酸水酸化亜
鉛粉末及びその製造方法に関するものである。更に詳し
くは、高度に配向した（００１）配向性含硫酸水酸化亜
鉛粉末及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to oriented sulfuric acid-containing zinc hydroxide powder and a method for producing the same. More specifically, the present invention relates to a highly oriented (001) oriented zinc oxide sulfate-containing powder and a method for producing the same.
【０００２】[0002]
【従来の技術】含硫酸水酸化亜鉛の製造方法としては、
硫酸亜鉛水溶液を尿素の存在下において沸騰させ、ゆっ
くり加水分解し得る方法、硫酸亜鉛水溶液と酸化亜鉛を
反応させ得る方法等が知られている。しかしながら、こ
れらの方法は、特に工業的製造方法として必ずしも適当
な方法ではない。又、これらの方法で（００１）が高度
に配向した（００１）配向性含硫酸水酸化亜鉛粉末が得
られた例は未だ存在しない。2. Description of the Related Art As a method for producing sulfuric acid-containing zinc hydroxide,
Known methods include a method of boiling an aqueous solution of zinc sulfate in the presence of urea to slowly hydrolyze it, a method of reacting an aqueous solution of zinc sulfate with zinc oxide, and the like. However, these methods are not always suitable as industrial manufacturing methods. In addition, there is no example in which a (001) -oriented sulfated zinc hydroxide powder in which (001) is highly oriented is obtained by these methods.
【０００３】ところで、例えば機能性セラミックスの利
用において、焼結体中の結晶粒子の結晶軸を配向させる
ことにより、その優れた特性を更に発揮させることが出
来、従来から配向性セラミックスに関し種々の方法が試
みられている。By the way, in the use of functional ceramics, for example, by orienting the crystal axes of the crystal grains in the sintered body, the excellent characteristics can be further exerted. Conventionally, various methods for oriented ceramics have been proposed. Is being attempted.
【０００４】この焼結体は、原料粉末を成形し、得られ
た成形体を焼成することにより得られ、配向性セラミッ
クスの原料粉末としては、配向性の粉末が必要である。
しかしながら、一般的には高度に配向した原料粉末は入
手困難な場合が多い。This sintered body is obtained by molding a raw material powder and firing the obtained molded body. Oriented powder is required as the raw material powder for oriented ceramics.
However, in general, highly oriented raw material powder is often difficult to obtain.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、高度
に配向した（００１）配向性含硫酸水酸化亜鉛粉末及び
それを簡単な方法でかつ容易に製造し得る方法を提供す
ることにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a highly oriented (001) -oriented zinc sulfate hydroxide powder and a method by which it can be produced easily and easily. ..
【０００６】[0006]
【課題を解決するための手段】本発明者等は、配向性含
硫酸水酸化亜鉛粉末及びその製造方法に関し鋭意検討し
た結果、硫酸亜鉛水溶液から含硫酸水酸化亜鉛を製造す
るに当たり、該亜鉛イオンに対し１．０〜２．０倍のモ
ル比の水酸イオンを生じる塩基を加え、その後得られた
含硫酸水酸化亜鉛粉末スラリーを熟成し、これを濾過、
洗浄の後乾燥することにより、Ｘ線回析による（００
１）回析線強度／（００２）回析線強度比が５以上であ
る、（００１）配向性含硫酸水酸化亜鉛粉末が得られる
ことを見出し本発明を完成した。Means for Solving the Problems The inventors of the present invention have made diligent studies on an oriented zinc sulfate-containing hydroxide powder and a method for producing the same. To 1.0 to 2.0 times the molar ratio of a base that produces hydroxide ions, and then the resulting sulfuric acid-containing zinc hydroxide powder slurry is aged and filtered,
After washing and drying, X-ray diffraction (00
The present invention was completed by finding that 1) a (001) oriented zinc sulfate-containing powder having a diffraction line strength / (002) diffraction line strength ratio of 5 or more can be obtained.
【０００７】以下本発明を詳細に説明する。The present invention will be described in detail below.
【０００８】[0008]
【作用】本発明の配向性は、通常の粉末法のＸ線回析装
置によるＸ線回析図形を用いて各々の回析線強度の比か
ら求めたものである。The orientation of the present invention is obtained from the ratio of the respective diffraction line intensities using an X-ray diffraction pattern obtained by an X-ray diffraction apparatus of a usual powder method.
【０００９】結晶の配向性は、Ｘ線回析法により評価す
ることが可能である。すなわち、結晶が材料中に３次元
的に規則的に配列している場合、そのＸ線回析図形は単
結晶の場合と同等な異方性を生じるはずであり、一方、
結晶が材料中にランダムに配列している場合、その得ら
れるＸ線回析図形は粉末Ｘ線と同等である。The crystal orientation can be evaluated by an X-ray diffraction method. That is, when crystals are three-dimensionally regularly arranged in the material, the X-ray diffraction pattern should produce anisotropy equivalent to that of a single crystal, while
When the crystals are randomly arranged in the material, the obtained X-ray diffraction pattern is equivalent to the powder X-ray.
【００１０】本発明で言う含硫酸水酸化亜鉛とは、基本
構造Ｚｎ4 ＳＯ4 （ＯＨ）6 で表される化合物である。
従来の方法による得られた含硫酸水酸化亜鉛粉末の（０
０１）配向比は、Ｘ線回析による（００１）回析線強度
／（００２）回析線強度比にして１〜２程度のものであ
る。The sulfated zinc hydroxide referred to in the present invention is a compound represented by the basic structure Zn 4 SO 4 (OH) 6 .
The sulfuric acid-containing zinc hydroxide powder obtained by the conventional method ((0
The (01) orientation ratio is about 1 to 2 in terms of (001) diffraction line intensity / (002) diffraction line intensity ratio by X-ray diffraction.
【００１１】本発明に用いる硫酸亜鉛水溶液に加える水
溶液系で水酸イオン（ＯＨ￣）を与える塩基としては、
水酸化ナトリウム、水酸化カリウム、アンモニア等使用
することが出来るが、不純物の混入がないことから、ア
ンモニアの使用が好ましい。本発明に於いては、硫酸亜
鉛水溶液から含硫酸水酸化亜鉛を製造するに当たり、該
亜鉛イオンに対し１．０〜２．０倍のモル比の水酸イオ
ンを生じる塩基を加える必要がある。As a base which gives a hydroxide ion (OH) in an aqueous solution system to be added to the zinc sulfate aqueous solution used in the present invention,
Although sodium hydroxide, potassium hydroxide, ammonia and the like can be used, it is preferable to use ammonia because impurities are not mixed. In the present invention, when producing a sulfuric acid-containing zinc hydroxide from an aqueous solution of zinc sulfate, it is necessary to add a base that produces a hydroxide ion in a molar ratio of 1.0 to 2.0 times the zinc ion.
【００１２】該モル比が１．０未満の場合、得られる薄
板状粒子がランダムに凝集し高度に配向した含硫酸水酸
化亜鉛粉末を得ることが困難となる。又、２．０を越え
る場合は、含硫酸水酸化亜鉛の溶解度が大きくなり、含
硫酸水酸化亜鉛粉末を得ることが困難となる。If the molar ratio is less than 1.0, it will be difficult to obtain highly sulphated zinc hydroxide-containing powder in which the resulting thin plate-like particles are randomly aggregated. On the other hand, when it exceeds 2.0, the solubility of the zinc sulfate-containing hydroxide increases, and it becomes difficult to obtain the zinc sulfate-containing hydroxide powder.
【００１３】また、反応系の濃度は特に制限されるもの
ではないが、出来るだけ希薄なものが好ましく、反応系
中の亜鉛濃度として０．２モル／リットル程度以下が好
ましい。The concentration of the reaction system is not particularly limited, but is preferably as dilute as possible, and the zinc concentration in the reaction system is preferably about 0.2 mol / liter or less.
【００１４】０．２モル／リットルを越える場合、粒子
の分散性が低下し高配向な含硫酸水酸化亜鉛粉末が得難
い。When it exceeds 0.2 mol / liter, the dispersibility of the particles is lowered and it is difficult to obtain a highly oriented zinc oxide hydroxide powder.
【００１５】本発明に於いては、上記方法により得られ
た含硫酸水酸化亜鉛スラリーを熟成することが必要であ
る。In the present invention, it is necessary to age the sulfuric acid-containing zinc hydroxide slurry obtained by the above method.
【００１６】熟成のない場合、粒子の凝集が激しく高配
向な含硫酸水酸化亜鉛粉末を得ることは困難である。Without aging, it is difficult to obtain highly sulphated zinc oxide hydroxide powder in which particles agglomerate strongly.
【００１７】又、本発明の方法に於ける熟成には配向比
の増加、粒径の増大の作用があり、適性な時間を選定す
ることにより、用途に適した配向度及び粒度の含硫酸水
酸化亜鉛粉末を容易に製造し得ることが可能である。特
に熟成時間に制限はない。Further, the ripening in the method of the present invention has the effect of increasing the orientation ratio and the particle size, and by selecting an appropriate time, the sulfuric acid-containing water having the orientation degree and particle size suitable for the application can be obtained. It is possible to easily produce zinc oxide powder. There is no particular limitation on the aging time.
【００１８】次に、上記本発明の含硫酸水酸化亜鉛スラ
リーを濾過、水洗後乾燥することにより、本発明の条件
を満足する（００１）配向性含硫酸水酸化亜鉛粉末を得
ることが出来る。Next, the above-mentioned sulfuric acid-containing zinc hydroxide hydroxide slurry of the present invention is filtered, washed with water, and dried to obtain a (001) oriented zinc oxide sulfate-containing powder satisfying the conditions of the present invention.
【００１９】乾燥温度は３００℃以下であれば特に制限
はないが、温度により得られる含硫酸水酸化亜鉛（Ｚｎ
4 ＳＯ4 （ＯＨ）6 ・ｎＨ2 Ｏ）の水和量ｎが異なり、
本発明では１００〜２００℃で行った。３００℃を越え
る場合、得られる含硫酸水酸化亜鉛の分解が起こり易く
好ましくない。The drying temperature is not particularly limited as long as it is 300 ° C. or lower, but the sulfuric acid-containing zinc hydroxide (Zn) obtained depending on the temperature is used.
The hydration amount n of 4 SO 4 (OH) 6 · nH 2 O) is different,
In the present invention, it was performed at 100 to 200 ° C. If the temperature exceeds 300 ° C., the obtained sulfuric acid-containing zinc hydroxide is likely to decompose, which is not preferable.
【００２０】[0020]
【実施例】以下実施例を述べるが、本発明はこれに限定
されるものではない。EXAMPLES Examples will be described below, but the present invention is not limited thereto.
【００２１】Ｘ線回析の測定は自動Ｘ線粉末回析装置
（ＰｈｉｌｉｐｓＰＷ１７２９）を使用した。測定条件
は、ＣｕＫα線、Ｘ線管電圧４０ＫＶ、電流５０ｍＡ、
走査速度２°／ｍｉｎで行った。For the measurement of X-ray diffraction, an automatic X-ray powder diffraction apparatus (Philips PW1729) was used. The measurement conditions are CuKα ray, X-ray tube voltage 40KV, current 50mA,
The scanning speed was 2 ° / min.
【００２２】実施例１ ０．５モルの硫酸亜鉛を３０℃純水１０ｋｇに溶解さ
せ、この硫酸亜鉛水溶液に１．４７モル／リットルのア
ンモニア水５１０ｇを２時間で添加し、その後撹拌下７
２時間３０℃で熟成した。得られたスラリーのＰＨは
８．１であった。この系における水酸イオン（ＯＨ-）
／亜鉛イオンのモル比は１．５であり本発明の条件を満
足するものである。Example 1 0.5 mol of zinc sulfate was dissolved in 10 kg of pure water at 30 ° C., 510 g of 1.47 mol / liter ammonia water was added to this zinc sulfate aqueous solution for 2 hours, and then the mixture was stirred under stirring for 7 hours.
Aged for 2 hours at 30 ° C. The pH of the obtained slurry was 8.1. Hydroxide in this system ion (OH -)
The molar ratio of / zinc ion is 1.5, which satisfies the conditions of the present invention.
【００２３】次に、得られたスラリーを濾過し、純水２
０ｋｇで洗浄した。つづいて、得られたケーキを空気中
１１０℃で２４時間乾燥させ、５９ｇの粉末を得た。Next, the obtained slurry is filtered to obtain pure water 2
It was washed with 0 kg. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours to obtain 59 g of powder.
【００２４】得られた粉末は、ＳＥＭ観察により非常に
分散性の良い平均粒子径７μｍ程度で平均粒子厚さ０．
０５μｍ程度の薄板状の結晶であった。The obtained powder has an average particle size of about 7 μm and a mean particle thickness of 0.
It was a thin plate-like crystal of about 05 μm.
【００２５】この粉末は、Ｘ線回析で調べたところ基本
構造Ｚｎ4 ＳＯ4 （ＯＨ）6 で表される含硫酸水酸化亜
鉛であり、（００１）回析線強度／（００２）回析線強
度比にして１５である非常に（００１）が高度に配向し
た配向性含硫酸水酸化亜鉛であり、本発明の要件を満足
するものであった。この粉末のＸ線回析図形を図１に示
した。This powder is zinc sulfate-containing hydroxide represented by the basic structure Zn 4 SO 4 (OH) 6 when examined by X-ray diffraction, and has (001) diffraction line intensity / (002) diffraction. Very (001) having a linear strength ratio of 15 was highly oriented oriented sulfated zinc hydroxide, which satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００２６】実施例２ ０．５モルの硫酸亜鉛を３０℃純水１０ｋｇに溶解さ
せ、この硫酸亜鉛水溶液に１．４７モル／リットルのア
ンモニア水５１０ｇを２時間で添加し、その後撹槇下１
０時間３０℃で熟成した。得られたスラリーのＰＨは
８．１であった。この系における水酸イオン（ＯＨ-）
／亜鉛イオンのモル比は１．５であり本発明の要件を満
足するものである。Example 2 0.5 mol of zinc sulfate was dissolved in 10 kg of pure water at 30 ° C., and 510 g of 1.47 mol / l ammonia water was added to this zinc sulfate aqueous solution for 2 hours, and then stirred under stirring 1
Aged at 30 ° C. for 0 hours. The pH of the obtained slurry was 8.1. Hydroxide in this system ion (OH -)
The molar ratio of / zinc ion is 1.5, which satisfies the requirements of the present invention.
【００２７】次に、得られたスラリーを濾過し、純水２
０ｋｇで洗浄した。つづいて、得られたケーキを空気中
１１０℃で２４時間乾燥させ、５８．５ｇの粉末を得
た。Next, the obtained slurry is filtered to obtain pure water 2
It was washed with 0 kg. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours to obtain 58.5 g of powder.
【００２８】得られた粉末は、ＳＥＭ観察により分散性
の良い平均粒子径２〜３μｍ程度で平均粒子厚さ０．０
５μｍ程度の薄板状の結晶であった。The obtained powder has an average particle diameter of about 2 to 3 μm with good dispersibility and an average particle thickness of 0.0 by SEM observation.
It was a thin plate-like crystal of about 5 μm.
【００２９】この粉末は、Ｘ線回析で調べたところ基本
構造Ｚｎ4 ＳＯ4 （ＯＨ）6 で表される含硫酸水酸化亜
鉛であり、（００１）回析線強度／（００２）回析線強
度比にして８．５であり、（００１）が高度に配向した
配向性含硫酸水酸化亜鉛であり、本発明の要件を満足す
るものであった。この粉末のＸ線回析図形を図２に示し
た。This powder is zinc sulfate-containing hydroxide represented by the basic structure Zn 4 SO 4 (OH) 6 when examined by X-ray diffraction, and has (001) diffraction line intensity / (002) diffraction. The linear strength ratio was 8.5, and (001) was highly oriented oriented zinc sulfate-containing hydroxide, which satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００３０】比較例．１ 水酸イオン（ＯＨ-）／亜鉛イオンのモル比を２．２と
大きくする以外は、実施例１と同様の条件下で、含硫酸
水酸化亜鉛粉末を得た。Comparative Example. 1 Sulfate-containing zinc hydroxide powder was obtained under the same conditions as in Example 1 except that the molar ratio of hydroxide ion (OH − ) / zinc ion was increased to 2.2.
【００３１】得られた粉末は、ＳＥＭで観察したとこ
ろ、薄板状粒子が強固に凝集した固いものであり、又、
（００１）回析線強度／（００２）回析線強度比にして
２．０であり、本発明の要件を満足する（００１）配向
性含硫酸水酸化亜鉛は得られなかった。The obtained powder was a solid material in which thin plate-like particles were strongly aggregated, as observed by SEM, and
The (001) diffraction line strength / (002) diffraction line strength ratio was 2.0, and no (001) -oriented zinc sulfate-containing hydroxide satisfying the requirements of the present invention was obtained.
【００３２】比較例．２ 水酸イオン（ＯＨ-）／亜鉛イオンのモル比を０．９と
小さくする以外は、実施例１と同様の条件下で、含硫酸
水酸化亜鉛粉末を得た。Comparative Example. A sulfuric acid-containing zinc hydroxide powder was obtained under the same conditions as in Example 1 except that the dihydroxide ion (OH − ) / zinc ion molar ratio was reduced to 0.9.
【００３３】得られた粉末は、ＳＥＭで観察したところ
粒子の凝集が強く大きな凝集体からなるものであり、
又、（００１）回析線強度／（００２）回析線強度比に
して２．０であり、本発明の要件を満足する（００１）
配向性含硫酸水酸化亜鉛は得られなかった。The obtained powder is composed of large agglomerates with strong agglomeration of particles as observed by SEM.
Further, the ratio of (001) diffraction line intensity / (002) diffraction line intensity is 2.0, which satisfies the requirements of the present invention (001).
No oriented sulfuric acid-containing zinc hydroxide was obtained.
【００３４】比較例３ 熟成処理がないことを除き実施例１と同様に以下の方法
で行った例である。Comparative Example 3 This is an example of carrying out by the following method as in Example 1 except that the aging treatment is not carried out.
【００３５】０．５モルの硫酸亜鉛を３０℃純水１０ｋ
ｇに溶解させ、この硫酸亜鉛水溶液に１．４７モル／リ
ットルのアンモニア水５１０ｇを２時間で添加し、ＰＨ
８．０のスラリーを得た。0.5 mol of zinc sulfate was added to pure water at 30 ° C. for 10 k.
g, and to this zinc sulfate aqueous solution, 510 g of 1.47 mol / liter ammonia water was added over 2 hours to obtain PH.
A slurry of 8.0 was obtained.
【００３６】次に、得られたスラリーを濾過し、純水２
０ｋｇで洗浄した。つづいて、得られたケーキを空気中
１１０℃で２４時間乾燥させた。Next, the obtained slurry is filtered to obtain pure water 2
It was washed with 0 kg. Subsequently, the obtained cake was dried in air at 110 ° C. for 24 hours.
【００３７】得られた粉末は、ＳＥＭ観察により０．８
μｍ程度で比較的凝集性の高いものであった。The obtained powder was 0.8 by SEM observation.
It had a relatively high cohesiveness at about μm.
【００３８】この粉末は、（００１）回析線強度／（０
０２）回析線強度比にして３程度と小さく、本発明の要
件を満足するものではなかった。この粉末のＸ線回析図
形を図３に示した。This powder has a (001) diffraction line strength / (0
02) The diffraction line strength ratio was as small as about 3 and did not satisfy the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００３９】[0039]
【発明の効果】本発明は、高度に配向した（００１）配
向性含硫酸水酸化亜鉛粉末を提供するものであり、本発
明により高度に配向した（００１）配向性含硫酸水酸化
亜鉛粉末を簡単な方法でかつ容易に得ることが可能とな
る。EFFECTS OF THE INVENTION The present invention provides highly oriented (001) -oriented zinc sulfate-containing hydroxide powder, which is highly oriented (001) -oriented zinc sulfate-containing powder. It can be obtained easily and easily.
【００４０】例えば、本発明の配向性含硫酸水酸化亜鉛
粉末を原料とし仮焼することにより、高度に配向した酸
化亜鉛が得られ、この酸化亜鉛を原料とし高度に配向し
た酸化亜鉛焼結体を得ることが出来る。For example, highly oriented zinc oxide is obtained by calcining the oriented sulfated zinc oxide hydroxide powder of the present invention as a raw material, and a highly oriented zinc oxide sintered body is obtained from this zinc oxide as a raw material. Can be obtained.
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例１の方法で得られたＸ線回析図形であ
る。1 is an X-ray diffraction pattern obtained by the method of Example 1. FIG.
【図２】実施例２の方法で得られたＸ線回析図形であ
る。2 is an X-ray diffraction pattern obtained by the method of Example 2. FIG.
【図３】比較例３の方法で得られたＸ線回析図形であ
る。3 is an X-ray diffraction pattern obtained by the method of Comparative Example 3. FIG.
Claims (2)
（００２）回析線強度比が５以上である、（００１）配
向性含硫酸水酸化亜鉛粉末。1. The intensity of (001) diffraction line by X-ray diffraction /
(001) Oriented sulfuric acid-containing zinc hydroxide powder having a diffraction line intensity ratio of 5 or more.
造するに当たり、該亜鉛イオンに対し１．０〜２．０倍
のモル比の水酸イオンを生じる塩基を加え、その後得ら
れた含硫酸水酸化亜鉛粉末スラリーを熟成し、これを濾
過、洗浄の後乾燥することを特徴とする、Ｘ線回析によ
る（００１）回析線強度／（００２）回析線強度比が５
以上である、（００１）配向性含硫酸水酸化亜鉛粉末の
製造方法。2. A process for producing a zinc sulfate-containing hydroxide from an aqueous zinc sulfate solution, which comprises adding a base capable of generating a hydroxide ion in a molar ratio of 1.0 to 2.0 times that of the zinc ion. A zinc sulfate sulfate powder slurry is aged, filtered, washed and then dried, and the (001) diffraction line intensity / (002) diffraction line intensity ratio by X-ray diffraction is 5
The above is the method for producing the (001) oriented zinc oxide sulfate-containing powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12288191A JPH05294624A (en) | 1991-04-26 | 1991-04-26 | Oriented sulfuric acid-containing zinc hydroxide powder and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12288191A JPH05294624A (en) | 1991-04-26 | 1991-04-26 | Oriented sulfuric acid-containing zinc hydroxide powder and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05294624A true JPH05294624A (en) | 1993-11-09 |
Family
ID=14846948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12288191A Pending JPH05294624A (en) | 1991-04-26 | 1991-04-26 | Oriented sulfuric acid-containing zinc hydroxide powder and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05294624A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311142A (en) * | 2011-07-22 | 2012-01-11 | 哈尔滨工程大学 | Method for preparing zinc oxide hollow ball with in situ gas growth |
| CN103771490A (en) * | 2014-01-04 | 2014-05-07 | 东华理工大学 | Simple method for preparing micrometer/nanometer zinc oxide by stirring at room temperature |
-
1991
- 1991-04-26 JP JP12288191A patent/JPH05294624A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311142A (en) * | 2011-07-22 | 2012-01-11 | 哈尔滨工程大学 | Method for preparing zinc oxide hollow ball with in situ gas growth |
| CN103771490A (en) * | 2014-01-04 | 2014-05-07 | 东华理工大学 | Simple method for preparing micrometer/nanometer zinc oxide by stirring at room temperature |
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