JPH0570124A - Electrically conductive crystal-oriented zinc oxide powder and its production - Google Patents
Electrically conductive crystal-oriented zinc oxide powder and its productionInfo
- Publication number
- JPH0570124A JPH0570124A JP25863991A JP25863991A JPH0570124A JP H0570124 A JPH0570124 A JP H0570124A JP 25863991 A JP25863991 A JP 25863991A JP 25863991 A JP25863991 A JP 25863991A JP H0570124 A JPH0570124 A JP H0570124A
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- Prior art keywords
- line intensity
- diffraction line
- powder
- zinc oxide
- oxide powder
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、導電性結晶配向酸化亜
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、導電性を有し、かつ（００２）が高度に結晶配向
した導電性結晶配向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 a conductive crystal oriented zinc oxide powder and a method for producing the same. More specifically, the present invention relates to a conductive crystal-oriented zinc oxide powder in which (002) has a high crystal orientation, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化亜鉛は、半導体性、圧電性、光導電
性等種々の機能を兼ね備えており、機能性粉末あるいは
機能性焼結体として広く利用されている。例えば、不純
物元素をド−プした導電性酸化亜鉛粉末は導電性フィラ
−に利用されている。2. Description of the Related Art Zinc oxide has various functions such as semiconductivity, piezoelectricity and photoconductivity, and is widely used as a functional powder or a functional sintered body. For example, a conductive zinc oxide powder doped with an impurity element is used as a conductive filler.
【０００３】従来、酸化亜鉛粉末の工業的製造方法とし
ては乾式法と湿式法があり、乾式法には、溶融させた金
属亜鉛を加熱し、発生する亜鉛蒸気を空気で酸化させる
フランス法、亜鉛鉱石にコークスなどを加え、ばい焼し
発生する亜鉛蒸気を空気で酸化するアメリカ法があり、
湿式法としては、塩化亜鉛等の溶液にソーダ灰等を加え
て製造する方法等が知られている。しかしながら、いず
れの方法によっても導電性の高い酸化亜鉛粉末を得るこ
とは困難であった。Conventionally, there are a dry method and a wet method as industrial methods for producing zinc oxide powder. In the dry method, a molten metal zinc is heated and a generated zinc vapor is oxidized by air, a zinc method and a zinc method. There is an American method that oxidizes zinc vapor generated by roasting and adding coke to ore,
As a wet method, a method of producing by adding soda ash or the like to a solution of zinc chloride or the like is known. However, it was difficult to obtain zinc oxide powder having high conductivity by any method.
【０００４】又、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でき、
従来から配向性セラミックスに関して種々の方法が試み
られている。しかしながら、酸化亜鉛粉末において結晶
軸が高度に配向した酸化亜鉛粉末を得ることは極めて困
難であった。Further, for example, in the use of functional ceramics, by orienting the crystal axes of the crystal grains in the sintered body, it is possible to further exhibit its excellent characteristics,
Conventionally, various methods have been tried for oriented ceramics. However, it has been extremely difficult to obtain a zinc oxide powder in which crystal axes are highly oriented in the zinc oxide powder.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、導電
性を有し、かつ高度に結晶配向した（００２）配向酸化
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。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a (002) oriented zinc oxide powder which is electrically conductive and highly crystallized, and a method capable of easily producing the same. To do.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、導電性配
向酸化亜鉛粉末の製造に関し鋭意検討した結果、正三価
以上の原子価を有する元素を含有する、（００１）配向
含硫酸水酸化亜鉛粉末を原料とすることにより容易に導
電性を有し、かつ高度に結晶配向した（００２）配向の
薄板状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 earnest studies on the production of conductive oriented zinc oxide powder, and as a result, (001) oriented sulfuric acid-containing hydroxide containing an element having a valence of positive trivalence or more. The inventors have found that by using zinc powder as a raw material, it is possible to easily obtain a thin plate-shaped zinc oxide powder having conductivity and highly crystallographically oriented (002) orientation, and thus completed the present invention.
【０００７】すなわち、本発明は、 （１）Ｘ線回折による（００２）回折線強度／（１０
１）回折線強度比が２以上であり、かつ正三価以上の原
子価を有する元素を含有する、導電性結晶配向酸化亜鉛
粉末。 （２）正三価以上の原子価を有する元素を含有する、Ｘ
線回折による（００１）回折線強度／（００２）回折線
強度比が５以上である（００１）配向性含硫酸水酸化亜
鉛粉末を仮焼することにより得られる、Ｘ線回折による
（００２）回折線強度／（１０１）回折線強度比が２以
上であり、かつ正三価以上の原子価を有する元素を含有
する、導電性結晶配向酸化亜鉛粉末の製造方法。を要旨
とするものである。That is, according to the present invention, (1) X-ray diffraction intensity (002) diffraction line intensity / (10
1) A conductive crystal-oriented zinc oxide powder containing an element having a diffraction line intensity ratio of 2 or more and having a valence of positive trivalence or more. (2) X containing an element having a valence of at least positive trivalence, X
(002) Diffraction by X-ray diffraction obtained by calcining a (001) oriented zinc sulfate-containing powder having a (001) diffraction line intensity / (002) diffraction line intensity ratio of 5 or more by line diffraction A method for producing a conductive crystal-oriented zinc oxide powder, which has a line intensity / (101) diffraction line intensity ratio of 2 or more and contains an element having a valence of positive trivalence or more. Is the gist.
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】本発明の配向性は、通常の粉末法のＸ線回
折測定装置によるＸ線回折図を用いて各々の面指数の回
折線強度の比から求めたものである。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
線回折図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線回折図は粉末Ｘ線と同等である。The orientation of the present invention is obtained from the ratio of the diffraction line intensities of the respective surface indices by using an X-ray diffraction diagram by an ordinary powder method X-ray diffraction measuring device. That is, when crystals are regularly arranged in a material in a three-dimensional manner, its X
The line diffractogram should produce anisotropy equivalent to that of a single crystal, whereas if the crystals are randomly arranged in the material, the resulting X-ray diffractogram is equivalent to a powder X-ray. ..
【００１０】本発明の導電性結晶配向酸化亜鉛粉末と
は、（００２）回折線強度／（１０１）回折線強度比が
２以上であり、かつ正三価以上の原子価を有する元素を
含有するものである。酸化亜鉛の（００２）面は、粉末
Ｘ線回折図において２θ＝３４．４度付近、（１０１）
面は、粉末Ｘ線回折図において２θ＝３６．２度付近に
現れる。The electrically conductive crystallographically-oriented zinc oxide powder of the present invention contains an element having a (002) diffraction line intensity / (101) diffraction line intensity ratio of 2 or more and an atomic valence of positive trivalence or more. Is. The (002) plane of zinc oxide is in the vicinity of 2θ = 34.4 degrees in the powder X-ray diffraction pattern, (101)
The surface appears in the vicinity of 2θ = 36.2 degrees in the powder X-ray diffraction pattern.
【００１１】本発明の酸化亜鉛粉末は、薄板状の含硫酸
水酸化亜鉛を仮焼し得られるものであり、酸化亜鉛結晶
粒子が薄板状に集合したものである。本発明の導電性結
晶配向酸化亜鉛粉末は、例えば正三価以上の原子価を有
する元素を含有し、かつ、（００１）回折線強度／（０
０２）回折線強度比が５以上である含硫酸水酸化亜鉛を
原料を仮焼することにより得られる。The zinc oxide powder of the present invention is obtained by calcining thin plate-shaped zinc hydroxide oxide, and is a thin plate-shaped aggregate of zinc oxide crystal particles. The conductive crystal oriented zinc oxide powder of the present invention contains, for example, an element having a valence of positive trivalence or more, and has (001) diffraction line intensity / (0
02) Obtained by calcining the raw material of sulfuric acid-containing zinc hydroxide having a diffraction line intensity ratio of 5 or more.
【００１２】前記回折線強度比が５未満の場合は、（０
０２）回折線強度／（１０１）回折線強度比が２以上で
ある導電性結晶配向酸化亜鉛粉末を得ることは困難であ
るが、５以上であれば特に上限はなく、高い方が望まし
い。特に８以上が望ましい。なお、含硫酸水酸化亜鉛の
（００１）面は、粉末Ｘ線回折図において２θ＝１２．
２度付近、（００２）面は、粉末Ｘ線回折図において２
θ＝２４．６度付近に現れる。If the diffraction line intensity ratio is less than 5, (0
It is difficult to obtain a conductive crystal-oriented zinc oxide powder having a (02) diffraction line intensity / (101) diffraction line intensity ratio of 2 or more, but if it is 5 or more, there is no particular upper limit, and a higher one is desirable. Particularly, 8 or more is desirable. The (001) plane of the sulfated zinc hydroxide was 2θ = 12.
Around the 2 degree, the (002) plane is 2 in the powder X-ray diffraction pattern.
Appears near θ = 24.6 degrees.
【００１３】本発明に用いる含硫酸水酸化亜鉛とは基本
構造Ｚｎ４ＳＯ４（ＯＨ）６で表される薄板状の化合物
であり、上記した条件を満たせば、どの様な方法で得た
含硫酸水酸化亜鉛粉末も用いることができる。Zinc sulfate-containing hydroxide used in the present invention is a thin plate-like compound having a basic structure of Zn 4 SO 4 (OH) 6 , and it can be obtained by any method as long as the above-mentioned conditions are satisfied. Zinc sulfate hydroxide powder can also be used.
【００１４】例えば、硫酸亜鉛水溶液から含硫酸水酸化
亜鉛を製造する場合には、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与える塩基を加え、
その後得られた含硫酸水酸化亜鉛スラリーを熟成し、こ
れを濾過、洗浄の後乾燥することにより得ることができ
る。For example, in the case of producing sulfuric acid-containing zinc hydroxide from an aqueous solution of zinc sulfate, when zinc oxide is added to the zinc ion. 1.0
Add a base that gives ~ 2.0 times the molar ratio of hydroxide ions,
The sulfuric acid-containing zinc hydroxide slurry obtained after that is aged, and this can be obtained by filtering, washing and drying.
【００１５】この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
できるが、不純物が混入しにくいことからアンモニアの
使用が好ましい。Sodium hydroxide, potassium hydroxide, ammonia or the like can be used as a base which gives hydroxide ion (OH − ) in the aqueous solution system to be added to this zinc sulfate aqueous solution. Is preferably used.
【００１６】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できない場合があり、又、モル
比が２．０を越えると含硫酸水酸化亜鉛の溶解度が大き
くなり、高度に配向した含硫酸水酸化亜鉛粉末を得るこ
とができない場合がある。従って、モル比としては特に
１．５±０．２の範囲が望ましい。When the molar ratio is less than 1.0, the resulting thin plate-like particles may be randomly aggregated to fail to obtain a highly oriented zinc sulfate-containing powder, and the molar ratio may be 2. If it exceeds 0, the solubility of the sulfated zinc hydroxide is increased, and it may not be possible to obtain a highly oriented sulfated zinc hydroxide powder. Therefore, the molar ratio is preferably in the range of 1.5 ± 0.2.
【００１７】また、反応系の濃度はできるだけ希薄なも
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。反応系の濃度が０．２モ
ル／リットルを越えると、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られない場合がある。The concentration of the reaction system is preferably as dilute as possible, and the concentration of zinc in the reaction system is 0.2 mol / mol.
It is preferably about 1 liter or less. If the concentration of the reaction system exceeds 0.2 mol / liter, the dispersibility of the particles may be deteriorated and a highly oriented sulfuric acid-containing zinc hydroxide powder may not be obtained.
【００１８】次に、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。熟成を行わないと、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
ができないことがある。又、熟成には配向比の増加、粒
径の増大の作用があり、用途に応じて、適性な時間、温
度を選定することができるが、熟成時間は２時間以上、
熟成温度は、５℃以上が好ましい。特に、熟成時間は、
５〜８０時間が好ましく、熟成温度は２０〜５０℃が好
ましい。Next, the sulfuric acid-containing zinc hydroxide slurry obtained by the above method is aged. Without aging, it may not be possible to obtain a highly-sulfated zinc hydroxide oxide powder in which particles are strongly aggregated. In addition, aging has the effect of increasing the orientation ratio and particle size, and an appropriate time and temperature can be selected according to the application, but the aging time is 2 hours or more,
The aging temperature is preferably 5 ° C or higher. Especially, the aging time is
It is preferably 5 to 80 hours, and the aging temperature is preferably 20 to 50 ° C.
【００１９】つづいて、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、Ｘ線回折による（００
１）回折線強度／（００２）回折線強度比が５以上であ
る（００１）配向性含硫酸水酸化亜鉛粉末を得ることが
できる。Subsequently, the sulfuric acid-containing zinc hydroxide slurry was filtered, washed with water and dried to obtain (00
It is possible to obtain (001) -oriented zinc oxide sulfate-containing powder having a ratio of 1) diffraction line intensity / (002) diffraction line intensity of 5 or more.
【００２０】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
４ＳＯ４（ＯＨ）６・ｎＨ２Ｏ）の水和量ｎが異なり、
１００〜２００℃が好ましい。３００℃を越えると、含
硫酸水酸化亜鉛の分解が起こり易くなり好ましくない。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.
4 SO 4 (OH) 6 · nH 2 O) has a different hydration amount n,
100-200 degreeC is preferable. If it exceeds 300 ° C, decomposition of zinc sulfate-containing hydroxide easily occurs, which is not preferable.
【００２１】本発明における酸化亜鉛に含有する正三価
以上の原子価を有する元素としては、ＩＩＩＡ族、ＩＩ
ＩＢ族、ＩＶＡ族、ＩＶＢ族、ＶＡ族、ＶＢ族、ＶＩＡ
族、ＶＩＢ族、ＶＩＩＡ族、ＶＩＩＩ族及びランタノイ
ド、アクチノイド系列の元素から選ばれた一種以上の元
素等を示すことができ、その含有量は０．１〜２０ａｔ
ｍ％で、特に好ましくは０．５〜５ａｔｍ％において優
れた導電性が得られる。The elements having a valence of positive trivalence or more contained in the zinc oxide in the present invention include Group IIIA and II.
Group IB, Group IVA, Group IVB, Group VA, Group VB, VIA
Group, VIB group, VIIA group, VIII group and lanthanoids, one or more elements selected from actinoid series elements, and the like, and the content thereof is 0.1 to 20 at
Excellent conductivity is obtained at m%, particularly preferably at 0.5 to 5 atm%.
【００２２】該元素の混合方法としては、上記の方法に
より得られた含硫酸水酸化亜鉛粉末を生成させる際に、
該元素の酸化物、イオンを硫酸亜鉛水溶液に共存させて
該元素を含有する含硫酸水酸化亜鉛粉末として共沈させ
ても良いし、上記の方法で得られる含硫酸水酸化亜鉛粉
末スラリ−に該元素の酸化物、イオンを共存させて共沈
させても良い。或いは、本発明の方法で得られる配向性
酸化亜鉛粉末をスラリ−とし該元素の酸化物、イオンを
共存させて共沈させても良い。As the method for mixing the elements, when the sulfuric acid-containing zinc hydroxide powder obtained by the above method is produced,
The oxides and ions of the element may be co-precipitated in the aqueous solution of zinc sulfate to coprecipitate as the sulfated zinc hydroxide powder containing the element, or in the sulfated zinc hydroxide powder slurry obtained by the above method. You may make it coprecipitate by making the oxide and ion of this element coexist. Alternatively, the oriented zinc oxide powder obtained by the method of the present invention may be used as a slurry and coprecipitated in the presence of oxides and ions of the element.
【００２３】上記本発明の条件を満足する含硫酸水酸化
亜鉛粉末を原料とし、仮焼することにより、本発明の条
件を満足する導電性結晶配向酸化亜鉛粉末を容易に得る
ことができる。By using the sulfuric acid-containing zinc hydroxide powder satisfying the above conditions of the present invention as a raw material and calcining, a conductive crystal-oriented zinc oxide powder satisfying the conditions of the present invention can be easily obtained.
【００２４】本発明に於ける仮焼は、窒素ガス、アルゴ
ンガス等の非酸化性ガス中、８００〜１４００℃の範囲
で行えばよい。仮焼温度が８００℃未満の場合、（００
２）回折線強度／（１０１）回折線強度比が２以上であ
る導電性結晶配向酸化亜鉛粉末を得ることができなかっ
たり、又、ＳＯ４が残留することがあり、好ましくな
い。一方、１４００℃を越えると粒子間の焼結が著しく
粗粒化し好ましくない。仮焼温度としては、特に８５０
〜１１００℃が望ましい。The calcination in the present invention may be carried out in the range of 800 to 1400 ° C. in a non-oxidizing gas such as nitrogen gas or argon gas. If the calcination temperature is less than 800 ° C, (00
2) It is not preferable because it is not possible to obtain a conductive crystal oriented zinc oxide powder having a ratio of diffraction line intensity / (101) diffraction line intensity of 2 or more, or SO 4 may remain. On the other hand, if the temperature exceeds 1400 ° C., the sintering between particles becomes remarkably coarse, which is not preferable. Especially as the calcination temperature, 850
-1100 ° C is desirable.
【００２５】以上の方法により、Ｘ線回折による（００
２）回折線強度／（１０１）回折線強度比が２以上であ
る導電性結晶配向酸化亜鉛粉末を得ることができる。By the above method, (00
2) It is possible to obtain a conductive crystal-oriented zinc oxide powder having a diffraction line intensity / (101) diffraction line intensity ratio of 2 or more.
【００２６】本発明の方法で得られる（００２）配向酸
化亜鉛粉末は、平均粒子径１〜１００μｍ、平均粒子厚
さ０．０２〜０．５μｍ、平均粒子径／平均粒子厚さ比
が２０以上であることが望ましい。本発明で言う平均粒
子径及び平均粒子厚さは、該薄板状集合体の平均粒子径
及び平均粒子厚さを走査型電子顕微鏡（ＳＥＭ）による
観察から求めたものである。The (002) oriented zinc oxide powder obtained by the method of the present invention has an average particle diameter of 1 to 100 μm, an average particle thickness of 0.02 to 0.5 μm, and an average particle diameter / average particle thickness ratio of 20 or more. Is desirable. The average particle diameter and the average particle thickness referred to in the present invention are obtained by observing the average particle diameter and the average particle thickness of the thin plate-shaped aggregate by a scanning electron microscope (SEM).
【００２７】[0027]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれに限定されるものではない。な
お、Ｘ線回折の測定には自動Ｘ線粉末回折装置（Ｐｈｉ
ｌｉｐｓＰＷ１７２９）を使用した。測定条件は、Ｃｕ
Ｋα線、Ｘ線管電圧４０ｋＶ、電流５０ｍＡ、走査速度
２°／ｍｉｎとした。又、体積固有抵抗は、粉末を内径
１３ｍｍの円筒に入れ、５００ｋｇ／ｃｍ２の圧力で成
形した成形物の抵抗をテスターで測定したものである。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. For the measurement of X-ray diffraction, an automatic X-ray powder diffractometer (Phi
Lips PW1729) was used. The measurement conditions are Cu
Kα ray, X-ray tube voltage 40 kV, current 50 mA, scanning speed 2 ° / min. Further, the volume resistivity is obtained by putting powder into a cylinder having an inner diameter of 13 mm and measuring the resistance of a molded product molded at a pressure of 500 kg / cm 2 with a tester.
【００２８】実施例１ （００１）回折線強度／（００２）回折線強度比９．１
のアルミニウム元素含有（００１）配向含硫酸水酸化亜
鉛を以下の方法で得た。Example 1 (001) Diffraction Line Intensity / (002) Diffraction Line Intensity Ratio 9.1
The aluminum element-containing (001) -oriented zinc sulfate-containing hydroxide was obtained by the following method.
【００２９】０．５モルの硫酸亜鉛と７．５ミリモルの
硫酸アルミニウムを３０℃純水１０ｋｇに溶解させ、こ
の硫酸亜鉛水溶液に１．５モル／リットルのアンモニア
水５６６ｇを２時間で添加し、その後撹拌下７２時間３
０℃で熟成した。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。0.5 mol of zinc sulfate and 7.5 mmol of aluminum sulfate were dissolved in 10 kg of pure water at 30 ° C., and 566 g of 1.5 mol / liter ammonia water was added to this zinc sulfate aqueous solution in 2 hours. 72 hours 3 with stirring
Aged at 0 ° C. 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.
【００３０】得られた粉末は、ＳＥＭ観察により高分散
な６μｍ程度の六角板状の結晶であり、Ｘ線回折で調べ
たところ基本構造Ｚｎ４ＳＯ４（ＯＨ）６で表される
（００１）回折線強度／（００２）回折線強度比にして
９．１である（００１）に高度に配向した配向性含硫酸
水酸化亜鉛であった。次に、これを窒素ガス中９００℃
で２時間仮焼した。The obtained powder is a highly dispersed hexagonal plate-like crystal with a size of about 6 μm by SEM observation, and when examined by X-ray diffraction, it is represented by the basic structure Zn 4 SO 4 (OH) 6 (001). The oriented sulfated zinc hydroxide was highly oriented to (001), which was 9.1 in terms of diffraction line intensity / (002) diffraction line intensity. Next, this is 900 ° C. in nitrogen gas.
It was calcined for 2 hours.
【００３１】得られた粉末は、Ｘ線回折で調べたところ
（００２）回折線強度／（１０１）回折線強度比９で表
せられる（００２）配向酸化亜鉛粉末であり、ＳＥＭ観
察により０．３μｍ程度の粒子が集合した平均粒子径５
〜１０μｍで平均厚さ０．１〜０．２μｍ程度の薄板状
粒子であった。この粉末のＸ線回折図を図１に示した。
又、この粉末の体積固有抵抗は０．５Ω・ｃｍであっ
た。The obtained powder is a (002) oriented zinc oxide powder expressed by a (002) diffraction line intensity / (101) diffraction line intensity ratio of 9 when examined by X-ray diffraction, and 0.3 μm by SEM observation. Average particle size of 5 particles
The particles were thin plate-like particles having an average thickness of about 0.1 to 0.2 μm and a thickness of about 10 μm. The X-ray diffraction pattern of this powder is shown in FIG.
The volume resistivity of this powder was 0.5 Ω · cm.
【００３２】実施例２ （００１）回折線強度／（００２）回折線強度比６．５
のアルミニウム元素含有（００１）配向含硫酸水酸化亜
鉛を以下の方法で得た。Example 2 (001) Diffraction Line Intensity / (002) Diffraction Line Intensity Ratio 6.5
The aluminum element-containing (001) -oriented zinc sulfate-containing hydroxide was obtained by the following method.
【００３３】０．５モルの硫酸亜鉛と７．５ミリモルの
硫酸アルミニウムを３０℃純水１０ｋｇに溶解させ、こ
の硫酸亜鉛水溶液に１．５モル／リットルのアンモニア
水５６６ｇを２時間で添加し、その後撹拌下１０時間３
０℃で熟成した。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。0.5 mol of zinc sulfate and 7.5 mmol of aluminum sulfate were dissolved in 10 kg of pure water at 30 ° C., and 566 g of 1.5 mol / liter ammonia water was added to this zinc sulfate aqueous solution in 2 hours. 10 hours 3 with stirring
Aged at 0 ° C. 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.
【００３４】得られた粉末は、ＳＥＭ観察により２〜３
μｍ程度の六角板状の結晶であり、Ｘ線回折で調べたと
ころ基本構造Ｚｎ４ＳＯ４（ＯＨ）６で表される（００
１）回折線強度／（００２）回折線強度比にして６．５
である（００１）に高度に配向した配向性含硫酸水酸化
亜鉛であった。次に、これを窒素ガス中９００℃で２時
間仮焼した。The obtained powder is 2 to 3 by SEM observation.
It is a hexagonal plate-like crystal with a size of about μm, and when it is examined by X-ray diffraction, it is represented by a basic structure Zn 4 SO 4 (OH) 6 (00
1) Diffraction line intensity / (002) Diffraction line intensity ratio of 6.5
It was a highly oriented zinc sulfate-containing zinc hydroxide having (001). Next, this was calcined in nitrogen gas at 900 ° C. for 2 hours.
【００３５】得られた粉末は、Ｘ線回折で調べたところ
（００２）回折線強度／（１０１）回折線強度比３．３
で表せられる（００２）配向酸化亜鉛粉末であり、ＳＥ
Ｍ観察により０．３μｍ程度の粒子が集合した平均粒子
径３〜５μｍで平均厚さ０．１〜０．２μｍ程度の薄板
状粒子であった。この粉末のＸ線回折図を図２に示し
た。又、この粉末の体積固有抵抗は５．０Ω・ｃｍであ
った。The powder obtained was examined by X-ray diffraction and the ratio of (002) diffraction line intensity / (101) diffraction line intensity was 3.3.
The (002) oriented zinc oxide powder represented by
According to M observation, the particles were thin plate-like particles having an average particle diameter of 3 to 5 μm and an average thickness of 0.1 to 0.2 μm in which particles of about 0.3 μm were aggregated. The X-ray diffraction pattern of this powder is shown in FIG. The volume resistivity of this powder was 5.0 Ω · cm.
【００３６】比較例１ （００１）回折線強度／（１０１）回折線強度比が０．
５の試薬酸化亜鉛粉末２４．５ｇに試薬酸化アルミニウ
ム０．５ｇを加え、窒素ガス中９００℃で２時間仮焼し
た。Comparative Example 1 The (001) diffraction line intensity / (101) diffraction line intensity ratio was 0.
0.5 g of reagent aluminum oxide was added to 24.5 g of the reagent zinc oxide powder of 5 and calcined in nitrogen gas at 900 ° C. for 2 hours.
【００３７】得られた粉末は、Ｘ線回折で調べたところ
（００２）回折線強度／（１０１）回折線強度が０．５
程度の酸化亜鉛粉末であり、本発明の要件を満足するも
のは得られなかった。この粉末のＸ線回折図を図３に示
した。The powder obtained had a (002) diffraction line intensity / (101) diffraction line intensity of 0.5 when examined by X-ray diffraction.
No zinc oxide powder was obtained which satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００３８】比較例２ （００１）回折線強度／（００２）回折線強度比が３と
配向性の小さいアルミニウム元素含有含硫酸水酸化亜鉛
粉末を、窒素ガス中９００℃で２時間仮焼した。Comparative Example 2 An aluminum element-containing zinc sulfate hydroxide powder having a (001) diffraction line intensity / (002) diffraction line intensity ratio of 3 and a small orientation was calcined in nitrogen gas at 900 ° C. for 2 hours.
【００３９】得られた粉末は、Ｘ線回折で調べたところ
（００２）回折線強度／（１０１）回折線強度比が１．
２程度の酸化亜鉛粉末であり、本発明の要件を満足する
ものは得られなかった。この粉末のＸ線回折図を図４に
示した。The powder thus obtained had a (002) diffraction line intensity / (101) diffraction line intensity ratio of 1. when examined by X-ray diffraction.
A zinc oxide powder of about 2 could not be obtained that satisfied the requirements of the present invention. The X-ray diffraction pattern of this powder is shown in FIG.
【００４０】[0040]
【発明の効果】本発明によれば、高度に（００２）に配
向した導電性配向酸化亜鉛粉末を容易に得ることが可能
となり、これらは、例えば、導電性フィラ−やコ−ティ
ング剤などとして幅広く使用できる。According to the present invention, it is possible to easily obtain a highly conductive (002) oriented conductive oriented zinc oxide powder, which can be used, for example, as a conductive filler or a coating agent. Can be widely used.
【図１】 実施例１で得られた導電性結晶配向酸化亜鉛
粉末のＸ線回折図である。1 is an X-ray diffraction diagram of a conductive crystal-oriented zinc oxide powder obtained in Example 1. FIG.
【図２】 実施例２で得られた導電性結晶配向酸化亜鉛
粉末のＸ線回折図である。2 is an X-ray diffraction diagram of the conductive crystal-oriented zinc oxide powder obtained in Example 2. FIG.
【図３】 比較例１で得られた粉末のＸ線回折図であ
る。FIG. 3 is an X-ray diffraction diagram of the powder obtained in Comparative Example 1.
【図４】 比較例２で得られた粉末のＸ線回折図であ
る。FIG. 4 is an X-ray diffraction pattern of the powder obtained in Comparative Example 2.
Claims (2)
（１０１）回折線強度比が２以上であり、かつ正三価以
上の原子価を有する元素を含有する、導電性結晶配向酸
化亜鉛粉末。1. The intensity of (002) diffraction line by X-ray diffraction /
(101) A conductive crystal-oriented zinc oxide powder containing an element having a diffraction line intensity ratio of 2 or more and a valence of positive trivalence or more.
する、Ｘ線回折による（００１）回折線強度／（００
２）回折線強度比が５以上である（００１）配向含硫酸
水酸化亜鉛粉末を仮焼することを特徴とする、Ｘ線回折
による（００２）回折線強度／（１０１）回折線強度比
が２以上であり、かつ正三価以上の原子価を有する元素
を含有する、導電性結晶配向酸化亜鉛粉末の製造方法。2. The (001) diffraction line intensity / (00) by X-ray diffraction containing an element having a valence of positive trivalence or more.
2) The (002) diffraction line intensity / (101) diffraction line intensity ratio by X-ray diffraction is characterized by calcining a (001) -oriented zinc sulfate-containing powder having a diffraction line intensity ratio of 5 or more. A method for producing a conductive crystal-oriented zinc oxide powder, which contains an element having a valence of 2 or more and a valence of positive trivalence or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25863991A JP3245905B2 (en) | 1991-09-11 | 1991-09-11 | Conductive crystal oriented zinc oxide powder and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25863991A JP3245905B2 (en) | 1991-09-11 | 1991-09-11 | Conductive crystal oriented zinc oxide powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570124A true JPH0570124A (en) | 1993-03-23 |
| JP3245905B2 JP3245905B2 (en) | 2002-01-15 |
Family
ID=17323066
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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| JP (1) | JP3245905B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5718047A (en) * | 1995-09-22 | 1998-02-17 | Yazaki Corporation | Method of manufacturing electrical junction box |
| WO2014007045A1 (en) * | 2012-07-02 | 2014-01-09 | 日本碍子株式会社 | Zinc oxide powder and process for manufacturing same |
| JP2015101493A (en) * | 2013-11-22 | 2015-06-04 | 宇部興産株式会社 | Conductive zinc oxide powder and method for producing the same |
-
1991
- 1991-09-11 JP JP25863991A patent/JP3245905B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5718047A (en) * | 1995-09-22 | 1998-02-17 | Yazaki Corporation | Method of manufacturing electrical junction box |
| WO2014007045A1 (en) * | 2012-07-02 | 2014-01-09 | 日本碍子株式会社 | Zinc oxide powder and process for manufacturing same |
| CN104395241A (en) * | 2012-07-02 | 2015-03-04 | 日本碍子株式会社 | Zinc oxide powder and process for manufacturing same |
| US9327994B2 (en) | 2012-07-02 | 2016-05-03 | Ngk Insulators, Ltd. | Zinc oxide powder and process for manufacturing same |
| JPWO2014007045A1 (en) * | 2012-07-02 | 2016-06-02 | 日本碍子株式会社 | Zinc oxide powder and method for producing the same |
| CN104395241B (en) * | 2012-07-02 | 2016-11-16 | 日本碍子株式会社 | Zinc oxide powder and manufacture method thereof |
| JP2015101493A (en) * | 2013-11-22 | 2015-06-04 | 宇部興産株式会社 | Conductive zinc oxide powder and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3245905B2 (en) | 2002-01-15 |
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