JP2724504B2 - Method for producing lead molybdate for single crystal raw material - Google Patents
Method for producing lead molybdate for single crystal raw materialInfo
- Publication number
- JP2724504B2 JP2724504B2 JP23085389A JP23085389A JP2724504B2 JP 2724504 B2 JP2724504 B2 JP 2724504B2 JP 23085389 A JP23085389 A JP 23085389A JP 23085389 A JP23085389 A JP 23085389A JP 2724504 B2 JP2724504 B2 JP 2724504B2
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- raw material
- lead
- single crystal
- powder
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は単結晶原料用モリブデン酸鉛の製造方法に関
し、殊に単結晶育成用原料として必須の条件である組成
変動のない高純度のモリブデン酸鉛原料粉末を提供する
ことを目的とするものである。Description: TECHNICAL FIELD The present invention relates to a method for producing lead molybdate for a single crystal raw material, and in particular, high-purity molybdenum having no composition fluctuation which is an essential condition as a raw material for growing a single crystal. It is an object to provide lead acid raw material powder.
（従来の技術） 光学用単結晶の育成に於いて、結晶の不純物に由来す
る欠陥として、例えばストリエーション、サブグレイン
等の光学的欠陥がよく発生することが知られている。(Prior Art) In growing optical single crystals, it is known that optical defects such as striations and sub-grains often occur as defects derived from impurities in the crystals.
従来よりこの欠陥の発生を回避するために、より高純
度の単結晶用原料を使用することが行われている。Conventionally, in order to avoid the generation of this defect, a higher purity single crystal raw material has been used.
しかしながら、モリブデン酸鉛単結晶の育成に於いて
は、5N（99.999％）以上の原料として一酸化鉛（PbO）
と三酸化モリブデン（MoO3）の粉末が使用されているに
も拘らず、この欠陥の発生が依然として生じやすい問題
がある。However, in growing lead molybdate single crystals, lead monoxide (PbO) is used as a raw material of 5N (99.999%) or more.
Despite the use of molybdenum trioxide (MoO 3 ) powder, there is still a problem that this defect is still likely to occur.
即ち、一般にモリブデン酸鉛単結晶は、通常チョクラル
スキー法によって育成されているが、この原料は高純度
の三酸化モリブデン粉末と一酸化鉛粉末とを湿式粉砕し
た後、700℃程度の温度で仮焼し、再び湿式粉砕して再
度仮焼、粉砕することにより原料粉末が製造される。That is, a lead molybdate single crystal is generally grown by the Czochralski method, but this raw material is obtained by wet-grinding high-purity molybdenum trioxide powder and lead monoxide powder at a temperature of about 700 ° C. The raw material powder is manufactured by calcining, wet grinding again, and calcining and grinding again.
しかしながら、このような酸化物粉末混合法による原
料の製造にあっては、 （１）700℃以上で仮焼する必要があるため原料が一部
昇華し、原料割合の組成変動が生じる。However, in the production of a raw material by such an oxide powder mixing method, (1) since it is necessary to calcine at 700 ° C. or more, the raw material partially sublimates, and the composition of the raw material ratio fluctuates.
（２）粉砕と仮焼を繰り返すために、粉砕機、仮焼炉か
らの不純物の混入を避け難い。(2) Since pulverization and calcination are repeated, it is difficult to avoid mixing of impurities from a crusher and a calcination furnace.
（３）湿式混合であるために、ミクロ的な均一混合物が
得られない。(3) Because of wet mixing, a microscopic uniform mixture cannot be obtained.
等の問題があり、恒常的に光学的欠陥のないモリブデン
酸鉛単結晶を製造することは甚だ困難であった。Therefore, it has been extremely difficult to produce a lead molybdate single crystal that is constantly free from optical defects.
（発明が解決しようとする課題） 前述のように、光学用結晶の光学的欠陥を低減させる
方法として、高純度原料の使用が必要であることは当然
であるが、主原料の組成変動の問題については充分に考
慮する必要がある。(Problems to be Solved by the Invention) As described above, as a method of reducing optical defects of an optical crystal, it is natural that a high-purity raw material must be used. Needs to be fully considered.
そこで本発明者らは前述の問題点を解決すべく、モリ
ブデン酸鉛単結晶用原料を製造する方法について各種検
討を重ねた結果、本発明に到達したものである。The present inventors have conducted various studies on a method for producing a raw material for a lead molybdate single crystal in order to solve the above-mentioned problems, and as a result, have reached the present invention.
（課題を解決するための手段） 即ち本発明は、三酸化モリブデン微粉末スラリーに鉛
塩水溶液を加え、次いでこれに炭酸アンモニウム又は重
炭酸アンモニウムの水溶液をCO3/Pb（モル比）0.9〜1.1
の範囲で加え、生成した沈殿物を350〜500℃で仮焼する
ことからなる単結晶原料用モリブデン酸鉛の製造方法に
関する。(Means for Solving the Problems) That is, according to the present invention, a lead salt aqueous solution is added to a molybdenum trioxide fine powder slurry, and then an aqueous solution of ammonium carbonate or ammonium bicarbonate is added to CO 3 / Pb (molar ratio) 0.9 to 1.1.
And calcining the generated precipitate at 350 to 500 ° C. to produce lead molybdate as a single crystal raw material.
（作用） 本発明で使用する三酸化モリブデン微粉末スラリー
は、その平均粒子径が概ね10μｍ以下のものを使用し、
この粒子径は小さい程組成の均一な本発明の原料粉末を
得ることができる。(Action) The molybdenum trioxide fine powder slurry used in the present invention has an average particle diameter of about 10 μm or less,
The smaller the particle size, the more uniform the raw material powder of the present invention can be obtained.
また、本発明で使用する鉛塩の種類としては、例えば
硝酸鉛、酢酸鉛等が挙げられる。In addition, examples of the type of lead salt used in the present invention include lead nitrate and lead acetate.
本発明では先ず前記の三酸化モリブデン微粉末を水に
分散し、スラリーを調製する。In the present invention, first, the molybdenum trioxide fine powder is dispersed in water to prepare a slurry.
このスラリー濃度は概ね２〜10重量％の範囲が好まし
い。The slurry concentration is preferably in the range of about 2 to 10% by weight.
次いで、この三酸化モリブデンのスラリーに前記の鉛
塩水溶液を加え、これに炭酸アンモニウム水溶液を加え
て三酸化モリブデンと炭酸鉛との共沈物を生成させる。Next, the above-mentioned aqueous solution of a lead salt is added to the molybdenum trioxide slurry, and an aqueous solution of ammonium carbonate is added thereto to form a coprecipitate of molybdenum trioxide and lead carbonate.
この際に使用する鉛塩水溶液は鉛塩の濃度を概ね２〜20
重量％とするが、この鉛塩の添加量は、前記三酸化モリ
ブデンと等モルとすることが必要である。The aqueous lead salt solution used at this time has a lead salt concentration of about 2 to 20.
However, the amount of the lead salt needs to be equimolar to the molybdenum trioxide.
また、鉛塩と炭酸アンモニウムとの使用割合は、CO3/
Pb（モル比）として0.9〜1.1の範囲であり、この範囲は
本発明に於いて殊に重要である。Also, the proportion of lead salt and ammonium carbonate used is CO 3 /
Pb (molar ratio) is in the range of 0.9 to 1.1, and this range is particularly important in the present invention.
即ち、このモル比の範囲を逸脱し、CO3/Pb（モル比）が
0.9を下廻ると原料の鉛塩が未反応で残留し、また反対
にこのモル比が1.1を上廻ると、三酸化モリブデンのス
ラリーが溶解し、三酸化モリブデンと炭酸鉛との共沈物
の組成割合が当量とならず、いずれの場合も単結晶用原
料として使用できないものとなる。That is, CO 3 / Pb (molar ratio) deviates from this molar ratio range.
When the molar ratio is less than 0.9, the lead salt of the raw material remains unreacted, and when the molar ratio exceeds 1.1, the slurry of molybdenum trioxide dissolves and the coprecipitate of molybdenum trioxide and lead carbonate forms. The composition ratio is not equivalent, and in any case, it cannot be used as a single crystal raw material.
また、沈殿反応に際しては、成分を均一にするために
充分な攪拌を行うことが望ましい。In the precipitation reaction, it is desirable to perform sufficient stirring to make the components uniform.
更に、沈殿反応は全て常温で行われるが、必要に応じて
加熱、加圧することを妨げるものではない。Furthermore, the precipitation reaction is all carried out at room temperature, but does not prevent heating and pressurization as required.
このようにして得られた沈殿物は、水溶液から分離、
水洗し、次いで仮焼するが、仮焼を行う前に適度に乾燥
を行うことが望ましい。The precipitate thus obtained is separated from the aqueous solution,
After rinsing with water and then calcining, it is desirable to dry appropriately before calcining.
仮焼方法は、通常の仮焼方法と同様に行えばよいが、
仮焼温度は350〜500℃の範囲で充分である。The calcining method may be performed in the same manner as a normal calcining method,
A calcining temperature in the range of 350 to 500 ° C is sufficient.
（発明の効果） 以上詳述したような方法により本発明原料は製造され
るが、その効果を列挙すれば次の通りである。(Effects of the Invention) The raw material of the present invention is produced by the method described in detail above, and the effects are as follows.
（１）本発明は湿式法によるものであるから、炭酸鉛と
酸化モリブデンがミクロ的に均一混合されている。(1) Since the present invention is based on a wet method, lead carbonate and molybdenum oxide are microscopically and uniformly mixed.
（２）粉砕、仮焼が一度でよいため、従来法に比べて不
純物の混入量が少ない。(2) Since the pulverization and calcination need only be performed once, the amount of impurities mixed is smaller than in the conventional method.
（３）仮焼温度が350〜500℃であるため原料の昇華が生
じず、原料割合の組成変動が回避される。(3) Since the calcining temperature is 350 to 500 ° C., the sublimation of the raw material does not occur, and the composition fluctuation of the raw material ratio is avoided.
このように、本発明の方法は従来の問題点を一挙に解
決したものであり、係る原料の使用により極めて良質の
単結晶を引き上げることができるものである。As described above, the method of the present invention solves the conventional problems at a glance, and it is possible to pull up a very high-quality single crystal by using such a raw material.
（実施例） 以下に本発明の実施例を掲げて更に説明を行うが、本
発明はこれらに限定されるものではない。また、実施例
に於いて％は特に断らない限り全て重量％を示す。(Examples) Hereinafter, the present invention will be described further with reference to Examples, but the present invention is not limited thereto. In the examples, all percentages are by weight unless otherwise specified.
実施例１ 三酸化モリブデン微粉末（平均粒子径７μm,レアメタ
リック（株）製，純度99.999％）の39.205gをイオン交
換水の1Lに懸濁させスラリーを調製した。Example 1 39.205 g of molybdenum trioxide fine powder (average particle size: 7 μm, manufactured by Rare Metallic Co., Ltd., purity: 99.999%) was suspended in 1 L of ion-exchanged water to prepare a slurry.
このスラリーに硝酸鉛（メルク社製，純度99.999％）の
90.212gをイオン交換水1Lに溶解させた溶液を添加混合
した後、攪拌を行いながらこれに第１表に示した所定量
の炭酸アンモニウム水溶液（10％）を加え、三酸化モリ
ブデンと炭酸鉛との共沈物を生成させた。To this slurry was added lead nitrate (Merck, purity 99.999%).
A solution obtained by dissolving 90.212 g in 1 L of ion-exchanged water was added and mixed, and while stirring, a predetermined amount of an aqueous solution of ammonium carbonate (10%) shown in Table 1 was added thereto, and molybdenum trioxide and lead carbonate were added. A co-precipitate was formed.
この沈殿物を濾過し、濾液中の鉛及びモリブデンの定性
試験を行った結果を第１表に示した。The precipitate was filtered, and the results of qualitative tests of lead and molybdenum in the filtrate are shown in Table 1.
尚、第１表の結果から明らかなように、CO3/Pbモル比
が0.9〜1.1の範囲外では、モリブデンあるいは鉛の濾液
への溶出があり、モリブデン酸鉛（PbMoO4）調製用原料
としては不適であることが判る。 As is clear from the results in Table 1, when the molar ratio of CO 3 / Pb is out of the range of 0.9 to 1.1, molybdenum or lead is eluted into the filtrate, and as a raw material for preparing lead molybdate (PbMoO 4 ). Is found to be unsuitable.
この本発明の原料調製用沈殿物No.2をイオン交換水で
洗浄し、再び濾過を行い、これを500℃で２時間焼成し
てアルミナ乳鉢で粉砕を行うことにより、本発明の単結
晶原料用モリブデン酸鉛粉末を得た。The precipitate No. 2 for raw material preparation of the present invention was washed with ion-exchanged water, filtered again, calcined at 500 ° C. for 2 hours, and pulverized in an alumina mortar to obtain a single crystal raw material of the present invention. Lead molybdate powder was obtained.
また比較のために、前記の三酸化モリブデン粉末と一
酸化鉛粉末（レアメタリック（株）製，純度99.999％）
とを使用し、これらの混合物を湿式粉砕し、500℃及び7
00℃で同様に焼成を行い、アルミナ乳鉢で粉砕して粉末
を得た。For comparison, the above molybdenum trioxide powder and lead monoxide powder (manufactured by Rare Metallic Co., Ltd., purity 99.999%)
And wet milling these mixtures at 500 ° C and 7 ° C.
Similarly, baking was performed at 00 ° C., and the mixture was pulverized in an alumina mortar to obtain a powder.
このようにして得た粉末及び本発明の単結晶原料用粉末
をＸ線回折の測定に供した。The powder thus obtained and the powder for a single crystal raw material of the present invention were subjected to X-ray diffraction measurement.
Ｘ線回折結果を第１〜３図に示したが、第１図は本発明
の原料用粉末（500℃焼成品）、第２図は従来法により
得た粉末（500℃焼成品）、第３図は従来法により得た
粉末（700℃焼成品）を各々示した。X-ray diffraction results are shown in FIGS. 1 to 3, wherein FIG. 1 is a powder for a raw material of the present invention (500 ° C. fired product), FIG. 2 is a powder obtained by a conventional method (500 ° C. fired product), and FIG. FIG. 3 shows powders (products fired at 700 ° C.) obtained by the conventional method.
第１〜３図の結果から明らかなように、従来法に基づ
いた方法によれば、500℃の焼成（第２図）ではＸ線的
に未反応の三酸化モリブデンとモリブデン酸鉛（2PbO・
MoO3）のピークが観察され、これを700℃で焼成（第３
図）しても依然これらのピークが観察される。As is clear from the results shown in FIGS. 1 to 3, according to the method based on the conventional method, molybdenum trioxide and lead molybdate (2PbO ·
MoO 3 ) peak was observed, which was calcined at 700 ° C (No. 3).
These peaks are still observed in FIG.
これに対して本発明の原料粉末（第１図）では、モリブ
デン酸鉛のピークのみを示しており、本発明の方法が単
結晶原料の製造法として優れていることが判る。On the other hand, in the raw material powder of the present invention (FIG. 1), only the peak of lead molybdate is shown, which indicates that the method of the present invention is excellent as a method for producing a single crystal raw material.
実施例２ 実施例１と同様に、三酸化モリブデン微粉末の784.14
gをイオン交換水10Lに懸濁させスラリーを調製した。Example 2 As in Example 1, 784.14 of molybdenum trioxide fine powder
g was suspended in 10 L of ion-exchanged water to prepare a slurry.
このスラリーに硝酸鉛の1804.32gをイオン交換水15Lに
溶解させた溶液を添加混合した後、攪拌を行いながらこ
れに5.23kgの10％炭酸アンモニウム水溶液（CO3/Pbモル
比1.0）を加えて三酸化モリブデンと炭酸鉛との共沈物
を生成させた。After adding and mixing a solution in which 1804.32 g of lead nitrate was dissolved in 15 L of ion-exchanged water, 5.23 kg of a 10% aqueous solution of ammonium carbonate (CO 3 / Pb molar ratio 1.0) was added to the slurry while stirring. A coprecipitate of molybdenum trioxide and lead carbonate was formed.
この沈殿物を濾過し、次いでイオン交換水で洗浄し、再
び濾過を行い、これを470℃で焼成してアルミナ乳鉢で
粉砕を行うことにより、本発明の単結晶原料用三酸化モ
リブデン酸鉛粉末を得た。The precipitate is filtered, washed with ion-exchanged water, filtered again, baked at 470 ° C., and pulverized in an alumina mortar to obtain the lead molybdate powder for a single crystal material of the present invention. I got
この三酸化モリブデン原料粉末を用いて、チョクラル
スキー法により単結晶の育成を行った結果、得られた単
結晶には点欠陥が見られなかった。Using this molybdenum trioxide raw material powder, a single crystal was grown by the Czochralski method. As a result, no point defect was found in the obtained single crystal.
第１〜３図は、本発明及び比較として従来法により得た
原料用粉末のＸ線回折における回折角度と回折強度との
関係を示す図である。 各図面に於いて、第１図は本発明原料粉末の500℃焼成
品のＸ線回折図、第２図は従来法により得た粉末の500
℃焼成品のＸ線回折図、第３図は従来法により得た粉末
の700℃焼成品のＸ線回折図を各々示す。FIGS. 1 to 3 are diagrams showing the relationship between the diffraction angle and the diffraction intensity in the X-ray diffraction of the raw material powder obtained by the present invention and a conventional method as a comparison. In each of the drawings, FIG. 1 is an X-ray diffraction diagram of a 500 ° C. baked product of the raw material powder of the present invention, and FIG.
X-ray diffraction diagram of the product baked at ℃. FIG. 3 shows the X-ray diffraction diagram of the product baked at 700 ° C. obtained by the conventional method.
Claims (1)
溶液を加え、次いでこれに炭酸アンモニウム又は重炭酸
アンモニウムの水溶液をCO3/Pb（モル比）0.9〜1.1の範
囲で加え、生成した沈殿物を350〜500℃で仮焼すること
からなる単結晶原料用モリブデン酸鉛の製造方法。1. A lead salt aqueous solution is added to a molybdenum trioxide fine powder slurry, and then an aqueous solution of ammonium carbonate or ammonium bicarbonate is added thereto in a CO 3 / Pb (molar ratio) range of 0.9 to 1.1 to form a precipitate. Of lead molybdate for single crystal raw material, comprising calcining at a temperature of 350 to 500 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23085389A JP2724504B2 (en) | 1989-09-05 | 1989-09-05 | Method for producing lead molybdate for single crystal raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23085389A JP2724504B2 (en) | 1989-09-05 | 1989-09-05 | Method for producing lead molybdate for single crystal raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0393629A JPH0393629A (en) | 1991-04-18 |
| JP2724504B2 true JP2724504B2 (en) | 1998-03-09 |
Family
ID=16914323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23085389A Expired - Lifetime JP2724504B2 (en) | 1989-09-05 | 1989-09-05 | Method for producing lead molybdate for single crystal raw material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2724504B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010006B (en) * | 2010-12-24 | 2012-05-30 | 金堆城钼业股份有限公司 | Method for synthesizing lead molybdate |
| CN102071466B (en) * | 2010-12-24 | 2012-10-17 | 金堆城钼业股份有限公司 | Method for preparing lead molybdate polycrystalline material |
-
1989
- 1989-09-05 JP JP23085389A patent/JP2724504B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0393629A (en) | 1991-04-18 |
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