JPS61295211A - Production of fine powder of high-purity amorphous boron nitride - Google Patents
Production of fine powder of high-purity amorphous boron nitrideInfo
- Publication number
- JPS61295211A JPS61295211A JP13593585A JP13593585A JPS61295211A JP S61295211 A JPS61295211 A JP S61295211A JP 13593585 A JP13593585 A JP 13593585A JP 13593585 A JP13593585 A JP 13593585A JP S61295211 A JPS61295211 A JP S61295211A
- Authority
- JP
- Japan
- Prior art keywords
- boron nitride
- guanidine
- fine powder
- amorphous boron
- urea
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高純度非晶質窒化硼素の微粉末の製造法に関
する。さらに詳しくは硼酸アンモニウムと尿素、メラミ
ンまたはグアニジンとを反応させて非晶質窒化硼素微粉
末を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing fine powder of high purity amorphous boron nitride. More specifically, the present invention relates to a method for producing amorphous boron nitride fine powder by reacting ammonium borate with urea, melamine, or guanidine.
（従来の技術）
窒化硼素はファインセラミックスの一種であり、大別し
て、非晶質窒化硼素、六方晶窒化硼素および立方晶窒化
硼素がある。非晶質窒化硼素に関しては、従来法である
無水硼酸をアンモニア中で還元窒化する方法により製造
されるが、得られる非晶質窒化硼素の純度は約８０％で
あり、不純物を多量に含んでいる。また、硼砂と尿素ま
たはメラミンとの混合物をアンモニア中で加熱する方法
（特公昭３８−１６１０および特開昭４７−２７２００
）があるが、得られる窒化硼素は不純物としてナトリ
ウムを含んでいる。(Prior Art) Boron nitride is a type of fine ceramics, and can be broadly classified into amorphous boron nitride, hexagonal boron nitride, and cubic boron nitride. Amorphous boron nitride is produced by the conventional method of reducing and nitriding boric anhydride in ammonia, but the purity of the obtained amorphous boron nitride is about 80%, and it contains a large amount of impurities. There is. Also, a method of heating a mixture of borax and urea or melamine in ammonia (Japanese Patent Publications No. 38-1610 and No. 47-27200)
), but the resulting boron nitride contains sodium as an impurity.
（発明が解決しようとする問題点）
本発明の目的は高純度で安価な非晶質窒化硼素微粉末を
製造することである。(Problems to be Solved by the Invention) An object of the present invention is to produce a highly pure and inexpensive amorphous boron nitride fine powder.
（問題点を解決するための手段）
本発明者らは、上記目的に関して種々検討した結果、原
料として硼酸アンモニウムと尿素、メラミンまたはグア
ニジンを用い、反応条件を設定することにより、高純度
非晶質窒化硼素微粉末が得られることを見出し、本発明
の方法に到った。(Means for Solving the Problems) As a result of various studies regarding the above object, the present inventors have found that by using ammonium borate and urea, melamine or guanidine as raw materials and setting reaction conditions, high purity amorphous It was discovered that boron nitride fine powder could be obtained, and the method of the present invention was developed.
本発明の方法は、硼酸アンモニウムと尿素、メラミンま
たはグアニジンを原料として、それらの混合物を加熱し
、反応させる。その反応はたとえば次式のように進行す
るものと考えられる。In the method of the present invention, ammonium borate and urea, melamine or guanidine are used as raw materials, and a mixture thereof is heated and reacted. The reaction is thought to proceed as shown in the following equation, for example.
（ＮＨ４）２ Ｂ４０７ ＋ ２ ＣＯ（ＮＨ２）２
→ ４ＢＮ ＋ ２ＮＨａ＋ ２ＣＯ２＋ ５Ｈ１ｌＯ
使用される硼酸アンモニウムは四硼酸アンモニウム（Ｎ
Ｈ４）２Ｂ４０７、五硼酸アンモニウムＮＨ４Ｂ５ｏ８
、四硼酸アンモニウム（Ｎ Ｈ４） ２Ｂ［１Ｏ１１１
およびＮＨ４ＨＢ４０？であり、無水物が最も望ましい
が、含水物であっても差し支えない。(NH4)2 B407 + 2 CO(NH2)2
→ 4BN + 2NHa+ 2CO2+ 5H1lO
The ammonium borate used is ammonium tetraborate (N
H4) 2B407, ammonium pentaborate NH4B5o8
, ammonium tetraborate (NH4) 2B[1O111
and NH4HB40? Anhydrous materials are most desirable, but hydrated materials are also acceptable.
硼酸アンモニウムおよび尿素、メラミンまたはグアニジ
ンの使用量は、すべての硼酸アンモニラたはグアニジン
を使用するのが望ましい。たとえば、前記式に示すよう
に、四硼酸アンモニウム１モルに対して２モル以上の尿
素を使用するのが望ましい。しかし、特に限定されるも
のではない。Regarding the amount of ammonium borate and urea, melamine or guanidine used, it is desirable to use all ammonium borate or guanidine. For example, as shown in the above formula, it is desirable to use 2 mol or more of urea per 1 mol of ammonium tetraborate. However, it is not particularly limited.
本発明において使用されるグアニジンにはグアニジン、
炭酸グアニジン、塩酸グアニジン、硝酸グアニジン、硫
酸グアニジン、酢酸グアニジン等があるが、特にグアニ
ジンおよび炭酸グアニジンを使用することが望ましい。The guanidine used in the present invention includes guanidine,
Examples include guanidine carbonate, guanidine hydrochloride, guanidine nitrate, guanidine sulfate, guanidine acetate, and it is particularly desirable to use guanidine and guanidine carbonate.
反応は不活性ガス中、常圧または加圧下において実施さ
れる。不活性ガスとしては窒素、ヘリウム、アルゴン等
があげられ、通常、窒素が用いられる。また、この反応
はアンモニアガス中、常圧または加圧下において実施さ
れる。The reaction is carried out in an inert gas under normal or elevated pressure. Examples of the inert gas include nitrogen, helium, argon, etc., and nitrogen is usually used. Moreover, this reaction is carried out in ammonia gas under normal pressure or increased pressure.
本発明の方法においては、反応温度は６５０〜１１００
℃、好ましくは７５０〜１０００℃の範囲である。６５
０℃未満では反応速度が遅く、１１００℃を越えると六
方晶窒化硼素が生成するので好ましくない。In the method of the present invention, the reaction temperature is 650-1100.
℃, preferably in the range of 750 to 1000℃. 65
If it is less than 0°C, the reaction rate is slow, and if it exceeds 1100°C, hexagonal boron nitride is produced, which is not preferable.
上記の反応による反応生成物は副生物が皆、気体となっ
て逃げるので、副生物を含有しない。とくにナトリウム
は原料中に含まれないので、反応生成物中に不純物とし
てナトリウムは含有しない。The reaction product from the above reaction does not contain any by-products because all of the by-products escape in the form of gas. In particular, since sodium is not included in the raw materials, the reaction product does not contain sodium as an impurity.
また、硼酸アンモニウムに対して、尿素、メラミンまた
はグアニジンの量が少ない時に反応生成物中に酸化硼素
を含有することがあるが、硼酸アンモニウムに対して尿
素、メラミンまたはグアニジンを理論量の５倍モル以上
使用することによって反応生成物は酸化硼素を殆ど含有
しな（なる。それ故、反応生成物は不純物を殆ど含有し
ないので、後処理として、水または鉱酸等で洗滌する必
要は特になく、高純度の窒化硼素を得ることができる。In addition, when the amount of urea, melamine or guanidine is small compared to ammonium borate, boron oxide may be contained in the reaction product, but the amount of urea, melamine or guanidine relative to ammonium borate is 5 times the theoretical amount. By using the above method, the reaction product contains almost no boron oxide. Therefore, since the reaction product contains almost no impurities, there is no particular need for washing with water or mineral acid as a post-treatment. High purity boron nitride can be obtained.
また得られた窒化硼素は蜂巣状の粉末の塊であり、軽く
押すだけで容易に粉末状になるので、特に粉砕の必要は
ない。Further, the obtained boron nitride is a honeycomb-like powder lump and can be easily turned into a powder by just pressing lightly, so there is no particular need for pulverization.
しかしながら、本発明においては、反応生成物を水洗、
乾燥してもよいが、水洗後さらに低沸点の有機溶剤、た
とえば、メタノール、エタノール、イソプロピルアルコ
ール、アセトン、メチルエチルケトン等で洗滌し、常圧
乾燥または減圧乾燥すれば高純度非晶質窒化硼素微粉末
が収率良く得られる。However, in the present invention, the reaction product is washed with water,
It may be dried, but after washing with water, washing with a low boiling point organic solvent such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, etc., followed by drying under normal pressure or reduced pressure will yield high purity amorphous boron nitride fine powder. can be obtained in good yield.
（発明の効果）
硼酸アンモニウムと尿素、メラミンまたはグアニジンの
混合物を６５０〜１１００℃で加熱して得られた反応生
成物は未反応原料および副生物、特にナトリウムを殆ど
含有しないので、容易に高純度の非晶質窒化硼素微粉末
を得ることができる。(Effect of the invention) The reaction product obtained by heating a mixture of ammonium borate and urea, melamine or guanidine at 650 to 1100°C contains almost no unreacted raw materials and by-products, especially sodium, so it can be easily purified to high purity. Amorphous boron nitride fine powder can be obtained.
したがって、本発明の方法はとくに電子材料、耐火材料
または潤滑剤として強く要望される高純度の非晶質窒化
硼素微粉末を提供する方法として極めて優れたものであ
る。Therefore, the method of the present invention is extremely excellent as a method for providing high-purity amorphous boron nitride fine powder, which is highly desired especially as an electronic material, a refractory material, or a lubricant.
（実施例） 次に、実施例をあげて本発明を具体的に説明する。(Example) Next, the present invention will be specifically explained with reference to Examples.
実施例１
内容２８０ ｃｃの蓋つきのアルミナ類るつぼに、粉砕
した無水四硼酸アンモニウム１３．１５ ？ （０，０
５モル）および尿素４５．（１（０，７５モル）の混合
物を入れた後、そのるつぼを電気炉に入れ、電気炉中に
毎分４００づの割合で窒素ガスを流しながら、るつぼを
電気炉で８００℃で４時間加熱した。Example 1 Contents: In a 280 cc alumina crucible with a lid, 13.15 ? (0,0
5 mol) and urea 45. (After adding a mixture of Heated.
反応後、窒素中で一晩放冷し、反応生成物をるつぼから
取り出し、スパチーラで押しつぶした結果、４．６２の
白色粉末を得た。After the reaction, the reaction product was left to cool in nitrogen overnight, and the reaction product was taken out from the crucible and crushed with a spatula to obtain a white powder of 4.62.
この物質は赤外線分析、Ｘ線解析によって、非晶質窒化
硼素であることを確認した。また、電子顕微鏡写真によ
り、粒度１〜５ミクロンの粒子であることを認めた。元
素分析により得られた窒化硼素の純度は９９，７％であ
り、ナトリウムの含有は認められなかった。また、使用
した硼砂に対する窒化硼素の収率は９６．１％であった
。This substance was confirmed to be amorphous boron nitride by infrared analysis and X-ray analysis. Moreover, it was confirmed by electron micrograph that the particles had a particle size of 1 to 5 microns. The purity of boron nitride obtained by elemental analysis was 99.7%, and no sodium content was observed. Further, the yield of boron nitride based on the borax used was 96.1%.
実施例２
実施例１で実施した方法において、尿素の代りにメラミ
ン３７．８ Ｆ （０，３モル）を使用し、その他は実
施例１と同様に実験した結果、純度９９７％、粒度１〜
５ミクロン、収率９２．８％で非晶質窒化硼素粉末を得
、ナトリウムの含有は認められなかった。Example 2 In the method carried out in Example 1, melamine 37.8 F (0.3 mol) was used in place of urea, and as a result of an experiment conducted in the same manner as in Example 1, the purity was 997% and the particle size was 1 to 1.
Amorphous boron nitride powder with a particle diameter of 5 microns and a yield of 92.8% was obtained, and no sodium content was observed.
実施例３
実施例１で実施した方法において、尿素の代りに炭酸グ
アニジン５４．０ｆ（０，３モル）を使用し、その他は
実施例１と同様に実験した結果、純度９９６％、粒度１
〜５ミクロン、収率９２．４％で非晶質窒化硼素粉末を
得、ナ） ＩＪウムの含有は認められなかった。Example 3 In the method carried out in Example 1, guanidine carbonate 54.0f (0.3 mol) was used in place of urea, and as a result of an experiment conducted in the same manner as in Example 1, the purity was 996% and the particle size was 1.
Amorphous boron nitride powder was obtained with a diameter of ~5 microns and a yield of 92.4%, and no IJium content was observed.
Claims (1)
ジンとの混合物を６５０〜１１００℃に加熱することを
特徴とする高純度非晶質窒化硼素微粉末の製法。(1) A method for producing high purity amorphous boron nitride fine powder, which comprises heating a mixture of ammonium borate and urea, melamine or guanidine to 650 to 1100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13593585A JPS61295211A (en) | 1985-06-24 | 1985-06-24 | Production of fine powder of high-purity amorphous boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13593585A JPS61295211A (en) | 1985-06-24 | 1985-06-24 | Production of fine powder of high-purity amorphous boron nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61295211A true JPS61295211A (en) | 1986-12-26 |
| JPH0547483B2 JPH0547483B2 (en) | 1993-07-16 |
Family
ID=15163280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13593585A Granted JPS61295211A (en) | 1985-06-24 | 1985-06-24 | Production of fine powder of high-purity amorphous boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61295211A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5230873A (en) * | 1988-09-10 | 1993-07-27 | Firna Siegfried Golz | Process for producing amorphous boron nitride of high hardness |
| JP2006188411A (en) * | 2004-12-28 | 2006-07-20 | General Electric Co <Ge> | Method for manufacturing boron nitride |
| CN1326768C (en) * | 2005-12-20 | 2007-07-18 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306358B1 (en) | 1998-06-02 | 2001-10-23 | Osamu Yamamoto | Crystalline turbostratic boron nitride powder and method for producing same |
-
1985
- 1985-06-24 JP JP13593585A patent/JPS61295211A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5230873A (en) * | 1988-09-10 | 1993-07-27 | Firna Siegfried Golz | Process for producing amorphous boron nitride of high hardness |
| JP2006188411A (en) * | 2004-12-28 | 2006-07-20 | General Electric Co <Ge> | Method for manufacturing boron nitride |
| CN1326768C (en) * | 2005-12-20 | 2007-07-18 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0547483B2 (en) | 1993-07-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |