JPH04160012A - Production of fine born carbide powder - Google Patents
Production of fine born carbide powderInfo
- Publication number
- JPH04160012A JPH04160012A JP2284492A JP28449290A JPH04160012A JP H04160012 A JPH04160012 A JP H04160012A JP 2284492 A JP2284492 A JP 2284492A JP 28449290 A JP28449290 A JP 28449290A JP H04160012 A JPH04160012 A JP H04160012A
- Authority
- JP
- Japan
- Prior art keywords
- boron carbide
- boron
- powder
- particle size
- carbon
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 62
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 abstract description 37
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000006229 carbon black Substances 0.000 abstract description 5
- 239000011164 primary particle Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 4
- 238000005453 pelletization Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 150000001639 boron compounds Chemical class 0.000 description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229910052810 boron oxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- -1 boron oxide Chemical class 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 1
- 102100021569 Apoptosis regulator Bcl-2 Human genes 0.000 description 1
- 101000971171 Homo sapiens Apoptosis regulator Bcl-2 Proteins 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は研磨材、熱中性子吸収材、焼結体を製造するに
好適な原料となる炭化ホウ素微粉末の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing fine boron carbide powder, which is a suitable raw material for producing abrasives, thermal neutron absorbers, and sintered bodies.
［従来の技術］
炭化ホウ素の従来の製造方法には（イ）ホウ素化合物を
炭素と反応させる方法、（ロ）ホウ素化合物を炭素と金
属Ｍｇとで反応させる方法、（ハ）金属ホウ素と炭素と
の反応による方法、（ニ）ＢＣｌ２およびＣＨ４等を用
いて気相反応させる方法等が知られている。[Prior Art] Conventional methods for producing boron carbide include (a) a method of reacting a boron compound with carbon, (b) a method of reacting a boron compound with carbon and metal Mg, and (c) a method of reacting a boron compound with carbon. (d) A method of performing a gas phase reaction using BCl2, CH4, etc. are known.
（イ）の方法では、酸化ホウ素等のホウ素化合物に炭素
材料を配合し、アーク炉等で２０００℃もしくはそれ以
上の高温で還元、炭化させる方法で、最も一般的な製造
方法である（特公昭４９−４４８８０、特開昭４８−３
９４００ ）。In method (a), a carbon material is blended with a boron compound such as boron oxide, and the mixture is reduced and carbonized at a high temperature of 2000°C or higher in an arc furnace or the like, and is the most common manufacturing method (Tokuko Showa). 49-44880, Japanese Patent Publication No. 48-3
9400).
［発明が解決しようとする課題］
ホウ素化合物を炭素とアーク炉を用いて反応させて炭化
ホウ素を造ると、電極下部に溶融、凝固した塊状の炭化
ホウ素が生成する。その粉末を得る場合には、それを所
望の粒度に粉砕するが、炭化ホウ素自体は高硬度のため
、インゴットを微粉にまで粉砕するのに多大なエネルギ
ーを要し、更に、長時間粉砕を要するため純度を低下さ
せ、不純物除去のため酸洗等の処理が必要であり、高純
度微粉を得るのは極めて収率が悪い。[Problems to be Solved by the Invention] When boron carbide is produced by reacting a boron compound with carbon using an arc furnace, a lump of molten and solidified boron carbide is produced at the bottom of the electrode. To obtain the powder, it is ground to the desired particle size, but since boron carbide itself is highly hard, it takes a lot of energy to grind the ingot into a fine powder, and it also requires a long time of grinding. Therefore, the purity is lowered, and treatments such as pickling are required to remove impurities, and the yield of obtaining high-purity fine powder is extremely low.
前述の特公昭４９−４４８８０ではアーク炉の代わりに
誘導炉を用いて、不活性ガス中で１７００〜２０００℃
に加熱し炭化ホウ素微粉末を得ているが、その粒度は１
〜１５０ｕｍと粗く、場合により５〜１０μｍの細粉を
得ているが微粉末とはいい難い。In the aforementioned Japanese Patent Publication No. 49-44880, an induction furnace was used instead of an arc furnace, and the heating temperature was 1700 to 2000°C in an inert gas.
Boron carbide fine powder is obtained by heating to
Although coarse powder of ~150 μm and fine powder of 5 to 10 μm was obtained in some cases, it is difficult to call it a fine powder.
また、ホウ素化合物を炭素と金ＪｔＥＭｇとで還元、炭
化する方法（特公昭４１−１５１６６ 、特公昭４１−
１５１６７、特開昭５７−１７５７１．７、特開昭６０
−４６９０９、特開昭６０−４６９１０ ）ではホウ素
化合物を単に炭素とで反応させる方法に比べ低温で炭化
ホウ素が合成できるが、その粒度の記載は見られない。Also, a method of reducing and carbonizing boron compounds with carbon and gold JtEMg (Japanese Patent Publication No. 41-15166, Japanese Patent Publication No. 41-1979)
15167, JP-A-57-17571.7, JP-A-60
46909, JP-A No. 60-46910), boron carbide can be synthesized at a lower temperature than a method in which a boron compound is simply reacted with carbon, but there is no description of its particle size.
この方法では、炉内反応帯体積の７５〜８０ ｖｏ１％
を反応副生成物であるＭｇＯが占め、焼成反応１バッチ
当りの実質的な炭化ホウ素の収量は極めて少なく、また
、反応が暴走したりガスの急膨張が起こり、試料の飛散
しやすい欠点がある。この後者の欠点を解決するために
、ＭｇＯ等の希釈剤を加えて反応を緩慢に進ませたり、
触媒として金属硫酸塩を加えて、より低温で反応させて
改良をはかっているが、それによって更に収量を低下さ
せている。In this method, 75 to 80 vol% of the reactor reaction zone volume
is dominated by MgO, a reaction by-product, and the actual yield of boron carbide per batch of calcination reaction is extremely small.In addition, there is a drawback that the reaction runs out of control, rapid gas expansion occurs, and the sample is easily scattered. . In order to solve this latter drawback, the reaction may be slowed down by adding a diluent such as MgO, or
Improvements have been made by adding metal sulfates as catalysts and allowing the reaction to occur at lower temperatures, but this further reduces yields.
本発明の目的は、従来製法の上記の種々の問題を解決し
、安価に炭化ホウ素微粉末を造ることにある。The purpose of the present invention is to solve the various problems mentioned above in conventional manufacturing methods and to produce fine boron carbide powder at low cost.
本発明者は上記の目的を達成すべくいろいろ検討した結
果、微粒子化促進剤として炭化ホウ素粉末を前・もって
原料に添加しておく製法、すなわち、ホウ素源と炭素源
とを原料とする炭化ホウ素の製造方法において、反応に
より新たに生成する炭化ホウ素１１００重量部に対し、
５〜６０重量部の炭化ホウ素粉末を前記原料に混合した
後、不活性ガス雰囲気中で１５００〜２０００℃にて加
熱することを特徴とする炭化ホウ素微粉末の製造方法を
見出した。As a result of various studies to achieve the above object, the inventor of the present invention has developed a manufacturing method in which boron carbide powder is added to the raw material as a microparticulation accelerator in advance, that is, boron carbide using a boron source and a carbon source as raw materials. In the production method, for 1100 parts by weight of boron carbide newly produced by the reaction,
We have found a method for producing fine boron carbide powder, which comprises mixing 5 to 60 parts by weight of boron carbide powder with the raw material and then heating the mixture at 1500 to 2000°C in an inert gas atmosphere.
原料であるホウ素源としては、金属ホウ素、酸化ホウ素
もしくは熱分解後酸化ホウ素等を生成する化合物を用い
る。As the boron source, which is a raw material, metal boron, boron oxide, or a compound that produces boron oxide after thermal decomposition is used.
熱分解後酸化ホウ素を生成する化合物とは、ホウ酸やホ
ウ酸エステル等をいう。ホウ酸エステルは、一般式Ｂ
（ＯＲ）ｎ（ＯＨ）ｘ−、、（ｎは１〜３の整数、Ｒは
アルキル基、シクロアルキル基、フェニル基）で表わさ
れるものをいう。The compound that generates boron oxide after thermal decomposition refers to boric acid, boric acid ester, and the like. Boric acid ester has general formula B
(OR)n(OH)x-, (n is an integer of 1 to 3, R is an alkyl group, a cycloalkyl group, or a phenyl group).
また、炭素源としてはカーボンブラック等の固体炭素も
しくは熱分解後炭素を生成する化合物を用いる。熱分解
後に炭素を生成する化合物とはフェノール樹脂、砂糖等
の不活性ガス中で熱分解させた後、炭素が残るものであ
れば何でもよ（、いずれの化合物を用いても同じ効果を
生ずる。Further, as the carbon source, solid carbon such as carbon black or a compound that produces carbon after thermal decomposition is used. A compound that produces carbon after pyrolysis is anything that leaves carbon behind after being pyrolyzed in an inert gas, such as phenol resin or sugar (the same effect is produced no matter which compound is used).
なお、本発明で使用できるカーボンブラックは、ファー
ネス法、アセチレン法等によって製造されるもののいず
れでもよ（、特に限定されるものではない。The carbon black that can be used in the present invention may be any one produced by a furnace method, an acetylene method, etc. (but is not particularly limited).
微粒子化促進剤として加える炭化ホウ素粉末の添加量は
、反応により新たに生成する炭化ホウ素１１００重量部
に対して５〜６０重量部加えるのが好ましい。５重量部
未満では生成する炭化ホウ素の微粒子化に対して効果が
なく、６０重量部を超えても微粒子化の効果はより優れ
ることはなく、経済性が劣ることになる。より好ましい
添加量は１０〜３０重量部である。The amount of boron carbide powder added as a particulate accelerator is preferably 5 to 60 parts by weight based on 1100 parts by weight of boron carbide newly produced by the reaction. If it is less than 5 parts by weight, it will not be effective in making the resulting boron carbide into fine particles, and if it exceeds 60 parts by weight, the effect of making fine particles will not be better and the economy will be poor. A more preferable addition amount is 10 to 30 parts by weight.
また、添加混合する炭化ホウ素粉末の粒度は、粗（でも
反応により生成する炭化ホウ素の微粒子化の効果はある
が、反応生成相中にそのまま残るため、よりよい炭化ホ
ウ素微粉末を得るためには微細な炭化ホウ素粉末がよく
、ｌＯμＩ以下の中心径のものが望ましく、粒径が小さ
い程望ましいことはいうまでもない。In addition, the particle size of the boron carbide powder to be added and mixed is coarse (although it has the effect of making the boron carbide produced by the reaction into fine particles, it remains as it is in the reaction product phase, so in order to obtain a better boron carbide fine powder) Fine boron carbide powder is preferred, preferably one with a center diameter of 1OμI or less, and it goes without saying that the smaller the particle size, the more desirable it is.
本発明のポイントである炭化ホウ素を前もって添加して
おくことにより生成される炭化ホウ素が微粒子（Ｈする
のは、添加した炭化ホウ素が核として作用して、炭化ホ
ウ素粉末無添加の場合に比べて、核の総数が増加したこ
とになり、その結果、核の成長が抑制され微粒子化が進
行すると考えられる。また、酸化ホウ素と炭素とで炭化
ホウ素が生成される反応は発熱反応で、原料中に炭化ホ
ウ素粉末を前もって添加しておくことにより、反応系の
実質の原料が希釈されたことになり、発熱反応による熱
が分散されるとともに、反応が緩慢に進行する結果、生
成される炭化ホウ素が微粒子化されると考えられる。The point of the present invention is that by adding boron carbide in advance, the boron carbide produced becomes fine particles (H) because the added boron carbide acts as a nucleus, and compared to the case without the addition of boron carbide powder. , the total number of nuclei has increased, and as a result, the growth of the nuclei is suppressed and the formation of fine particles is considered to proceed.In addition, the reaction in which boron carbide is produced between boron oxide and carbon is an exothermic reaction, and By adding boron carbide powder in advance, the actual raw material in the reaction system is diluted, the heat from the exothermic reaction is dispersed, and as a result of the reaction proceeding slowly, the boron carbide produced is It is thought that the particles become fine particles.
このことは原料中に添加する炭化ホウ素の粒径を小さく
する程、生成される炭化ホウ素の粒径が小さ（なる傾向
が見られるが、これは、原料中に同−重量部の炭化ホウ
素を加えた場合、炭化ホウ素の粒径が小さい程粒子数が
多くなり、核総数を増していることになることからもう
なずける。This means that the smaller the particle size of boron carbide added to the raw material, the smaller the particle size of the boron carbide produced. This is understandable because when added, the smaller the particle size of boron carbide, the greater the number of particles, which increases the total number of nuclei.
本発明では、ホウ素源と炭素源の原料と添加炭化ホウ素
を充分に混合した後、ハンドリングの問題等からしてペ
レット化することが望ましい。それをＡｒ、 Ｎｚ等の
不活性ガス雰囲気中で焼成する。In the present invention, it is desirable to thoroughly mix the boron source, carbon source materials, and added boron carbide, and then pelletize them in view of handling problems. It is fired in an inert gas atmosphere such as Ar or Nz.
炭化ホウ素を生成させる焼成温度は１５００〜２０００
℃が好ましく、１５００℃未満では未反応の酸化ホウ素
や炭素が多量に残り、また、２０００℃を超えると生成
した炭化ホウ素の粒成長を起こし好ましくない。The firing temperature to generate boron carbide is 1500-2000
C. is preferable; if it is less than 1500.degree. C., a large amount of unreacted boron oxide and carbon will remain, and if it exceeds 2000.degree. C., grain growth of the boron carbide produced will occur, which is not preferable.
本発明により生成される炭化ホウ素はＸ線回折的には、
Ｂ４ＣまたはＢ、３Ｃ，、またはそれらの混合物である
。In terms of X-ray diffraction, boron carbide produced according to the present invention has the following characteristics:
B4C or B, 3C, or mixtures thereof.
［実施例］ 本発明を実施例にて詳細に説明する。[Example] The present invention will be explained in detail by way of examples.
実施例１〜９
ホウ素源として金属ホウ素（Ｓｔａｒｋ社製アモ社製７
スルフアスＢ５ｇｍ、純度９５〜９７％）を７．２ｇ、
炭素源としてカーボンブラック（昭和ギヤボット■製シ
ョウブラックＮ２２０）を２．０ｇに対し、表・１のご
とく炭化ホウ素８４Ｃ粉末（５ｔａｒｋ社製Ｆ −１５
００、粒度１〜２μｍ、純度９５〜９７％）を０．４６
〜５．５２ｇの範囲の９種類の添加量（炭化ホウ素生成
量１００重量部に対して５〜６０重量部に相当）で加え
、アセトン４０ ｍβを分散媒として５時間湿式ボール
ミル混合した。得られたスラリーを乾燥、解砕した後、
ペレット状に成形し、Ａｒ気流中において、１７００℃
、１時間の条件で焼成した。Examples 1 to 9 Metallic boron (manufactured by Stark Co., Ltd., Amo Co., Ltd. 7) was used as a boron source.
7.2 g of sulfurous B (5 gm, purity 95-97%),
As shown in Table 1, boron carbide 84C powder (F-15 manufactured by 5tark) was added to 2.0 g of carbon black (Show Black N220 manufactured by Showa Gearbot ■) as a carbon source.
00, particle size 1-2 μm, purity 95-97%) is 0.46
Nine types of addition amounts ranging from ~5.52 g (corresponding to 5 to 60 parts by weight per 100 parts by weight of boron carbide produced) were added, and wet ball mill mixing was performed for 5 hours using 40 mβ of acetone as a dispersion medium. After drying and crushing the obtained slurry,
Formed into pellets and heated at 1700°C in an Ar flow.
, for 1 hour.
Ｘ線回折により、生成物の同定を行なったところ、いず
れも８４Ｇ （又はＢ＋ｚＣ２）の回折ピークのみが認
められた。When the products were identified by X-ray diffraction, only the 84G (or B+zC2) diffraction peak was observed in each case.
また、合成された粉末の一次粒子径をＳＥＭにより観察
したところ、 １．５〜２．５μ田程度であり、Ｂ、Ｃ
添加量が多い程、−次粒子径が小さくなる傾向があるこ
とがわかる。In addition, when the primary particle size of the synthesized powder was observed by SEM, it was about 1.5 to 2.5 μm, and B, C
It can be seen that the larger the amount added, the smaller the secondary particle diameter tends to be.
比較例１〜５
８４Ｃ粉末を原料混合段階で０〜０．３７ｇ （炭化ホ
ウ素生成量に対して１〜４重量部相当）の範囲の５種類
の添加量で加えること以外は、実施例１〜９と同様の手
順、条件でＢ４Ｃ（又はＢ＋５Ｃｚ）を合成した。表・
１に原料配合および生成粉特性等を示す。原料として８
４Ｃ無添加の場合、生成したＢ、Ｃ（又はＢ＋５Ｃｚ）
の粒径は５０μｍに達した。Comparative Examples 1 to 5 Examples 1 to 5 except that 84C powder was added in five different amounts ranging from 0 to 0.37 g (equivalent to 1 to 4 parts by weight based on the amount of boron carbide produced) at the raw material mixing stage. B4C (or B+5Cz) was synthesized using the same procedure and conditions as in Example 9. table·
1 shows the raw material composition and the characteristics of the resulting powder. 8 as a raw material
In the case of no addition of 4C, the generated B, C (or B + 5Cz)
The particle size reached 50 μm.
また、４重量部添加の場合でも、生成したものの一次粒
子の平均粒径は１０μＩを超えていた。Furthermore, even when 4 parts by weight was added, the average particle diameter of the primary particles produced exceeded 10 μI.
Ｃ以下余白）
実施例１０〜１７
ホウ素源として市販品ｏａｏｏｚ （関東化学■製、特
級品）を２０ｇ、炭素源として砂糖（三井精糖■製グラ
ニュー糖、市販品、残炭率２０％）を１２ｇ用い、更に
、表・２に示す様に粒度の異なる８種類の８４Ｃを０．
３２ｇ （炭化ホウ素生成量に対し２０重量部相当）加
え、純水１２０ ｍβを分散媒として、５時間湿式ボー
ルミル混合した。Examples 10 to 17 As a boron source, 20 g of commercial product oaooz (manufactured by Kanto Kagaku ■, special grade), and as a carbon source, 12 g of sugar (granulated sugar manufactured by Mitsui Seito ■, commercial product, residual carbon rate 20%) Furthermore, as shown in Table 2, eight types of 84C with different particle sizes were added at 0.
32 g (equivalent to 20 parts by weight based on the amount of boron carbide produced) was added and mixed in a wet ball mill for 5 hours using 120 mβ of pure water as a dispersion medium.
この場合、原料として配合する平均粒径２μｍ以上の粗
い粒度の８４Ｃ粉末は、５ｔａｒｋ社製の銘柄Ｆ−１５
００（粒度１〜３μｍ）からＦ−４００（粒度８〜３２
μｍ）の各種の粒度の市販品をそのまま用いたが、２μ
ｍ未満の粒度のものについては、市販品Ｂ、Ｃ粉末を水
中分散させ、沈降法により分級し微粉末８４Ｇを採取し
た。In this case, the coarse 84C powder with an average particle size of 2 μm or more to be blended as a raw material is brand F-15 manufactured by 5tark.
00 (particle size 1-3μm) to F-400 (particle size 8-32μm)
Commercially available products with various particle sizes of 2μm) were used as they were;
For those with a particle size of less than m, commercially available powders B and C were dispersed in water and classified by a sedimentation method to collect fine powder 84G.
原料配合して得られた混合スラリーを乾燥、解砕した後
、ベレット状に成形し、Ａｒ気流中において１７００℃
、１時間で焼成した。After drying and crushing the mixed slurry obtained by blending the raw materials, it was formed into a pellet shape and heated at 1700°C in an Ar gas flow.
, baked in 1 hour.
得られた生成８４Ｇ （又はＢ＋５Ｃｚ）の特性を表・
２に示す。The characteristics of the obtained generated 84G (or B+5Cz) are shown in the table below.
Shown in 2.
粒度の粗いＢ、Ｃを用いても、比較的細かいＢ、Ｃ（又
はＢ１３Ｃ２）が生成するが、原料中に加えたＢ、Ｃは
そのまま残るため、平均粒径は若干粗くなる。原料中に
加える８４Ｃ粒度が細かい程、生成したＢ４Ｃ（又はＢ
＋５Ｃｚ）は細か（なり、原料添加の８４Ｃがサブミク
ロンであると、生成したＢ、Ｃ（又はＢ＋ｚＣｔ）の平
均粒径もサブミクロンとなった。Even if B and C with coarse particle sizes are used, relatively fine B and C (or B13C2) are produced, but since the B and C added to the raw materials remain as they are, the average particle size becomes slightly coarse. The finer the 84C particle size added to the raw material, the more
+5Cz) was fine (and when 84C added as a raw material was submicron), the average particle size of the produced B and C (or B+zCt) was also submicron.
比較例６〜１３
原料に対し、平均粒径０．２μｍおよび２．０μｍの８
４Ｃ粉末を０〜０．０６ｇ （炭化ホウ素生成量に対し
Ｏ〜３．７５重量部相当）を表・２のごとく添加する以
外は、実施例１０〜１７と同様にＢ、Ｃ（又はＢ＋５Ｃ
ｔ）を合成した。Comparative Examples 6 to 13 For the raw material, 8 with an average particle size of 0.2 μm and 2.0 μm
B, C (or B+5C
t) was synthesized.
得られた合成粉末の特性を表・２に示す。The properties of the obtained synthetic powder are shown in Table 2.
８４Ｃ添加量を同じとした場合、平均粒径の小さいＢ、
Ｃを用いた方が、合成された８４Ｇ （又はＢ、、Ｃｍ
）の粒径は小さくなったが、いずれも平均粒径は、１０
μｍを超えていた。When the amount of 84C added is the same, B with a small average particle size,
Using C, the synthesized 84G (or B, , Cm
) became smaller, but the average particle size was 10
It exceeded μm.
（以下余白）
実施例１８〜２５、比較例１４〜１９
ホウ素源としてＢ２Ｏ３（関東化学■製、市販特級品）
を１０ｇ、炭素源としてカーボンブラック（実施例１〜
９と同一物）を５゜Ｏｇに対し、表・３のごとく平均粒
径０．５および１．０μｍの８４Ｃ分級粉末を０．４９
ｇ （生成炭化ホウ素量に対し１５重量部相当）加え、
純水５７膳βを分散媒として５時間湿式ボールミル混合
した。得られたスラリーを乾燥、解砕した後、ベレット
状に成形し、Ａｒ気流中において、表・３のごと＜ １
３００〜２２００℃の温度範囲で２時間保持して焼成し
た。(Left below) Examples 18-25, Comparative Examples 14-19 B2O3 as a boron source (manufactured by Kanto Kagaku ■, commercially available special grade product)
10g, carbon black as a carbon source (Example 1~
9) to 5°Og, 84C classified powder with average particle diameters of 0.5 and 1.0 μm was added to 0.49g as shown in Table 3.
g (equivalent to 15 parts by weight based on the amount of boron carbide produced), and
Wet ball mill mixing was carried out for 5 hours using 57 units of pure water β as a dispersion medium. After drying and crushing the obtained slurry, it was formed into a pellet shape, and in an Ar air flow, it was heated as shown in Table 3 < 1
Firing was carried out by holding at a temperature in the range of 300 to 2200°C for 2 hours.
焼成温度を１５００℃以下では生成物の酸素含有量が高
くなり、１５００℃未満では急激に酸素含有量を増し、
未反応Ｂ、０．が残っていることを表わしている。この
ことは、炭素含有量からもわかり、Ｂ、Ｃの理論炭素量
で２１．７４％を１５００℃以下の焼成温度では超えて
いて、１５００℃未満の焼成温度では極端に未反応炭素
が含まれている。If the calcination temperature is below 1500°C, the oxygen content of the product will be high, and if it is below 1500°C, the oxygen content will increase rapidly.
Unreacted B, 0. This indicates that there are still . This can be seen from the carbon content; the theoretical carbon content of B and C exceeds 21.74% at a firing temperature of 1500°C or lower, and unreacted carbon is extremely contained at a firing temperature of less than 1500°C. ing.
焼成温度が１６００℃以上では酸素、遊離炭素濃度の低
い炭化ホウ素粉末が得られるが、２０００℃を超えると
炭化ホウ素の粒成長が進行していることがわかる。It can be seen that when the firing temperature is 1,600°C or higher, boron carbide powder with low oxygen and free carbon concentrations is obtained, but when the firing temperature exceeds 2,000°C, grain growth of boron carbide progresses.
（以下余白）
比較例２０〜２７
平均粒径０．５および１．０μｍの８４Ｃの原料中への
添加量をＯ〜０．１３ｇ （生成炭化ホウ素に対して０
〜４．０重量部相当）にしたこと以外は実施例２０．２
１と同様の手順、条件で炭化ホウ素を合成した。よって
、焼成条件は１７００℃で２時間である。(Left below) Comparative Examples 20 to 27 The amount of 84C with average particle diameters of 0.5 and 1.0 μm added to the raw material was 0 to 0.13 g (0 to 0.13 g relative to the boron carbide produced).
Example 20.2 except that the amount was changed to (equivalent to ~4.0 parts by weight)
Boron carbide was synthesized using the same procedure and conditions as in Example 1. Therefore, the firing conditions are 1700° C. for 2 hours.
８４Ｃ添加量が同一の場合、その平均粒径が小さい程、
合成される炭化ホウ素粉末の粒径は小さ（なるが、合成
された炭化ホウ素の平均粒径は、いずれも１０μｍを超
えていた。When the amount of 84C added is the same, the smaller the average particle size,
The particle size of the synthesized boron carbide powder was small (although the average particle size of the synthesized boron carbide was all over 10 μm).
（以下余白）
実施例２６〜２８
炭素源としてフェノール樹脂（固形フェノール樹脂、昭
和高分子■製ＢＲＭ−５９５，残炭率４０％）を使用し
、表・５に示すごとく種々のホウ素源ならびに炭化ホウ
素生成量に対し１０重量部相当の８４Ｃ粉末を混合する
以外は、実施例１〜９と同一条件、手順にて炭化ホウ素
を合成した。(Left below) Examples 26 to 28 Phenol resin (solid phenol resin, BRM-595 manufactured by Showa Kobunshi ■, residual carbon ratio 40%) was used as a carbon source, and various boron sources and carbonization were used as shown in Table 5. Boron carbide was synthesized under the same conditions and procedures as in Examples 1 to 9, except that 84C powder was mixed in an amount equivalent to 10 parts by weight based on the amount of boron produced.
その結果、合成された炭化ホウ素の粉末粒度も表・５に
示す。As a result, the powder particle size of the synthesized boron carbide is also shown in Table 5.
（以下余白）
実施例２９
実施例１０の合成炭化ホウ素粉末を、ＳｉＣボールをメ
ディアとして振動ミルで１時間粉砕した。(The following is a blank space) Example 29 The synthetic boron carbide powder of Example 10 was pulverized for 1 hour in a vibrating mill using SiC balls as a media.
得られた粉末の粒度を粒度分布測定機で測定した二次粒
子に相当する平均粒径は０．４μｍであった。また、粉
砕後の不純物分析をしたところＳｉＣボールによると思
われるＳｉ不純物が最も多く３５０ｐｐｍ含有されてい
ることがわかった。The particle size of the obtained powder was measured using a particle size distribution analyzer, and the average particle size corresponding to secondary particles was 0.4 μm. In addition, an analysis of impurities after pulverization revealed that Si impurities, which are thought to be caused by SiC balls, were contained in the largest amount at 350 ppm.
実施例３０
実施例１４の合成粉末につき実施例２９と同様に振動ミ
ル粉砕した。ただ、粉砕時間は５時間とした。Example 30 The synthetic powder of Example 14 was crushed by a vibratory mill in the same manner as in Example 29. However, the grinding time was 5 hours.
得られた粉末の平均粒径を実施例２９と同様に測定した
ところ０．７μＩであり、Ｓｉ不純物含量は７００ｐｐ
ｍであった
比較例２８
比較例１の合成炭化ホウ素粉末につき実施例２９と同様
に振動ミル粉砕した。ただ、粉砕時間は１０倍の１０時
間で粉砕した。しかし、得られた粉砕粉の平均粒径を実
施例２９と同様に測定したところ、８．０μｍであり、
Ｓｉ不純物含量は５．２ｗｔ％であった。The average particle size of the obtained powder was measured in the same manner as in Example 29 and was found to be 0.7μI, and the Si impurity content was 700pp.
Comparative Example 28 The synthetic boron carbide powder of Comparative Example 1 was pulverized in a vibratory mill in the same manner as in Example 29. However, the grinding time was 10 hours, which is 10 times longer. However, when the average particle size of the obtained pulverized powder was measured in the same manner as in Example 29, it was 8.0 μm.
The Si impurity content was 5.2 wt%.
本発明により、−次粒子経が２μｍ以下の炭化ホウ素粉
末を容易に合成することができ、また、粉砕により簡単
に二次粒子径としてサブミクロンの微粉末が得られる。According to the present invention, boron carbide powder having a secondary particle size of 2 μm or less can be easily synthesized, and fine powder with a secondary particle size of submicrons can be easily obtained by pulverization.
Claims (1)
において、反応により新たに生成する炭化ホウ素量１０
０重量部に対し、５〜６０重量部の炭化ホウ素粉末を前
記原料に混合した後、不活性ガス雰囲気中で１５００〜
２０００℃にて加熱することを特徴とする炭化ホウ素微
粉末の製造方法。In a method for producing boron carbide using a boron source and a carbon source as raw materials, the amount of boron carbide newly generated by reaction is 10
After mixing 5 to 60 parts by weight of boron carbide powder to the raw material,
A method for producing fine boron carbide powder, which comprises heating at 2000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2284492A JP2911207B2 (en) | 1990-10-24 | 1990-10-24 | Method for producing fine boron carbide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2284492A JP2911207B2 (en) | 1990-10-24 | 1990-10-24 | Method for producing fine boron carbide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04160012A true JPH04160012A (en) | 1992-06-03 |
| JP2911207B2 JP2911207B2 (en) | 1999-06-23 |
Family
ID=17679220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2284492A Expired - Lifetime JP2911207B2 (en) | 1990-10-24 | 1990-10-24 | Method for producing fine boron carbide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2911207B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009067642A (en) * | 2007-09-14 | 2009-04-02 | Doshisha | Boron carbide ceramic and its production method |
| JP2010535693A (en) * | 2007-08-08 | 2010-11-25 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Method for producing pressureless sintered high density boron carbide material |
| JP2019142757A (en) * | 2018-02-23 | 2019-08-29 | 太平洋セメント株式会社 | Method for producing boron carbide |
| KR20210008060A (en) * | 2018-06-13 | 2021-01-20 | 사반치 유니버시티 | Low temperature manufacturing method of boron carbide |
-
1990
- 1990-10-24 JP JP2284492A patent/JP2911207B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010535693A (en) * | 2007-08-08 | 2010-11-25 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Method for producing pressureless sintered high density boron carbide material |
| JP2009067642A (en) * | 2007-09-14 | 2009-04-02 | Doshisha | Boron carbide ceramic and its production method |
| JP2019142757A (en) * | 2018-02-23 | 2019-08-29 | 太平洋セメント株式会社 | Method for producing boron carbide |
| KR20210008060A (en) * | 2018-06-13 | 2021-01-20 | 사반치 유니버시티 | Low temperature manufacturing method of boron carbide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2911207B2 (en) | 1999-06-23 |
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