JP2730086B2 - Aluminum nitride powder and method for producing the same - Google Patents
Aluminum nitride powder and method for producing the sameInfo
- Publication number
- JP2730086B2 JP2730086B2 JP63252774A JP25277488A JP2730086B2 JP 2730086 B2 JP2730086 B2 JP 2730086B2 JP 63252774 A JP63252774 A JP 63252774A JP 25277488 A JP25277488 A JP 25277488A JP 2730086 B2 JP2730086 B2 JP 2730086B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- aluminum nitride
- nitride powder
- alumina
- less
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
- C01B21/0726—Preparation by carboreductive nitridation
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はタップ密度が高く、凝集粒が少なく、粒径分
布のシャープな成形性に優れた窒化アルミニウム粉末お
よびその製造方法に関するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum nitride powder having a high tap density, a small amount of agglomerated particles, a sharp particle size distribution, and excellent moldability, and a method for producing the same.
ICパッケージ、基板材料には従来よりアルミナが用い
られているが、LSI等の高集積化、高速化、高出力化に
伴い、チップの発熱を効率よく系外に逃がす必要性が高
まり、アルミナよりも熱伝導性が良く、放熱性に優れた
材料が要望されている。Alumina has been used for IC package and substrate materials.However, with high integration, high speed, and high output of LSI etc., the need to efficiently release the heat of the chip to the outside of the system has increased. Also, a material having good heat conductivity and excellent heat dissipation is demanded.
窒化アルミニウムは高い熱伝導性を有すると共に絶縁
抵抗、絶縁耐圧、誘電率等の電気的特性および強度等の
機械的特性に優れており、放熱性に優れたパッケージ、
基板材料として注目されている材料である。Aluminum nitride has high thermal conductivity and excellent electrical properties such as insulation resistance, withstand voltage, dielectric constant and mechanical properties such as strength.
It is a material that has attracted attention as a substrate material.
窒化アルミニウム粉末の製造方法としては（１）金属
アルミニウム粉末を窒素を含む雰囲気中で加熱して窒化
する直接窒化法、（２）アルミナもしくはアルミナ水和
物とカーボンとの混合物を窒素を含む雰囲気中で加熱す
る還元窒化法の二つが従来から知られている。前者の方
法で得られる窒化アルミニウム粉末はタップ密度の大き
い成形しやすい粉末であるが、鉄等の陽イオン不純物が
比較的多く含まれており、高熱伝導の焼結体を得るには
必ずしも満足できるものではない。それ故、高熱伝導性
基板を得るための粉末としては後者の還元窒化法によっ
て合成された窒化アルミニウム粉末が有力視されてい
る。しかし、還元窒化法で得られる窒化アルミニウム粉
末は酸素や鉄等の陽イオン不純物が少ないという長所を
有する反面、タップ密度が小さく成形しにくいという欠
点を有している。Examples of the method for producing aluminum nitride powder include (1) a direct nitriding method in which metallic aluminum powder is heated and nitrided in an atmosphere containing nitrogen, and (2) a mixture of alumina or alumina hydrate and carbon in an atmosphere containing nitrogen. Conventionally, two of the reduction nitriding methods in which heating is performed are known. The aluminum nitride powder obtained by the former method is a powder having a large tap density and easy to be formed, but contains a relatively large amount of cationic impurities such as iron, and thus is not always satisfactory for obtaining a sintered body having high thermal conductivity. Not something. Therefore, as the powder for obtaining a high thermal conductive substrate, aluminum nitride powder synthesized by the latter reduction nitriding method is considered to be promising. However, aluminum nitride powder obtained by the reduction nitridation method has the advantage that there are few cation impurities such as oxygen and iron, but has the disadvantage that the tap density is small and it is difficult to mold.
窒化アルミニウム粉末がカサ高く、そのタップ密度が
小さいと、溶媒への分散がしづらく、かつ成形時に高い
成形体密度が得られ難いという課題が生じる。実際、還
元窒化法で得られた粉末は直接窒化法で得られた粉末に
比べて成形性の点で劣るということが指摘されている。When the aluminum nitride powder has a high bulk and a low tap density, there is a problem that dispersion in a solvent is difficult, and a high compact density is difficult to obtain during compaction. In fact, it has been pointed out that the powder obtained by the reduction nitriding method is inferior in the formability as compared with the powder obtained by the direct nitriding method.
本発明は還元窒化法で得られる粉末の欠点を解決しよ
うとするものであり、その目的とするところは酸素含有
量、陽イオン不純物量が少なく、かつタップ密度が高
く、凝集粒が少ない粒径分布のシャープな成形性に優れ
た窒化アルミニウム粉末およびその製造方法を提供する
ことにある。The present invention aims to solve the drawbacks of powders obtained by the reduction nitriding method, and aims at reducing the oxygen content, the amount of cationic impurities, the tap density, and the particle size of the aggregated particles. An object of the present invention is to provide an aluminum nitride powder excellent in formability having a sharp distribution and a method for producing the same.
すなわち本発明はアルミナとカーボンの混合物を窒素
を含む雰囲気中で加熱反応させて得られた窒化アルミニ
ウム粉末において、酸素2.0重量％以下、鉄20ppm以下、
珪素100ppm以下およびチタン20ppm以下を含有する窒化
アルミニウム粉末であって、タップ密度が1.0g/cm3以上
からなる窒化アルミニウム粉末を提供するものである。That is, the present invention, in an aluminum nitride powder obtained by heating and reacting a mixture of alumina and carbon in an atmosphere containing nitrogen, oxygen 2.0 wt% or less, iron 20 ppm or less,
The present invention provides an aluminum nitride powder containing 100 ppm or less of silicon and 20 ppm or less of titanium and having a tap density of 1.0 g / cm 3 or more.
また本発明はアルミナ粉末とカーボン粉末の混合物を
窒素を含む雰囲気中で加熱して得られた反応生成物を粉
砕した後、余剰のカーボン粉末を空気中で燃焼除去する
ことを特徴とする窒化アルミニウム粉末の製造方法を提
供するものである。Further, the present invention is characterized in that, after a reaction product obtained by heating a mixture of alumina powder and carbon powder in an atmosphere containing nitrogen is pulverized, excess carbon powder is burned and removed in air. A method for producing a powder is provided.
さらに本発明はアルミナ粉末とカーボン粉末の混合物
を窒素を含む雰囲気中で加熱反応させた後、余剰のカー
ボン粉末を空気中で燃焼除去して得られた窒化アルミニ
ウム粉末を粉砕することを特徴とする窒化アルミニウム
粉末の製造方法を提供するものである。Further, the present invention is characterized in that after heating and reacting a mixture of alumina powder and carbon powder in an atmosphere containing nitrogen, aluminum nitride powder obtained by burning and removing excess carbon powder in air is pulverized. An object of the present invention is to provide a method for producing aluminum nitride powder.
以下、本発明の窒化アルミニウム粉末について詳述す
る。Hereinafter, the aluminum nitride powder of the present invention will be described in detail.
原料粉末中に含まれる酸素、鉄、珪素およびチタン
は、その原料粉末を用いて得られる焼結体の熱伝導度を
低下させることが知られている。その傾向はこれら不純
物の含有量が増えるほど大きくなる。従って、酸化イッ
トリウムを焼結助剤とした焼結において180W/mK以上の
高熱伝導度を安定して得るためには、一定限度以上の上
記不純物を含まない原料粉末が要求される。還元窒化法
においてはこのような酸素2.0重量％以下、鉄20ppm以
下、珪素100ppm以下およびチタン20ppm以下を含有する
高純度の粉末の合成は容易である。しかし、還元窒化法
ではせいぜいタップ密度が0.8g/cm3程度の粉末しか得ら
れていなかった。本発明はこのような高純度の粉末であ
って、かつ1.0g/cm3以上のタップ密度を有する窒化アル
ミニウム粉末を提供するものである。タップ密度の小さ
い粉末では成形する際にしまりが悪く、高い成形体密度
の成形体が得られにくく、焼結時の収縮率が大きくなり
寸法精度の良い焼結体が得られにくい。また、ゴム、樹
脂等の高分子材料等に窒化アルミニウム粉末を高熱伝導
性フィラーとして添加する際にも、充填性が劣るという
課題がある。特に1.0g/cm3未満ではその粉末を収納する
際も20容器に20kgを収納することが出来ず、特製の容
器が必要になる。It is known that oxygen, iron, silicon and titanium contained in the raw material powder reduce the thermal conductivity of a sintered body obtained using the raw material powder. The tendency increases as the content of these impurities increases. Therefore, in order to stably obtain a high thermal conductivity of 180 W / mK or more in sintering using yttrium oxide as a sintering aid, a raw material powder containing no more than a certain limit of the above impurities is required. In the reductive nitridation method, it is easy to synthesize a high-purity powder containing 2.0% by weight of oxygen, 20 ppm or less of iron, 100 ppm or less of silicon, and 20 ppm or less of titanium. However, only powders having a tap density of at most about 0.8 g / cm 3 were obtained by the reduction nitriding method. The present invention provides an aluminum nitride powder having such a high purity and a tap density of 1.0 g / cm 3 or more. Powder having a small tap density has poor tightness in molding, it is difficult to obtain a molded body having a high molded body density, and the shrinkage ratio during sintering is large, so that it is difficult to obtain a sintered body having high dimensional accuracy. Further, when aluminum nitride powder is added as a high thermal conductive filler to a polymer material such as rubber or resin, there is a problem that the filling property is poor. In particular, if the content is less than 1.0 g / cm 3 , 20 kg cannot be stored in 20 containers even when storing the powder, and a special container is required.
次に本発明の製造方法について詳述する。 Next, the production method of the present invention will be described in detail.
本発明はまず還元窒化法によりアルミナ粉末とカーボ
ン粉末の混合物を窒素を含む雰囲気中、1500〜1700℃で
２〜10時間反応させて窒化アルミニウム粉末を合成す
る。In the present invention, first, a mixture of alumina powder and carbon powder is reacted at 1500 to 1700 ° C. for 2 to 10 hours in an atmosphere containing nitrogen by a reduction nitridation method to synthesize aluminum nitride powder.
原料アルミナ粉末は大量に製造販売されているバイヤ
ー法で製造されたものを始めとして、各種の方法で製造
されているものを用いることができるが、還元窒化反応
時に揮散しにくい珪素、チタン等の金属不純物の含量の
少ないアルミナ粉末を用いることが好ましい。アルミナ
粉末は微粉のものを用いることが好ましい。As the raw material alumina powder, those manufactured by various methods, including those manufactured by the Bayer method, which are manufactured and sold in large quantities, can be used, but silicon, titanium, etc., which are difficult to volatilize during the reductive nitridation reaction, can be used. It is preferable to use alumina powder having a low content of metal impurities. It is preferable to use fine alumina powder.
また、原料カーボン粉末はできるだけ高純度で微粉の
ものを用いることが好ましい。より好ましくはカーボン
粉末は一次粒子径が１μｍ以下、灰分0.3重量％以下の
粉末が使用される。このようなカーボン粉末としてはア
セチレンブラック、チャンネルブラック、ファーネスブ
ラック等が挙げられる。この中でもより高純度という点
でアセチレンブラックが好ましい。また取り扱いの点か
ら分散が容易であれば、0.3〜1.5mmに造粒した粒状のも
のや、プレス圧縮した粉状のものを用いるのが有利であ
る。Further, it is preferable to use a raw carbon powder having a purity as high as possible and a fine powder. More preferably, a carbon powder having a primary particle diameter of 1 μm or less and an ash content of 0.3% by weight or less is used. Examples of such carbon powder include acetylene black, channel black, furnace black and the like. Among them, acetylene black is preferable in terms of higher purity. If it is easy to disperse from the viewpoint of handling, it is advantageous to use a granular material granulated to 0.3 to 1.5 mm or a powdered material obtained by pressing.
アルミナ粉末とカーボン粉末を混合分散する方法とし
ては超音波分散法等の一般的な方法やボールミル、バー
ティカルグラニュレーター等の各種混合機を用いること
ができる。またこれらの原料と直接接触する装置の部品
は金属不純物が混入しないような材料から構成されたも
のを使用することが望ましい。そのような材料としてポ
リエチレン、ナイロン、ウレタン等の合成樹脂、天然あ
るいは合成ゴムおよびアルミナ製、窒化アルミニウム製
のもの、またはこれらの材料で内張りあるいはコーティ
ングされたものを用いることが望ましい。As a method for mixing and dispersing the alumina powder and the carbon powder, a general method such as an ultrasonic dispersion method or various mixers such as a ball mill and a vertical granulator can be used. In addition, it is desirable to use components made of a material that does not contain metal impurities as components of the apparatus that come into direct contact with these raw materials. As such a material, it is desirable to use a synthetic resin such as polyethylene, nylon, urethane or the like, a natural or synthetic rubber, and a material made of alumina or aluminum nitride, or a material lined or coated with these materials.
混合物の乾燥方法としては通常の工業的方法を用いる
ことができるが、混合時のスラリー粘度が低く乾燥時に
アルミナ粉末とカーボン粉末の分離等が生じる恐れのあ
るときは、スプレードライ、凍結乾燥、ロータリーエバ
ポレーター等の方法を用いるのが好ましい。また、必要
に応じて混合や乾燥と共に20μｍ〜3mm程度の大きさの
粒子に造粒することもでき、造粒すると以後の取り扱い
がよりたやすくなるという利点がある。As a method for drying the mixture, ordinary industrial methods can be used.However, when the slurry viscosity during mixing is low and separation of alumina powder and carbon powder may occur during drying, spray drying, freeze drying, rotary It is preferable to use a method such as an evaporator. Further, if necessary, the particles can be granulated into particles having a size of about 20 μm to 3 mm together with mixing and drying, and the granulation has an advantage that subsequent handling becomes easier.
還元窒化反応を完結しやすくするため、通常アルミナ
粉末に対し反応当量以上のカーボン粉末が用いられる。
アルミナ粉末とカーボン粉末の混合比率はカーボン／ア
ルミナのモル比で３〜10の範囲が好ましい。該モル比が
３未満のときは未反応のアルミナが残存し、一方10より
大きいときは後工程でカーボンを除去することが困難と
なり、また経済的にも好ましくない。従って還元窒化反
応で得られた反応生成物は通常窒化アルミニウム粉末と
余剰のカーボン粉末との混合物であり、これを空気中ま
たは乾燥空気中で600〜750℃に加熱し、余剰のカーボン
を燃焼除去して窒化アルミニウム粉末を得ている。In order to easily complete the reductive nitridation reaction, carbon powder having a reaction equivalent or more to alumina powder is usually used.
The mixing ratio of the alumina powder and the carbon powder is preferably in the range of 3 to 10 in terms of the molar ratio of carbon / alumina. When the molar ratio is less than 3, unreacted alumina remains, while when it is greater than 10, it becomes difficult to remove carbon in a subsequent step, and it is not economically preferable. Therefore, the reaction product obtained by the reduction nitriding reaction is usually a mixture of aluminum nitride powder and excess carbon powder, which is heated to 600 to 750 ° C in air or dry air to burn off excess carbon. To obtain aluminum nitride powder.
しかし、このような工程で得られた窒化アルミニウム
粉末は通常少量の凝集粒を含有し、かつタップ密度の低
い粉末である。However, the aluminum nitride powder obtained by such a process usually contains a small amount of agglomerated particles and has a low tap density.
本発明の製造方法は上記還元窒化反応により得られた
窒化アルミニウム粉末と余剰のカーボン粉末との混合物
を粉砕した後、これを空気中で600〜750℃に加熱し、余
剰のカーボンを燃焼除去して凝集粒の少ないタップ密度
の大きい窒化アルミニウム粉末を得たものである。The production method of the present invention is to pulverize a mixture of the aluminum nitride powder and excess carbon powder obtained by the above-mentioned reduction nitridation reaction, and then heat the mixture to 600 to 750 ° C. in air to burn and remove excess carbon. Thus, an aluminum nitride powder having a small tapping density and a large tap density was obtained.
また、本発明の別の製造方法は上記還元窒化反応によ
り得られた窒化アルミニウム粉末と余剰のカーボン粉末
との混合物を空気中で600〜750℃に加熱し、余剰のカー
ボンを燃焼除去して得られた窒化アルミニウム粉末を粉
砕することにより凝集粒の少ないタップ密度の大きい窒
化アルミニウム粉末を得たものである。Further, another production method of the present invention is obtained by heating a mixture of the aluminum nitride powder obtained by the above reduction nitridation reaction and excess carbon powder to 600 to 750 ° C. in air and burning and removing excess carbon. The obtained aluminum nitride powder was pulverized to obtain an aluminum nitride powder having few aggregate particles and a large tap density.
上記の二つの製造方法における粉砕方法としてはボー
ルミル、振動ミル、ジェットミル等の通常の粉砕機は用
いればよい。しかし、窒化アルミニウム粉末は加水分解
されやすく、粉砕の課程で酸素含有量が増加する傾向が
ある。また、粉砕によりBET比表面積が大きくなった
り、１μｍ未満の微粉末含量が増加すると窒化アルミニ
ウム粉末の表面が酸化されやすくなり、その結果酸素含
量が増加する。従って、粉砕はBET比表面積が6m2以上に
ならないように行い、１μｍ未満の微粉末含量が50％以
下、好ましくは30％以下とする。また、粉砕の操作は乾
燥空気中、または乾燥窒素ガス中で、出来るだけ短時間
で行うことが好ましい。通常はメタノール、オレイン
酸、ラウリン酸、ステアリン酸カルシウム、アリールア
ルキルスルフォン酸等の粉砕助剤を適当量添加して粉砕
効率を高め、乾燥空気中、もしくは乾燥窒素ガス中で短
時間に粉砕を行うことが好ましい。さらに粉砕機および
粉砕媒体の材質によっては鉄、珪素等の金属不純物によ
る汚染が生じることがあるので、その材質としては窒化
アルミニウム、アルミナあるいはプラスチック、ゴム等
でライニングまたはコーテイングされたものを用いるこ
とが好ましい。As a pulverization method in the above two production methods, a normal pulverizer such as a ball mill, a vibration mill, and a jet mill may be used. However, aluminum nitride powder is easily hydrolyzed, and the oxygen content tends to increase during the pulverization process. Further, when the BET specific surface area is increased by pulverization or the content of fine powder of less than 1 μm is increased, the surface of the aluminum nitride powder is easily oxidized, and as a result, the oxygen content is increased. Therefore, pulverization is performed so that the BET specific surface area does not exceed 6 m 2 , and the content of fine powder having a particle size of less than 1 μm is 50% or less, preferably 30% or less. The pulverizing operation is preferably performed in dry air or dry nitrogen gas in as short a time as possible. Usually, an appropriate amount of grinding aid such as methanol, oleic acid, lauric acid, calcium stearate, arylalkylsulfonic acid, etc. is added to increase the grinding efficiency, and grinding is performed in dry air or dry nitrogen gas in a short time. Is preferred. Furthermore, depending on the material of the pulverizer and the pulverizing medium, contamination by metal impurities such as iron and silicon may occur. Therefore, it is preferable to use a material lined or coated with aluminum nitride, alumina, plastic, rubber, or the like. preferable.
本発明で得られた窒化アルミニウム粉末は酸素、鉄、
珪素、およびチタンの含有量が少なく凝集粒を殆ど含ま
ないタップ密度の大きい、成形性に優れた粉末であり、
これを用いることにより焼結時の収縮率を小さくでき、
かつ殆ど気孔を含まない高密度で熱伝導性に優れた焼結
体を容易に得ることができ、熱伝導性に優れた窒化アル
ミニウム焼結体製造用原料として有用なものである。Aluminum nitride powder obtained in the present invention is oxygen, iron,
Silicon, and a large tap density with little content of agglomerates with a low content of titanium, is a powder excellent in moldability,
By using this, the shrinkage rate during sintering can be reduced,
Further, it is possible to easily obtain a high-density sintered body excellent in thermal conductivity containing almost no pores and useful as a raw material for producing an aluminum nitride sintered body excellent in thermal conductivity.
以下、実施例により本発明を具体的に説明するが、本
発明はこれらにより限定されるものではない。Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
実施例１ 純度99.9％、セディグラフによる中心粒径0.7μｍ、
１μｍ以下80％の低ソーダアルミナ粉末306gと灰分0.00
5％のアセチレンブラック100％プレス品216gおよび硝酸
アルミニウム［Al（NO3）３・9H2O］11.3g、ポリエチレ
ングリコール5.2gおよびポリオキシエチレンアルキルフ
ェニルエーテルからなるノニオン系界面活性剤（第一工
業薬品（株）製ノイゲンEA137）15.1gを溶解したイオン
交換水2600gを、直径15mmのナイロンボール600個と共に
ポリエチレン製のポットに入れ40rpmの回転速度で10時
間湿式混合を行った。Example 1 Purity 99.9%, center particle size 0.7 μm according to Cedigraph,
306g of 80% low soda alumina powder of 1% or less and ash content of 0.00
Nonionic surfactant consisting of 216 g of 5% acetylene black 100% pressed product, 11.3 g of aluminum nitrate [Al (NO 3 ) 3 .9H 2 O], 5.2 g of polyethylene glycol and polyoxyethylene alkylphenyl ether (Daiichi Kogyo) 2600 g of ion-exchanged water in which 15.1 g of Neugen EA137 (produced by Yakuhin Co., Ltd.) were dissolved was placed in a polyethylene pot together with 600 nylon balls having a diameter of 15 mm, and wet-mixed at a rotation speed of 40 rpm for 10 hours.
このようにして得られた混合スラリーを乾燥器で乾燥
させた後、その500gをグラファイト製トレイに採取し、
電気炉を用いて200cm/min.の速度で窒素ガスを流しなが
ら1580℃で７時間加熱し、還元窒化反応を行った。次い
でこの反応生成物150gを２ポリエチレン製ポットにと
り直径15mmのアルミナ製ボール2.5kgとラウリン酸1.5g
を加え、窒素ガスでポット内を十分置換した後、60rpm
の回転速度で３時間乾式ボールミル粉砕を行った。さら
にこの粉砕物を乾燥空気中にて700℃で３時間加熱して
余剰カーボンを燃焼除去して窒化アルミニウム粉末を得
た。この窒化アルミニウム粉末の諸物性を第１表に示
す。この粉末は凝集粒の殆どない粒径分布のシャープな
高純度微粉末であった。After drying the thus obtained mixed slurry in a dryer, 500 g of the mixed slurry was collected on a graphite tray,
The mixture was heated at 1580 ° C. for 7 hours while flowing a nitrogen gas at a speed of 200 cm / min. Using an electric furnace to perform a reductive nitridation reaction. Then, 150 g of the reaction product was placed in a 2 polyethylene pot, 2.5 kg of alumina balls having a diameter of 15 mm and 1.5 g of lauric acid.
, And after thoroughly replacing the inside of the pot with nitrogen gas, 60 rpm
Dry ball mill pulverization was performed at a rotation speed of 3 hours. The pulverized product was further heated in dry air at 700 ° C. for 3 hours to burn off excess carbon to obtain an aluminum nitride powder. Table 1 shows the physical properties of this aluminum nitride powder. This powder was a high-purity fine powder having a sharp particle size distribution with almost no aggregated particles.
なお、酸素の測定はインパルス加熱−赤外線吸収法
（LECO社TC−436型酸素窒素同時分析装置）、金属イオ
ンの測定はICP発光分光法（島津製作所カントレットGQM
−75）、粒径分布の測定はセディグラフ（Micromeritic
s社Sedi Graph 5000ET）、カサ密度およびタップ密度の
測定はJIS H−1902に基づきそれぞれ行った。また以後
の実施例および比較例の各々の測定も同様とした。The measurement of oxygen was performed by impulse heating-infrared absorption method (LECO TC-436 oxygen-nitrogen simultaneous analyzer), and the measurement of metal ions was performed by ICP emission spectroscopy (Cantlet GQM, Shimadzu Corporation)
-75), particle size distribution is measured by a Sedigraph (Micromeritic
s company Sedi Graph 5000ET), bulk density and tap density were measured based on JIS H-1902, respectively. The same measurement was performed for each of the following examples and comparative examples.
この粉末に焼結助剤としてCaO換算１重量％の炭酸カ
ルシウムおよび３重量％の酸化イットリウムを添加し
て、1500kg/cm2でプレス成形した後、成形体を窒化アル
ミニウムと窒化ホウ素の混合粉末に埋め、窒素雰囲気中
で1850℃に３時間常圧で焼結した。成形体の相対密度は
58.5％と大きく焼結時の収縮率は16％と小さい値を示し
た。また、得られた焼結体は気孔のない焼結体で、その
熱伝導度は200W/mKと高い値を示した。After adding 1% by weight of calcium carbonate in terms of CaO and 3% by weight of yttrium oxide as a sintering aid to the powder and press-molding at 1500 kg / cm 2 , the compact was formed into a mixed powder of aluminum nitride and boron nitride. It was filled and sintered at 1850 ° C. for 3 hours at normal pressure in a nitrogen atmosphere. The relative density of the compact is
The shrinkage ratio during sintering was as large as 58.5% and as small as 16%. The obtained sintered body had no pores, and its thermal conductivity was as high as 200 W / mK.
なお、熱伝導度の測定はレーザーフラッシュ法（真空
理工TC−7000）に基づき行った。また以後の実施例およ
び比較例の測定も同様とした。The measurement of the thermal conductivity was performed based on the laser flash method (Vacuum Riko TC-7000). The same applies to the measurements in the following Examples and Comparative Examples.
実施例２ アルミナ原料として純度99.7％、中心粒径0.6μｍ、
１μｍ以下80％のバイヤー法による普通アルミナ粉末を
用いた以外は実施例１と同様にして還元窒化反応を行
い、窒化アルミニウム粉末とカーボン粉末とから成る反
応生成物を得た。次いでこの反応生成物を乾燥空気中に
て700℃で３時間加熱して余剰カーボンを燃焼除去して
窒化アルミニウム粉末を得た。この窒化アルミニウム粉
末150gを２ポリエチレン製ポットにとり直径15mmのア
ルミナ製ボール2.5kgとメタノール1.5gを加え、乾燥空
気でポット内を十分置換した後、60rpmの回転速度で３
時間乾式ボールミル粉砕を行った。Example 2 As an alumina raw material, the purity was 99.7%, the central particle diameter was 0.6 μm,
A reduction nitridation reaction was carried out in the same manner as in Example 1 except that a normal alumina powder of 1% or less and 80% by a Bayer method was used to obtain a reaction product comprising an aluminum nitride powder and a carbon powder. Next, the reaction product was heated in dry air at 700 ° C. for 3 hours to burn off excess carbon to obtain aluminum nitride powder. 150 g of this aluminum nitride powder was placed in a 2 polyethylene pot, 2.5 kg of alumina balls having a diameter of 15 mm and 1.5 g of methanol were added, and the inside of the pot was sufficiently replaced with dry air.
Dry ball mill grinding was performed for hours.
この窒化アルミニウム粉末の諸物性を第１表に示す。
この粉末は凝集粒の殆どない粒径分布のシャープな高純
度微粉末であった。Table 1 shows the physical properties of this aluminum nitride powder.
This powder was a high-purity fine powder having a sharp particle size distribution with almost no aggregated particles.
得られた粉末を実施例１と同様の方法で成形焼結した
ところ、成形体の相対密度は59％と大きく、焼結時の収
縮率は16％と小さい値を示した。また、得られた焼結体
の熱伝導度は205W/mKと高い値を示した。When the obtained powder was compacted and sintered in the same manner as in Example 1, the relative density of the compact was as large as 59% and the shrinkage ratio during sintering was as small as 16%. The thermal conductivity of the obtained sintered body was as high as 205 W / mK.
比較例 純度99.9％、セディグラフによる中心粒径0.7μｍ、
１μｍ以下80％の低ソーダアルミナ粉末306gと灰分0.00
5％のアセチレンブラック100％プレス品216gおよび硝酸
アルミニウム［Al（NO3）３・9H2O］11.3g、ポリエチレ
ングリコール5.2gおよびポリオキシエチレンアルキルフ
ェニルエーテルからなるノニオン系界面活性剤（第一工
業薬品（株）製ノイゲンEA137）15.1gを溶解したイオン
交換水2600gを、直径15mmのナイロンボール600個と共に
ポリエチレン製のポットに入れ40rpmの回転速度で10時
間湿式混合を行った。Comparative Example Purity 99.9%, center particle size 0.7 μm by Cedigraph,
306g of 80% low soda alumina powder of 1% or less and ash content of 0.00
Nonionic surfactant consisting of 216 g of 5% acetylene black 100% pressed product, 11.3 g of aluminum nitrate [Al (NO 3 ) 3 .9H 2 O], 5.2 g of polyethylene glycol and polyoxyethylene alkylphenyl ether (Daiichi Kogyo) 2600 g of ion-exchanged water in which 15.1 g of Neugen EA137 (produced by Yakuhin Co., Ltd.) were dissolved was placed in a polyethylene pot together with 600 nylon balls having a diameter of 15 mm, and wet-mixed at a rotation speed of 40 rpm for 10 hours.
このようにして得られた混合スラリーを乾燥器で乾燥
させた後、その500gをグラファイト製トレイに採取し、
電気炉を用いて200cm/min.の速度で窒素ガスを流しなが
ら1580℃で７時間加熱し、還元窒化反応を行った。次い
でこの反応生成物を乾燥空気中にて700℃で３時間加熱
して余剰カーボンを燃焼除去して窒化アルミニウム粉末
を得た。この窒化アルミニウム粉末の諸物性を第１表に
示す。この粉末は凝集粒が若干存在する高純度微粉末で
あった。After drying the thus obtained mixed slurry in a dryer, 500 g of the mixed slurry was collected on a graphite tray,
The mixture was heated at 1580 ° C. for 7 hours while flowing a nitrogen gas at a speed of 200 cm / min. Using an electric furnace to perform a reductive nitridation reaction. Next, the reaction product was heated in dry air at 700 ° C. for 3 hours to burn off excess carbon to obtain aluminum nitride powder. Table 1 shows the physical properties of this aluminum nitride powder. This powder was a high-purity fine powder having some aggregated particles.
得られた粉末を実施例１と同様の方法で成形焼結した
ところ、成形体の相対密度は52％であり、焼結時の収縮
率は20％と大きく収縮した。また、得られた焼結体の熱
伝導度は195W/mKであった。When the obtained powder was molded and sintered in the same manner as in Example 1, the relative density of the molded body was 52%, and the shrinkage during sintering was as large as 20%. The thermal conductivity of the obtained sintered body was 195 W / mK.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村上 秀明 愛媛県新居浜市惣開町５番１号 住友化 学工業株式会社内 (56)参考文献 特開 昭63−242909（ＪＰ，Ａ) 特開 昭62−241814（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Hideaki Murakami 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Industries, Ltd. (56) References JP-A-63-242909 (JP, A) JP-A Sho 62-241814 (JP, A)
Claims (3)
雰囲気中で加熱反応させて得られた窒化アルミニウム粉
末において、酸素2.0重量％以下、鉄20ppm以下、珪素10
0ppm以下およびチタン20ppm以下を含有する窒化アルミ
ニウム粉末であって、タップ密度が1.0g/cm3以上からな
る窒化アルミニウム粉末。An aluminum nitride powder obtained by heating and reacting a mixture of alumina and carbon in an atmosphere containing nitrogen contains 2.0% by weight or less of oxygen, 20 ppm or less of iron,
An aluminum nitride powder containing 0 ppm or less and titanium of 20 ppm or less, wherein the tap density is 1.0 g / cm 3 or more.
素を含む雰囲気中で加熱して得られた反応生成物を粉砕
した後、余剰のカーボン粉末を空気中で燃焼除去するこ
とを特徴とする窒化アルミニウム粉末の製造方法。2. A nitriding method comprising heating a mixture of alumina powder and carbon powder in an atmosphere containing nitrogen, pulverizing a reaction product obtained, and burning off excess carbon powder in air. Manufacturing method of aluminum powder.
素を含む雰囲気中で加熱反応させた後、余剰のカーボン
粉末を空気中で燃焼除去して得られた窒化アルミニウム
粉末を粉砕することを特徴とする窒化アルミニウム粉末
の製造方法。3. An aluminum nitride powder obtained by heating and reacting a mixture of alumina powder and carbon powder in an atmosphere containing nitrogen and then burning and removing excess carbon powder in air. Of producing aluminum nitride powder.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252774A JP2730086B2 (en) | 1988-10-05 | 1988-10-05 | Aluminum nitride powder and method for producing the same |
| US07/417,104 US5049367A (en) | 1988-10-05 | 1989-10-04 | Aluminum nitride powder and process for preparation of the same |
| DE89310205T DE68907868T2 (en) | 1988-10-05 | 1989-10-05 | Production of aluminum nitride powder by carboreductive nitriding. |
| EP89310205A EP0372691B1 (en) | 1988-10-05 | 1989-10-05 | Production of aluminium nitride powder by carboreductive nitridation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252774A JP2730086B2 (en) | 1988-10-05 | 1988-10-05 | Aluminum nitride powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02102109A JPH02102109A (en) | 1990-04-13 |
| JP2730086B2 true JP2730086B2 (en) | 1998-03-25 |
Family
ID=17242102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63252774A Expired - Fee Related JP2730086B2 (en) | 1988-10-05 | 1988-10-05 | Aluminum nitride powder and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2730086B2 (en) |
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|---|---|---|---|---|
| JP5877684B2 (en) * | 2011-10-21 | 2016-03-08 | 株式会社トクヤマ | Method for producing aluminum nitride sintered granules |
| JP7129892B2 (en) * | 2018-11-29 | 2022-09-02 | 株式会社トクヤマ | aluminum nitride powder |
| KR20220138379A (en) | 2020-02-10 | 2022-10-12 | 가부시끼가이샤 도꾸야마 | Aluminum nitride powder and manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0651561B2 (en) * | 1986-04-11 | 1994-07-06 | 住友電気工業株式会社 | Aluminum nitride powder |
| JPS63242909A (en) * | 1987-03-31 | 1988-10-07 | Nippon Light Metal Co Ltd | Production of aluminum nitride powder |
| JPS63225507A (en) * | 1987-03-16 | 1988-09-20 | Toyo Alum Kk | Aluminum nitride powder |
-
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- 1988-10-05 JP JP63252774A patent/JP2730086B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02102109A (en) | 1990-04-13 |
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