JPS6330307A - Production of aluminum nitride - Google Patents
Production of aluminum nitrideInfo
- Publication number
- JPS6330307A JPS6330307A JP17460286A JP17460286A JPS6330307A JP S6330307 A JPS6330307 A JP S6330307A JP 17460286 A JP17460286 A JP 17460286A JP 17460286 A JP17460286 A JP 17460286A JP S6330307 A JPS6330307 A JP S6330307A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum hydroxide
- substance
- aluminum
- residual carbon
- heated
- 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
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 28
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 229920000620 organic polymer Polymers 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 239000005011 phenolic resin Substances 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 5
- -1 aluminum alkoxide Chemical class 0.000 abstract description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000005121 nitriding Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011134 resol-type phenolic resin Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、窒化アルミニウム（以下ｒＡＪ２ＮＪと記す
、）の製造方法に係り、特に高い反応効率で、高結晶性
の微粉体状ＡｊＺＮ粉体を製造する方法に関するもので
ある。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing aluminum nitride (hereinafter referred to as rAJ2NJ). It relates to a manufacturing method.
［従来の技術］
ＡＩＮは１８６０年代に初めて合成された物質であり、
ウルツ鉱型六方晶系に属し、約２５００℃で昇華分解す
る。通常、絶縁体の熱伝導率は自由フォノン伝導に依存
することから、このような共存結合性が強いウルツ鉱型
結晶構造をもつＡＩＮは、理論的に良好な高温熱伝導体
であるとして期待され、その無毒性や、高周波特性など
の点からも、ベリリヤやアルミナに代わるものとして今
後の発展が強く望まれている。[Prior art] AIN is a substance that was first synthesized in the 1860s.
It belongs to the wurtzite hexagonal crystal system and decomposes by sublimation at about 2500℃. Normally, the thermal conductivity of an insulator depends on free phonon conduction, so AIN, which has a wurtzite crystal structure with strong coexistence, is theoretically expected to be a good high-temperature thermal conductor. Due to its non-toxicity and high frequency properties, its future development as an alternative to beryllia and alumina is strongly desired.
ＡｕＮの焼結体は、耐熱性、耐食性、高温熱伝導性、耐
熱衝撃性、絶縁性及び比較的高い強度を有しているため
、高放熱基板、各種ヒートシンク材等の電子工業材料、
溶融金属用温材、真空蒸着用容器など、工業的に幅広い
分野でその応用、発展が大いに望まれている。AuN sintered bodies have heat resistance, corrosion resistance, high-temperature thermal conductivity, thermal shock resistance, insulation properties, and relatively high strength, so they can be used as electronic industry materials such as high heat dissipation boards and various heat sink materials.
Its application and development are highly desired in a wide range of industrial fields, such as heating materials for molten metals and containers for vacuum evaporation.
ところで、ＡＩＮは、ＳｉＣや５ｉａＮ＋と同様に共有
結合性の高い物質であり、難焼結性であることから、良
好な焼結体が得難いという欠点を有しているが、ＡｕＮ
の焼結性やその特、性の向上には、焼結するＡＩＮ粉体
の性質の改良に負うところが大きい。By the way, like SiC and 5iaN+, AIN is a substance with high covalent bonding properties and is difficult to sinter, so it has the disadvantage that it is difficult to obtain a good sintered body.
Improvements in the sinterability and properties of AIN are largely due to improvements in the properties of the AIN powder to be sintered.
従来、Ａｊ２Ｎの合成方法は、大きく分けて次の４通り
の方法が知られている。Conventionally, the following four methods are known for synthesizing Aj2N.
■ アルミナ（ＡｆＬ２０ｇ ）の窒素中での炭素によ
る還元反応
■ 金属アルミニウムと窒素あるいはアンモニアとの反
応
■ アルミニウムのアンモニウム化合物の熱分解反応
■ アルミニウム化合物とアンモニアの反応これらの方
法のうち、特に■の方法については種々検討がなされて
おり、多くの特許が提案されている。■ Reduction reaction of alumina (AfL20g) with carbon in nitrogen ■ Reaction of metallic aluminum with nitrogen or ammonia ■ Thermal decomposition reaction of ammonium compounds of aluminum ■ Reaction of aluminum compounds with ammonia Among these methods, especially method (■) Various studies have been made regarding this, and many patents have been proposed.
［発明が解決しようとする間′照点］
しかしながら、一般に、上記■のような窒化反応を効率
良く行なわせることは難しく、通常、未反応アルミナが
残存してしまう。この解決策として、例えば特開昭５９
−５０００８にみられるように、アルミナに対し炭素を
化学量論比以上に添加する方法が提案されているが、こ
の場合には、反応後、余剰炭素除去のために空気中で加
熱処理が必要となる。[Points to be solved by the invention] However, it is generally difficult to carry out the nitriding reaction as described in (2) efficiently, and unreacted alumina usually remains. As a solution to this problem, for example,
-50008, a method has been proposed in which carbon is added to alumina at a higher than stoichiometric ratio, but in this case, heat treatment in air is required to remove excess carbon after the reaction. becomes.
また、■の還元窒化反応は、１５００℃以上という高温
が必要である上に、得られる粉体も粉砕しなければ数μ
ｍ以下にならず、そのために焼結に悪影響を及ぼす不純
物や酸素の混入が避けられないという欠点も有している
。この欠点を軽減するものとして、特開昭５９−５００
０８にあるように反応原料として特別なアルミナ及び炭
素粒子を用いたり、特開昭６０−６０９１０などのよう
に、液体分散媒を用いて原料を混合するなどの方策が提
案されているが、十分な効果が得られていない。In addition, the reductive nitriding reaction (①) requires a high temperature of 1,500°C or higher, and the resulting powder must be crushed by several microns.
It also has the disadvantage that it cannot be reduced to less than m, and as a result, the contamination of impurities and oxygen, which have an adverse effect on sintering, is unavoidable. To alleviate this drawback, JP-A-59-500
Measures have been proposed, such as using special alumina and carbon particles as reaction raw materials as in 2008, and mixing raw materials using a liquid dispersion medium as in JP-A-60-60910. No effect has been obtained.
一方、■の反応の応用として、アルミナの代わりに水酸
化アルミニウムを出発原料として用いる合成方法が既に
特公昭５９−５１４８３に記載されており、この方法に
おいては、炭素質としてはカーボンブラック、オイルコ
ークス、グラファイトの粉末が用いられている。この方
法では、ＡｆＬとＣとの比によって、例えば化学量論比
付近においても、窒化反応副生成物が多種多様に生成す
るという問題がある。On the other hand, as an application of the reaction (2), a synthesis method using aluminum hydroxide as a starting material instead of alumina has already been described in Japanese Patent Publication No. 51483/1983. , graphite powder is used. This method has a problem in that a wide variety of nitriding reaction by-products are generated depending on the ratio of AfL and C, even when the ratio is near the stoichiometric ratio.
このように、従来のＡ℃Ｎ製造技術では様々な問題点が
あるために、製造されたＡｉＮ粉体から得られるＡｆＬ
Ｎ焼結体はＡｉＮ焼結体本来の十分な性能を示さないも
のとなる。As described above, there are various problems with the conventional A℃N manufacturing technology, so the AfL obtained from the manufactured AiN powder
The N sintered body does not exhibit the sufficient performance inherent to the AiN sintered body.
［問題点を解決するための手段］
本発明は上記従来法の欠点を、製造プロセスに新しい概
念を導入することにより取り除き、より低温かつ短時間
の加熱で、焼結性の良好なＡｆＮ微粉体を製造する方法
を提供するものであって、水酸化アルミニウム又は水酸
化アルミニウムを生成する物質と、残炭率の高い有機物
質とを含む混合物を炭化処理した後、窒素元素を含む雰
囲気中で加熱することを特徴とする窒化アルミニウムの
製造方法、
を要旨とするものである。[Means for Solving the Problems] The present invention eliminates the drawbacks of the above-mentioned conventional methods by introducing a new concept to the manufacturing process, and produces AfN fine powder with good sinterability by heating at a lower temperature and in a shorter time. Provides a method for producing aluminum hydroxide, which comprises carbonizing a mixture containing aluminum hydroxide or a substance that produces aluminum hydroxide and an organic substance with a high residual carbon content, and then heating it in an atmosphere containing nitrogen element. A method for producing aluminum nitride, characterized by:
即ち、本発明者らは、前述の従来の合成方法をもとに鋭
意検討を重ねた結果、ＡＪ：ＬＮ微粉体を効率的かつ高
純度で低温合成するためには、反応系にアルミニウムを
含む原料と炭素質原料とが高い均一性のもとに存在する
必要があるという結論に達し、そのためには、分子レベ
ルの混合状態に近い状態で混合されていることが不可欠
であると確信するに到った。しかして、更に研究を行な
った結果、炭素質原料として残炭率の高い有機物質を、
また、アルミニウム源として水酸化アルミニウムあるい
は水酸化アルミニウムを生成する物質を用い、両者が均
一に混合されることにより、このような混合状態が得ら
れることを見出し、本発明を完成させた。That is, as a result of intensive studies based on the conventional synthesis method described above, the present inventors found that in order to synthesize AJ:LN fine powder efficiently and with high purity at a low temperature, it is necessary to include aluminum in the reaction system. We have come to the conclusion that the raw material and the carbonaceous raw material need to exist in a highly homogeneous state, and are convinced that to achieve this, it is essential that they be mixed in a state close to that at the molecular level. It has arrived. However, as a result of further research, we found that organic materials with a high residual carbon content were used as carbonaceous raw materials.
Furthermore, the inventors have discovered that such a mixed state can be obtained by using aluminum hydroxide or a substance that generates aluminum hydroxide as an aluminum source and uniformly mixing the two, thereby completing the present invention.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において、アルミニウム源として用いられる水酸
化アルミニウムは、反応効率の点から、その平均粒径は
８０μｍ以下であることが望ましく、更に好ましくは平
均粒径が２５μｍ以下の粉体であることが望ましい、こ
の平均粒径に関しては小さければ小さいほど、本発明の
目的を達成するのを容島にする。従って、水酸化アルミ
ニウムは、特に粒径１０μｍ以下の微粉を用いるのが好
ましい。In the present invention, from the viewpoint of reaction efficiency, the aluminum hydroxide used as the aluminum source preferably has an average particle size of 80 μm or less, more preferably a powder with an average particle size of 25 μm or less. The smaller the average particle size, the easier it is to achieve the object of the present invention. Therefore, it is particularly preferable to use fine powder of aluminum hydroxide with a particle size of 10 μm or less.
上記のような水酸化アルミニウム粉末以外にも水酸化ア
ルミニウムを生成する物質を用いても良く、例えばこの
ような物質としては、アルミニウムアルコキシドのよう
に加水分解によって水酸化アルミニウムを生成する物質
等が挙げられる。In addition to the above-mentioned aluminum hydroxide powder, a substance that generates aluminum hydroxide may be used. Examples of such substances include substances that generate aluminum hydroxide through hydrolysis, such as aluminum alkoxide. It will be done.
一方、残炭率の高い有機物質としては、非酸化性雰囲気
下で加熱したときに炭素を生成するものであればよく、
特に制限はないが、好ましくは、非酸化性雰囲気下、８
００℃で３０分加熱したときの残炭率が２０重量％以上
の有機高分子が好適である。このような高分子としては
、例えば、フェノール樹脂、ポリイソシアネート、フラ
ン樹脂、メラミン樹脂等を挙げることができるが、作業
性の点からは、フェノール樹脂が望ましい。On the other hand, organic substances with a high residual carbon content may be those that generate carbon when heated in a non-oxidizing atmosphere.
There is no particular restriction, but preferably under a non-oxidizing atmosphere.
An organic polymer having a residual carbon content of 20% by weight or more when heated at 00° C. for 30 minutes is suitable. Examples of such polymers include phenol resins, polyisocyanates, furan resins, and melamine resins, but phenol resins are preferred from the viewpoint of workability.
フェノール樹脂としては、レゾール型フェノール樹脂あ
るいはノボラック型フェノール樹脂等が採用し得るが、
これに限定されるものではない。また、その形態として
は、比較的低分子量の液状物から高分子量の粉体、粒状
物まで、いずれの形態のものをも用いることができる。As the phenol resin, resol type phenol resin or novolak type phenol resin can be adopted, but
It is not limited to this. Moreover, any form can be used, from relatively low molecular weight liquids to high molecular weight powders and granules.
なお、本発明においては、炭素質原料として、これらの
残炭率の高い有機物質と共に粉末状炭素を併用すること
もできる。In addition, in the present invention, powdered carbon can also be used together with these organic substances having a high residual carbon content as the carbonaceous raw material.
アルミニウム源の水酸化アルミニウム又は水酸化アルミ
ニウムを生成する物質と、炭素質原料の残炭率の高い有
機物質との混合比は、炭素質原料の有機物質を非酸化性
雰囲気中で８００℃、３０分加熱することにより残存す
る炭素量とアルミニウム源のアルミニウムとの比、ＡＩ
Ｌ／Ｃモル比で決定される。即ち、通常、アルミナとカ
ーボンにより理想的に反応が進行した場合にはＡ ｆＬ
／Ｃのモル比は２／３となる０反応は、この化学量論比
付近で行なうことが経済上好ましいが、Ａ１１ｌＣ比が
大きいところでは副生成物であるアルミナが生成する可
能性があり、また、この比が小さい場合には、残存する
炭素の脱炭処理に時間がかかり好ましくない、ゆえに、
Ａｎ／Ｃモル比は、０．２＜Ａｎ／Ｃ＜０．８の範囲内
、特に脱炭処理を行なわない場合には、０．６＜ＡＩｔ
／Ｃ＜０．８の範囲内となるように、各原料を混合する
のが好ましい。しかし、これらの比に関しては、生成す
るＡＪＺＮの性能を損なわない限り、任意に選択するこ
とが可能であり、本発明においては特に制限されるもの
ではない。The mixing ratio of aluminum hydroxide as an aluminum source or a substance that generates aluminum hydroxide and an organic substance with a high residual carbon content as a carbonaceous raw material is as follows: The ratio of the amount of carbon remaining by heating for 30 minutes to the aluminum of the aluminum source, AI
It is determined by the L/C molar ratio. That is, normally, when the reaction progresses ideally between alumina and carbon, A fL
It is economically preferable to carry out the 0 reaction in which the molar ratio of /C is 2/3 near this stoichiometric ratio, but where the A11lC ratio is large, there is a possibility that alumina as a by-product will be produced. Also, if this ratio is small, it takes a long time to decarburize the remaining carbon, which is undesirable.
The An/C molar ratio is within the range of 0.2<An/C<0.8, especially when no decarburization treatment is performed, 0.6<AIt.
It is preferable to mix each raw material so that /C<0.8. However, these ratios can be arbitrarily selected as long as they do not impair the performance of the produced AJZN, and are not particularly limited in the present invention.
本発明においては、アルミニウム源の水酸化アルミニウ
ム又は水酸化アルミニウムを生成する物質と、炭素質原
料の残炭率の高い有機物質とを含む混合物を調製してこ
れを炭化処理するにあたっては、この混合物を固化して
おくことが好ましく、このために、有機物質を硬化させ
るための硬化触媒を同時に混合使用するのが好ましい、
硬化触媒としては、例えば炭素質原料がレゾール型フェ
ノール樹脂の場合には、塩酸、硫酸等の無機酸、又は、
トルエンスルフォン酸等の有機酸等が使用でき、また、
ノボラック型フェノール樹脂の場合には、アルカリ系触
媒、アンモニア、アミン等が使用できる。In the present invention, when preparing and carbonizing a mixture containing aluminum hydroxide as an aluminum source or a substance that generates aluminum hydroxide and an organic substance with a high residual carbon content as a carbonaceous raw material, this mixture is It is preferable to solidify the organic substance, and for this purpose, it is preferable to simultaneously use a curing catalyst for curing the organic substance.
As a curing catalyst, for example, when the carbonaceous raw material is a resol type phenolic resin, an inorganic acid such as hydrochloric acid or sulfuric acid, or
Organic acids such as toluenesulfonic acid can be used, and
In the case of novolac type phenolic resin, alkaline catalysts, ammonia, amines, etc. can be used.
即ち、本発明の好適な実施方法においては、必要に応じ
てこれらの硬化触媒と前述の如きアルミニウム源及び炭
素質原料とを混合、好ましくは極めて十分に攪拌混合し
、必要に応じて加熱することにより、混合物中の有機物
質を均一に固化させて固形物とする。この場合、より高
度な混合のためには、回転するロール間において強い剪
断力をかける方法を採用することもできる。また、後の
還元窒化反応を妨げない限りにおいては、原料物質の混
合均一性向上のために界面活性剤を添加する方法も採用
し得る。That is, in a preferred method of carrying out the present invention, these curing catalysts are mixed with the aluminum source and carbonaceous raw material as described above, preferably thoroughly stirred and mixed, and heated as necessary. The organic substance in the mixture is uniformly solidified into a solid substance. In this case, for more advanced mixing, a method of applying strong shearing force between rotating rolls may be adopted. Furthermore, a method of adding a surfactant to improve the mixing uniformity of the raw materials may be adopted as long as it does not interfere with the subsequent reduction-nitridation reaction.
このようにして得られた混合物の固形物は、非酸化性雰
囲気中、例えば窒素、アルゴン、ヘリウム雰囲気中で、
５００℃以上、望ましくはａＯＯ℃以上１２００℃以下
の温度で加熱することにより、炭素質成分を炭化させる
。The solid mixture thus obtained can be prepared in a non-oxidizing atmosphere, e.g. nitrogen, argon, helium atmosphere.
The carbonaceous component is carbonized by heating at a temperature of 500°C or higher, preferably aOO°C or higher and 1200°C or lower.
炭化処理により得られた炭化物前駆体は、更に窒素元素
を含む雰囲気、たとえば窒素、アンモニア等の雰囲気中
で、好ましくは１４００〜１８００℃において加熱焼成
する。The carbide precursor obtained by the carbonization treatment is further heated and calcined in an atmosphere containing a nitrogen element, such as an atmosphere of nitrogen, ammonia, etc., preferably at 1400 to 1800°C.
このような本発明の方法によれば、比較的低温加熱にて
、ＡｆＬＮ微粉体を高反応効率で製造することが可能で
ある。According to the method of the present invention, it is possible to produce AfLN fine powder with high reaction efficiency by heating at a relatively low temperature.
［作用］
本発明のＡＪ２Ｎの製造方法では、原料物置として、化
学反応可能な官能基を有する原料の均一混合物を炭化し
て得られた物質を用いているために、アルミナとカーボ
ンあるいは水酸化アルミニウムとカーボンを用いる従来
法には見られない、非常に高度で均一な還元窒化反応が
生起し、その反応をより低温で進行させることを可能と
する。[Function] In the AJ2N manufacturing method of the present invention, since a material obtained by carbonizing a homogeneous mixture of raw materials having functional groups capable of chemical reaction is used as a raw material storeroom, alumina and carbon or aluminum hydroxide are used. A highly uniform reduction-nitridation reaction occurs, which is not seen in conventional methods using carbon and carbon, and allows the reaction to proceed at lower temperatures.
即ち、本発明で用いる原料は、アルミニウム酸化物を還
元するための炭素が分子レベルでアルミニウム酸化物と
均一に接し、このため、アルミニウム酸化物の還元及び
窒素分子による極めて効率的な窒化反応を容易に生起す
ることが可能となるのである。That is, in the raw material used in the present invention, carbon for reducing aluminum oxide is in uniform contact with aluminum oxide at the molecular level, which facilitates the reduction of aluminum oxide and the extremely efficient nitriding reaction by nitrogen molecules. It becomes possible for this to occur.
このように効率的な炭素還元及び窒化が行なわれること
により、高純度かつ高結晶性の微粒ＡＪＺＮ粉体をより
低温度で得ることが可能とされる。By performing efficient carbon reduction and nitriding in this manner, it is possible to obtain fine grain AJZN powder with high purity and high crystallinity at a lower temperature.
更に、本発明においては、従来不可能であった化学量論
比での反応を行なわせることも可能であり、後に続く脱
炭処理を省略することができる。Furthermore, in the present invention, it is also possible to perform the reaction at a stoichiometric ratio, which was previously impossible, and the subsequent decarburization treatment can be omitted.
［実施例］
次に実施例及び比較例を挙げて本発明をより具体的に説
明するが、本発明はその要旨を超えない限り以下の実施
例に限定されるものではない。[Examples] Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例１
水酸化アルミニウム（平均粒径１．０μｍ）４０．０ｇ
とレゾール型フェノール樹脂１８．４８ｇを混合し、ト
ルエンスルフォン酸を硬化剤として４．６２ｇを加えて
、３本ロールを用いてよく混合し硬化反応を行なった。Example 1 Aluminum hydroxide (average particle size 1.0 μm) 40.0 g
and 18.48 g of resol type phenolic resin were mixed, 4.62 g of toluenesulfonic acid was added as a curing agent, and the mixture was thoroughly mixed using a three-roll roll to perform a curing reaction.
得られた固体を、窒素雰囲気下、３℃／ｍｉｎ、で８０
０℃まで昇温しな。この操作により上記固体は固化され
黒色化した。The obtained solid was heated at 80°C at 3°C/min under a nitrogen atmosphere.
Do not raise the temperature to 0℃. Through this operation, the solid solidified and turned black.
得られた炭化物前駆体を、窒素雰囲気中（流量４４２／
ｍ１ｎ）、１４００℃まで６℃／ ｍ ｉ ｎで昇温し
、１４００℃で２時間保持した（還元窒化反応）後、冷
却して取り出しサンプルとした。The obtained carbide precursor was heated in a nitrogen atmosphere (flow rate 442/
m1n), the temperature was raised to 1400°C at a rate of 6°C/min, held at 1400°C for 2 hours (reduction nitridation reaction), and then cooled and taken out to be used as a sample.
サンプルのＸ線回折分析の結果、ＡｕＮのピークが鋭く
検出され、そのプロフィールは、ＪＣＰＤＳカード２５
−１１３３に記載されているＡｌＮの回折線の位置、強
度とも良い一致がみられた。なお、このサンプルのＡｆ
Ｈの強度比、色は第１表に示す通りである。As a result of X-ray diffraction analysis of the sample, a sharp peak of AuN was detected, and its profile was determined according to JCPDS card 25.
A good agreement was observed with the position and intensity of the AlN diffraction line described in -1133. In addition, Af of this sample
The intensity ratio and color of H are as shown in Table 1.
ところで、水酸化アルミニウムを同様の方法で１４００
℃に加熱するとα−Ａｆｔ２０３となるが、本例では、
炭化物前駆体、焼成したサンプルのどちらにおいてもα
−ＡｆＬ２０３に相当するピークは全く検出されなかっ
た。また、水酸化アルミニウムのピークが、炭化物前駆
体において検出されなかフたことから、炭化物前駆体中
においてアルミニウム酸化物は均一に分散し、結晶状態
゛では存在しないものと判断される。By the way, aluminum hydroxide was prepared in a similar manner to 1400
When heated to ℃, it becomes α-Aft203, but in this example,
α in both the carbide precursor and the calcined sample
-No peak corresponding to AfL203 was detected. Further, since no peak of aluminum hydroxide was detected in the carbide precursor, it was determined that aluminum oxide was uniformly dispersed in the carbide precursor and did not exist in a crystalline state.
また、焼成したサンプルを電子顕微鏡で観察したところ
、平均粒径０．５μｍ以下の非常に微細な粒子からなる
均一微粉体であることが認められた。Furthermore, when the fired sample was observed under an electron microscope, it was found to be a uniform fine powder consisting of very fine particles with an average particle size of 0.5 μm or less.
比較例１
アルミナ（平均粒径０．４μｍ）とカーボン（灰分０．
２％、平均粒径７２ｎｍ）を揮発性有機液体中で良く混
合し、乾燥したものを、実施例１と同様に還元窒化反応
を行なった。Comparative Example 1 Alumina (average particle size 0.4 μm) and carbon (ash content 0.
2%, average particle size 72 nm) was mixed well in a volatile organic liquid, dried, and subjected to a reductive nitridation reaction in the same manner as in Example 1.
得られたサンプルのＸ線回折分析によると、主生成物は
アルミナで、その他にＡｌＮも生成したが、実施例１で
得られたサンプルのＡＪ２Ｎの最強線強度と比較すると
強度比は２１％であった。なお、このサンプルのＡＩＮ
強度比及び色は第１表に示す通りである。According to X-ray diffraction analysis of the obtained sample, the main product was alumina, and AlN was also produced, but the intensity ratio was 21% compared to the strongest line intensity of AJ2N of the sample obtained in Example 1. there were. In addition, this sample's AIN
Intensity ratios and colors are shown in Table 1.
比較例２
水酸化アルミニウム（平均粒径１．０μｍ）とカーボン
（灰分０．２％、平均粒径７２ｎｍ）を用いて、比較例
１と同様に還元窒化反応を行なった。Comparative Example 2 A reductive nitriding reaction was carried out in the same manner as in Comparative Example 1 using aluminum hydroxide (average particle size 1.0 μm) and carbon (ash content 0.2%, average particle size 72 nm).
得られたサンプルの分析によれば、やはり主生成物はア
ルミナで、ＡＪ２Ｎも生成したが、実施例１で得られた
サンプルと比較するとＡｉＮの最強線の強度比は１６％
であった。なお、このサンプルのＡ２Ｎ強度比及び色は
第１表に示す通りである。According to the analysis of the obtained sample, the main product was alumina, and AJ2N was also produced, but when compared with the sample obtained in Example 1, the intensity ratio of the strongest line of AiN was 16%.
Met. Note that the A2N intensity ratio and color of this sample are as shown in Table 1.
実施例２
水酸化アルミニウム（平均粒径ｉ、ｏμｍ）４０．０ｇ
とレゾール型フェノール樹脂１８．４８ｇを混合し、ト
ルエンスルフォン酸を硬化剤として４．６２ｇ加え、更
によく混合し硬化反応を行なった。Example 2 Aluminum hydroxide (average particle size i, oμm) 40.0g
and 18.48 g of resol type phenolic resin were mixed, 4.62 g of toluenesulfonic acid was added as a curing agent, and the mixture was further mixed well to perform a curing reaction.
得られた固体を、非酸化性雰囲気下、３℃／ｍｉｎで８
００℃まで昇温した。この操作により上記固体物は炭化
され黒色化した。The obtained solid was heated at 3°C/min in a non-oxidizing atmosphere at 8°C.
The temperature was raised to 00°C. Through this operation, the solid material was carbonized and turned black.
得られた炭化物前駆体を窒素雰囲気中（流量４４！／ｍ
１ｎ）、１０００℃まで７５℃／ｍｉｎで、更に１６０
０℃まで３０℃／ ｍ ｉ ｎで昇温した。１６００℃
で４時間保持した後、冷却して取り出してサンプルとし
た。The obtained carbide precursor was heated in a nitrogen atmosphere (flow rate 44!/m
1n), 75°C/min up to 1000°C, and further 160°C
The temperature was raised to 0°C at a rate of 30°C/min. 1600℃
After being held for 4 hours, it was cooled and taken out to be used as a sample.
このサンプルのＸ線回折分析結果を第１図に示す、第１
図より、得られたサンプルはＡＪｌＮ粉体であることが
明らかである。なお、このサンプルのＡλＮ強度比及び
色は第１表に示す通りである。The X-ray diffraction analysis results of this sample are shown in Figure 1.
From the figure, it is clear that the obtained sample is AJIN powder. Note that the AλN intensity ratio and color of this sample are as shown in Table 1.
また、焼成したサンプルを電子顕微鏡で観察すると、平
均粒径０．５μｍ以下の非常に微細な粒子からなりたっ
ていることがわかった。このサンプル粉体の走査型電子
顕微鏡写真を第２図に示す。Furthermore, when the fired sample was observed under an electron microscope, it was found that it was composed of very fine particles with an average particle size of 0.5 μm or less. A scanning electron micrograph of this sample powder is shown in FIG.
以上の結果を第１表にまとめて示す。The above results are summarized in Table 1.
第１表
※ Ａ４Ｎ強度比は、ＡｉＮ（１）Ｘ線回折ピーク（ｄ
＝２．６９５Ａ）１７）相対的強度比で簡易的に示しで
ある。Table 1* The A4N intensity ratio is based on the AiN(1) X-ray diffraction peak (d
=2.695A) 17) It is simply shown as a relative intensity ratio.
［発明の効果］
以上詳述した通り、本発明の窒化アルミニウムの製造方
法は、水酸化アルミニウムあるいは水酸化アルミニウム
を生成する物質を、加熱することにより炭素を生じる有
機物質と混合し、これを好ましくは硬化触媒により硬化
させ、炭化して得られた前駆体を原料とし、これを窒素
を含む雰囲気中で加熱焼成することにより窒化アルミニ
ウムを得る新規合成法であり、アルミニウム質と炭素質
を極めて高度に反応させることができる。[Effects of the Invention] As detailed above, the method for producing aluminum nitride of the present invention mixes aluminum hydroxide or a substance that generates aluminum hydroxide with an organic substance that generates carbon by heating, and preferably mixes this with an organic substance that generates carbon by heating. is a new synthesis method that obtains aluminum nitride by heating and sintering the precursor in a nitrogen-containing atmosphere, using a precursor obtained by curing with a curing catalyst and carbonizing it. can be reacted to.
このため、本発明によれば、より低温での反応の進行が
可能となり、高い収率で、副生成物であるアルミナを含
まない高純度かつ高結晶性の粉体を得ることができる。Therefore, according to the present invention, the reaction can proceed at a lower temperature, and a highly pure and highly crystalline powder containing no alumina, which is a by-product, can be obtained with a high yield.
しかも、得られる粉体は、非常に高度な微粉であり、Ａ
ｉＮ焼結体の製造にあたり、粉砕を必要としムい。従っ
て、各種用途の高特性ＡＪ２Ｎ焼結体用原料粉体として
極めて有用である。Moreover, the powder obtained is a very fine powder, and A
When producing an iN sintered body, pulverization is not necessary. Therefore, it is extremely useful as a raw material powder for high-performance AJ2N sintered bodies for various uses.
第１図は実施例２で得られたＡＩＬＮの粉末Ｘ線回折図
である。第２図はサンプル粉体の粒子構造を示す顕微鏡
写真である。
代理人 弁理士 重 野 剛第２図
１０μｍ
手続補正書
昭和６２年６月３日FIG. 1 is a powder X-ray diffraction diagram of AILN obtained in Example 2. FIG. 2 is a micrograph showing the particle structure of the sample powder. Agent Patent Attorney Tsuyoshi Shigeno Figure 2 10μm Procedural Amendment June 3, 1988
Claims (4)
成する物質と、残炭率の高い有機物質とを含む混合物を
炭化処理した後、窒素元素を含む雰囲気中で加熱するこ
とを特徴とする窒化アルミニウムの製造方法。(1) After carbonizing a mixture containing aluminum hydroxide or a substance that generates aluminum hydroxide and an organic substance with a high residual carbon content, aluminum nitride is heated in an atmosphere containing a nitrogen element. Production method.
する特許請求の範囲第１項に記載の窒化アルミニウムの
製造方法。(2) The method for producing aluminum nitride according to claim 1, wherein the mixture is carbonized after being solidified.
８００℃で３０分加熱したときの残炭率が２０重量％以
上の有機高分子であることを特徴とする特許請求の範囲
第１項又は第２項に記載の窒化アルミニウムの製造方法
。(3) A patent claim characterized in that the organic substance with a high residual carbon content is an organic polymer with a residual carbon content of 20% by weight or more when heated at 800°C for 30 minutes in a non-oxidizing atmosphere. A method for producing aluminum nitride according to scope 1 or 2.
許請求の範囲第１項ないし第３項のいずれか１項に記載
の窒化アルミニウムの製造方法。(4) The method for producing aluminum nitride according to any one of claims 1 to 3, characterized in that the mixture contains powdered carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174602A JP2564804B2 (en) | 1986-07-24 | 1986-07-24 | Method for manufacturing aluminum nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174602A JP2564804B2 (en) | 1986-07-24 | 1986-07-24 | Method for manufacturing aluminum nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6330307A true JPS6330307A (en) | 1988-02-09 |
| JP2564804B2 JP2564804B2 (en) | 1996-12-18 |
Family
ID=15981443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61174602A Expired - Lifetime JP2564804B2 (en) | 1986-07-24 | 1986-07-24 | Method for manufacturing aluminum nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2564804B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4985225A (en) * | 1987-10-26 | 1991-01-15 | Matsushita Electric Works, Ltd. | Process for producing aluminum nitride powders |
| JPH0323206A (en) * | 1989-06-20 | 1991-01-31 | Showa Denko Kk | Aluminum nitride powder and its production |
| US5221527A (en) * | 1990-06-30 | 1993-06-22 | Hoechst Aktiengesellschaft | Process for producing aluminum nitride |
-
1986
- 1986-07-24 JP JP61174602A patent/JP2564804B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4985225A (en) * | 1987-10-26 | 1991-01-15 | Matsushita Electric Works, Ltd. | Process for producing aluminum nitride powders |
| JPH0323206A (en) * | 1989-06-20 | 1991-01-31 | Showa Denko Kk | Aluminum nitride powder and its production |
| US5221527A (en) * | 1990-06-30 | 1993-06-22 | Hoechst Aktiengesellschaft | Process for producing aluminum nitride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2564804B2 (en) | 1996-12-18 |
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