JPS62283900A - Production of aln whisker - Google Patents
Production of aln whiskerInfo
- Publication number
- JPS62283900A JPS62283900A JP12561986A JP12561986A JPS62283900A JP S62283900 A JPS62283900 A JP S62283900A JP 12561986 A JP12561986 A JP 12561986A JP 12561986 A JP12561986 A JP 12561986A JP S62283900 A JPS62283900 A JP S62283900A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- carbon black
- transition metal
- fine powder
- mixed
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 150000002823 nitrates Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 13
- 150000003623 transition metal compounds Chemical class 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052593 corundum Inorganic materials 0.000 abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910002804 graphite Inorganic materials 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は、生成収率の高いＡｌＮウィスカーの製造方法
に関する。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing AlN whiskers with a high production yield.
Ａ Ｑ Ｎウィスカーの生成技術としては、以下の方法
が知られている。The following methods are known as techniques for generating AQN whiskers.
（１）昇華法
、Ａ Ｑ Ｎ粉末を黒鉛ルツボに入れて例えば水平型黒
鉛管状抵抗炉のような加熱炉にセントし、炉内をＮ２ガ
ス雰囲気に保ちながら２０００°Ｃ近傍の温度に加熱す
る。原料となる、へＱＮ粉末は１５５０〜１７００°Ｃ
の温度領域で急速に昇華再結晶し単結晶ウィスカーとし
てルツボ壁に生成付着する。(1) Sublimation method: A Q N powder is placed in a graphite crucible, placed in a heating furnace such as a horizontal graphite tubular resistance furnace, and heated to a temperature around 2000°C while maintaining an N2 gas atmosphere inside the furnace. . The raw material, HeQN powder, is heated to 1550-1700°C.
It rapidly sublimes and recrystallizes in the temperature range of 200 to 3000 mL, forming and adhering to the crucible wall as single crystal whiskers.
（２）金属ＡＱとＮ２による反応生成性金属ＡＱを黒鉛
ルツボに入れＮ２ガス雰囲気下で加熱処理することによ
りルツボ内部にＡＣＮウィスカーを生成する（ Ｐｏｒ
ｔｏｎ： ｅｔａｌ、 Ｐｏｒｏｓｈ。(2) Reaction produced by metal AQ and N2 ACN whiskers are generated inside the crucible by placing metal AQ in a graphite crucible and heat-treating it in an N2 gas atmosphere (Por
ton: etal, Porosh.
Ｍｅｔ、（ＵＳＳＲ）１０−５． １０（１９７０））
。Met, (USSR) 10-5. 10 (1970))
.
（３） Ａｌ２２０３． ＣおよびＮ、による反応生成
法ＡＱｔＯ３粉末を黒鉛ルツボに入れ、Ｎ、雰囲気に保
持した黒鉛抵抗炉中で２１００〜２２００℃に加熱し、
その後空気を導入して黒鉛ルツボを燃焼させてＡ＆Ｎウ
ィスカーを得る（ Ｋｏｈｎｅｔａｌ。(3) Al2203. Reaction production method using C and N AQtO3 powder was placed in a graphite crucible and heated to 2100-2200°C in a graphite resistance furnace maintained in an atmosphere of N.
Air is then introduced to combust the graphite crucible to obtain A&N whiskers (Kohnetal).
Ｍｉｎｅｒａｌｏｇｉｓｔ ４１．３５５（１９６５）
）。この方法はＮ２雰囲気下でＡｌ２ＯａをＣで還元す
る生成機構によるもので、下記の反応式に従うも％式％
〔発明が解決しようとする問題点〕
しかしながら、上記従来の方法による場合には粒状のＡ
ｆ２Ｎが多く生成し、Ａ１２Ｎウイスカーとしての生成
収率は良くない問題点があった。Mineralogist 41.355 (1965)
). This method relies on a generation mechanism in which Al2Oa is reduced with C in an N2 atmosphere, and although it follows the reaction formula below, the % formula % [Problems to be solved by the invention] However, when using the above conventional method, granular A
There was a problem that a large amount of f2N was produced and the yield of A12N whiskers was not good.
本発明は従来方法に比べ高収率で生成しえるＡＱ、Ｎウ
ィスカーの製造方法を提供するもので、その構成はＡＱ
ｔ０３微粉末を遷移金属化合物の溶液と混和したのち加
熱処理して液媒を蒸発除去し、処理後のＡσ２０３微粉
末にカーボンブラックを均質混合して嵩密度０．０５〜
Ｏ，１５ｙ／ｃｃの混合物を調製し、該混合物をＮ、ガ
ス流下の反応炉中で１６５０〜１８５０℃の温度に加熱
することを特徴とする。The present invention provides a method for producing AQ and N whiskers that can be produced in higher yield than conventional methods.
After mixing the t03 fine powder with a solution of a transition metal compound, heat treatment is performed to remove the liquid medium by evaporation, and after the treatment, carbon black is homogeneously mixed with the Aσ203 fine powder to give a bulk density of 0.05 to 0.05.
It is characterized in that a mixture of O, 15y/cc is prepared and the mixture is heated to a temperature of 1650-1850° C. in a reactor under a flow of N, gas.
ＡＱ源原料となるＡ（ｂｏｓとしては、粒径５０μ次以
下、望ましくは１〜３０μ屑の微粉末が用いられる。Ａ
＋２２０３微粉末は、まず遷移金属化合物の溶液と混和
する。As the AQ source material A (bos), a fine powder with a particle size of 50 μm or less, preferably 1 to 30 μm particles is used.
The +2203 fine powder is first mixed with a solution of the transition metal compound.
遷移金属化合物は触媒成分となるもので、水溶性の化合
物とくにＦｅ、Ｎｉ、Ｃｏの塩化物らしくは硝酸塩が有
効に用いられる。混和の手段としてはＡｌ２Ｏ３微粉末
を遷移金属化合物の溶液中に投入して攪拌する方法がと
らえるが、この際の溶液濃度はＡＬｏｔ微粉末に対する
遷移金属元素の量として０．５〜１０重量％になるよう
に調整する。The transition metal compound serves as a catalyst component, and water-soluble compounds, particularly chlorides of Fe, Ni, and Co, and nitrates are effectively used. A method of mixing may be to add fine Al2O3 powder into a solution of a transition metal compound and stir it, but the concentration of the solution at this time is 0.5 to 10% by weight as the amount of transition metal element relative to the fine ALot powder. Adjust accordingly.
この量が０．５％未満のときはウィスカー成長に有効作
用せずに粒状ＡＩ：／、Ｎの状態で残留する比率が増し
、他方、１０重量％を越える量はもはや結晶促進化に寄
与しなくなる。When this amount is less than 0.5%, it does not have an effective effect on whisker growth and the proportion of granular AI:/N increases, while when it exceeds 10% by weight, it no longer contributes to crystallization promotion. It disappears.
混和後の溶液は加熱処理して液媒を蒸発除去し、Ａｌ２
Ｏ３微粉末を触媒成分が表面に均一付着した状態で乾個
させる。After mixing, the solution is heated to remove the liquid medium by evaporation, and Al2
The O3 fine powder is dried with the catalyst component uniformly attached to the surface.
上記の処理を施したＡρ２０３微粉末は、還元材となる
カーボンブラックと混合する。カーボンブラックとして
は、窒素吸着比表面積４０ｍ”７９以上およびＤＢＰ吸
油量９０ ｍＱ／ １００ｇ以上の性状特性のものを選
択使用することが好ましい。カーボンブラックはコーク
ス扮、黒鉛粉のような通常の炭素質物とは異質の表面性
状と粒子構造を備えており、とくに窒素吸着比表面積が
４０ｔｔｔ”７ｇ以上の微細粒子径のものを用いるとＡ
ｈＯ３微粉末との接触面積が増大して還元反応が効果的
に進行し、またストラフチア−の指標となるＤＢＰ吸油
量が９０ｙ（！／１００９以上の粒子凝集構造をもつも
のはＡぐＮウィスカーの生成に好適な多孔性を具備して
おり、得られるウィスカーの性状ならびに収率の向上に
機能する。The Aρ203 fine powder subjected to the above treatment is mixed with carbon black as a reducing agent. As carbon black, it is preferable to select and use one with physical properties such as a nitrogen adsorption specific surface area of 40 m"79 or more and a DBP oil absorption of 90 mQ/100 g or more. Carbon black is a common carbonaceous material such as coke or graphite powder. It has a surface texture and particle structure that is different from that of A.
The contact area with hO3 fine powder increases and the reduction reaction progresses effectively, and the DBP oil absorption, which is an indicator of straphthiae, has a particle agglomeration structure of 90y (!/1009 or more). It has porosity suitable for whisker production, and functions to improve the properties and yield of the whiskers obtained.
カーボンブラックはＡｆ！ｚＯ３微粉末１００部に対し
１００〜２００部の比率で配合し、適宜なミキサーによ
り強攪拌して嵩密度０．０５〜０．１５ｙ／ｃｃの均一
混合物を調製する。この低嵩密度か針状結晶を発達させ
るに有効な成長空間を形成し、曲がり、技あるいは毛玉
等の異形物を含まないＡσＮウィスカーを生成するため
に動く。なお、混合物の嵩密度が０．０５ｙ／ｃｃを下
回る場合には、１回当りの反応処理量が減少するため生
産性の低下を招き好ましくない。Carbon black is Af! It is blended at a ratio of 100 to 200 parts to 100 parts of zO3 fine powder and stirred vigorously with an appropriate mixer to prepare a homogeneous mixture having a bulk density of 0.05 to 0.15 y/cc. This low bulk density creates an effective growth space for the development of needle-shaped crystals and moves to produce AσN whiskers that are free of irregularities such as bends, grains, or pilling. It should be noted that if the bulk density of the mixture is less than 0.05 y/cc, the amount of reaction processed per reaction decreases, which is undesirable as it leads to a decrease in productivity.
混合物は０．０５〜０．１５９／ｃｃの嵩密度を保持し
た状態に黒鉛ルツボに填め、図示のような反反応炉を用
いてＮ２ガス流下、１６５０〜１８５０℃の温度に加熱
反応させる。The mixture is charged into a graphite crucible while maintaining a bulk density of 0.05 to 0.159/cc, and reacted by heating at a temperature of 1650 to 1850° C. under a flow of N2 gas using a reactor as shown.
図は本発明の実施に適用される反応炉を例示した縦断面
図で、１は反応室、２は上記混合物３を充填した黒鉛ル
ツボ、４はコークス粒５を投入したＮ２ガス加熱室、６
はＮ２ガス導入管、７は加熱されたＮ２ガスを反応室１
に送入するための通路、８はガス排出管、９は測温管、
そして１０は反応炉を加熱するための高周波コイルであ
る。The figure is a longitudinal cross-sectional view illustrating a reactor applied to the implementation of the present invention, in which 1 is a reaction chamber, 2 is a graphite crucible filled with the above-mentioned mixture 3, 4 is an N2 gas heating chamber into which coke grains 5 are charged, and 6
7 is the N2 gas introduction pipe, and 7 is the heated N2 gas introduced into the reaction chamber 1.
8 is a gas discharge pipe, 9 is a temperature measuring pipe,
And 10 is a high frequency coil for heating the reactor.
反応室■内にセットされた黒鉛ルツボ２は高周波コイル
により加熱され、同時に加熱されたＮ２ガスが通路７を
通って反応室ｌに流入する。この段階でＡｌ２Ｏ３、カ
ーボンブラックおよびＮ２が反応してＡ （２Ｎウィス
カーに転化するが、反応過程は以下のようなＶＬＳ機構
によって進行するものと推測される。The graphite crucible 2 set in the reaction chamber 1 is heated by a high frequency coil, and at the same time the heated N2 gas flows into the reaction chamber 1 through the passage 7. At this stage, Al2O3, carbon black, and N2 react to convert into A(2N whiskers), and the reaction process is presumed to proceed by the VLS mechanism as described below.
まず黒鉛ルツボが加熱されるに伴ってＡρ２０３微粉末
の表面に存在する触媒成分（遷移金属）はＡｉ２，０３
に固溶し、やがて局部的にＡＱ、Ｏおよび触媒成分とか
らなる液滴を生じる。この液敵にＮ２ガスおよびＡｇ２
Ｏ３とＣ（カーボンブラック）の還元反応によって生成
したＡＱｔＯまたはＡＱｏの蒸気が溶解して行き、飽和
濃度を越えるとＡｌＮとして析出する。ＡｌＮの析出が
連続すると、黒鉛ルツボ内の生成空間にＡσＮウィスカ
ーが生成する。First, as the graphite crucible is heated, the catalyst component (transition metal) present on the surface of the Aρ203 fine powder changes to Ai2,03.
AQ, O, and catalyst components are formed into local droplets. This liquid enemy contains N2 gas and Ag2.
AQtO or AQo vapor generated by the reduction reaction of O3 and C (carbon black) gradually dissolves, and when the saturation concentration is exceeded, it precipitates as AlN. When AlN continues to precipitate, AσN whiskers are generated in the generation space within the graphite crucible.
このようにして黒鉛ルツボ中にＡ（２Ｎウイスカーを生
成させたのち、残留する未反応のカーボンブラック成分
を消却処理により除去する。After A(2N whiskers are produced in the graphite crucible in this manner), the remaining unreacted carbon black components are removed by an extinguishing process.
消却処理後の生成物は、灰白色のＡｌ２ＮでこのうちＡ
ＣＮウィスカーの占める比率は６０％を越える。また、
得られたＡｌＮウィスカーの性状は直径０．１＝１．０
μｍ、長さ５〜１００μｇの真直性に、優れた針状単結
晶である。The product after the incineration process is grayish-white Al2N, of which A
The proportion of CN whiskers exceeds 60%. Also,
The properties of the obtained AlN whiskers are: diameter 0.1 = 1.0
It is a needle-like single crystal with excellent straightness and a length of 5 to 100 μm.
本発明によれば、触媒となる遷移金属元素が主原料であ
るｌ！２０３微粉末の表面に均一付着しているから、上
記したＶＬＳ機構による反応過程で触媒成分が昇華飛散
する前にＡｇ２Ｏ３に固溶し、極めて効果的な成長活性
点（液滴）をつくる。この′ 特有の結晶成長作用がカ
ーボンブランクによる十分な成長空間保有性の作用と相
俟って、性状の浸れたＡｌ２Ｎウィスカーの生成を著し
く促進させろ機能を営む。According to the present invention, the transition metal element serving as the catalyst is the main raw material l! Since it is uniformly adhered to the surface of the 203 fine powder, it dissolves in Ag2O3 as a solid solution before the catalyst component sublimates and scatters during the reaction process by the VLS mechanism described above, creating extremely effective growth active points (droplets). This unique crystal growth effect, together with the sufficient growth space provided by the carbon blank, serves to significantly promote the formation of Al2N whiskers with a soaked texture.
〔実施例１〕
平均粒径５μｍのＡ４２０３微粉末２０９を２％Ｆ ｅ
ｃ＆２水溶液１００ｚｃに投入分散し、十分に混和した
。[Example 1] A4203 fine powder 209 with an average particle size of 5 μm was mixed with 2% Fe
The mixture was added to and dispersed in 100 zc of c&2 aqueous solution and thoroughly mixed.
この溶液濃度は、Ａｌ２Ｏ３微粉末に対するＦｅ量とし
て４４重量％になる。The concentration of this solution is 44% by weight as the amount of Fe based on the Al2O3 fine powder.
混和後の溶液を加熱煮沸して水分を蒸発乾個し、Ｆｅ触
媒成分が均一に表面付着したＡ Ｑ ２０３微粉末を得
た。The mixed solution was heated and boiled to evaporate water to dryness, yielding A Q 203 fine powder to which the Fe catalyst component was uniformly adhered to the surface.
処理後のＡｌ２Ｏ３ 微粉末に窒素吸着比表面積９９究
２／７、ＤＢＰ吸油爪１２９π０．／１００９の特性を
備えるカーボンブラック３０９を配合し、回転翼ミキサ
ーで強攪拌して嵩密度０ 、０９９／ＣＣの混合物を調
整した。After treatment, the Al2O3 fine powder has a nitrogen adsorption specific surface area of 99 2/7 and a DBP oil absorption claw of 129π0. Carbon black 309 having the properties of /1009 was blended and strongly stirred with a rotary blade mixer to prepare a mixture with a bulk density of 0 and 099/CC.
混合物をそのまま内径１２０ｍｍ、高さ６０Ｒｍの黒鉛
ルツボに移し入れ、図示の反応炉にセットした。ついで
、炉を昇温し炉内にＮ２ガスを５Ｑ／分の流速で送入し
戸がら１８００°Ｃの温度に４時間保持した。内容物を
黒鉛ルツボから取出し、大気中で７００°Ｃの温度に熱
処理して残留するカーボンブラック成分を完全に燃焼除
去した。The mixture was directly transferred to a graphite crucible with an inner diameter of 120 mm and a height of 60 Rm, and set in the reactor shown in the figure. Next, the temperature of the furnace was raised, and N2 gas was fed into the furnace at a flow rate of 5Q/min, and the temperature was maintained at 1800°C for 4 hours. The contents were taken out from the graphite crucible and heat treated in the atmosphere at a temperature of 700°C to completely burn off the remaining carbon black components.
得られた生成物は灰白色を呈するＡｊＮからなるウィス
カーと粒状物の混在物であった。このうちＡｌＮウィス
カーは直径０．１〜１０μ辺、長さ５〜１００μＷの真
直性の針状単結晶で、全生成物に占めるウィスカーの比
率は７５％と高収率であることが確認された。The obtained product was a mixture of whiskers and particulate matter made of AjN which was grayish white. Among these, AlN whiskers are straight needle-shaped single crystals with a side diameter of 0.1 to 10μ and a length of 5 to 100μW, and the ratio of whiskers to the total product was 75%, which was confirmed to be a high yield. .
〔実施例２〕
実施例１と同一のＡ（！２０ｈ 微粉末２０９を２％
Ｃ０Ｃ（！２水溶液（Ａｌ２Ｏ３に対するＣｏｆｉとし
て４５重量％）および３％Ｎ ！（Ｎ Ｏ３）２水溶ｔ
ｆＬ（Ａ ｔ：１２０３に対するＮｌ量として４８重量
％）にそれぞれ混和し、実施例１と同処理を施してＣｏ
およびＮ１触媒成分が均一に表面付着したＡ Ｑ ｔ
Ｏ３微粉末を作成した。[Example 2] Same as Example 1 A (!20h 2% fine powder 209
C0C(!2 aqueous solution (45 wt% as Cofi relative to Al2O3) and 3% N!(N O3)2 aqueous solution t
Co
and A Q t with N1 catalyst components uniformly attached to the surface.
O3 fine powder was created.
処理後の各ＡＬＯｉ微粉末と窒素吸着比表面積８０ｍ”
／９、ＤＢＰ吸浦ｍ ９８ ｍＱ／ １ｏｏｙの特性を
もつカーボンブラックを激しく攪拌して嵩密度０ 、
ｌ ２ ｇ／ｃｃの混合物を調製し、実施例１と同一の
装置および条件を用いて生成反応させｆコ。After treatment, each ALOi fine powder has a nitrogen adsorption specific surface area of 80m”
/9, DBP suction m 98 mQ/1ooy carbon black with the characteristics of vigorously stirring to give a bulk density of 0,
A mixture of 1 2 g/cc was prepared and subjected to a production reaction using the same equipment and conditions as in Example 1.
残留カーホンブラック成分を燃焼除去したのちの生成物
はＡｌ２Ｎのウィスカーおよび粒状物が混在する組成で
あったが、このうちＡａＮウィスカーの占める比率は、
Ｃｏ触媒を使用した場合は７０％、Ｎｊ触媒使用時は６
５％であった。得られたＡ Ｑ Ｎウィスカーは、直径
０．１〜１．０μｍ、長さ５〜５０μ肩の真直状単結晶
であった。The product after burning off the residual carphone black component had a composition in which Al2N whiskers and particulates were mixed, but the proportion of AaN whiskers among these was as follows:
70% when using Co catalyst, 6 when using Nj catalyst
It was 5%. The obtained A Q N whiskers were straight single crystals with a diameter of 0.1 to 1.0 μm and a length of 5 to 50 μm.
〔比較例１〕
カーボンブラックの代りに平均粒径５０μの黒鉛粉末を
用い、嵩密度０．６２９７ｃｃの混合物としたほかは実
施例１と同一の方法を用いて生成反応をおこなった。得
られた生成物はＡ Ｑ ２０３およびＡｅＮの混在粒状
物で、ＡｅＮウィスカーの生成は認められなかった。[Comparative Example 1] A production reaction was carried out in the same manner as in Example 1, except that graphite powder with an average particle size of 50 μm was used instead of carbon black, and a mixture with a bulk density of 0.6297 cc was used. The obtained product was a mixed particle of A Q 203 and AeN, and no AeN whiskers were observed.
〔比較例２〕
平均粒径５μ尻のＡ Ｑ ２０３微粉末２０９にＦｅ２
Ｏ３粉１０９と実施例１で用いたカーボンブラック３０
Ｌｉを混合して嵩密度０．０９ｇ／ｃｃの混合物とし、
これを実施例１と同一手法により生成反応を実施した。[Comparative Example 2] Fe2 was added to AQ 203 fine powder 209 with an average particle size of about 5 μm.
O3 powder 109 and carbon black 30 used in Example 1
Mix Li to make a mixture with a bulk density of 0.09 g/cc,
A production reaction was performed using the same method as in Example 1.
生成物はＡｌＮのウィスカーと粒状物との混在組成を呈
していたが、全生成物に占めるＡＣＮウィスカーの比率
は４０％と低収率であった。The product had a mixed composition of AlN whiskers and particulate matter, but the ratio of ACN whiskers to the total product was 40%, which was a low yield.
以上のとおり、本発明によれば特有の触媒作用と結晶空
間形成作用により優れた性状のＡｌＮウィスカーを高収
率で製造することができる。したがって、各種の複合用
途に有効な強化材として量産化が可能となる。As described above, according to the present invention, AlN whiskers with excellent properties can be produced in high yield due to the unique catalytic action and crystal space forming action. Therefore, it becomes possible to mass-produce it as a reinforcing material that is effective for various composite uses.
図は本発明の実施に適用される反応炉を例示した縦断面
図である。
■・・反応室、２・・・黒鉛ルツボ、３・・・原料混合
物、４・・・Ｎ、ガス加熱室、ｌＯ・高周波コイル。The figure is a longitudinal cross-sectional view illustrating a reactor to which the present invention is applied. ■... Reaction chamber, 2... Graphite crucible, 3... Raw material mixture, 4... N, gas heating chamber, lO/high frequency coil.
Claims (3)
混和したのち加熱処理して液媒を蒸発除去し、処理後の
Ａｌ＿２Ｏ＿３微粉末にカーボンブラックを均質混合し
て嵩密度０．０５〜０．１５ｇ／ｃｃの混合物を調製し
、該混合物をＮ＿２ガス流下の反応炉中で１６５０〜１
８５０℃の温度に加熱することを特徴とするＡｌＮウィ
スカーの製造方法。(1) Al_2O_3 fine powder is mixed with a solution of a transition metal compound, heat-treated to remove the liquid medium by evaporation, and carbon black is homogeneously mixed with the treated Al_2O_3 fine powder to have a bulk density of 0.05 to 0.15 g. /cc of the mixture was prepared and the mixture was heated to 1650-1 cc in a reactor under N_2 gas flow.
A method for producing AlN whiskers, which comprises heating to a temperature of 850°C.
くは硝酸塩から選択され、その溶液濃度をＡｌ＿２Ｏ＿
３微粉末に対する遷移金属元素の量として０．５〜１０
重量％になるように調整する特許請求の範囲第１項記載
のＡｌＮウィスカーの製造方法。(2) The transition metal compound is selected from chlorides or nitrates of Fe, Ni, and Co, and the solution concentration is set to Al_2O_
3 0.5 to 10 as the amount of transition metal element to fine powder
The method for producing AlN whiskers according to claim 1, wherein the content is adjusted to % by weight.
／ｇ以上、ＤＢＰ吸油量９０ｍｌ／１００ｇ以上の特性
を有するものであり、処理後のＡｌ＿２Ｏ＿３微粉末１
００部に対し１００〜２００部の割合で混合する特許請
求の範囲第１項記載の ＡｌＮウィスカーの製造方法。(3) Carbon black has a nitrogen adsorption specific surface area of 40 m^2
/g or more, DBP oil absorption of 90ml/100g or more, and the Al_2O_3 fine powder 1 after treatment.
The method for producing AlN whiskers according to claim 1, wherein the AlN whiskers are mixed at a ratio of 100 to 200 parts to 00 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12561986A JPS62283900A (en) | 1986-06-02 | 1986-06-02 | Production of aln whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12561986A JPS62283900A (en) | 1986-06-02 | 1986-06-02 | Production of aln whisker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283900A true JPS62283900A (en) | 1987-12-09 |
| JPH0323519B2 JPH0323519B2 (en) | 1991-03-29 |
Family
ID=14914556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12561986A Granted JPS62283900A (en) | 1986-06-02 | 1986-06-02 | Production of aln whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283900A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693305A (en) * | 1995-10-19 | 1997-12-02 | Advanced Refractory Technologies, Inc. | Method for synthesizing aluminum nitride whiskers |
| JP2006315940A (en) * | 2005-04-13 | 2006-11-24 | Sumitomo Electric Ind Ltd | METHOD FOR GROWING AlN SINGLE CRYSTAL AND AlN SINGLE CRYSTAL |
| JP2010180126A (en) * | 2004-07-08 | 2010-08-19 | Ngk Insulators Ltd | Method for producing aluminum nitride single crystal |
| JP2012041254A (en) * | 2010-08-23 | 2012-03-01 | Tohoku Univ | Aluminum nitride wire, method for producing the same, and apparatus for producing aluminum nitride wire |
| CN106801258A (en) * | 2016-12-28 | 2017-06-06 | 中国科学院上海硅酸盐研究所 | A kind of preparation method with hexa-prism aluminium nitride whisker |
| JP2017149624A (en) * | 2016-02-26 | 2017-08-31 | 株式会社トクヤマ | Method for producing aluminum nitride whisker |
| JP2020158355A (en) * | 2019-03-27 | 2020-10-01 | 株式会社トクヤマ | Composite structure made of aluminum nitride |
| CN112210833A (en) * | 2020-10-13 | 2021-01-12 | 哈尔滨化兴软控科技有限公司 | Device and method for improving purity of aluminum nitride crystal growth raw material |
-
1986
- 1986-06-02 JP JP12561986A patent/JPS62283900A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693305A (en) * | 1995-10-19 | 1997-12-02 | Advanced Refractory Technologies, Inc. | Method for synthesizing aluminum nitride whiskers |
| JP2010180126A (en) * | 2004-07-08 | 2010-08-19 | Ngk Insulators Ltd | Method for producing aluminum nitride single crystal |
| JP2006315940A (en) * | 2005-04-13 | 2006-11-24 | Sumitomo Electric Ind Ltd | METHOD FOR GROWING AlN SINGLE CRYSTAL AND AlN SINGLE CRYSTAL |
| JP2012041254A (en) * | 2010-08-23 | 2012-03-01 | Tohoku Univ | Aluminum nitride wire, method for producing the same, and apparatus for producing aluminum nitride wire |
| JP2017149624A (en) * | 2016-02-26 | 2017-08-31 | 株式会社トクヤマ | Method for producing aluminum nitride whisker |
| CN106801258A (en) * | 2016-12-28 | 2017-06-06 | 中国科学院上海硅酸盐研究所 | A kind of preparation method with hexa-prism aluminium nitride whisker |
| JP2020158355A (en) * | 2019-03-27 | 2020-10-01 | 株式会社トクヤマ | Composite structure made of aluminum nitride |
| CN112210833A (en) * | 2020-10-13 | 2021-01-12 | 哈尔滨化兴软控科技有限公司 | Device and method for improving purity of aluminum nitride crystal growth raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0323519B2 (en) | 1991-03-29 |
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