JP3011785B2 - AlN whisker composite material - Google Patents
AlN whisker composite materialInfo
- Publication number
- JP3011785B2 JP3011785B2 JP3125257A JP12525791A JP3011785B2 JP 3011785 B2 JP3011785 B2 JP 3011785B2 JP 3125257 A JP3125257 A JP 3125257A JP 12525791 A JP12525791 A JP 12525791A JP 3011785 B2 JP3011785 B2 JP 3011785B2
- Authority
- JP
- Japan
- Prior art keywords
- aln
- whiskers
- thermal conductivity
- composite material
- whisker
- 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面の滑らかな無色透
明状のＡｌＮウィスカーを含有する複合材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material containing a colorless and transparent AlN whisker having a smooth surface.
【０００２】[0002]
【従来の技術】窒化アルミニウム（ＡｌＮ）は、アルミ
ナの約10倍の高熱伝導性セラミックスであることが知ら
れており、有毒性の酸化ベリリウムに代る高放熱基板材
料として注目されている。また、高純度なＡｌＮウィス
カー（ひげ結晶）は、高熱伝導性および高強度を有する
ため、セラミックスの強化用や、金属あるいはプラスチ
ックスとの複合体など高熱伝導性複合材料としての利用
が期待されている。2. Description of the Related Art Aluminum nitride (AlN) is known to be a ceramic having a high thermal conductivity about 10 times that of alumina, and is attracting attention as a high heat radiation substrate material replacing toxic beryllium oxide. In addition, since high-purity AlN whiskers (whiskers) have high thermal conductivity and high strength, they are expected to be used for reinforcing ceramics and as high thermal conductive composite materials such as composites with metals or plastics. I have.
【０００３】ＡｌＮウィスカーは、既に発明者等によっ
て大量に生産し得る技術が確立されている。すなわち、
本発明者等は、Ａｌ粉末の浮上窒化法によるＡｌＮ微粉
末の連続合成法を考案した際に、該粉末合成に付随して
繊維状ＡｌＮ、あるいはＡｌＮウィスカーが合成される
ことを見い出し、さらにその後の研究により、該合成法
において窒化反応を起こさせる際に使用する反応ガスと
してＮ2 −ＮＨ3 混合ガスを用いることにより、ＡｌＮ
ウィスカーの成長速度を増加させ、より欠陥の少ない表
面の滑らかな無色透明状のＡｌＮウィスカーを得たので
ある。[0003] The art of producing AlN whiskers in large quantities has already been established by the inventors. That is,
The present inventors have found that when devising a continuous synthesis method of AlN fine powder by a floating nitriding method of Al powder, fibrous AlN or AlN whiskers are synthesized accompanying the powder synthesis, and further thereafter. According to the research of AlN, by using a mixed gas of N 2 -NH 3 as a reaction gas used for causing a nitridation reaction in the synthesis method, AlN
The whisker growth rate was increased, and a colorless and transparent AlN whisker having a smoother surface with fewer defects was obtained.
【０００４】上記ＡｌＮウィスカーの製造法において
は、図１に示すような下端に原料供給部１、上端に捕集
器５を有し、周囲部に加熱設備として電気炉４が装備さ
れた高純度アルミナ管２が垂直に設置されて成る装置が
使用された。この装置を使用したＡｌＮウィスカー複合
材料の製造法とは、原料供給部１にＡｌ粉末６を供給
し、撹拌機３で撹拌しながらＮ2 ガス７でＡｌ粉末６を
浮上させ、アルミナ管２の中央部にてＮ2 −ＮＨ3 混合
ガス８を反応ガスとして導入し、電気炉４で加熱するこ
とによりＡｌ粉末を窒化させ、合成されたＡｌＮ粉末を
捕集器５で回収し、冷却後アルミナ管２の内壁に生成し
たＡｌＮウィスカーを採取するというものである。[0004] In the above-described method for producing an AlN whisker, a high-purity source having a raw material supply unit 1 at the lower end and a collector 5 at the upper end as shown in FIG. An apparatus having an alumina tube 2 installed vertically was used. The manufacturing method of the AlN whisker composite material using this apparatus is as follows. The Al powder 6 is supplied to the raw material supply unit 1 and the Al powder 6 is floated with the N 2 gas 7 while being stirred by the stirrer 3. At the center, an N 2 —NH 3 mixed gas 8 is introduced as a reaction gas, the Al powder is nitrided by heating in an electric furnace 4, the synthesized AlN powder is collected by a collector 5, and after cooling, alumina This is to collect AlN whiskers generated on the inner wall of the tube 2.
【０００５】[0005]
【発明が解決しようとする課題】上述のように、ＡｌＮ
ウィスカーを大量に生産する技術は確立されたが、得ら
れたＡｌＮウィスカーの用途としてセラミックスの強化
用や、金属あるいはプラスチックスとの複合など高熱伝
導性複合材料としての利用が期待されているにもかかわ
らず、具体的な製品化が成されていなかった。As described above, AlN
Although the technology for mass-producing whiskers has been established, the obtained AlN whiskers are expected to be used for strengthening ceramics and as highly thermally conductive composite materials such as composites with metals or plastics. Nevertheless, no specific commercialization has been achieved.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究したところ、ＡｌＮウィスカー
と、ＡｌＮ粉末または基板用エポキシ樹脂とを複合化す
ることによって熱伝導率に優れたセラミックスならびに
複合エポキシ樹脂が得られることを見い出し、本発明を
提供することができた。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, by combining AlN whiskers with AlN powder or epoxy resin for a substrate, excellent heat conductivity was obtained. The present inventors have found that ceramics and composite epoxy resins can be obtained, and have provided the present invention.
【０００７】すなわち、本発明は、高純度Ａｌを原料と
して用い、Ｎ2 −ＮＨ3 混合ガスを反応ガスとした浮上
窒化法により生成された表面の滑らかな無色透明状の高
純度ＡｌＮウィスカーと、高純度ＡｌＮ微粉末とを混合
し、さらに焼結助剤を添加したものを成形し、その成形
体を焼結させて得たセラミックスであって、90W/mK以上
の熱伝導率および50％以上の相対密度を有することを特
徴とするＡｌＮウィスカー複合材料；および、高純度Ａ
ｌを原料として用い、Ｎ2 −ＮＨ3 混合ガスを反応ガス
とした浮上窒化法により生成された表面の滑らかな無色
透明状の高純度ＡｌＮウィスカーを成形し、その成形体
に基板用エポキシ樹脂を含浸させた後、これを加熱する
ことによって該エポキシ樹脂を硬化させて得た複合材で
あって、3.5 W/mK以上の熱伝導率および40.0×10-6Ｋ-1
以下の熱膨張率を有することを特徴とするＡｌＮウィス
カー複合材料を提供するものである。That is, the present invention provides a high-purity AlN whisker having a smooth colorless and transparent surface produced by a floating nitriding method using high-purity Al as a raw material and a N 2 -NH 3 mixed gas as a reaction gas. A ceramic obtained by mixing a high-purity AlN fine powder, further adding a sintering aid, and sintering the formed body, and having a thermal conductivity of 90 W / mK or more and a thermal conductivity of 50% or more. Whisker composite material characterized by having a relative density of
l as a raw material, a colorless and transparent high-purity AlN whisker having a smooth surface generated by a floating nitriding method using a N 2 -NH 3 mixed gas as a reaction gas is molded, and the molded body is coated with an epoxy resin for a substrate. A composite material obtained by curing the epoxy resin by heating it after impregnation, which has a thermal conductivity of 3.5 W / mK or more and 40.0 × 10 −6 K −1.
An object of the present invention is to provide an AlN whisker composite material having the following coefficient of thermal expansion.
【０００８】[0008]
【作用】本発明において使用されるＡｌＮウィスカー
は、図１に示すような装置を使用した浮上窒化法によっ
て製造され、その際反応ガスとしてＮ2 −ＮＨ3 混合ガ
スを用いることによって、より欠陥の少ない表面の滑ら
かな無色透明状のＡｌＮウィスカーを得ることができ
る。この方法により得られる表面の滑らかなＡｌＮウィ
スカーの成長機構は、ウィスカーの成長先端に球状のＦ
ｅあるいはＳｉなどが認められないことからも、ＶＬＳ
機構の成長ではなくＶＳ機構であると考えられる。The AlN whisker used in the present invention is manufactured by a floating nitriding method using an apparatus as shown in FIG. 1, and in this case, by using an N 2 —NH 3 mixed gas as a reaction gas, more defects can be obtained. AlN whiskers in a smooth colorless and transparent state with a small surface can be obtained. The growth mechanism of AlN whiskers with a smooth surface obtained by this method is that a spherical F
e or Si is not recognized,
It is considered to be a VS mechanism, not a growth of the mechanism.
【０００９】ＡｌＮウィスカーは、高熱伝導性および高
強度を有することが知られているが、特に上記表面の滑
らかなＡｌＮウィスカーには、次のような性質があるこ
とが確認された。すなわち、表面の滑らかなＡｌＮウィ
スカーの大気中における安定性を調べたところ、大気中
に６カ月以上放置したものでさえも、大気中の水蒸気と
反応して水酸化アルミニウムとアンモニアを生成し、そ
の重量が増加してしまうようなことはなく、極めて安定
性に優れていた。Although AlN whiskers are known to have high thermal conductivity and high strength, it has been confirmed that the AlN whiskers having a smooth surface particularly have the following properties. That is, when the stability of AlN whiskers having a smooth surface in the air was examined, even those that had been left in the air for 6 months or more reacted with water vapor in the air to produce aluminum hydroxide and ammonia, There was no increase in weight, and the stability was extremely excellent.
【００１０】また、該ＡｌＮウィスカーの水に対する安
定性を調べたところ、５日間水につけた場合でも、その
分解反応率は４％以下であり、極めて安定性に優れてい
た。このことから、水との接触によるウィスカーの高熱
伝導性および高強度性の劣化は少ないものと考えられる
ため、他の材料との複合化の際に取扱いが容易であり、
場合によっては水による混合も可能となり、複合材料の
製造コストの低減化が図れる。In addition, the stability of the AlN whiskers to water was examined. As a result, even if the AlN whiskers were soaked in water for 5 days, the decomposition reaction rate was 4% or less, and the stability was extremely excellent. From this, it is considered that the deterioration of the high thermal conductivity and high strength of the whisker due to contact with water is small, so that it is easy to handle when compounding with other materials,
In some cases, mixing with water is also possible, and the production cost of the composite material can be reduced.
【００１１】さらに、該ＡｌＮウィスカーの高温耐酸化
性について、大気中において1000℃に加熱することによ
って調べたところ、酸化反応率が３％未満と極めて小さ
い値を示したことなどから、高温耐酸化性に非常に優れ
るものであることが確認された。したがって、該ＡｌＮ
ウィスカーは高温材料用の分散強化材として十分に使用
し得るものであるといえる。Further, when the AlN whiskers were examined for high-temperature oxidation resistance by heating to 1000 ° C. in the air, the oxidation reaction rate showed an extremely small value of less than 3%. It was confirmed that the composition had excellent properties. Therefore, the AlN
It can be said that whiskers can be sufficiently used as a dispersion strengthening material for high-temperature materials.
【００１２】上記のような性質を有するＡｌＮウィスカ
ーは、共有結合性の強い化合物であるため、燃焼性が低
く焼結性が悪いという欠点を有していた。一方、ＡｌＮ
粉末は、金属に対する高耐食性、高熱伝導性および低熱
膨脹性を有し、かつ焼結性が良いという性質を有するこ
とが知られている。すなわち、本発明のＡｌＮウィスカ
ー複合材料は、上記のような性質を有する表面の滑らか
なＡｌＮウィスカーとＡｌＮ粉末とを複合化することに
より、互いの有用な性質を生かし、かつ互いの欠点を補
いあっているのである。また、上記表面の滑らかなＡｌ
Ｎウィスカーとエポキシ樹脂とを複合化することによ
り、エポキシ樹脂の熱伝導率の向上および熱膨脹率の低
減を図り、半導体基板としての熱的特性を改善している
のである。Since AlN whiskers having the above-mentioned properties are compounds having a strong covalent bond, they have a drawback of low flammability and poor sinterability. On the other hand, AlN
Powders are known to have high corrosion resistance to metals, high thermal conductivity, low thermal expansion, and good sinterability. That is, the AlN whisker composite material of the present invention makes use of each other's useful properties and compensates for each other's drawbacks by compounding AlN whiskers having the above-mentioned properties and having a smooth surface with AlN powder. -ing In addition, the smooth Al
By combining the N whiskers and the epoxy resin, the thermal conductivity of the epoxy resin is improved and the coefficient of thermal expansion is reduced, thereby improving the thermal characteristics of the semiconductor substrate.
【００１３】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited by the following examples.
【００１４】[0014]
【実施例１】まず、平均粒径が15μｍであり、純度が9
9.9％および 99.99％のアトマイズ粉末（昭和アルミニ
ウム製）からなるＡｌ粉末６を、図１に示すウィスカー
製造用反応器内の高純度アルミナ（Ａｌ2 Ｏ3 ）管２
（内径42mm、長さ1000mm）下部の原料供給部１に充填し
た。次いで、Ａｌ粉末６を攪拌機３で攪拌しながらＮ2
ガス７（11/min）を吹き込み、電気炉４で加熱した反応
器中にＡｌ粉末６を浮上させて窒化反応させ、さらにＮ
2 ガス７（1.35 l/min）で該粉末６を浮上させ、反応器
の中央部にてＮ2 −ＮＨ3 混合ガス８（0.65 l/min）を
導入して窒化反応を起こさせてＡｌＮ粉末およびＡｌＮ
ウィスカーを合成し、ＡｌＮ粉末は捕集器５で回収し、
反応器内壁に付着したＡｌＮウィスカーは冷却後回収し
た。なお、上記製造工程における反応温度は1450℃〜15
50℃、反応時間は０〜120min、ＮＨ3ガスの濃度は全ガ
ス流量に対して 0〜30 vol％が好ましく、本実施例では
反応温度は1550℃、反応時間は120minで窒化反応させ、
最大長15mm、最大径 120μｍ、径平均約10μｍに成長し
たＡｌＮウィスカーを得た。また、ＡｌＮウィスカーの
成長速度は、長さ方向に２μｍ／ｓ、径方向に0.0014〜
0.017 μｍ／ｓで成長し、長さ方向への成長速度が極め
て速かった。Example 1 First, the average particle size was 15 μm and the purity was 9
An Al powder 6 composed of 9.9% and 99.99% atomized powder (manufactured by Showa Aluminum) was placed in a high purity alumina (Al 2 O 3 ) tube 2 in a whisker production reactor shown in FIG.
(Inner diameter 42 mm, length 1000 mm) The lower raw material supply section 1 was filled. Next, while stirring the Al powder 6 with the stirrer 3, N 2
Gas 7 (11 / min) was blown, and Al powder 6 was floated in a reactor heated by electric furnace 4 to cause a nitriding reaction.
The powder 6 is levitated with 2 gas 7 (1.35 l / min), and N 2 -NH 3 mixed gas 8 (0.65 l / min) is introduced into the center of the reactor to cause a nitriding reaction to cause AlN powder. And AlN
A whisker is synthesized, and the AlN powder is collected by the collector 5,
The AlN whiskers attached to the inner wall of the reactor were recovered after cooling. The reaction temperature in the above manufacturing process is 1450 ° C. to 15
It is preferable that the reaction temperature is 50 ° C., the reaction time is 0 to 120 min, and the concentration of NH 3 gas is 0 to 30 vol% with respect to the total gas flow rate.
AlN whiskers were grown with a maximum length of 15 mm, a maximum diameter of 120 μm, and an average diameter of about 10 μm. The growth rate of AlN whiskers is 2 μm / s in the length direction and 0.0014 to
It grew at 0.017 μm / s, and the growth rate in the length direction was extremely fast.
【００１５】次に、得られたＡｌＮウィスカーとＡｌＮ
粉末との割合が、 0、25、50、75、100 wt％ＡｌＮウィ
スカーとなるように配合し、さらに焼結助剤としてＹ2
Ｏ3粉末を３wt％添加し、無水メタノールを用いてめの
う乳鉢で湿式混合した。次いで、得られた混合粉末を十
分に乾燥し、150MPaの成形圧でφ10mmおよびφ20mmに成
形した。これらの成形体は、内壁を窒化ホウ素（ＢＮ）
で被覆したφ10mmおよびφ20mmのカーボン型に入れ、30
MPa の印加圧下、１気圧の窒素雰囲気中でホットプレス
焼結を行いＡｌＮウィスカー複合材料を得た。なお、ホ
ットプレス焼結における焼結温度は1900℃、焼結時間は
120minとした。Next, the obtained AlN whiskers and AlN
Ratio of the powder was blended so that 0, 25, 50, 75 wt% AlN whiskers, Y 2 further as a sintering aid
3 wt% of O 3 powder was added and wet-mixed in an agate mortar using anhydrous methanol. Next, the obtained mixed powder was sufficiently dried and formed into φ10 mm and φ20 mm at a molding pressure of 150 MPa. These molded products have an inner wall of boron nitride (BN).
Put into φ10mm and φ20mm carbon molds covered with
Hot press sintering was performed in a nitrogen atmosphere at 1 atm under an applied pressure of MPa to obtain an AlN whisker composite material. The sintering temperature in hot press sintering is 1900 ° C, and the sintering time is
120 minutes.
【００１６】上記のようにして得た焼結体すなわちＡｌ
Ｎウィスカー複合材料について、嵩密度の測定、アルキ
メデス法による焼結密度の測定、走査型電子顕微鏡写真
（ＳＥＭ）による微細構造の観察、レーザーフラッシュ
法による室温での熱伝導率の測定および３点曲げ強度の
測定を行った。なお、熱伝導率の測定の際、試料の厚さ
は約３mm程度とした。また、曲げ強度の測定の際、試料
の大きさを約４mm×３mm×20mm、スパンを15mm、荷重を
500kg および荷重速度を 0.5mm/minとした。The sintered body obtained as described above, ie, Al
Measurement of bulk density, measurement of sintered density by Archimedes method, observation of microstructure by scanning electron micrograph (SEM), measurement of thermal conductivity at room temperature by laser flash method, and three-point bending of N whisker composite material The strength was measured. When measuring the thermal conductivity, the thickness of the sample was about 3 mm. When measuring the bending strength, the sample size was about 4 mm x 3 mm x 20 mm, the span was 15 mm, and the load was
The load speed was set at 0.5 kg / min at 500 kg.
【００１７】以上の測定結果を以下に示し、ＡｌＮウィ
スカーの配合比率と焼結体および焼結前の成形体の相対
密度との関係を図２に、ＡｌＮウィスカーの配合比率と
熱伝導率および相対密度との関係を図３に示した。The results of the above measurements are shown below. FIG. 2 shows the relationship between the mixing ratio of AlN whiskers and the relative density of the sintered body and the green body before sintering. FIG. 3 shows the relationship with the density.
【００１８】（１）成形性 ＡｌＮウィスカーの配合比が増加するにしたがって成形
体の成形密度は増加するが（図２）、ＡｌＮウィスカー
は成形性が非常に悪いため、ＡｌＮウィスカーの配合比
が75wt％および 100wt％の試料については、成形体の形
を保つことができず崩れたり割れてしまった。(1) Formability As the compounding ratio of AlN whiskers increases, the molding density of the molded body increases (FIG. 2). However, since AlN whiskers have very poor moldability, the compounding ratio of AlN whiskers is 75 wt. % And 100% by weight, the shape of the molded body could not be maintained, and it collapsed or cracked.
【００１９】（２）焼結性 ＡｌＮウィスカーの配合比が 100wt％で焼結助剤無添加
の焼結体の破断面のＳＥＭを観察したところ、緻密化し
ていないＡｌＮウィスカーが確認された。この焼結体の
相対密度は75％、焼結前の成形体の相対密度は65％であ
り（図２）、緻密化すなわち焼結の進行はわずかであっ
た。一方、ＡｌＮウィスカーの配合比が100wt％で焼結
助剤としてＹ2 Ｏ3 粉末を３wt％添加した焼結体の破断
面のＳＥＭを観察したところ、焼結助剤無添加の場合と
同様に焼結の進行はわずかであった。(2) Sinterability When the blending ratio of AlN whiskers was 100% by weight and the SEM of the fracture surface of the sintered body without the addition of a sintering aid was observed, undensified AlN whiskers were confirmed. The relative density of this sintered body was 75%, and the relative density of the molded body before sintering was 65% (FIG. 2), and the progress of densification, ie, sintering, was slight. On the other hand, SEM of a fractured surface of a sintered body in which the mixing ratio of AlN whiskers was 100 wt% and Y 2 O 3 powder was added as a sintering aid at 3 wt% was observed. Progress of sintering was slight.
【００２０】図２からも分かるように、ＡｌＮウィスカ
ーの配合比が増加するに従って相対密度（焼結性）は低
下し、特にＡｌＮウィスカーの配合比が50wt％を越える
と相対密度（焼結性）が著しく低下することから、Ａｌ
ＮウィスカーよりもＡｌＮ粉末の方が焼結性に優れてい
ることが確認された。As can be seen from FIG. 2, the relative density (sintering property) decreases as the mixing ratio of AlN whiskers increases, and particularly when the mixing ratio of AlN whiskers exceeds 50 wt%, the relative density (sintering property) increases. Significantly decreases, so that Al
It was confirmed that AlN powder had better sinterability than N whiskers.
【００２１】（３）熱伝導率 熱伝導率はＡｌＮウィスカーの配合比が50wt％のとき、
最大値160 W/mKを示した。ＡｌＮウィスカーの配合比が
25wt％の焼結体と50wt％の焼結体との熱伝導率を比較す
ると、配合比が25wt％の焼結体のほうが相対密度が高い
にもかかわらず、熱伝導率は低かった。これは、相対密
度の低下に伴う熱伝導率の低下よりも、ＡｌＮウィスカ
ー配合比の増加による熱伝導率の向上の効果が大きいた
めであると考えられる。しかしながら、ＡｌＮウィスカ
ーの配合比が25wt％の焼結体の熱伝導率が、該配合率が
0wt％の焼結体の熱伝導率よりも低下したのは、相対密
度の減少の影響によるものと考えられる。(3) Thermal conductivity The thermal conductivity is as follows when the mixing ratio of AlN whiskers is 50% by weight.
The maximum value was 160 W / mK. The mixing ratio of AlN whiskers is
When the thermal conductivity of the sintered body of 25 wt% and that of the sintered body of 50 wt% were compared, the sintered body having a blending ratio of 25 wt% had a lower thermal conductivity despite the higher relative density. This is considered to be because the effect of improving the thermal conductivity by increasing the AlN whisker mixing ratio is greater than the decrease in the thermal conductivity due to the decrease in the relative density. However, the thermal conductivity of a sintered body having a mixing ratio of AlN whiskers of 25 wt% is
It is considered that the decrease in the thermal conductivity of the sintered body of 0 wt% was due to the decrease in the relative density.
【００２２】また、熱伝導率については図４に示すよう
に、ＡｌＮウィスカー複合材料９にレーザービーム１０
を当ててＡｌＮウィスカーの配向方向の違いによる熱伝
導率の違いを測定し、その結果を下記表に示した。な
お、測定に先立って図４（ａ）に示すように、ＡｌＮウ
ィスカー複合材料９内におけるＡｌＮウィスカー１１
が、熱伝導率測定面１２に対して平行に配向している場
合には、熱は多くの粒界を横切って伝導し、同図（ｂ）
に示すようにＡｌＮウィスカー１１が熱伝導率測定面１
２に対して垂直に配向している場合には、ＡｌＮウィス
カーの長軸を通って熱が伝導するため、垂直に配向して
いるほうが熱伝導率は向上すると考えられた。しかしな
がら、下記の表１からも分かるように、配向方向の違う
両試料間において、熱伝導率の差はほとんど見られなか
った。これは、原料配合時にＡｌＮウィスカーが粉砕さ
れ、熱伝導率に対するＡｌＮウィスカーの配向方向の影
響が少なかったためであると考えられる。As shown in FIG. 4, the thermal conductivity of the AlN whisker composite material 9 was
And the difference in thermal conductivity due to the difference in the orientation direction of the AlN whiskers was measured. The results are shown in the following table. Prior to the measurement, as shown in FIG. 4A, the AlN whiskers 11 in the AlN whisker composite material 9 were used.
Is oriented parallel to the thermal conductivity measurement surface 12, heat is conducted across many grain boundaries, and FIG.
As shown in FIG. 3, the AlN whiskers 11
In the case of the orientation perpendicular to 2, the heat is conducted through the long axis of the AlN whiskers, so it was considered that the thermal conductivity is improved when the orientation is perpendicular. However, as can be seen from Table 1 below, almost no difference in thermal conductivity was observed between the two samples having different orientation directions. This is considered to be because the AlN whiskers were pulverized at the time of mixing the raw materials, and the influence of the orientation direction of the AlN whiskers on the thermal conductivity was small.
【００２３】[0023]
【表１】 ウィスカーの配向方向は、熱伝導率測定面に対して示し
た。[Table 1] The orientation direction of the whiskers is shown with respect to the thermal conductivity measurement surface.
【００２４】（４）曲げ強度 径がφ20mm、ＡｌＮウィスカーの配合比が50wt％の焼結
体を切り出して３点曲げにより曲げ強度を測定した。ま
た、比較のためＡｌＮセラミックスについても同様の測
定を行い、両者の測定結果を下記の表２に示した。(4) Bending Strength A sintered body having a diameter of φ20 mm and a mixing ratio of AlN whiskers of 50 wt% was cut out, and the bending strength was measured by three-point bending. For comparison, the same measurement was performed on AlN ceramics, and the results of both measurements are shown in Table 2 below.
【００２５】[0025]
【表２】 [Table 2]
【００２６】上記表からも分かるように、ＡｌＮウィス
カーを配合した焼結体の曲げ強度は、ＡｌＮセラミック
スの半分であった。これは、ウィスカーが太く、しか
も、原料の配合が均一でなく欠陥が多く残存したためで
あると考えられる。As can be seen from the above table, the bending strength of the sintered body containing the AlN whiskers was half that of the AlN ceramics. This is considered to be because the whiskers were thick and the raw materials were not uniformly mixed, leaving many defects.
【００２７】[0027]
【実施例２】本実施例では、実施例１で得られたＡｌＮ
ウィスカーを150MPaの成形圧で成形し、減圧中でエポキ
シ樹脂を含浸させた後、これを 120℃で150min加熱する
ことにより、該エポキシ樹脂を硬化させてＡｌＮウィス
カー複合エポキシ樹脂を得た。 得られたＡｌＮウィス
カー複合エポキシ樹脂について、熱伝導率および熱膨張
率を測定したところ以下のような結果が得られた。Embodiment 2 In this embodiment, the AlN obtained in Embodiment 1 is used.
The whisker was molded at a molding pressure of 150 MPa, impregnated with an epoxy resin under reduced pressure, and then heated at 120 ° C. for 150 minutes to cure the epoxy resin to obtain an AlN whisker composite epoxy resin. The thermal conductivity and thermal expansion coefficient of the obtained AlN whisker composite epoxy resin were measured, and the following results were obtained.
【００２８】（１）熱伝導率 ＡｌＮウィスカー複合エポキシ樹脂におけるＡｌＮウィ
スカーの体積分率、エポキシ樹脂の体積分率、ウィスカ
ーの配向方向、空隙率および熱伝導率の関係を下記の表
３に示した。(1) Thermal Conductivity Table 3 below shows the relationship among the volume fraction of AlN whiskers, the volume fraction of epoxy resin, the orientation direction of the whiskers, the porosity, and the thermal conductivity in the AlN whisker composite epoxy resin. .
【００２９】[0029]
【表３】 [Table 3]
【００３０】ウィスカーの配向方向は、熱伝導率測定面
に対して示した。The orientation direction of the whiskers is shown with respect to the thermal conductivity measurement surface.
【００３１】上記表より、ＡｌＮウィスカーを垂直に配
向させた試料は、空隙率が16.9％あるにもかかわらず、
熱伝導率が6.12(W/mK)と高い値を示した。これは、一般
のエポキシ樹脂の約26倍の熱伝導率であり、ＡｌＮウィ
スカーの影響が現れたものと考えられる。また、試料の
空隙を減らすことにより、さらに熱伝導率は向上するも
のと考えられる。From the above table, it can be seen that although the sample in which the AlN whiskers are vertically oriented has a porosity of 16.9%,
The thermal conductivity showed a high value of 6.12 (W / mK). This is about 26 times the thermal conductivity of a general epoxy resin, and it is considered that the influence of AlN whiskers appeared. Further, it is considered that the thermal conductivity is further improved by reducing the voids in the sample.
【００３２】（２）熱膨張率 ＡｌＮウィスカー複合セラミックスおよびＡｌＮウィス
カー複合エポキシ樹脂の熱膨張率を下記の表４に示し
た。(2) Thermal Expansion Coefficient The thermal expansion coefficients of the AlN whisker composite ceramics and the AlN whisker composite epoxy resin are shown in Table 4 below.
【００３３】[0033]
【表４】 [Table 4]
【００３４】上記表からも分かるように、ＡｌＮウィス
カー複合エポキシ樹脂の熱膨張率は、エポキシ樹脂の熱
膨張率の約1/3.5 に低下しており、半導体基板としての
熱的特性が改善されていることが確認された。As can be seen from the above table, the thermal expansion coefficient of the AlN whisker composite epoxy resin is reduced to about 1 / 3.5 of the thermal expansion coefficient of the epoxy resin, and the thermal characteristics as a semiconductor substrate are improved. It was confirmed that.
【００３５】[0035]
【発明の効果】本発明のＡｌＮウィスカー複合材料にお
いて、ＡｌＮウィスカーおよびＡｌＮ粉末からなる複合
材料は、熱伝導性および強度特性に優れ、ＡｌＮウィス
カーおよびエポキシ樹脂からなる複合材料は、熱伝導率
および熱膨張率に優れるものである。また、本発明のＡ
ｌＮウィスカー複合材料は、簡易な手段により製造する
ことができるため、極めて商業的価値が高いものであ
る。According to the AlN whisker composite material of the present invention, the composite material composed of AlN whiskers and AlN powder has excellent thermal conductivity and strength characteristics, and the composite material composed of AlN whiskers and epoxy resin has the thermal conductivity and thermal conductivity. It has excellent expansion coefficient. In addition, A of the present invention
The 1N whisker composite is of extremely high commercial value because it can be manufactured by simple means.
【図１】本発明の原料であるＡｌＮウィスカーおよびＡ
ｌＮ粉末の製造の際に使用される装置の一例を示す断面
図である。FIG. 1 shows AlN whiskers and A as raw materials of the present invention.
It is sectional drawing which shows an example of the apparatus used at the time of manufacture of 1N powder.
【図２】ウィスカー配合比と相対密度との関係を示すグ
ラフである。FIG. 2 is a graph showing a relationship between a whisker mixing ratio and a relative density.
【図３】ウィスカー配合比と相対密度および熱伝導率と
の関係を示すグラフである。FIG. 3 is a graph showing a relationship between a whisker mixing ratio and a relative density and a thermal conductivity.
【図４】ＡｌＮウィスカー複合材料内におけるウィスカ
ーの配向方向を示す断面図である。FIG. 4 is a cross-sectional view showing the orientation direction of whiskers in an AlN whisker composite material.
１‥‥‥原料供給部 ２‥‥‥Ａｌ2 Ｏ3 管 ３‥‥‥撹拌機 ４‥‥‥電気炉 ５‥‥‥捕集器 ６‥‥‥Ａｌ粉末 ７‥‥‥Ｎ2 ８‥‥‥ＮＨ3 ＋Ｎ2 ９‥‥‥ＡｌＮウィスカー複合材料 １０‥‥‥レーザービーム １１‥‥‥ＡｌＮウィスカー １２‥‥‥熱伝導率測定面1 Raw material supply unit 2 Al 2 O 3 tube 3 Stirrer 4 Electric furnace 5 Collector 6 Al powder 7 N 2 8 ‥ NH 3 + N 2 9 ‥‥‥ AlN whisker composite material 10 ‥‥‥ laser beam 11 ‥‥‥ AlN whiskers 12 ‥‥‥ thermal conductivity measuring surface
Claims (2)
Ｈ3 混合ガスを反応ガスとした浮上窒化法により生成さ
れた表面の滑らかな無色透明状の高純度ＡｌＮウィスカ
ーと、高純度ＡｌＮ微粉末とを混合し、さらに焼結助剤
を添加したものを成形し、その成形体を焼結させて得た
セラミックスであって、90W/mK以上の熱伝導率および50
％以上の相対密度を有することを特徴とするＡｌＮウィ
スカー複合材料。1. A method using N 2 -N
A mixture of high-purity AlN whiskers having a smooth surface and a colorless and transparent surface produced by a floating nitriding method using a H 3 mixed gas as a reaction gas, and high-purity AlN fine powder, and further adding a sintering aid. A ceramic obtained by molding and sintering the molded body, having a thermal conductivity of 90 W / mK or more and a
% AlN whisker composite material characterized by having a relative density of not less than%.
Ｈ3 混合ガスを反応ガスとした浮上窒化法により生成さ
れた表面の滑らかな無色透明状の高純度ＡｌＮウィスカ
ーを成形し、その成形体に基板用エポキシ樹脂を含浸さ
せた後、これを加熱することによって該エポキシ樹脂を
硬化させて得た複合材であって、 3.5W/mK以上の熱伝導
率および40.0×10-6Ｋ-1以下の熱膨張率を有することを
特徴とするＡｌＮウィスカー複合材料。2. A method using N 2 -N
A colorless, transparent, high-purity AlN whisker having a smooth surface generated by a floating nitriding method using a H 3 mixed gas as a reaction gas is molded, and the molded body is impregnated with an epoxy resin for a substrate, and then heated. A composite material obtained by curing the epoxy resin thereby having a thermal conductivity of 3.5 W / mK or more and a thermal expansion coefficient of 40.0 × 10 −6 K −1 or less. material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3125257A JP3011785B2 (en) | 1991-04-26 | 1991-04-26 | AlN whisker composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3125257A JP3011785B2 (en) | 1991-04-26 | 1991-04-26 | AlN whisker composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06219857A JPH06219857A (en) | 1994-08-09 |
| JP3011785B2 true JP3011785B2 (en) | 2000-02-21 |
Family
ID=14905625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3125257A Expired - Fee Related JP3011785B2 (en) | 1991-04-26 | 1991-04-26 | AlN whisker composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3011785B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5416367B2 (en) * | 2008-06-10 | 2014-02-12 | 互応化学工業株式会社 | Heat dissipating solder resist composition and heat dissipating printed wiring board |
| JP6090833B2 (en) * | 2012-09-11 | 2017-03-08 | 株式会社デンソー | AlN whisker and method for producing AlN whisker |
| US11345640B2 (en) * | 2017-03-17 | 2022-05-31 | National University Corporation Nagoya University | Method and apparatus for producing AlN whiskers, AlN whisker bodies, AlN whiskers, resin molded body, and method for producing resin molded body |
| JP6938012B2 (en) * | 2017-03-17 | 2021-09-22 | 国立大学法人東海国立大学機構 | AlN whisker manufacturing method and resin molded product and its manufacturing method |
| WO2023149472A1 (en) * | 2022-02-04 | 2023-08-10 | 国立大学法人東海国立大学機構 | Resin molded product and method for producing same |
-
1991
- 1991-04-26 JP JP3125257A patent/JP3011785B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06219857A (en) | 1994-08-09 |
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