JPH06235031A - Al-aln composite material and its production - Google Patents
Al-aln composite material and its productionInfo
- Publication number
- JPH06235031A JPH06235031A JP4023197A JP2319792A JPH06235031A JP H06235031 A JPH06235031 A JP H06235031A JP 4023197 A JP4023197 A JP 4023197A JP 2319792 A JP2319792 A JP 2319792A JP H06235031 A JPH06235031 A JP H06235031A
- Authority
- JP
- Japan
- Prior art keywords
- aln
- surface layer
- powder
- content
- composite material
- 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.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000002344 surface layer Substances 0.000 claims abstract description 58
- 239000010410 layer Substances 0.000 claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000010030 laminating Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005121 nitriding Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- -1 aluminate compound Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、成分濃度が高Ａｌ側か
ら高ＡｌＮ側まで連続的に変化するＡｌ−ＡｌＮ系複合
材料及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Al-AlN composite material in which the component concentration continuously changes from the high Al side to the high AlN side, and a method for producing the same.
【０００２】[0002]
【従来の技術】ＡｌＮ系セラミックスは、優れた熱伝導
性，電気絶縁性，圧電性等の特性を活かし、半導体基
板，ヒートシンク，各種機能材料等としての使用が期待
されている。また、溶融金属による侵食に対しても高い
抵抗を示し、且つ耐熱性も十分であることから、各種溶
融金属を収容する容器としても使用されている。2. Description of the Related Art AlN-based ceramics are expected to be used as semiconductor substrates, heat sinks, various functional materials, etc. by taking advantage of their excellent properties such as thermal conductivity, electrical insulation and piezoelectricity. Further, since it exhibits high resistance to corrosion by molten metal and has sufficient heat resistance, it is also used as a container for storing various molten metals.
【０００３】ＡｌＮ系セラミックスは、焼結によって通
常製造される。たとえば、常圧で焼結する場合、ＡｌＮ
微粉末と焼結助剤との混合粉末を所定形状に圧粉成形
し、圧粉体を窒素，アルゴン等の非酸化性雰囲気中で１
６００〜１８５０℃程度の高温に加熱することにより焼
結している。AlN ceramics are usually manufactured by sintering. For example, when sintering at normal pressure, AlN
A powder mixture of fine powder and a sintering aid is compacted into a predetermined shape, and the compact is molded in a non-oxidizing atmosphere such as nitrogen or argon.
It is sintered by heating at a high temperature of about 600 to 1850 ° C.
【０００４】難焼結物質であるＡｌＮのみで緻密な焼結
体を製造することは困難である。また、ＡｌＮは、液相
を呈せずに２４５０℃で昇華分解する性質がある。そし
て、常圧で製造されたＡｌＮ焼結体の強度は、単に粒子
間の固体拡散に依存する。そのため、十分な固体拡散を
図る上で、極めて長時間或いは高温度の加熱が必要とな
る。It is difficult to produce a dense sintered body only with AlN, which is a difficult-to-sinter material. Further, AlN has a property of subliming and decomposing at 2450 ° C. without exhibiting a liquid phase. Then, the strength of the AlN sintered body manufactured at normal pressure simply depends on the solid diffusion between particles. Therefore, in order to sufficiently diffuse the solid, heating for a very long time or at a high temperature is required.
【０００５】このような問題を克服する焼結法として、
Ａｌ粉とＡｌＮ粉の混合粉末を窒化反応させて焼結する
反応焼結方法が検討されている。この方法は、Ａｌの窒
化に伴う発熱反応を利用するものである。As a sintering method that overcomes such problems,
A reactive sintering method has been studied in which a mixed powder of Al powder and AlN powder is nitrided and sintered. This method utilizes the exothermic reaction that accompanies the nitridation of Al.
【０００６】本発明者等も、反応焼結法の一種として極
めて微細なＡｌ粉末を使用する方法を開発し、特開平２
−２７５７７２号公報で紹介した。この方法において
は、平均粒径が０．５μｍ以下のＡｌ粉末を他の粉末原
料と混合し、粉末混合物を圧粉成形した圧粉体を窒素雰
囲気下で加熱することによって、ＡｌＮ焼結体を製造し
ている。使用するＡｌ粉末は、粒径がサブミクロンオー
ダーであることから非常に表面活性が高い。そのため、
従来の焼結法に比較して大幅に低い６００〜８００℃程
度の温度において十分な窒化反応が進行し、密度，強度
等の物理的特性に優れたＡｌＮ焼結体が得られる。The present inventors also developed a method of using extremely fine Al powder as a kind of reaction sintering method, and disclosed in Japanese Unexamined Patent Publication
It was introduced in Japanese Patent Publication No. 275772. In this method, Al powder having an average particle size of 0.5 μm or less is mixed with another powder raw material, and the green compact obtained by compacting the powder mixture is heated in a nitrogen atmosphere to form an AlN sintered body. Manufacturing. The Al powder used has a very high surface activity because the particle size is on the order of submicrons. for that reason,
A sufficient nitriding reaction proceeds at a temperature of about 600 to 800 ° C., which is significantly lower than that of the conventional sintering method, and an AlN sintered body excellent in physical properties such as density and strength can be obtained.
【０００７】[0007]
【発明が解決しようとする課題】新しく提案した方法に
よって製造されたＡｌＮ焼結体は、ＡｌＮ本来の特性を
活かして、放熱部品，電気絶縁材料，半導体搭載基板，
圧電素子，耐熱・耐火構造部材等の広範な分野における
素材として期待される。The AlN sintered body manufactured by the newly proposed method takes advantage of the original characteristics of AlN to dissipate the heat dissipation component, the electrically insulating material, the semiconductor mounting board,
It is expected as a material in a wide range of fields such as piezoelectric elements and heat / fire resistant structural members.
【０００８】しかし、ＡｌＮ単体であることから、他の
構造部材に組み付けることが難しい。たとえば、はんだ
に対する濡れ性が悪いことから、金属製の構造部品には
んだ付けすることができない。また、高温流体が通過す
るダクト，排気管等の内張材として使用する場合、ボル
ト止め等ができないため施工が困難になる。However, since it is an AlN simple substance, it is difficult to assemble it to other structural members. For example, because of poor wettability with solder, it cannot be soldered to metal structural parts. Further, when it is used as a lining material for ducts, exhaust pipes, etc. through which a high-temperature fluid passes, it cannot be bolted and the construction becomes difficult.
【０００９】本発明は、このような問題を解消すべく案
出されたものであり、ＡｌＮ本来の特性を損なうことな
く、他の部材に対して容易に組み付けることができる性
質を付与したＡｌＮ系複合材料を提供することを目的と
する。The present invention has been devised to solve such a problem, and an AlN-based material having a property of being easily assembled to other members without impairing the original characteristics of AlN. The purpose is to provide a composite material.
【００１０】[0010]
【課題を解決するための手段】本発明のＡｌ−ＡｌＮ系
複合材料は、その目的を達成するため、表面層のＡｌＮ
含有量が９０重量％以上、裏面層のＡｌ含有量が９０重
量％以上で、表面層から裏面層に向けた厚み方向に関し
てＡｌ含有量が傾斜的に増加していることを特徴とす
る。In order to achieve the object, the Al--AlN composite material of the present invention has a surface layer of AlN.
It is characterized in that the Al content is 90% by weight or more, the Al content in the back surface layer is 90% by weight or more, and the Al content gradually increases in the thickness direction from the front surface layer to the back surface layer.
【００１１】このＡｌ−ＡｌＮ系複合材料は、サブミク
ロン以下の平均粒径をもつＡｌ−ＡｌＮ超微粉末と１μ
ｍ以下の平均粒径を持つＡｌ金属粉末との混合比率をＡ
ｌＮ／（Ａｌ＋ＡｌＮ）換算で表面層形成層では９５以
上，裏面層形成層では５以下，中間層形成層では裏面層
形成層から表面層形成層に向けて段階的に高くなるよう
に、異なる混合比率で配合したＡｌ−ＡｌＮ超微粉末及
びＡｌ金属粉末の粉末混合物を多層状に積み重ね、窒素
雰囲気中で一体的に加熱焼結することにより製造され
る。This Al-AlN composite material comprises Al-AlN ultrafine powder having an average particle size of submicron or less and 1 μm.
The mixing ratio with Al metal powder having an average particle diameter of m or less is A
In terms of 1N / (Al + AlN), the surface layer forming layer has 95 or more, the back surface layer forming layer has 5 or less, and the intermediate layer forming layer has different mixing so that the surface layer forming layer gradually increases from the back surface layer forming layer. It is manufactured by stacking a powder mixture of Al-AlN ultrafine powder and Al metal powder mixed in a ratio in multiple layers and integrally heating and sintering in a nitrogen atmosphere.
【００１２】[0012]
【作 用】本発明のＡｌ−ＡｌＮ系複合材料において
は、表面側のＡｌＮ含有量を高くすることにより、Ａｌ
Ｎ本来の特性を発揮させている。他方、裏面側のＡｌ含
有量を高くすることにより、ネジ切り等の機械切削性や
はんだ付け性を向上させている。そして、裏面側から表
面側の厚み方向に関してＡｌとＡｌＮとの混合比率を傾
斜的に変化させることにより、内部に亀裂や応力集中の
原因となる不連続点の発生を抑えている。これにより、
ＡｌＮの特性が活用され、しかも施工が容易な複合材料
となる。[Operation] In the Al-AlN composite material of the present invention, by increasing the AlN content on the surface side, Al
N The original characteristics are exhibited. On the other hand, by increasing the Al content on the back surface side, mechanical cutting property such as thread cutting and solderability are improved. Then, by changing the mixing ratio of Al and AlN in an inclined manner in the thickness direction from the back surface side to the front surface side, the occurrence of discontinuities causing cracks and stress concentration inside is suppressed. This allows
The characteristics of AlN are utilized, and the composite material is easy to construct.
【００１３】表面層のＡｌＮ含有量は、熱伝導性，耐熱
・耐火性等のＡｌＮ本来の特性を利用する上から９０重
量％以上が必要である。特に電気絶縁性を利用した用途
にあっては、表面層のＡｌＮ含有量を９９重量％以上に
することが好ましい。The AlN content of the surface layer must be 90% by weight or more in order to utilize the original properties of AlN such as thermal conductivity, heat resistance and fire resistance. In particular, for applications using electric insulation, the AlN content of the surface layer is preferably 99% by weight or more.
【００１４】裏面層のＡｌ含有量は、機械切削性，はん
だ付け性等を考慮して９０重量％以上が必要である。Ａ
ｌ含有量が９０重量％未満の裏面層では、Ａｌ含有量の
低下に応じてＡｌＮ含有量が多くなる。そのため、裏面
側に機械切削を行うとき、欠け，破損等の欠陥が発生す
る。また、はんだ付け前処理等としてプレコートを施す
場合、形成された予備めっき層にブリスター等の欠陥が
発生し易くなる。The Al content of the back surface layer is required to be 90% by weight or more in consideration of machinability, solderability and the like. A
In the back surface layer having an I content of less than 90% by weight, the AlN content increases as the Al content decreases. Therefore, when performing mechanical cutting on the back surface side, defects such as chipping and breakage occur. Further, when precoating is performed as a soldering pretreatment, defects such as blisters are likely to occur in the formed preliminary plating layer.
【００１５】そして、裏面層から表面層に向けて、Ａｌ
Ｎ含有比率が傾斜的に高くなっている。このような濃度
勾配をもつ複合材料は、表面層形成層，中間層形成層及
び裏面層形成層ごとにＡｌ−ＡｌＮ超微粉末とＡｌ金属
粉末との混合比率を変え、異なる混合比率の混合粉末を
層状に積み重ね、全体を一体的に焼結することにより製
造される。その際に、Ａｌ−ＡｌＮ超微粉末中のＡｌは
窒化されてＡｌＮとなり、Ａｌ−ＡｌＮ超微粉の含有比
率が高い部分のＡｌＮ含有比率が高くなる。Then, from the back surface layer to the front surface layer, Al
The N content ratio is gradually increasing. The composite material having such a concentration gradient has different mixing ratios of Al-AlN ultrafine powder and Al metal powder for each of the surface layer forming layer, the intermediate layer forming layer and the back surface layer forming layer, and the mixed powders having different mixing ratios are used. Are stacked in layers and the whole is integrally sintered. At that time, Al in the Al-AlN ultrafine powder is nitrided to AlN, and the AlN content ratio in the portion where the content ratio of the Al-AlN ultrafine powder is high becomes high.
【００１６】表面層形成層，中間層形成層及び裏面層形
成層におけるＡｌ−ＡｌＮ超微粉末とＡｌ金属粉末との
混合比率は、最終製品の濃度勾配を考慮して定められ
る。しかし、表面層のＡｌＮ含有量が９０重量％以上で
裏面層のＡｌ含有量が９０重量％以上のＡｌーＡｌＮ焼
結体を得るためには、ＡｌＮ／（Ａｌ＋ＡｌＮ）換算
（重量比）で、表面層形成層では９５以上，裏面層形成
層では５以下，中間層形成層では裏面層形成層から表面
層形成層に向けて段階的に高くすることが必要である。
また、中間層形成層は、製品焼結体の厚みに応じて１層
或いは２層以上とし、各層間で混合比率を変えても良
い。The mixing ratio of the Al-AlN ultrafine powder and the Al metal powder in the surface layer forming layer, the intermediate layer forming layer and the back surface layer forming layer is determined in consideration of the concentration gradient of the final product. However, in order to obtain an Al-AlN sintered body in which the AlN content of the front surface layer is 90% by weight or more and the Al content of the back surface layer is 90% by weight or more, in terms of AlN / (Al + AlN) conversion (weight ratio), It is necessary that the surface layer forming layer has 95 or more, the back surface layer forming layer has 5 or less, and the intermediate layer forming layer has a stepwise increase from the back surface layer forming layer to the surface layer forming layer.
Further, the intermediate layer forming layer may be one layer or two or more layers depending on the thickness of the product sintered body, and the mixing ratio may be changed between the respective layers.
【００１７】使用されるＡｌ−ＡｌＮ超微粉末は、１μ
ｍ以下すなわちサブミクロンオーダの平均粒径をもつこ
とが必要である。平均粒径がサブミクロンオーダとなる
と、従来の粉末とは異なった挙動を呈し、反応活性が非
常に高くなる。そのため、６００〜８００℃程度の比較
的低い温度でも、十分に窒化焼結反応が進行する。The Al-AlN ultrafine powder used is 1 μm.
It is necessary to have an average particle size of m or less, that is, a submicron order. When the average particle size is on the order of submicron, the behavior is different from that of the conventional powder, and the reaction activity becomes very high. Therefore, the nitriding / sintering reaction sufficiently proceeds even at a relatively low temperature of about 600 to 800 ° C.
【００１８】このような超微細粉末は、たとえばＡｌに
窒素プラズマを照射して強制的に溶融・蒸発させ、雰囲
気中の窒素と反応させた後、凝縮して回収することによ
り製造される。このときの蒸発速度，雰囲気中の窒素分
圧等を制御することにより、得られたＡｌ−ＡｌＮ超微
粉末のＡｌＮ含有量を変えることができる。また、Ａｌ
−ＡｌＮ超微粉末中のＡｌは、焼結雰囲気中の窒素と反
応してＡｌＮとなるので、原料段階でのＡｌ−ＡｌＮ超
微粉末のＡｌＮ含有量を大幅に低減させる必要はない。
むしろ、所定量のＡｌを含有している方が焼結時の窒化
反応が円滑に進行する。Such ultra-fine powder is produced, for example, by irradiating Al with nitrogen plasma to forcibly melt and evaporate Al, reacting with nitrogen in the atmosphere, and then condensing and collecting. The AlN content of the obtained Al-AlN ultrafine powder can be changed by controlling the evaporation rate at this time, the partial pressure of nitrogen in the atmosphere, and the like. Also, Al
Since Al in the -AlN ultrafine powder reacts with nitrogen in the sintering atmosphere to form AlN, it is not necessary to significantly reduce the AlN content of the Al-AlN ultrafine powder in the raw material stage.
Rather, the nitriding reaction at the time of sintering proceeds more smoothly when the alloy contains a predetermined amount of Al.
【００１９】Ａｌ−ＡｌＮ系の超微粉と混合されるＡｌ
粉末としては、数ミクロン程度の粒径をもつ市販の金属
粉末を使用することができる。この程度の粒径は、金属
粉末の活性度向上に影響を与えず、焼結時にＡｌの融点
近傍に加熱されても窒化反応はほとんど進行しない。Al mixed with Al-AlN superfine powder
As the powder, a commercially available metal powder having a particle size of about several microns can be used. The particle size of this extent does not affect the improvement of the activity of the metal powder, and the nitriding reaction hardly progresses even when heated near the melting point of Al during sintering.
【００２０】更に、焼結反応を促進させ、焼結体の密度
を向上させる少量の添加物を配合することも可能であ
る。この種の添加物としては、ＳｒＣＯ3 ，ＢａＣＯ
3 ，Ｙ2Ｏ3 ，Ｌａ2 Ｏ3 ，ＣｅＯ，ＰｒＯ2 ，ＮｄＯ3
，Ｓｍ2 Ｏ3 等のアルカリ土類金属酸化物や希土類金
属酸化物等がある。これらアルカリ土類金属酸化物や希
土類金属酸化物等は、ＡｌＮと濡れ性のよい低融点アル
ミネート化合物を形成して液相焼結を進行させる。Further, it is possible to add a small amount of an additive which promotes the sintering reaction and improves the density of the sintered body. Additives of this type include SrCO 3 , BaCO
3 , Y 2 O 3 , La 2 O 3 , CeO, PrO 2 , NdO 3
, Sm 2 O 3 and other alkaline earth metal oxides and rare earth metal oxides. These alkaline earth metal oxides and rare earth metal oxides form a low melting point aluminate compound having good wettability with AlN and promote liquid phase sintering.
【００２１】また、Ａｌ−ＡｌＮ系超微粉によって焼結
性が改善されることから、焼結体の緻密化を阻害するも
のとして扱われていたＢＮ，Ｓｉ3 Ｎ4 ，ＭｇＯ，Ｓｉ
Ｏ2，ＭｎＯ2 ，ＳｉＣ等、或いはスピネル相を形成す
るＡｌ2 Ｏ3 ，ＺｒＯ2 ，ＴｉＯ2 ，Ｃｒ2 Ｏ3 ，Ｎｉ
ＣＯ3 ，Ｎｉ等を配合させることも可能である。これら
の添加物は、熱伝導率，熱膨張率等を調整する助剤とし
て使用される。特にＳｉＣを配合した複合材料は、熱伝
導率が低い全率固溶体を形成する特徴を活用し、基材を
保護する用途が期待される。Further, since the sinterability is improved by the Al--AlN superfine powder, BN, Si 3 N 4 , MgO, Si, which has been treated as an obstacle to the densification of the sintered body, is used.
O 2 , MnO 2 , SiC, etc., or Al 2 O 3 , ZrO 2 , TiO 2 , Cr 2 O 3 , Ni that form a spinel phase
It is also possible to mix CO 3 , Ni and the like. These additives are used as an auxiliary agent for adjusting thermal conductivity, thermal expansion coefficient and the like. In particular, a composite material containing SiC is expected to be used for protecting a base material by utilizing the characteristic of forming a solid solution having a low thermal conductivity.
【００２２】[0022]
【実施例】Ａｌ−ＡｌＮ系粉末として、アークプラズマ
法によって調製した平均粒径０．２μｍの超微粉を使用
した。このＡｌ−ＡｌＮ系粉末のＡｌＮ含有量は、３０
重量％であった。他方、Ａｌ金属粉末としては、粒径が
５〜１２μｍで純度９９．８重量％の市販Ａｌ粉末を使
用した。Ａｌ−ＡｌＮ系粉末及びＡｌ金属粉末を表１に
示す割合で配合し、均一に混合し、６種類の粉末混合物
Ａ〜Ｆを調製した。そして、各粉末混合物Ａ〜Ｆをそれ
ぞれ表１に示す厚みで６層に積み重ね、全体の厚みが１
０ｍｍの多層状粉末積層体を得た。Example As the Al-AlN-based powder, ultrafine powder having an average particle size of 0.2 μm prepared by an arc plasma method was used. The AlN content of this Al-AlN powder is 30.
% By weight. On the other hand, as the Al metal powder, a commercially available Al powder having a particle size of 5 to 12 μm and a purity of 99.8% by weight was used. The Al-AlN-based powder and the Al metal powder were mixed in the proportions shown in Table 1 and uniformly mixed to prepare 6 types of powder mixtures AF. Then, each of the powder mixtures A to F was stacked in 6 layers with the thickness shown in Table 1, and the total thickness was 1
A 0 mm multilayer powder laminate was obtained.
【００２３】[0023]
【表１】 [Table 1]
【００２４】多層粉末積層体を内径１３ｍｍの鋼製ダイ
ス中に入れ、２０ＭＰａの圧力を加えて全体の厚みを５
ｍｍに減厚した圧粉成形体に成形した。次いで、圧粉成
形体を電気炉に装入した。炉内に窒素ガスを送り込みな
がら、窒素気流中で圧粉成形体を６５０℃に２４時間加
熱焼結した。加熱中に炉内を観察したところ、２Ａｌ＋
Ｎ2 →２ＡｌＮの窒化反応に基づく発光がみられた。The multi-layered powder laminate was put into a steel die having an inner diameter of 13 mm, and a pressure of 20 MPa was applied to make the total thickness 5
It was molded into a powder compact having a thickness reduced to mm. Then, the green compact was placed in an electric furnace. The green compact was heated and sintered at 650 ° C. for 24 hours in a nitrogen stream while feeding nitrogen gas into the furnace. When observing the inside of the furnace during heating, 2Al +
Light emission based on the nitriding reaction of N 2 → 2AlN was observed.
【００２５】焼結が終了した段階で、炉冷し、常温近く
まで降温した焼結体を電気炉から取り出した。得られた
焼結体の表面及び裏面をそれぞれ０．１ｍｍの厚みで研
削して、厚み４．８ｍｍの焼結体製品を得た。ＡｌＮリ
ッチの表面層は、硬度がＨv＝１３００と高く、ほぼＡ
ｌＮ単体製品と同じ値を示した。他方、Ａｌリッチの裏
面層は、金属Ａｌよりも若干高いＨv ＝１５０の硬度を
もっていた。When the sintering was completed, the furnace was cooled and the temperature of the sintered body was lowered to near room temperature, and the sintered body was taken out of the electric furnace. The front surface and the back surface of the obtained sintered body were ground to a thickness of 0.1 mm to obtain a sintered product having a thickness of 4.8 mm. The AlN-rich surface layer has a hardness as high as H v = 1300 and is almost A
It showed the same value as the 1N single product. On the other hand, the Al-rich backside layer had a hardness of Hv = 150, which was slightly higher than that of metallic Al.
【００２６】焼結体をダイヤモンドカッターで切断し、
厚み方向に沿った成分変動及び切断面の組織を調査し
た。成分変動は、焼結体の厚み方向に直角に０．２ｍｍ
ごとに切断し、各切断面のＸ線回折ピーク強度からＡｌ
Ｎ含有量を推定した。The sintered body is cut with a diamond cutter,
The composition variation along the thickness direction and the structure of the cut surface were investigated. The component variation is 0.2 mm perpendicular to the thickness direction of the sintered body.
Each of the cut surfaces, and from the X-ray diffraction peak intensity of each cut surface,
The N content was estimated.
【００２７】得られたＡｌＮ含有量を焼結体の厚み方向
との関係で表したところ、図１に示す関係が成立してい
ることが判った。粉末混合物Ａから形成された裏面層で
は、ＡｌＮ含有量が５重量％と低く、９２重量％以上の
Ａｌを含有していた。他方、粉末混合物Ｆから形成され
た表面層では、ＡｌＮ含有量が９３重量％と高く、２重
量％未満のＡｌを含んでいるに過ぎなかった。そして、
粉末混合物Ｂ〜Ｅから形成された中間層では、それぞれ
の粉末混合物Ｂ〜ＥのＡｌＮ含有量を中心として、裏面
層側でＡｌＮ含有量が低く、表面層側でＡｌＮ含有量が
高い濃度勾配をもっていた。When the obtained AlN content was expressed in relation to the thickness direction of the sintered body, it was found that the relation shown in FIG. 1 was established. The back layer formed from the powder mixture A had a low AlN content of 5% by weight, and contained 92% by weight or more of Al. On the other hand, the surface layer formed from the powder mixture F had a high AlN content of 93% by weight and contained only less than 2% by weight of Al. And
In the intermediate layer formed from the powder mixtures B to E, the AlN content is low on the back surface side and the AlN content is high on the front surface side with a concentration gradient centering on the AlN content of each of the powder mixtures B to E. I was there.
【００２８】圧粉状態で各粉末混合物Ａ〜Ｆの界面に相
当する部分には、不連続的な成分変動が検出されなかっ
た。ＡｌＮ含有量は、図１に示すように裏面層から表面
層に向けて連続的に高くなっていた。これは、多層粉末
積層体を加圧成形する際に粉末混合物Ａ〜Ｆが形成する
各層の間に部分的な均一化が行われ、各粉末混合物Ａ〜
Ｆ間でＡｌＮ含有量の差が緩和されたことを示すもので
ある。また、加熱中の拡散反応も、各層間の均一化を促
進させる一因となっている。In the pressed state, no discontinuous component fluctuation was detected in the portions corresponding to the interfaces of the powder mixtures AF. The AlN content was continuously higher from the back surface layer toward the front surface layer as shown in FIG. This is because partial homogenization is performed between the layers formed by the powder mixtures A to F when the multi-layer powder laminate is pressure-molded.
This shows that the difference in AlN content between F was relaxed. In addition, the diffusion reaction during heating also contributes to promoting the homogenization between the layers.
【００２９】また、顕微鏡観察の結果、ＡｌＮ含有量の
高い表面層側では、ＡｌＮマトリックスの中にＡｌが分
散した組織が形成されていた。そして、分散しているＡ
ｌ粒子の中にＡｌＮが巻き込まれていることが観察され
た。他方、純Ａｌに近い裏面側では、Ａｌの粒界にＡｌ
Ｎが分散した組織が形成されていた。Ａｌ粒子の粒界に
分散しているＡｌＮは、表面層側に向かうほど視野に占
める割合が多くなり、ＡｌＮ含有量４０〜５０重量％に
当る中間部分でマトリックスを形成していることが判っ
た。As a result of microscopic observation, a structure in which Al was dispersed in an AlN matrix was formed on the surface layer side having a high AlN content. And the dispersed A
It was observed that AlN was caught in the 1 particle. On the other hand, on the back surface side close to pure Al, Al
A structure in which N was dispersed was formed. It was found that the AlN dispersed in the grain boundary of the Al particles has a larger proportion in the visual field as it goes toward the surface layer side, and forms a matrix in the intermediate portion where the AlN content is 40 to 50% by weight. .
【００３０】この組織変化は、焼結体の厚み方向に関し
て連続して観察された。すなわち、ごく一部に不均質な
組織がみられるものの、全体としてＡｌベースからＡｌ
Ｎベースのマトリックスへと連続的に変化していた。こ
の組織変化は、図１に示したＡｌＮ含有量の変化と整合
性よく対応していた。また、厚み方向全体を通じて、Ａ
ｌの結晶粒径は数十μｍ程度であった。This structural change was continuously observed in the thickness direction of the sintered body. That is, although an inhomogeneous structure is seen in only a small part, the Al base to Al
It was continuously changing to an N-based matrix. This microstructural change corresponded well with the change in the AlN content shown in FIG. In addition, in the entire thickness direction, A
The crystal grain size of 1 was about several tens of μm.
【００３１】得られたＡｌ−ＡｌＮ系複合材料は、Ａｌ
Ｎの性質を示す表面層及びＡｌに近い性質を示す裏面層
とをもっている。そして、表面層と裏面層との間では、
連続的に変化する成分及び組織となっている。そのた
め、表面層側を高熱伝導性，高電気絶縁性，圧電性，耐
溶湯侵食性，耐火・耐熱性等を活かした用途に使用し、
裏面層側を他の構造部材に固定する部分とすることがで
きる。The obtained Al-AlN composite material is Al
It has a front surface layer showing the property of N and a back surface layer showing the property close to Al. And between the front surface layer and the back surface layer,
The composition and structure change continuously. Therefore, the surface layer side is used for applications that take advantage of high thermal conductivity, high electrical insulation, piezoelectricity, molten metal erosion resistance, fire resistance, heat resistance, etc.
The back surface layer side can be a portion fixed to another structural member.
【００３２】たとえば、高温の溶融金属が流動する溶湯
供給管等の内面に対するライニング材として使用すると
き、耐久性に優れた且つ配管系が容易に得られる。ま
た、半導体搭載基板，ヒートシンク等として使用すると
き、放熱特性に優れ且つ周辺部材に対する接合が容易な
ものとなる。また、Ａｌリッチな裏面層に直接ワイヤボ
ンディングすることができる長所ももっている。For example, when it is used as a lining material for the inner surface of a molten metal supply pipe or the like in which a molten metal at high temperature flows, a pipe system having excellent durability can be easily obtained. Further, when used as a semiconductor mounting board, a heat sink, etc., it has excellent heat dissipation characteristics and can be easily joined to peripheral members. Further, it has an advantage that it can be directly wire-bonded to the Al-rich back surface layer.
【００３３】なお、以上の実施例においては、常圧下で
の焼結によってＡｌ−ＡｌＮ系複合材料を製造する場合
を説明した。しかし、本発明はこれに拘束されるもので
はなく、圧粉成形と加熱焼結とを同時に行うホットプレ
ス等の他の焼結法によってＡｌ−ＡｌＮ系複合材料を製
造することができるのは勿論である。In the above examples, the case where an Al-AlN composite material is manufactured by sintering under normal pressure has been described. However, the present invention is not limited to this, and it goes without saying that the Al—AlN composite material can be manufactured by another sintering method such as hot pressing in which powder compacting and heat sintering are simultaneously performed. Is.
【００３４】[0034]
【発明の効果】以上に説明したように、本発明のＡｌ−
ＡｌＮ系複合材料は、ＡｌＮリッチの表面層とＡｌリッ
チの裏面層とをもち、表面層と裏面層との間で成分及び
組織が連続的に変化している。そのため、Ａｌリッチの
裏面層側を周辺構造部材に容易に取り付けることがで
き、表面層側にあるＡｌＮの特性を活かした高機能部品
として使用される。As described above, according to the present invention, the Al-
The AlN-based composite material has an AlN-rich front surface layer and an Al-rich back surface layer, and the components and the structure are continuously changed between the front surface layer and the back surface layer. Therefore, the Al-rich back surface layer side can be easily attached to the peripheral structural member, and the Al-rich back surface layer side is used as a high-performance component utilizing the characteristics of AlN on the surface layer side.
【図１】 本発明実施例で製造されたＡｌ−ＡｌＮ系複
合材料における厚み方向に沿ったＡｌＮ含有量の変化を
示す。FIG. 1 shows a change in AlN content along the thickness direction in an Al—AlN composite material manufactured in an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大崎 勝久 千葉県市川市高谷新町７番地の１ 日新製 鋼株式会社新材料研究所内 (72)発明者 新谷 光二 北海道札幌市北区北十三条西八丁目文部省 用地（番地なし）北海道大学工学部内 (72)発明者 吉田 知身 北海道札幌市北区北十三条西八丁目文部省 用地（番地なし）北海道大学工学部内 (72)発明者 永井 忠雄 北海道札幌市北区北十三条西八丁目文部省 用地（番地なし）北海道大学工学部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Katsuhisa Osaki, Inventor, Katsuhisa, 1st, 7th Takatani Shinmachi, Ichikawa City, Chiba, Nisshin Steel Co., Ltd., New Materials Research Center (72) Koji Shintani, Kita-kujo, Kita-ku, Sapporo, Hokkaido West 8-chome Ministry of Education (no street number) Hokkaido University Faculty of Engineering (72) Inventor Satoshi Yoshida Kita-kujojo, Kita-ku, Sapporo-shi, Hokkaido Hokkaido 8-chome Ministry of Education (no street number) Hokkaido University Faculty of Engineering (72) Inventor Tadao Nagai Hokkaido, Kita-ku, Kita-Sanjo Nishi 8-chome Ministry of Education Land (no street number) Hokkaido University Faculty of Engineering
Claims (2)
上、裏面層のＡｌ含有量が９０重量％以上で、表面層か
ら裏面層に向けた厚み方向に関してＡｌ含有量が傾斜的
に増加していることを特徴とするＡｌ−ＡｌＮ系複合材
料。1. The surface layer has an AlN content of 90% by weight or more and the back layer has an Al content of 90% by weight or more, and the Al content gradually increases in the thickness direction from the surface layer to the back layer. An Al-AlN composite material.
−ＡｌＮ超微粉末と１μｍ以上の平均粒径を持つＡｌ金
属粉末との混合比率をＡｌＮ／（Ａｌ＋ＡｌＮ）換算で
表面層形成層では９５以上，裏面層形成層では５以下，
中間層形成層では裏面層形成層から表面層形成層に向け
て段階的に高くなるように、異なる混合比率で配合した
Ａｌ−ＡｌＮ超微粉末及びＡｌ金属粉末の粉末混合物を
多層状に積み重ね、窒素雰囲気中で一体的に加熱焼結す
ることを特徴とするＡｌ−ＡｌＮ系複合材料の製造方
法。2. Al having an average particle size of submicron or less
-The mixing ratio of the AlN ultrafine powder and the Al metal powder having an average particle size of 1 μm or more is 95 or more in the surface layer forming layer and 5 or less in the back surface layer forming layer in terms of AlN / (Al + AlN).
In the intermediate layer forming layer, a powder mixture of Al-AlN ultrafine powder and Al metal powder mixed in different mixing ratios is stacked in multiple layers so that the surface layer forming layer gradually increases in height from the back surface layer forming layer. A method for producing an Al-AlN-based composite material, which comprises integrally heating and sintering in a nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4023197A JPH06235031A (en) | 1992-01-13 | 1992-01-13 | Al-aln composite material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4023197A JPH06235031A (en) | 1992-01-13 | 1992-01-13 | Al-aln composite material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06235031A true JPH06235031A (en) | 1994-08-23 |
Family
ID=12103947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4023197A Withdrawn JPH06235031A (en) | 1992-01-13 | 1992-01-13 | Al-aln composite material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06235031A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464904C (en) * | 2007-06-01 | 2009-03-04 | 北京科技大学 | Method for preparing Al/AlN electronic package material |
| CN111515404A (en) * | 2020-05-15 | 2020-08-11 | 富耐克超硬材料股份有限公司 | Preparation method of cBN/Al composite material |
-
1992
- 1992-01-13 JP JP4023197A patent/JPH06235031A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464904C (en) * | 2007-06-01 | 2009-03-04 | 北京科技大学 | Method for preparing Al/AlN electronic package material |
| CN111515404A (en) * | 2020-05-15 | 2020-08-11 | 富耐克超硬材料股份有限公司 | Preparation method of cBN/Al composite material |
| CN111515404B (en) * | 2020-05-15 | 2023-05-12 | 富耐克超硬材料股份有限公司 | Preparation method of cBN/Al composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4997431B2 (en) | Method for producing high thermal conductivity silicon nitride substrate | |
| WO2020203787A1 (en) | Silicon nitride substrate, silicon nitride-metal complex, silicon nitride circuit board, and semiconductor package | |
| Omori | Sintering, consolidation, reaction and crystal growth by the spark plasma system (SPS) | |
| US8575051B2 (en) | Heat sink having a high thermal conductivity | |
| US8511535B1 (en) | Innovative braze and brazing process for hermetic sealing between ceramic and metal components in a high-temperature oxidizing or reducing atmosphere | |
| JP2011524466A (en) | Metal-infiltrated silicon titanium and aluminum carbide bodies | |
| JP3629783B2 (en) | Circuit board | |
| Yan et al. | Thermoelectric properties of n-type ZrNiSn prepared by rapid non-equilibrium laser processing | |
| JP2005184021A (en) | Heat sink using high temperature conductive diamond sintered body and its manufacturing method | |
| JP3450570B2 (en) | High thermal conductive silicon nitride circuit board | |
| JPH06235031A (en) | Al-aln composite material and its production | |
| CN112334239A (en) | Ceramic metalized substrate and preparation method thereof | |
| JP3461054B2 (en) | Composite material | |
| KR102660216B1 (en) | Dense composite material, method for producing the same, joined body, and member for semiconductor manufacturing device | |
| JPH06321511A (en) | Ultrafine aluminum nitride particle, its production and ultrafine particulate sintered compact | |
| JPH07172921A (en) | Aluminum nitride sintered material and its production | |
| JPH0693468A (en) | Formation of a1n series ceramics coating | |
| US10202681B2 (en) | Copper-gallium sputtering target | |
| US8232232B2 (en) | Oxide target for laser vapor deposition and method of manufacturing the same | |
| US5605558A (en) | Nitrogenous aluminum-silicon powder metallurgical alloy | |
| JP4177467B2 (en) | High toughness hard alloy and manufacturing method thereof | |
| Atarashiya | Aluminum nitride/metal composites using ultra-fine aluminum particles and their application for joining | |
| JPH01272770A (en) | Formation of ceramic layer on metallic body | |
| JPH0292872A (en) | Bonding between ceramic material and copper material | |
| WO2023145339A1 (en) | Thermoelectric conversion material, thermoelectric conversion material composition, thermoelectric conversion element, thermoelectric conversion module, thermoelectric conversion system, method for producing thermoelectric conversion material composition, and method for producing thermoelectric conversion material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990408 |