JP4598033B2 - Copper Al2O3 composite powder sintered body and method for producing the same - Google Patents
Copper Al2O3 composite powder sintered body and method for producing the same Download PDFInfo
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Description
本発明は、放熱性に優れかつ高密度の焼結体を製造することができる放熱性に優れかつ高密度である鍍銅Ａｌ２Ｏ３複合粉末焼結体及び同焼結体の製造方法に関する。 The present invention relates to a sintered copper Al 2 O 3 composite powder sintered body having excellent heat dissipation and high density capable of producing a sintered body having excellent heat dissipation and high density, and a method for producing the sintered body. .
アルミナ（Ａｌ２Ｏ３）は、工業的にはボーキサイトを原料としバイヤー法によって製造される。密度は４．０ｇ・ｃｍ−３、融点は２０５０°Ｃである。１０００°Ｃ以上でα−Ａｌ２Ｏ３となり、熱的に極めて安定である。
このアルミナは、研磨剤、砥石、耐火材、絶縁体、触媒、乾燥剤、吸着材、レーザー材料などの広範囲な用途がある。特に、銅とＡｌ２Ｏ３の焼結体は放熱性が向上し、半導体装置の放熱板等として有用である。
Alumina (Al 2 O 3 ) is industrially produced by the buyer method using bauxite as a raw material. The density is 4.0 g · cm −3 and the melting point is 2050 ° C. It becomes α-Al 2 O 3 at 1000 ° C. or higher and is extremely stable thermally.
This alumina has a wide range of uses such as abrasives, grindstones, refractory materials, insulators, catalysts, desiccants, adsorbents, laser materials and the like. In particular, a sintered body of copper and Al 2 O 3 has improved heat dissipation and is useful as a heat sink for semiconductor devices.
一般に、銅の粉とＡｌ２Ｏ３粉を単に混合して成形・焼結しただけでは、十分な強度をもつ均一な焼結体が得られない。したがって、予めＡｌ２Ｏ３粉に銅を被覆し、これによって得られた銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末を成形・焼結して所定の焼結体を得る手法が採られている。
しかし、従来このような銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末を焼結しても密度が十分に上がらず、まためっき等による被膜が均一でなく、Ａｌ２Ｏ３粉末の一部は被膜が形成されていない等、問題があった。
Generally, a uniform sintered body having sufficient strength cannot be obtained by simply mixing and molding and sintering copper powder and Al 2 O 3 powder. Therefore, a method is adopted in which Al 2 O 3 powder is coated with copper in advance, and copper-plated Al 2 O 3 composite powder having a copper coating layer obtained thereby is molded and sintered to obtain a predetermined sintered body. It has been.
However, conventionally, even if sintered copper Al 2 O 3 composite powder having such a copper coating layer is sintered, the density is not sufficiently increased, the coating film by plating or the like is not uniform, and the Al 2 O 3 powder is not uniform. There was a problem that the film was not formed on the part.
このようなことから、従来は銅被覆層を形成する処理方法、銅被覆層の厚さ、焼結の条件等を、それなりに変えてＡｌ２Ｏ３複合金属焼結体を製造する試みはいくつかなされてきたが、満足のいくものが得られていないというのが現状である。 For this reason, there have been several attempts to produce an Al 2 O 3 composite metal sintered body by changing the treatment method for forming the copper coating layer, the thickness of the copper coating layer, the sintering conditions, and the like. It has been done, but the current situation is that no satisfactory one has been obtained.
本発明は、放熱性に優れかつ高密度の焼結体を製造することができる放熱性に優れかつ高密度である鍍銅Ａｌ２Ｏ３複合粉末焼結体及び同焼結体の製造方法を得ることを課題とする。 The present invention relates to a copper bromide Al 2 O 3 composite powder sintered body having excellent heat dissipation and high density capable of producing a sintered body having high heat dissipation and high density, and a method for producing the sintered body. It is a problem to obtain.
本発明者らは、上記問題点を解決するために被覆に使用するめっきの条件や被覆層の厚さ、焼結条件を種々検討し、めっき層形成方法の改善を図り、被覆層を全体的に均一かつ厚く形成する等の工夫により、放熱性に優れかつ高密度の焼結体を製造することができるとの知見を得た。
本発明はこの知見に基づいて、
１．銅量が６０質量％以上、残量がＡｌ ２ Ｏ ３ である銅被覆層を備えた鍍銅Ａｌ ２ Ｏ ３ 複合粉末の焼結体であり、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上であることを特徴とする銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末からなる焼結体
２．銅量が７０質量％以上、残量がＡｌ ２ Ｏ ３ である銅被覆層を備えた鍍銅Ａｌ ２ Ｏ ３ 複合粉末の焼結体であり、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上であることを特徴とする銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末からなる焼結体
３．銅量が６０質量％以上、残量がＡｌ ２ Ｏ ３ である銅被覆層を備えた鍍銅Ａｌ ２ Ｏ ３ 複合粉末を、成形圧力４ｔ／ｃｍ２以上で成形し、これを焼結することを特徴とする銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末からなる、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上である焼結体の製造方法
４．銅量が７０質量％以上、残量がＡｌ ２ Ｏ ３ である銅被覆層を備えた鍍銅Ａｌ ２ Ｏ ３ 複合粉末を、成形圧力３ｔ／ｃｍ２以上で成形し、これを焼結することを特徴とする銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末からなる、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上である焼結体の製造方法、を提供するものである。
In order to solve the above problems, the present inventors have studied various plating conditions used for coating, the thickness of the coating layer, and sintering conditions, and have improved the plating layer forming method. The inventors have obtained the knowledge that a high-density sintered body with excellent heat dissipation can be produced by means of uniform and thick formation.
The present invention is based on this finding,
1. A sintered body of copper-plated Al 2 O 3 composite powder having a copper coating layer with a copper amount of 60% by mass or more and a remaining amount of Al 2 O 3 , and a density ratio ([measured density of the sintered body] / [Density when there is no void in the sintered body ]) is 80% or more, the sintered body comprising copper-plated Al 2 O 3 composite powder provided with a copper coating layer, Density copper content is 70 wt% or more, the remaining amount is a sintered body of 鍍
以上に示す通り、本発明は、銅被覆層の形成すなわちめっき条件を最適にすることにより、銅被覆層を均一かつ厚く形成した鍍銅Ａｌ２Ｏ３複合粉末を得ることができ、これを焼結することにより放熱性に優れかつ高密度であり、かつ強度も著しく向上した焼結体を製造することができるという優れた特徴を有している。 As described above, according to the present invention, by optimizing the formation of the copper coating layer, that is, the plating conditions, a copper-plated Al 2 O 3 composite powder in which the copper coating layer is formed uniformly and thick can be obtained. As a result, it has an excellent feature that a sintered body having excellent heat dissipation, high density, and significantly improved strength can be produced.
本発明の鍍銅Ａｌ２Ｏ３複合粉末焼結体を半導体装置の放熱板等に利用するには、放熱性を向上させることが必要であるが、そのためには鍍銅Ａｌ２Ｏ３複合粉末焼結体の密度を高めることが必要である。
このような高密度の焼結体を得る方法として、銅量が６０質量％以上の厚くかつ均一な銅被覆層を備え、残量がＡｌ ２ Ｏ ３ である鍍銅Ａｌ２Ｏ３複合粉末を用いることが有効であることが分かった。特に、銅量が７０質量％以上の銅被覆層の鍍銅Ａｌ２Ｏ３複合粉末であることが望ましい。
鍍銅Al 2 O 3 composite powder sintered body to be used for heat dissipation plate of the semiconductor device, it is necessary to improve the heat radiation property, in order that the鍍銅Al 2 O 3 composite powder of the present invention It is necessary to increase the density of the sintered body.
As a method for obtaining such a high-density sintered body, a copper-copper Al 2 O 3 composite powder comprising a thick and uniform copper coating layer with a copper amount of 60% by mass or more and a remaining amount of Al 2 O 3 is used. It has been found effective to use. In particular, it is desirable to be a copper-plated Al 2 O 3 composite powder having a copper coating layer with a copper content of 70 mass % or more.
この厚くかつ均一な銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末を製造するには、Ａｌ２Ｏ３粉を予めイミダゾールシランと塩化パラジウムによる触媒付与の前処理を施した後、無電解めっきにより銅を１〜１０質量％被覆し、さらに硫酸銅水溶液に鉄粉を添加し、該鉄との置換めっきにより銅を被覆することによって得ることができる。
上記の工程による無電解めっきを行わない場合には、その後の銅の置換めっきの際に未付着のＡｌ２Ｏ３粉が出るようになり、均一性に劣る焼結体となることがあるので、好ましくない。
置換めっきには、Ｃｕ１０〜８５ｇ／Ｌ、硫酸５〜５０ｇ／Ｌ、塩素イオン０〜７０ｍｇ／Ｌを含有する硫酸銅水溶液を用いることが望ましい。
このめっき工程によって、銅量が６０質量％以上、さらに銅量が７０質量％以上である銅被覆層を備え、残量がＡｌ ２ Ｏ ３ である鍍銅Ａｌ２Ｏ３複合粉末を製造することができる。
In order to produce this copper-plated Al 2 O 3 composite powder having a thick and uniform copper coating layer, the Al 2 O 3 powder is pretreated with imidazole silane and palladium chloride, and then electroless. It can be obtained by coating 1 to 10% by mass of copper by plating, adding iron powder to a copper sulfate aqueous solution, and coating copper by displacement plating with the iron.
In the case where electroless plating is not performed by the above process, unattached Al 2 O 3 powder comes out during subsequent copper substitution plating, which may result in a sintered body with poor uniformity. It is not preferable.
For displacement plating, it is desirable to use a copper sulfate aqueous
By this plating step, a copper copper Al 2 O 3 composite powder having a copper coating layer with a copper content of 60% by mass or more and a copper content of 70% by mass or more and having a remaining amount of Al 2 O 3 is manufactured. Can do.
上記によって得られた銅被覆層を備え、残量がＡｌ ２ Ｏ ３ である鍍銅Ａｌ２Ｏ３複合粉末を成形圧力３ｔ／ｃｍ２以上で成形し、これを焼結することにより、下記実施例に示すように、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の焼結体が得られる。
成形圧力３ｔ／ｃｍ ２ 未満では、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の鍍銅Ａｌ２Ｏ３複合粉末焼結体が得られ難いので、焼結体の成形圧力を４ｔ／ｃｍ ２ 以上、特に５ｔ／ｃｍ２以上とすることが望ましい。
銅被覆層を備え、残量がＡｌ ２ Ｏ ３ である鍍銅Ａｌ２Ｏ３複合粉末の銅量と真密度及び焼結密度との関係を図１に示す。図において実線は焼結体の真密度、点線は密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％を示す。銅被覆層の銅量の増加と共に焼結体の真密度及び密度比は上がり、成形圧力４ｔ／ｃｍ ２ 以上、特に５ｔ／ｃｍ２以上で安定した密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の焼結体が得られる。
The copper coating layer obtained as described above is provided, and a copper-plated Al 2 O 3 composite powder having a remaining amount of Al 2 O 3 is molded at a molding pressure of 3 t / cm 2 or more, and sintered, thereby performing the following. As shown in the example, a sintered body having a density ratio ([measured density of the sintered body] / [density when the sintered body has no voids]) of 80% or more is obtained.
When the molding pressure is less than 3 t / cm 2 , the copper ratio Al 2 O 3 composite having a density ratio ([measured density of the sintered body] / [density when there is no void in the sintered body]) is 80% or more. Since it is difficult to obtain a powder sintered body, it is desirable that the compacting pressure of the sintered body is 4 t / cm 2 or more, particularly 5 t / cm 2 or more.
Comprising a copper coating layer, showing the relationship between the copper content and the true density and the sintering density of鍍銅Al 2 O 3 composite powder remaining is Al 2 O 3 in Figure 1. In the figure, the solid line represents the true density of the sintered body, and the dotted line represents the density ratio ([actually measured density of sintered body] / [density when there is no void in the sintered body]) . As the amount of copper in the copper coating layer increases, the true density and density ratio of the sintered body increase, and the density ratio is stable at a molding pressure of 4 t / cm 2 or more, particularly 5 t / cm 2 or more ([actually measured density of sintered body]. / [Density when the sintered body has no voids]) is obtained with a sintered body of 80% or more.
次に、本発明の実施例について説明する。なお、本実施例はあくまで１例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。
（実施例１）
市販のＡｌ２Ｏ３粉（ＡＳ−１０、昭和電工製）にイミダゾールシラン及び塩化パラジウムによる触媒付与の前処理を施した後、予め無電解めっきしたものを原料として、下記の置換めっきによりトータルの銅量が６４．９質量％被覆された鍍銅Ａｌ２Ｏ３粉を作製した。
（置換めっき条件）
１）置換めっき液組成
Ｃｕ：６０ｇ／Ｌ
硫酸：３０ｇ／Ｌ
塩素イオン：６ｍｇ／Ｌ
２）置換用還元剤
市販の還元鉄粉（−１００メッシュ）
３）置換めっき方法
原料粉（前処理したＡｌ２Ｏ３粉）と鉄粉をよく混合した後、必要量の上記めっき液を徐々に添加しながら攪拌する。これによって、めっき反応が起こる。鉄粉及びめっき液の量は、目標とする銅めっき量と原料粉量により算出される。めっき後は水洗及び乾燥を行うことにより鍍銅Ａｌ２Ｏ３粉が得られる。
Next, examples of the present invention will be described. In addition, a present Example is an example to the last, and is not restrict | limited to this example. That is, all aspects or modifications other than the embodiments are included within the scope of the technical idea of the present invention.
Example 1
A commercially available Al 2 O 3 powder (AS-10, manufactured by Showa Denko) was subjected to pretreatment for catalyst application with imidazole silane and palladium chloride, and then subjected to electroless plating in advance as a raw material. Copper copper Al 2 O 3 powder coated with 64.9% by mass of copper was prepared.
(Displacement plating conditions)
1) Displacement plating solution composition Cu: 60 g / L
Sulfuric acid: 30 g / L
Chlorine ion: 6mg / L
2) Replacement reducing agent Commercially available reduced iron powder (-100 mesh)
3) Displacement plating method After thoroughly mixing the raw material powder (pretreated Al 2 O 3 powder) and iron powder, the mixture is stirred while gradually adding the required amount of the plating solution. This causes a plating reaction. The amounts of iron powder and plating solution are calculated based on the target copper plating amount and raw material powder amount. After plating, the copper-plated Al 2 O 3 powder is obtained by washing with water and drying.
（めっき粉の評価）
上記により得られた鍍銅Ａｌ２Ｏ３粉を金型成形して、１１．３ｍｍφ×１０ｍｍＨの円柱状圧粉体（試験片）を作製して、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）を測定した。
成形圧力３ｔ／ｃｍ２では、７４．７％であったが、成形圧力４ｔ／ｃｍ２で７８．３％、成形圧力５ｔ／ｃｍ２で８０．８％となり、５ｔ／ｃｍ２の成形圧力で、安定した密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の圧粉体を得ることができた。
また、これらの圧粉体を水素気流雰囲気中で保持温度８７５°Ｃ、保持時間６０分焼結した後の焼結体の密度比を測定したところ、いずれも圧粉体の密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）を上回り、成形圧力４ｔ／ｃｍ２以上で密度比８０％以上の焼結体を得ることができた。 以上の結果を表１に示す。また、図１に実施例１の結果をプロットしたものを○印で示す。
(Evaluation of plating powder)
The copper-plated Al 2 O 3 powder obtained above is molded to produce a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio ([actually measured density of sintered body] ] / [Density when the sintered body has no voids]) .
In molding pressure 3t / cm 2, was 74.7% 78.3% at a molding pressure of 4t / cm 2, it becomes 80.8% at a molding pressure of 5t / cm 2, at a molding pressure of 5t / cm 2 It was possible to obtain a green compact having a stable density ratio ([measured density of sintered body] / [density when there is no void in the sintered body]) of 80% or more.
The density ratio of the compact holding temperature 875 ° in a hydrogen stream atmosphere C, where the density ratio of the sintered body after 60 minutes sintered retention time was measured, both green compact ([baked The measured density of the bonded body] / [density when the sintered body has no voids]) was exceeded, and a sintered body having a density ratio of 80% or more was obtained at a molding pressure of 4 t / cm 2 or more. . The results are shown in Table 1. Moreover, what plotted the result of Example 1 in FIG. 1 is shown by (circle).
（実施例２）
実施例１と同じ材料を使用し、同様にして予め銅を４．９質量％無電解めっきしたＡｌ２Ｏ３を原料として、同様の置換めっき条件によりトータルの銅量が７１．８質量％被覆された鍍銅Ａｌ２Ｏ３粉を作製した。
これによって得られた鍍銅Ａｌ２Ｏ３粉を金型成形して、１１．３ｍｍφ×１０ｍｍＨの円柱状圧粉体（試験片）を作製して、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）を測定した。
成形圧力３ｔ／ｃｍ２では、７６．３％であったが、成形圧力４ｔ／ｃｍ２で８０．３％、成形圧力５ｔ／ｃｍ２で８３．９％となり、４ｔ／ｃｍ２の成形圧力で、安定した密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の圧粉体を得ることができた。
また、これらの圧粉体を実施例１と同様に、水素気流雰囲気中で保持温度８７５°Ｃ、保持時間６０分焼結した後の焼結体の密度比を測定したところ、いずれも圧粉体の密度比を上回り、成形圧力３ｔ／ｃｍ２以上で密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の焼結体を得ることができた。
以上の結果を実施例１と同様に、表１に示す。また、図１に実施例２の結果をプロットしたものを◇印で示す。
(Example 2)
Using the same material as in Example 1 and similarly using Al 2 O 3 previously electrolessly plated with 4.9% by mass of copper as a raw material, the total copper content is 71.8% by mass under the same displacement plating conditions. A copper bronze Al 2 O 3 powder was produced.
The copper-plated Al 2 O 3 powder obtained in this way was molded to produce a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio ([actually measured density of sintered body] ] / [Density when the sintered body has no voids]) .
In molding pressure 3t / cm 2, but was 76.3% 80.3% at a molding pressure of 4t / cm 2, becomes 83.9% at a molding pressure of 5t / cm 2, at a molding pressure of 4t / cm 2 It was possible to obtain a green compact having a stable density ratio ([measured density of sintered body] / [density when there is no void in the sintered body]) of 80% or more.
Further, when these green compacts were sintered in a hydrogen stream atmosphere at a holding temperature of 875 ° C. and a holding time of 60 minutes, the density ratio of the sintered bodies was measured. The density ratio ([sintered density of the sintered body] / [density when there are no voids in the sintered body]) is 80% or higher at a molding pressure of 3 t / cm 2 or higher. I was able to get a tie.
The results are shown in Table 1 as in Example 1. Moreover, what plotted the result of Example 2 in FIG.
（比較例１）
実施例１と同じ材料を使用し、同様にして予め銅を４．８質量％無電解めっきしたＡｌ２Ｏ３を原料として、同様の置換めっき条件によりトータルの銅量が４５．１ｗｔ％被覆された鍍銅Ａｌ２Ｏ３粉を作製した。
これによって得られた鍍銅Ａｌ２Ｏ３粉を金型成形して、１１．３ｍｍφ×１０ｍｍＨの円柱状圧粉体（試験片）を作製して、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）を測定した。
成形圧力３ｔ／ｃｍ２で７２．３％、成形圧力４ｔ／ｃｍ２で７４．９％、成形圧力５ｔ／ｃｍ２でも７７．０％であり、５ｔ／ｃｍ２の成形圧力においても、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の圧粉体を得ることはできなかった。
また、これらの圧粉体を実施例１と同様に、水素気流雰囲気中で保持温度８７５°Ｃ、保持時間６０分焼結した後の焼結体の密度比を測定したところ、いずれも圧粉体の密度比と差がなく、成形圧力５ｔ／ｃｍ２以上で密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の焼結体を得られなかった。
以上の結果を実施例１と同様に、表１に示す。また、図１に比較例１の結果をプロットしたものを＋印で示す。
(Comparative Example 1)
Using the same material as in Example 1 and using Al 2 O 3 preliminarily plated with 4.8% by mass of copper in the same manner as a raw material, a total copper amount of 45.1 wt% was coated under the same displacement plating conditions. Copper copper Al 2 O 3 powder was prepared.
The copper-plated Al 2 O 3 powder obtained in this way was molded to produce a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio ([actually measured density of sintered body] ] / [Density when the sintered body has no voids]) .
72.3% at a molding pressure of 3t / cm 2, 74.9% at a molding pressure of 4t / cm 2, and 77.0.% To molding pressure 5t / cm 2, even in a molding pressure of 5t / cm 2, density ratio It was not possible to obtain a green compact with 80% or more ([the measured density of the sintered body] / [density when there is no void in the sintered body]) .
Further, when these green compacts were sintered in a hydrogen stream atmosphere at a holding temperature of 875 ° C. and a holding time of 60 minutes, the density ratio of the sintered bodies was measured. There is no difference from the density ratio of the body, and the density ratio ([measured density of the sintered body] / [density when the sintered body has no voids]) is 80% or more at a molding pressure of 5 t / cm 2 or more. No sintered body could be obtained.
The results are shown in Table 1 as in Example 1. Moreover, what plotted the result of the comparative example 1 in FIG. 1 is shown by + mark.
（比較例２）
実施例１で使用したものと同じＡｌ２Ｏ３粉にイミダゾールシラン及び塩化パラジウムによる触媒付与の前処理を施した後、無電解めっきを実施し、さらに塩素イオンを添加せずに置換めっきを行なった。これによって、トータルの銅量が６４．９質量％被覆された鍍銅Ａｌ２Ｏ３粉を作製した。
以上によって得られた鍍銅Ａｌ２Ｏ３粉を金型成形して、１１．３ｍｍφ×１０ｍｍＨの円柱状圧粉体（試験片）を作製して、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）を測定した。
成形圧力３ｔ／ｃｍ２では７１．７％であったが、成形圧力４ｔ／ｃｍ２で７４．６％、成形圧力５ｔ／ｃｍ２で７７．６％となり、成形圧力５ｔ／ｃｍ２においても、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の圧粉体を得ることはできなかった。
また、これらの圧粉体を実施例１と同様に、水素気流雰囲気中で保持温度８７５°Ｃ、保持時間６０分焼結した後の焼結体の密度比を測定したところ、何れも圧粉体の密度比と差が無く、密度比（［焼結体の実測した密度］／［焼結体に空孔がないとした場合の密度］）が８０％以上の焼結体を得ることはできなかった。
以上の結果を実施例１と同様に、表１に示す。また、図１に比較例２の結果をプロットしたものを▲印で示す。
(Comparative Example 2)
The same Al 2 O 3 powder as used in Example 1 was subjected to pretreatment for catalyst application with imidazole silane and palladium chloride, then electroless plating was performed, and substitution plating was performed without adding chlorine ions. It was. In this way, copper copper Al 2 O 3 powder coated with a total copper amount of 64.9% by mass was produced.
The copper-plated Al 2 O 3 powder obtained as described above was molded to produce a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio ([actually measured density of sintered body] ] / [Density when the sintered body has no voids]) .
Molding pressure 3t / cm 2 in it was 71.7% 74.6% at a molding pressure of 4t / cm 2, it becomes 77.6% at a molding pressure of 5t / cm 2, even in the molding pressure 5t / cm 2, It was not possible to obtain a green compact having a density ratio ([actually measured density of sintered body] / [density when there is no void in the sintered body]) of 80% or more.
In addition, when these green compacts were sintered in a hydrogen stream atmosphere at a holding temperature of 875 ° C. and a holding time of 60 minutes, the density ratio of the sintered bodies was measured. It is possible to obtain a sintered body having no difference from the density ratio of the body and having a density ratio ([measured density of sintered body] / [density when there is no void in the sintered body]) of 80% or more. could not.
The results are shown in Table 1 as in Example 1. Moreover, what plotted the result of the comparative example 2 in FIG.
以上に示す通り、本発明は、銅被覆層の形成すなわちめっき条件を最適にすることにより、銅被覆層を均一かつ厚く形成した鍍銅Ａｌ２Ｏ３複合粉末を得ることができ、これを焼結することにより放熱性に優れかつ高密度であり、かつ強度も著しく向上した焼結体を製造することができるという優れた特徴を有しているので、半導体装置の放熱板等として有用である。 As described above, according to the present invention, by optimizing the formation of the copper coating layer, that is, the plating conditions, a copper-plated Al 2 O 3 composite powder in which the copper coating layer is formed uniformly and thick can be obtained. Since it has an excellent feature that it can produce a sintered body with excellent heat dissipation and high density and significantly improved strength, it is useful as a heat sink for semiconductor devices, etc. .
銅被覆層を備えた鍍銅Ａｌ２Ｏ３複合粉末の銅量と真密度及び圧粉体密度との関係を示す図である。 It is a diagram showing the relationship between the copper content and the true density and compact density of鍍銅Al 2 O 3 composite powder having a copper coating layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01136974A (en) * | 1987-11-20 | 1989-05-30 | Kobe Steel Ltd | Surface treatment of filament material |
| JPH01168869A (en) * | 1987-12-23 | 1989-07-04 | Tsurumi Soda Kk | Production of composite powder |
| JPH04304303A (en) * | 1991-04-01 | 1992-10-27 | Mitsubishi Materials Corp | Cu-based sintered alloy electrode for electric igniter of internal combustion engine |
| WO2001081652A1 (en) * | 2000-04-25 | 2001-11-01 | Nikko Materials Co., Ltd. | Pretreating agent for metal plating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01136974A (en) * | 1987-11-20 | 1989-05-30 | Kobe Steel Ltd | Surface treatment of filament material |
| JPH01168869A (en) * | 1987-12-23 | 1989-07-04 | Tsurumi Soda Kk | Production of composite powder |
| JPH04304303A (en) * | 1991-04-01 | 1992-10-27 | Mitsubishi Materials Corp | Cu-based sintered alloy electrode for electric igniter of internal combustion engine |
| WO2001081652A1 (en) * | 2000-04-25 | 2001-11-01 | Nikko Materials Co., Ltd. | Pretreating agent for metal plating |
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