JP2003328055A - COPPER PLATED SiC COMPOSITE POWDER, METHOD FOR MANUFACTURING THE COMPOSITE METALLIC POWDER, COPPER PLATED SiC COMPOSITE POWDER SINTERED BODY, AND METHOD FOR MANUFACTURING THE SINTERED BODY - Google Patents
COPPER PLATED SiC COMPOSITE POWDER, METHOD FOR MANUFACTURING THE COMPOSITE METALLIC POWDER, COPPER PLATED SiC COMPOSITE POWDER SINTERED BODY, AND METHOD FOR MANUFACTURING THE SINTERED BODYInfo
- Publication number
- JP2003328055A JP2003328055A JP2002139477A JP2002139477A JP2003328055A JP 2003328055 A JP2003328055 A JP 2003328055A JP 2002139477 A JP2002139477 A JP 2002139477A JP 2002139477 A JP2002139477 A JP 2002139477A JP 2003328055 A JP2003328055 A JP 2003328055A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- sintered body
- composite powder
- powder
- sic composite
- 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
- 239000010949 copper Substances 0.000 title claims abstract description 85
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 81
- 239000000843 powder Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title description 8
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 238000000465 moulding Methods 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 21
- 238000006073 displacement reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000007772 electroless plating Methods 0.000 claims description 4
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- -1 chlorine ions Chemical class 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 46
- 229910010271 silicon carbide Inorganic materials 0.000 description 46
- 230000017525 heat dissipation Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】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鍍銅ＳｉＣ複合
粉末及び同複合金属粉末の製造方法、並びに放熱性に優
れかつ高密度である鍍銅ＳｉＣ複合粉末焼結体及び同焼
結体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper-clad SiC composite powder capable of manufacturing a sintered body having excellent heat dissipation and high density, a method for manufacturing the same, and a composite metal powder, and excellent heat dissipation and high density. The present invention relates to a copper-plated SiC composite powder sintered body and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】炭化珪素（ＳｉＣ）は一般にカーボラン
ダム（商品名）と言われている。工業的にはケイ砂（二
酸化ケイ素）とコークスの混合物を１８００〜１９００
°Ｃに加熱して製造される。密度は３．２ｇ・ｃ
ｍ−３、融点は２７００°Ｃ以上である。このように工
業的に製造されたものは、純度の高い緑色系のものと、
これより低い黒色系のものとがある。硬さはルビーとダ
イヤモンドとの間のなで、細粉として研磨剤、砥石、耐
火材、抵抗体として用いられる。特に、銅とＳｉＣ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。2. Description of the Related Art Silicon carbide (SiC) is generally called carborundum (trade name). Industrially, a mixture of silica sand (silicon dioxide) and coke is from 1800 to 1900.
It is manufactured by heating to ° C. Density is 3.2g · c
m −3 , melting point is 2700 ° C. or higher. Those industrially produced in this way are of high purity green type,
There are black ones lower than this. Since the hardness is between ruby and diamond, it is used as a fine powder as an abrasive, a grindstone, a refractory material, and a resistor. In particular, a sintered body of copper and SiC has improved heat dissipation and is useful as a heat dissipation plate for semiconductor devices.
【０００３】一般に、銅の粉とＳｉＣ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ＳｉＣ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ＳｉＣ
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ＳｉＣ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、ＳｉＣ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 copper powder and SiC powder and molding and sintering them. Therefore, a copper-plated SiC having a copper coating layer obtained by coating the SiC powder with copper in advance
A method of molding and sintering the composite powder to obtain a predetermined sintered body is adopted. However, even if the copper-clad SiC composite powder having such a copper coating layer is conventionally sintered, the density is not sufficiently increased, and the film formed by plating or the like is not uniform, and a film is formed on a part of the SiC powder. There was a problem such as not
【０００４】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ＳｉＣ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。In view of the above, conventionally, how many attempts have been made to manufacture a SiC composite metal sintered body by appropriately changing the treatment method for forming the copper coating layer, the thickness of the copper coating layer, the sintering conditions, etc. Although it has been achieved, the current situation is that satisfactory results have not been obtained.
【０００５】[0005]
【発明が解決しようとする課題】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鍍銅Ｓｉ
Ｃ複合粉末及び同複合金属粉末の製造方法、並びに放熱
性に優れかつ高密度である鍍銅ＳｉＣ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。DISCLOSURE OF THE INVENTION The present invention provides a copper-plated Si which is excellent in heat dissipation and can produce a high-density sintered body.
An object of the present invention is to obtain a method for producing C composite powder and the same composite metal powder, and a method for producing a copper-plated SiC composite powder sintered body having excellent heat dissipation and high density and the same.
【０００６】[0006]
【課題を解決するための手段】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７０ｗｔ％以上であることを特徴とする銅被
覆層を備えた鍍銅ＳｉＣ複合粉末
２．銅量が７５ｗｔ％以上であることを特徴とする銅被
覆層を備えた鍍銅ＳｉＣ複合粉末
３．ＳｉＣ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１〜１０ｗｔ％被覆し、次に置換めっきにより
銅を被覆することを特徴とする鍍銅ＳｉＣ複合粉末の製
造方法
４．Ｃｕ１０〜８５ｇ／Ｌ、硫酸５〜５０ｇ／Ｌ及びさ
らに塩素イオン５０ｍｇ／Ｌ以下を含有する硫酸銅水溶
液を用いて置換めっきすることを特徴とする上記３記載
の鍍銅ＳｉＣ複合粉末の製造方法
５．銅量が７０ｗｔ％以上であることを特徴とする銅被
覆層を備えた上記３又は４記載の鍍銅ＳｉＣ複合粉末の
製造方法
６．銅量が７５ｗｔ％以上であることを特徴とする銅被
覆層を備えた上記３又は４記載の鍍銅ＳｉＣ複合粉末の
製造方法
７．銅量が７０ｗｔ％以上であり、密度比８０％以上で
あることを特徴とする銅被覆層を備えた鍍銅ＳｉＣ複合
粉末焼結体
８．銅量が７５ｗｔ％以上であり、密度比８０％以上で
あることを特徴とする銅被覆層を備えた鍍銅ＳｉＣ複合
粉末焼結体
９．成形圧力４ｔ／ｃｍ２以上で成形することを特徴と
する銅量が７０ｗｔ％以上であり、密度比８０％以上で
ある銅被覆層を備えた鍍銅ＳｉＣ複合粉末焼結体の製造
方法
１０．成形圧力４ｔ／ｃｍ２以上で成形することを特徴
とする銅量が７０ｗｔ％以上であり、密度比８０％以上
である銅被覆層を備えた鍍銅ＳｉＣ複合粉末焼結体の製
造方法を提供するものである。The inventors of the present invention have variously studied the conditions of plating used for coating, the thickness of the coating layer, and the sintering conditions in order to solve the above-mentioned problems, and It was found that it is possible to manufacture a sintered body having excellent heat dissipation and high density by making improvements and forming a coating layer uniformly and thickly as a whole. The present invention is based on this finding. 1. A copper-plated SiC composite powder provided with a copper coating layer characterized in that the amount of copper is 70 wt% or more. 2. A copper-plated SiC composite powder having a copper coating layer, characterized in that the amount of copper is 75 wt% or more. Pre-treatment of SiC powder with imidazole silane and palladium chloride to give a catalyst, and then 1 to 10 wt% of copper is coated by electroless plating, and then copper is coated by displacement plating. 3. Method of manufacturing composite powder Displacement plating is carried out using an aqueous copper sulfate solution containing 10 to 85 g / L of Cu, 5 to 50 g / L of sulfuric acid, and 50 mg / L or less of chloride ions. ． 5. The method for producing a copper-plated SiC composite powder according to the above 3 or 4, wherein the copper coating layer has a copper content of 70 wt% or more. 7. The method for producing a copper-plated SiC composite powder according to the above 3 or 4, which comprises a copper coating layer characterized in that the amount of copper is 75 wt% or more. 7. Copper-plated SiC composite powder sintered body having a copper coating layer, which has a copper content of 70 wt% or more and a density ratio of 80% or more 8. 8. A copper-plated SiC composite powder sintered body having a copper coating layer having a copper content of 75 wt% or more and a density ratio of 80% or more 9. 10. A method for producing a copper-plated SiC composite powder sintered body having a copper coating layer having a copper content of 70 wt% or more and a density ratio of 80% or more, which is characterized by being molded at a molding pressure of 4 t / cm 2 or more. Provided is a method for producing a copper-plated SiC composite powder sintered body having a copper coating layer having a copper content of 70 wt% or more and a density ratio of 80% or more, which is characterized by being molded at a molding pressure of 4 t / cm 2 or more. To do.
【０００７】[0007]
【発明の実施の形態】本発明の鍍銅ＳｉＣ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ＳｉＣ
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７０ｗ
ｔ％以上の厚くかつ均一な銅被覆層を備えた鍍銅ＳｉＣ
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７５ｗｔ％以上の銅被覆層の鍍銅ＳｉＣ複合
粉末であることが望ましい。BEST MODE FOR CARRYING OUT THE INVENTION In order to utilize the copper-plated SiC composite powder sintered body of the present invention for a heat radiation plate of a semiconductor device, it is necessary to improve the heat radiation property.
It is necessary to increase the density of the composite powder sintered body. As a method for obtaining such a high-density sintered body, the amount of copper is 70w.
Bronze SiC with a thick and uniform copper coating layer of t% or more
It has been found effective to use composite powders. In particular, it is desirable that the copper-clad SiC composite powder with a copper coating layer having a copper content of 75 wt% or more.
【０００８】この厚くかつ均一な銅被覆層を備えた鍍銅
ＳｉＣ複合粉末を製造するには、ＳｉＣ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１〜１０ｗｔ％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ＳｉＣ粉が
出るようになり、均一性に劣る焼結体となる虞があるの
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０〜５０ｍｇ／
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７０ｗｔ％以上、さらに
銅量が７５ｗｔ％以上である銅被覆層を備えた鍍銅Ｓｉ
Ｃ複合粉末を製造することができる。In order to produce the copper-plated SiC composite powder provided with this thick and uniform copper coating layer, the SiC powder is pretreated by applying a catalyst with imidazolesilane and palladium chloride, and then copper is electroless-plated. 1 to 10% by weight, iron powder is further added to the copper sulfate aqueous solution, and copper is coated by displacement plating with the iron. If electroless plating is not performed in the above steps, unadhered SiC powder will come out during subsequent copper displacement plating, which may result in a sintered body with poor uniformity, which is not preferable. . For displacement plating, Cu 10-85g
/ L, sulfuric acid 5 to 50 g / L, chloride ion 0 to 50 mg /
It is desirable to use a copper sulfate aqueous solution containing L. By this plating step, a copper plated Si having a copper coating layer having a copper amount of 70 wt% or more and further a copper amount of 75 wt% or more
C composite powder can be produced.
【０００９】上記によって得られた銅被覆層を備えた鍍
銅ＳｉＣ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により、銅量が７０ｗｔ％以
上、好ましくは銅量が７５ｗｔ％以上であり、密度比８
０％以上の銅被覆層を備えた鍍銅ＳｉＣ複合粉末焼結体
が得られる。成形圧力４ｔ／ｃｍ２未満では、密度比８
０％以上の鍍銅ＳｉＣ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／ｃｍ２以上とすることが
望ましい。銅被覆層を備えた鍍銅ＳｉＣ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、成形圧力にもよるが、成形圧力４ｔ／ｃｍ２
以上で密度比がほぼ８０％以上となる。さらに成形圧力
５ｔ／ｃｍ２以上で確実に密度比が８０％以上の焼結体
が得られる。The copper-clad SiC composite powder having the copper coating layer obtained as described above is molded at a molding pressure of 4 t / cm 2 or more, and is sintered to obtain a copper content of 70 wt% or more, preferably a copper content. Is 75 wt% or more, and the density ratio is 8
A copper-plated SiC composite powder sintered body having a copper coating layer of 0% or more is obtained. If the molding pressure is less than 4 t / cm 2 , the density ratio is 8
Since it is difficult to obtain a 0% or more copper-clad SiC composite powder sintered body, it is desirable to set the forming pressure of the sintered body to 4 t / cm 2 or more. FIG. 1 shows the relationship between the copper density and the true density and the sintered density of the copper-plated SiC composite powder provided with the copper coating layer. In the figure, the solid line shows the true density of the sintered body, and the dotted line shows the density ratio of 80%.
The true density and density ratio of the sintered body increase as the amount of copper in the copper coating layer increases, and depending on the molding pressure, the molding pressure is 4 t / cm 2
With the above, the density ratio becomes approximately 80% or more. Further, at a molding pressure of 5 t / cm 2 or more, a sintered body having a density ratio of 80% or more can be reliably obtained.
【００１０】[0010]
【実施例及び比較例】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。Examples and Comparative Examples Next, examples of the present invention will be described. It should be noted that this embodiment is merely an example, and the present invention is not limited to this example. That is, it includes all aspects or modifications other than the examples within the scope of the technical idea of the present invention.
【００１１】（実施例１）市販のＳｉＣ粉（＃７００、
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７２．６ｗｔ％被覆された鍍銅ＳｉＣ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（リッター）
硫酸：３０ｇ／ｌ
塩素イオン：４０ｍｇ／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ＳｉＣ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ＳｉＣ粉が得られる。Example 1 Commercially available SiC powder (# 700,
(Showa Denko Co., Ltd.), which is pre-treated by applying a catalyst with imidazole silane and palladium chloride, and is then electroless plated in advance, and using the following displacement plating, the total amount of copper is 72.6 wt% SiC powder was produced. (Displacement plating condition) 1) Composition of displacement plating solution: Cu: 60 g / l (liter) Sulfuric acid: 30 g / l Chloride ion: 40 mg / l 2) Reduction agent for substitution Commercially available reduced iron powder (-100 mesh) 3) Displacement plating Method Raw material powder (pretreated SiC powder) and iron powder are mixed well, and then the necessary amount of the plating solution is gradually added and stirred. This causes a plating reaction. The amounts of iron powder and plating solution are calculated based on the target amount of copper plating and the amount of raw material powder. After plating, the copper plating SiC powder is obtained by washing with water and drying.
【００１２】上記により得られた鍍銅ＳｉＣ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、密度比を測定した。成形圧力３
ｔ／ｃｍ２では、７４．０％であったが、成形圧力４ｔ
／ｃｍ２で８０．２％、成形圧力５ｔ／ｃｍ２で８２．
５％となり、４ｔ／ｃｍ２の成形圧力で、安定した密度
比８０％以上の圧粉体を得ることができた。また、これ
らの圧粉体を水蒸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、いずれも圧粉体時の密度比を上回り、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。The copper-plated SiC powder obtained as described above was die-molded to produce a columnar green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio was measured. Molding pressure 3
At t / cm 2 , it was 74.0%, but the molding pressure was 4t.
/ Cm 2 80.2%, molding pressure 5 t / cm 2 82.
It was 5%, and a compact having a stable density ratio of 80% or more could be obtained at a molding pressure of 4 t / cm 2 . Further, the holding temperature of these green compacts in a steam flow atmosphere is 875 ° C,
When the density ratio of the sintered body after the holding time of 60 minutes was measured, it was found that both exceeded the density ratio at the time of compacting, and a sintered body having a density ratio of 80% or more at a molding pressure of 4 t / cm 2 or more was obtained. I was able to get it. The above results are shown in Table 1. In addition, a plot of the results of Example 1 is shown in FIG.
【００１３】[0013]
【表１】 [Table 1]
【００１４】（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９．１ｗｔ％無電解めっきした
ＳｉＣ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８１．０ｗｔ％被覆された鍍銅ＳｉＣ粉を
作製した。これによって得られた鍍銅ＳｉＣ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、密度比を測定した。成形圧力３
ｔ／ｃｍ２では、７６．２％であったが、成形圧力４ｔ
／ｃｍ２で８１．８％、成形圧力５ｔ／ｃｍ２で８５．
５％となり、４ｔ／ｃｍ２の成形圧力で、安定した密度
比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、水蒸気流雰囲気中で保
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、いずれも圧粉体時の密度比
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。(Embodiment 2) Using the same material as in Embodiment 1 and using SiC preliminarily electroplated with 9.1 wt% of copper in the same manner as the raw material, the total copper amount was 81. A copper-plated SiC powder coated with 0 wt% was prepared. The copper-plated SiC powder thus obtained was die-molded to prepare a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio was measured. Molding pressure 3
At t / cm 2 , it was 76.2%, but the molding pressure was 4t.
/ Cm 2 of 81.8% and a molding pressure of 5 t / cm 2 of 85.
It was 5%, and a compact having a stable density ratio of 80% or more could be obtained at a molding pressure of 4 t / cm 2 . Further, as in Example 1, the green compacts were sintered in a steam flow atmosphere at a holding temperature of 875 ° C. for a holding time of 60 minutes, and the density ratio of the sintered bodies was measured. It was possible to obtain a sintered body having a density ratio of 80% or more at a molding pressure of 4 t / cm 2 or more, which is higher than the density ratio in the body. The above results are shown in Example 1.
Similarly to the above, shown in Table 1. Further, a plot of the results of Example 2 is shown in FIG.
【００１５】（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９．１ｗｔ％無電解めっきした
ＳｉＣ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６１．１ｗｔ％被覆された鍍銅ＳｉＣ粉を
作製した。これによって得られた鍍銅ＳｉＣ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、密度比を測定した。成形圧力３
ｔ／ｃｍ２で７０．４％、成形圧力４ｔ／ｃｍ２で７
４．２％、成形圧力５ｔ／ｃｍ２でも７７．３％であ
り、５ｔ／ｃｍ２の成形圧力においても、密度比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、水蒸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、いずれも圧粉体時の密度比と
差がなく、成形圧力４ｔ／ｃｍ２以上で密度比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 SiC preliminarily electrolessly plated with 9.1 wt% of copper in the same manner as the raw material, the total copper amount was 61. A copper-plated SiC powder coated with 1 wt% was produced. The copper-plated SiC powder thus obtained was die-molded to prepare a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio was measured. Molding pressure 3
70.4% in t / cm 2, at a molding pressure 4t / cm 2 7
4.2%, 77.3% even at a molding pressure of 5 t / cm 2 , and a density ratio of 80% even at a molding pressure of 5 t / cm 2.
The above green compact could not be obtained. Further, as in Example 1, the green compacts were sintered in a steam flow atmosphere at a holding temperature of 875 ° C. for a holding time of 60 minutes, and the density ratio of the sintered bodies was measured. There was no difference from the density ratio in the body, and a sintered body having a density ratio of 80% or more could not be obtained at a molding pressure of 4 t / cm 2 or more. The above results are shown in Table 1 as in Example 1. In addition, a plot of the results of Comparative Example 1 is shown in FIG.
【００１６】（比較例２）実施例１で使用したものと同
じＳｉＣ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、無電解めっきのみ
で、銅量が７０．１ｗｔ％被覆された鍍銅ＳｉＣ粉を作
製した。これによって得られた鍍銅ＳｉＣ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、密度比を測定した。成形圧力４ｔ／
ｃｍ２で７６．４％となり、密度比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、水蒸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、圧粉体の密度比を上回ったが、密度比８０
％以上の焼結体は得られなかった。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 2 The same SiC powder as used in Example 1 was pretreated by applying a catalyst with imidazolesilane and palladium chloride and then coated with electroless plating to a copper content of 70.1 wt%. The obtained copper-plated SiC powder was produced. The copper-plated SiC powder thus obtained was die-molded to prepare a cylindrical green compact (test piece) of 11.3 mmφ × 10 mmH, and the density ratio was measured. Molding pressure 4t /
It was 76.4% in cm 2 , and it was not possible to obtain a green compact having a density ratio of 80% or more. Also, these green compacts were held at a holding temperature of 875 ° in a steam flow atmosphere as in Example 1.
When the density ratio of the sintered body after C and the holding time of 60 minutes was measured, it was higher than that of the green compact, but the density ratio was 80.
% Or more sintered body was not obtained. The above results are shown in Table 1 as in Example 1. In addition, a plot of the results of Comparative Example 1 is shown in FIG.
【００１７】[0017]
【発明の効果】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ＳｉＣ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, it is possible to obtain a copper-plated SiC composite powder in which the copper coating layer is uniformly and thickly formed. It has an excellent feature that it is possible to manufacture a sintered body having excellent heat dissipation and high density and also having significantly improved strength by sintering.
【図１】銅被覆層を備えた鍍銅ＳｉＣ複合粉末の銅量と
真密度及び焼結密度との関係を示す図である。FIG. 1 is a diagram showing a relationship between a copper amount and a true density and a sintered density of a copper-plated SiC composite powder having a copper coating layer.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｃ 18/38 Ｃ２３Ｃ 18/38 ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI Theme Coat (Reference) C23C 18/38 C23C 18/38
Claims (10)
とする銅被覆層を備えた鍍銅ＳｉＣ複合粉末。1. A copper-plated SiC composite powder having a copper coating layer, which has a copper content of 70 wt% or more.
とする銅被覆層を備えた鍍銅ＳｉＣ複合粉末。2. A copper-plated SiC composite powder having a copper coating layer, wherein the amount of copper is 75 wt% or more.
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１〜１０ｗｔ％被覆し、次に置換め
っきにより銅を被覆することを特徴とする鍍銅ＳｉＣ複
合粉末の製造方法。3. A SiC powder is pretreated by applying a catalyst with imidazole silane and palladium chloride, then coated with 1 to 10 wt% of copper by electroless plating, and then coated with copper by displacement plating. And a method for producing a copper-plated SiC composite powder.
／Ｌ及びさらに塩素イオン５０ｇ／Ｌ以下を含有する硫
酸銅水溶液を用いて置換めっきすることを特徴とする請
求項３記載の鍍銅ＳｉＣ複合粉末の製造方法。4. Cu 10 to 85 g / L, sulfuric acid 5 to 50 g
/ L and further, displacement plating is performed using an aqueous copper sulfate solution containing chlorine ions of 50 g / L or less, and the method for producing a copper-plated SiC composite powder according to claim 3, wherein.
とする銅被覆層を備えた請求項３又は４記載の鍍銅Ｓｉ
Ｃ複合粉末の製造方法。5. The copper-plated Si according to claim 3, further comprising a copper coating layer having a copper content of 70 wt% or more.
Method for producing C composite powder.
とする銅被覆層を備えた請求項３又は４記載の鍍銅Ｓｉ
Ｃ複合粉末の製造方法。6. The copper-plated Si according to claim 3, further comprising a copper coating layer having a copper content of 75 wt% or more.
Method for producing C composite powder.
０％以上であることを特徴とする銅被覆層を備えた鍍銅
ＳｉＣ複合粉末焼結体。7. The amount of copper is 70 wt% or more, and the density ratio is 8
A copper-plated SiC composite powder sintered body having a copper coating layer, which is characterized by being 0% or more.
０％以上であることを特徴とする銅被覆層を備えた鍍銅
ＳｉＣ複合粉末焼結体。8. The amount of copper is 75 wt% or more, and the density ratio is 8
A copper-plated SiC composite powder sintered body having a copper coating layer, which is characterized by being 0% or more.
とを特徴とする銅量が７０ｗｔ％以上であり、密度比８
０％以上である銅被覆層を備えた鍍銅ＳｉＣ複合粉末焼
結体の製造方法。9. Molding at a molding pressure of 4 t / cm 2 or more, the amount of copper is 70 wt% or more, and the density ratio is 8
A method for producing a copper-plated SiC composite powder sintered body having a copper coating layer of 0% or more.
ことを特徴とする銅量が７０ｗｔ％以上であり、密度比
８０％以上である銅被覆層を備えた鍍銅ＳｉＣ複合粉末
焼結体の製造方法。10. A copper-plated SiC composite powder sintered body having a copper coating layer having a copper content of 70 wt% or more and a density ratio of 80% or more, characterized by being molded at a molding pressure of 4 t / cm 2 or more. Manufacturing method.
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