JPH05179303A - Metal-coated powder and production thereof - Google Patents
Metal-coated powder and production thereofInfo
- Publication number
- JPH05179303A JPH05179303A JP3359126A JP35912691A JPH05179303A JP H05179303 A JPH05179303 A JP H05179303A JP 3359126 A JP3359126 A JP 3359126A JP 35912691 A JP35912691 A JP 35912691A JP H05179303 A JPH05179303 A JP H05179303A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- powder
- coated
- resin
- alloy layer
- 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.)
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Powder Metallurgy (AREA)
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗料用、接着剤用、粉
末冶金用、射出成型用、電磁シールド用、分散強化材用
などに使用して好適な金属被覆粉体及びその製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-coated powder suitable for use in paints, adhesives, powder metallurgy, injection molding, electromagnetic shielding, dispersion reinforcement and the like, and a method for producing the same. It is a thing.
【０００２】[0002]
【従来の技術】従来の金属被覆粉体としては、表面を粗
面処理した樹脂粉体上に金属又は合金層を形成したもの
である。又、その製造方法としては、樹脂粉体表面をク
ロム酸などを用いてエッチングして親水化およびポーラ
ス化し、その表面に増感処理および活性化処理を行い、
その後、無電解めっき法により金属又は合金層を形成す
ることにより金属被覆粉体を得ていた。2. Description of the Related Art As a conventional metal-coated powder, a metal or alloy layer is formed on a resin powder whose surface is roughened. Further, as its manufacturing method, the surface of the resin powder is etched with chromic acid or the like to make it hydrophilic and porous, and the surface is subjected to sensitization treatment and activation treatment,
After that, a metal-coated powder was obtained by forming a metal or alloy layer by an electroless plating method.
【０００３】[0003]
【発明が解決しようとする課題】しかしこれらの方法
は、樹脂の材質において制約がある。即ち、エッチング
処理により、その表面を親水化およびポーラス化するこ
とができる樹脂が限られている。従って、目的に応じた
樹脂を選定することができない。又、エッチング処理に
より樹脂表面を親水化およびポーラス化する際に、エッ
チング液が樹脂表面に吸着し、この吸着したエッチング
液がめっき液に混入することによりめっき液が不安定と
なる。従って、めっき液の分解或いはめっきが不可能に
なるということがあった。However, these methods have restrictions on the material of the resin. That is, the resins that can make the surface hydrophilic and porous by etching are limited. Therefore, it is not possible to select a resin suitable for the purpose. Further, when the resin surface is made hydrophilic and porous by the etching treatment, the etching solution is adsorbed on the resin surface, and the adsorbed etching solution mixes with the plating solution, which makes the plating solution unstable. Therefore, the decomposition or plating of the plating solution may become impossible.
【０００４】[0004]
【課題を解決するための手段】そこで本発明は、前記問
題に鑑みなされたものであって、樹脂粉体上に金属粒子
を付着・固定し、金属粒子の外方に金属又は合金層を形
成した金属被覆粉体を第１の要旨とし、樹脂粉体上に、
金属粒子又は金属で被覆した無機粉体を付着・固定し、
その外方に金属又は合金層を形成した金属被覆粉体を第
２の要旨とし、樹脂粉体上に金属粒子を付着・固定し、
その後無電解めっき法により金属又は合金層を形成した
金属被覆粉体の製造方法を第３の要旨とし、樹脂粉体上
に、予め金属粒子又は金属で被覆した無機粉体を付着・
固定し、その後無電解めっき法により金属又は合金層を
形成した金属被覆粉体の製造方法を第４の要旨とするも
のである。Therefore, the present invention has been made in view of the above problems, in which metal particles are attached and fixed on a resin powder, and a metal or alloy layer is formed outside the metal particles. The first gist of the metal-coated powder is the resin powder,
Attach and fix metal particles or inorganic powder coated with metal,
The second gist is the metal-coated powder having the metal or alloy layer formed on the outside thereof, and the metal particles are attached and fixed on the resin powder,
The third gist is the method for producing metal-coated powder in which a metal or alloy layer is formed by electroless plating, and then metal particles or inorganic powder previously coated with metal is attached to the resin powder.
A fourth gist is a method for producing a metal-coated powder in which a metal or alloy layer is fixed and then formed by an electroless plating method.
【０００５】本発明の金属被覆粉体は、以下の二つのタ
イプよりなっている。第１のタイプは、図１に模式的に
示したように、樹脂粉体１と、該樹脂粉体１上に形成し
た金属粒子２と、該金属粒子２の外方に形成した金属又
は金属層３とよりなっている。先ず、基材となる樹脂粉
体１としては、天然繊維、天然樹脂、ポリエチレン、ポ
リプロピレン、ポリアミド樹脂、ポリアセタール樹脂、
ポリカーボネート、ＡＢＳ、ＳＡＮ、ＡＳ、スチロール
樹脂、塩化ビニル樹脂、ポリアクリル酸樹脂、ポリアセ
タール、ポリアクリロニトリル、ポリエステル等の熱可
塑性樹脂、フェノール樹脂、尿素樹脂、ユリア樹脂、ア
ルキッド樹脂、メラミン樹脂などの熱硬化性樹脂などが
挙げられる。これら樹脂粉体の外面形状は、球状、無定
形繊維状、コイル状などが、又、その内面形状は、中実
状、中空状、多孔質状など種々のものが採用可能であ
る。The metal-coated powder of the present invention is of the following two types. The first type is, as schematically shown in FIG. 1, a resin powder 1, metal particles 2 formed on the resin powder 1, and a metal or metal formed outside the metal particles 2. Composed of layer 3. First, as the resin powder 1 as the base material, natural fiber, natural resin, polyethylene, polypropylene, polyamide resin, polyacetal resin,
Thermoplastic resin such as polycarbonate, ABS, SAN, AS, styrene resin, vinyl chloride resin, polyacrylic acid resin, polyacetal, polyacrylonitrile, polyester, etc., thermosetting of phenol resin, urea resin, urea resin, alkyd resin, melamine resin, etc. And the like. The outer surface shape of these resin powders may be spherical, amorphous fibrous shape, coil shape, and the like, and the inner surface shape thereof may be solid, hollow or porous.
【０００６】次に金属粒子２としては、Ｆｅ、Ｎｉ、Ｃ
ｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｃｒ、Ａｇ、Ａｕ、Ｐｔ、Ｐ
ｄ、Ｒｈ及びこれら金属の合金などが挙げられる。これ
らは一種もしくは二種以上混合して使用される。尚、こ
の金属粒子の形状は前記樹脂粉体と同様に種々採用で
き、又、その大きさは、その目的に応じ種々選定され
る。Next, as the metal particles 2, Fe, Ni and C are used.
o, Cu, Zn, Al, Cr, Ag, Au, Pt, P
Examples thereof include d, Rh and alloys of these metals. These are used alone or in combination of two or more. The shape of the metal particles can be variously adopted similarly to the resin powder, and the size thereof can be variously selected according to the purpose.
【０００７】更に、金属又は合金層３としては、Ｎｉ−
Ｐ、Ｎｉ−Ｂ、Ｃｏ−Ｂ、Ｃｏ−Ｐ、Ｎｉ、Ｃｏ、Ｆ
ｅ、Ａｇ、Ａｕ、Ｐｔ、Ｃｕ、Ｐｄ、Ｒｈ、Ｒｕ、Ｓ
ｎ、Ｚｎ、Ｚｎ−Ｃｕ、Ｎｉ−Ｃｏ−Ｐ、Ｎｉ−Ｗ−
Ｐ、Ｎｉ−Ｆｅ−Ｐ、Ｃｏ−Ｆｅ−Ｐ、Ｃｏ−Ｗ−Ｐ等
が挙げられる。又、これら金属又は合金層は２層、３層
などに形成してもよいし、金属又は合金にＡｌ 2Ｏ 3、
ＺｒＯ 2、ＳｉＯ 2、ＴｉＯ2、ＴｉＮ、ＴｉＣ、Ｓｉ
Ｃ、Ｃ、ＭｏＳ 2、ＷＳ 2、ＢＮ、ＢａＳＯ 4、ＣｒＢ
2、ＺｒＢ 2等の酸化物、炭化物、窒化物、ホウ化物、
硫化物などの無機物、ＰＴＦＦ、ＡＢＳ、ＰＰ、ＰＥ、
ポリカーボネート、ラテックス等の有機物などを含んだ
複合層としてもよい。尚、本発明における金属又は合金
層３としては、図２に模式的に示すように、樹脂粉体１
上に不連続に付着・固定した金属粒子２の外方に膜を形
成したものをも包含する。Further, as the metal or alloy layer 3, Ni-
P, Ni-B, Co-B, Co-P, Ni, Co, F
e, Ag, Au, Pt, Cu, Pd, Rh, Ru, S
n, Zn, Zn-Cu, Ni-Co-P, Ni-W-
P, Ni-Fe-P, Co-Fe-P, Co-WP, etc. are mentioned. Further, these metal or alloy layers may be formed in two layers, three layers, etc., or the metal or alloy may be formed of Al 2 O 3 ,
ZrO 2 , SiO 2 , TiO 2 , TiN, TiC, Si
C, C, MoS 2 , WS 2 , BN, BaSO 4 , CrB
2 , oxides such as ZrB 2 , carbides, nitrides, borides,
Inorganic substances such as sulfide, PTFEF, ABS, PP, PE,
A composite layer containing an organic material such as polycarbonate or latex may be used. Incidentally, as the metal or alloy layer 3 in the present invention, as shown schematically in FIG.
It also includes those in which a film is formed on the outside of the metal particles 2 that are discontinuously attached and fixed thereon.
【０００８】第２のタイプは、図３に模式的に示したよ
うに、樹脂粉体１と、金属粒子又は金属で被覆した被覆
部５を有する無機粉体４と、該無機粉体４の外方に形成
した金属又は合金層３とよりなっている。基材となる樹
脂粉体１並びに金属又は合金層３は前記した第１のタイ
プと同じである。The second type is, as schematically shown in FIG. 3, a resin powder 1, an inorganic powder 4 having a metal particle or a coating portion 5 coated with a metal, and the inorganic powder 4. It is composed of a metal or alloy layer 3 formed on the outside. The resin powder 1 as the base material and the metal or alloy layer 3 are the same as those of the above-mentioned first type.
【０００９】又、無機粉体４としては、天然鉱物、Ｓ
ｉ、Ａｌ、Ｔｉ、Ｍｇ、Ｆｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｚｎ
等の酸化物、チッ化物、硫化物などが一種もしくは二種
以上混合して使用されるが、これらの無機粉体は前記樹
脂粉体よりも小さければよい。更に、金属粒子又は金属
よりなる被覆部５としては、前記第１のタイプにおける
金属粒子や、金属又は合金層として例示したものが使用
される。As the inorganic powder 4, natural minerals, S
i, Al, Ti, Mg, Fe, Cu, Ni, Co, Zn
One kind or a mixture of two or more kinds of oxides, nitrides, sulfides and the like are used, and the inorganic powder may be smaller than the resin powder. Further, as the metal particles or the coating portion 5 made of a metal, those exemplified as the metal particles in the first type or the metal or alloy layer are used.
【００１０】次に、製造方法について述べる。先ず、樹
脂粉体上に金属粒子を付着・固定（第１のタイプ）、或
いは金属粒子又は金属で被覆した無機粉体を付着・固定
（第２のタイプ）する方法としては、これらの混合物を
自動乳鉢、ボールミル、ジェットミル、アトマイザー、
ハイブリダイザー等を用い処理することにより、樹脂粉
体上に、金属粒子、又は金属粒子或いは金属層で被覆し
た無機粉体を機械的に付着・固定する。その後公知の無
電解めっき法により、金属粒子、又は金属粒子或いは金
属層で被覆した無機粉体の外方に金属又は合金層を形成
する。尚、第２のタイプにおいて、無機粉体に金属粒子
又は金属を被覆する方法としては、金属粒子を被覆する
場合は無機粉体と金属粒子の混合物を前記したと同様の
分散機を用いて処理すればよく、又、金属を被覆する場
合は公知の無電解めっき法により処理すればよい。Next, the manufacturing method will be described. First, as a method for adhering / fixing metal particles on resin powder (first type) or for adhering / fixing metal particles or inorganic powder coated with metal (second type), a mixture of these is used. Automatic mortar, ball mill, jet mill, atomizer,
By treating with a hybridizer or the like, the metal powder or the inorganic powder coated with the metal particles or the metal layer is mechanically attached and fixed onto the resin powder. After that, a metal or alloy layer is formed on the outside of the metal particles or the inorganic powder coated with the metal particles or the metal layer by a known electroless plating method. In the second type, as a method for coating the inorganic powder with the metal particles or the metal, when the metal particles are coated, a mixture of the inorganic powder and the metal particles is treated with the same disperser as described above. The metal may be coated by a known electroless plating method.
【００１１】[0011]
【作用】本発明は、樹脂粉体上に金属粒子、又は金属粒
子或いは金属層で被覆した無機粉体を付着・固定し、そ
の外方に金属又は合金層を形成したので、従来の樹脂の
エッチングによるめっき液の汚染がなくなり、安定に金
属又は合金層を形成することが可能であると共に種々の
樹脂への処理が可能となるものである。In the present invention, the metal particles or the inorganic powder coated with the metal particles or the metal layer is adhered and fixed on the resin powder, and the metal or alloy layer is formed on the outer side thereof. Contamination of the plating solution due to etching is eliminated, a metal or alloy layer can be stably formed, and various resins can be treated.
【００１２】[0012]
（実施例１）樹脂粉体として住友化学工業（株）製ファ
インパール３０００ＳＰ（ポリスチレン、平均粒子径６
μｍ）を用い、金属粒子として三井金属鉱業（株）ＭＦ
Ｐ−２０３０（Ｎｉ微粒子、平均粒子径０．３５μｍ）
を用い、３０００ＳＰを１０部、Ｎｉ微粒子を３０部を
混合しハイブリダイザー（（株）奈良機械製作所製）に
て５分間処理することにより樹脂粉体上にＮｉ粒子を付
着・固定した粉体を得た。その後無電解めっき液の塩化
ニッケル３０ｇ／l、次亜リン酸ナトリウム１０ｇ／l、
ヒドロキシ酢酸ナトリウム５０ｇ／l、ｐＨ４．５、９
０℃に１０分間処理することによりＮｉ−Ｐの合金層が
形成された粉体を得た。(Example 1) As a resin powder, Sumitomo Chemical Co., Ltd. Fine Pearl 3000SP (polystyrene, average particle size 6
μm) and used as metal particles by Mitsui Mining & Smelting Co., Ltd. MF
P-2030 (Ni fine particles, average particle diameter 0.35 μm)
Was mixed with 10 parts of 3000SP and 30 parts of Ni fine particles, and the mixture was treated with a hybridizer (manufactured by Nara Machinery Co., Ltd.) for 5 minutes to obtain a powder in which Ni particles were adhered and fixed on the resin powder Obtained. Then electroless plating solution of nickel chloride 30g / l, sodium hypophosphite 10g / l,
Sodium hydroxyacetate 50g / l, pH 4.5, 9
By treating at 0 ° C. for 10 minutes, a powder in which a Ni—P alloy layer was formed was obtained.
【００１３】（実施例２）無機粉体として富士デヴィソ
ン（株）製サイロイド１５０（シリカ、粒子径１．４μ
ｍ）を用い、これを塩化第１スズ２０ｇ／l、塩化パラ
ジウム０．２ｇ／l、中に室温で５分間処理した。これ
をメンブランフィルターにて濾過し十分水洗した後乾燥
した。次にこれを無電解めっき液の日本カニゼン（株）
製ブルーシューマを５倍に希釈した液に分散させて９０
℃にて５分間処理することによりＮｉ−Ｐの合金層を被
覆した無機粉体を得た。次にこの無機粉体２０部と、樹
脂粉体である住友化学工業（株）製ファインパールＰＢ
−３０１２（ポリスチレン、平均粒子径２００μｍ）１
００部をボールミルにて６０分間混合処理し樹脂粉体上
にＮｉ−Ｐを被覆した無機粉体を付着・固定した。その
後この無機粉体を無電解めっき液である奧野製薬工業
（株）製ＯＰＣムデンゴールド２５を１０倍に希釈した
液に分散させて９０℃にて５分間処理することによりＡ
ｕを被覆した粉体を得た。Example 2 As an inorganic powder, Syloid 150 (silica, particle size 1.4 μ, manufactured by Fuji Davisson Co., Ltd.)
m) was treated with 20 g / l stannous chloride, 0.2 g / l palladium chloride at room temperature for 5 minutes. This was filtered with a membrane filter, washed thoroughly with water, and then dried. Next, this is the electroless plating solution of Nippon Kanigen Co., Ltd.
90% by dispersing the Blue Suma made in a solution diluted 5 times
An inorganic powder coated with a Ni-P alloy layer was obtained by processing at 5 ° C for 5 minutes. Next, 20 parts of this inorganic powder and resin powder, Fine Pearl PB manufactured by Sumitomo Chemical Co., Ltd.
-3012 (polystyrene, average particle size 200 μm) 1
00 parts were mixed by a ball mill for 60 minutes to adhere and fix the inorganic powder coated with Ni-P on the resin powder. Thereafter, this inorganic powder was dispersed in a solution obtained by diluting OPC Muden Gold 25 manufactured by Utano Pharmaceutical Co., Ltd., which is an electroless plating solution, 10 times, and treated at 90 ° C. for 5 minutes to obtain A.
A powder coated with u was obtained.
【００１４】（実施例３）無機粉体子として大明化学工
業（株）製タイミクロンＡＧ（アルミナ、平均粒子径
０．２μｍ）を用い、これを１００部に東京鉄鋼（株）
製Ｆｅ微粒子（平均粒子径０．０５μｍ）５０部を混合
し、ハイブリダイザー（（株）奈良機械製作所製）にて
５分間処理することにより無機粉体上にＦｅ粒子を付着
・固定した粉体を得た。その後、無電解めっき液である
奧野製薬工業（株）製ＯＰＣカッパー液に分散させて５
０℃にて２０分間処理することによりＣｕを被覆した粉
体を得た。(Example 3) As an inorganic powder, Taimicron AG (alumina, average particle diameter 0.2 μm) manufactured by Daimei Chemical Industry Co., Ltd. was used, and 100 parts of this was used by Tokyo Steel Co., Ltd.
Powder in which 50 parts of Fe fine particles (average particle diameter: 0.05 μm) are mixed and treated with a hybridizer (manufactured by Nara Machinery Co., Ltd.) for 5 minutes to attach and fix Fe particles on the inorganic powder Got Then, it was dispersed in an electroless plating solution, OPC copper solution manufactured by Utano Pharmaceutical Co., Ltd.
A powder coated with Cu was obtained by treating at 0 ° C. for 20 minutes.
【００１５】以上、本発明について、その概略を述べた
が、本発明は、前記説明に限定されるものではない。例
えば、その使用目的に応じ樹脂粉体上に形成した金属粒
子や、金属粒子又は金属で被覆した無機粉体と金属又は
合金層との間に他の層を介在させたり、その利用分野に
おいても、本発明の金属被覆粉体を、例えば、圧延して
片状、フィルム状、シート状物となすことによって、そ
の使用用途を拡大したり、更には、金属被覆粉体を化学
的に発色させることにより、新たな着色剤とする等であ
る。The outline of the present invention has been described above, but the present invention is not limited to the above description. For example, metal particles formed on the resin powder according to the purpose of use, or another layer interposed between the inorganic powder coated with metal particles or metal and the metal or alloy layer, or in the field of use thereof , By expanding the metal-coated powder of the present invention into, for example, a piece, a film, or a sheet by rolling, and further, the metal-coated powder is chemically colored. As a result, a new colorant is used.
【００１６】[0016]
【発明の効果】以上の実施例１〜３で得られた金属被覆
粉体について、金属の被覆性を確認したところ、完全に
被覆されていることが確認できた。又、工程中における
めっき液の安定性についてみたところ、全て安定であっ
た。EFFECTS OF THE INVENTION The metal-coated powders obtained in Examples 1 to 3 above were confirmed to be metal-covered, and it was confirmed that they were completely coated. Moreover, the stability of the plating solution during the process was all stable.
【図１】本発明の金属被覆粉体の一実施例を模式的に示
した図である。FIG. 1 is a view schematically showing an example of the metal-coated powder of the present invention.
【図２】本発明の金属被覆粉体の他の実施例を模式的に
示した図である。FIG. 2 is a view schematically showing another example of the metal-coated powder of the present invention.
【図３】本発明の金属被覆粉体の更に他の実施例を模式
的に示した図である。FIG. 3 is a diagram schematically showing still another example of the metal-coated powder of the present invention.
１ 樹脂粉体 ２ 無機質粒子 ３ 金属又は合金層 ４ 無機粉体 ５ 金属粒子又は金属で被覆した被覆部 DESCRIPTION OF SYMBOLS 1 Resin powder 2 Inorganic particles 3 Metal or alloy layer 4 Inorganic powder 5 Covered part coated with metal particles or metal
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０８Ｌ 25:00 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display area // C08L 25:00
Claims (4)
金属粒子の外方に金属又は合金層を形成した金属被覆粉
体。1. Metal particles are attached and fixed on a resin powder,
A metal-coated powder in which a metal or alloy layer is formed outside metal particles.
した無機粉体を付着・固定し、その外方に金属又は合金
層を形成した金属被覆粉体。2. A metal-coated powder in which metal particles or an inorganic powder coated with a metal is adhered and fixed on a resin powder, and a metal or alloy layer is formed on the outside thereof.
その後無電解めっき法により金属又は合金層を形成した
金属被覆粉体の製造方法。3. Attaching and fixing metal particles on resin powder,
Then, a method for producing a metal-coated powder having a metal or alloy layer formed by an electroless plating method.
被覆した無機粉体を付着・固定し、その後無電解めっき
法により金属又は合金層を形成した金属被覆粉体の製造
方法。4. A method for producing a metal-coated powder, which comprises depositing and fixing metal particles or an inorganic powder previously coated with a metal on a resin powder, and then forming a metal or alloy layer by an electroless plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3359126A JPH05179303A (en) | 1991-12-26 | 1991-12-26 | Metal-coated powder and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3359126A JPH05179303A (en) | 1991-12-26 | 1991-12-26 | Metal-coated powder and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05179303A true JPH05179303A (en) | 1993-07-20 |
Family
ID=18462876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3359126A Pending JPH05179303A (en) | 1991-12-26 | 1991-12-26 | Metal-coated powder and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05179303A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2777215A1 (en) * | 1998-04-09 | 1999-10-15 | Onera (Off Nat Aerospatiale) | COMPOSITE POWDER FOR SOLDER-DIFFUSION |
| JP2011168631A (en) * | 2010-02-16 | 2011-09-01 | Nippon Shokubai Co Ltd | Method for producing metal-coated particle |
-
1991
- 1991-12-26 JP JP3359126A patent/JPH05179303A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2777215A1 (en) * | 1998-04-09 | 1999-10-15 | Onera (Off Nat Aerospatiale) | COMPOSITE POWDER FOR SOLDER-DIFFUSION |
| WO1999052671A1 (en) * | 1998-04-09 | 1999-10-21 | Onera (Office National D'etudes Et De Recherches Aerospatiales) | Composite powder for diffusion-welding |
| JP2011168631A (en) * | 2010-02-16 | 2011-09-01 | Nippon Shokubai Co Ltd | Method for producing metal-coated particle |
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