JP2714470B2 - Graphite particle dispersion silver plating method - Google Patents
Graphite particle dispersion silver plating methodInfo
- Publication number
- JP2714470B2 JP2714470B2 JP2049420A JP4942090A JP2714470B2 JP 2714470 B2 JP2714470 B2 JP 2714470B2 JP 2049420 A JP2049420 A JP 2049420A JP 4942090 A JP4942090 A JP 4942090A JP 2714470 B2 JP2714470 B2 JP 2714470B2
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- particles
- silver plating
- plating solution
- plating
- graphite particles
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Description
【発明の詳細な説明】 ［発明の属する技術分野］ 本発明は黒鉛粒子分散銀めっき方法の改良に関し、更
に詳しくは分散銀めっきのための分散黒鉛粒子の前処理
方法に関する。Description: TECHNICAL FIELD [0001] The present invention relates to an improvement in a graphite particle-dispersed silver plating method, and more particularly to a pretreatment method of dispersed graphite particles for dispersed silver plating.
［従来の技術］ 第４図は例えば「複合めっき」（榎本英彦著、日刊工
業新聞社発行、1989/8/30）の14頁に記載された従来の
分散めっき方法を表す図である。第４図において、
（１）はめっき槽、（２）は陽極、（３）は陰極、
（４）はめっき液、（５）は撹拌器、（６）はめっき電
源、（７）はめっき液中に分散している粒子を表してい
る。[Prior Art] FIG. 4 is a diagram showing a conventional dispersion plating method described on page 14 of, for example, “Composite Plating” (Hidehiko Enomoto, published by Nikkan Kogyo Shimbun, Aug. 30, 1989). In FIG.
(1) is a plating tank, (2) is an anode, (3) is a cathode,
(4) is a plating solution, (5) is a stirrer, (6) is a plating power supply, and (7) is particles dispersed in the plating solution.
また、第５図には、得られるめっき皮膜の断面の概略
を示す。第５図において、（８）はマトリックスとなる
めっき皮膜を表している。FIG. 5 shows a schematic cross section of the plating film obtained. In FIG. 5, (8) represents a plating film serving as a matrix.
粒子（７）がめっき液（４）中で、安定に存在し、且
つ均一な分散系を構成している場合、適当な撹拌条件と
電解条件下では、粒子（７）はめっき皮膜（８）中に取
り込まれ、めっき金属をマトリックスとして粒子（７）
を共析した皮膜が得られる。粒子（７）が共析しためっ
き皮膜（８）は共析しない皮膜に比べると、粒子（７）
とマトリックスとなるめっき皮膜（８）の組み合わせに
もよるが、耐摩耗性が向上するなどの特徴を有する。When the particles (7) are stably present in the plating solution (4) and constitute a uniform dispersion system, the particles (7) can form the plating film (8) under appropriate stirring and electrolysis conditions. Particles that are taken in and have plating metal as matrix (7)
Is obtained. The plating film (8) on which the particles (7) were eutectoid was compared with the film on which the particles (7) were not eutectoid
It has characteristics such as improved abrasion resistance, though it depends on the combination of the plating film (8) serving as a matrix.
［発明が解決しようとする課題］ 従来の分散めっきでは、めっき液（４）と分散させる
粒子（７）の選択が重要である。粒子（７）とめっき液
（４）の組み合わせによっては、粒子（７）がめっき液
（４）に溶解する場合もあり、また、めっき液（４）中
に安定に存在しても、粒子（７）がめっき皮膜（８）中
に全く共析しない場合もある。[Problems to be Solved by the Invention] In the conventional dispersion plating, it is important to select a plating solution (4) and particles (7) to be dispersed. Depending on the combination of the particles (7) and the plating solution (4), the particles (7) may be dissolved in the plating solution (4). 7) may not be co-eutected in the plating film (8) at all.
粒子（７）がめっき皮膜（８）中に共析する要因の詳
細は解っていないが、粒子（７）に関する因子では、粒
子（７）表面の電荷（表面電位）、形状や大きさ、めっ
き液（４）に対するぬれ性、更に吸着イオンなどが影響
しているものと考えられる。Although the details of the factors that cause the particles (7) to eutect into the plating film (8) are unknown, the factors relating to the particles (7) include the charge (surface potential) on the surface of the particles (7), the shape and size, and the plating. It is considered that the wettability to the liquid (4), and the adsorbed ions and the like have an influence.
粒子（７）とめっき液（４）との相性を良くするため
に、めっき液（４）中に界面活性剤などを添加する方法
や粒子（７）表面に予め金属陽イオンを吸着させる方法
が採られている。In order to improve the compatibility between the particles (7) and the plating solution (4), a method of adding a surfactant or the like to the plating solution (4) or a method of previously adsorbing metal cations on the surface of the particles (7) are available. Has been adopted.
例えば特開昭61-127900号公報には、粒子（７）表面
にアルミナコロイドと金属イオンを吸着させてめっき液
（４）中に添加する方法が記載されている。For example, JP-A-61-127900 describes a method in which alumina colloid and metal ions are adsorbed on the surface of particles (7) and are added to a plating solution (4).
また、上記「複合めっき」の38〜40頁には、粒子
（７）として表面エネルギーの低いBN、PTFT、(CF)x、
黒鉛、MoS2、有機ポリマー粒子等を使用する場合には、
粒子（７）がめっき液（４）中に均一に分散懸濁できる
ように界面活性剤の添加を行うことが記載されている。Also, on page 38 to 40 of the above “composite plating”, BN, PTFT, (CF) x ,
When using graphite, MoS 2 , organic polymer particles, etc.
It describes that a surfactant is added so that the particles (7) can be uniformly dispersed and suspended in the plating solution (4).
これらの方法は、分散させる粒子（７）表面を改質
し、めっき液（４）中での分散懸濁性や粒子（７）のめ
っき皮膜（８）中への共析量を増加させるのに効果があ
る。These methods modify the surface of the particles (7) to be dispersed and increase the dispersibility of the particles (7) in the plating solution (4) and the eutectoid amount of the particles (7) in the plating film (8). Is effective.
しかし、これらの方法は全ての粒子（７）とめっき液
（４）の組み合わせにおいて有効ではなく、各組み合わ
せにおいて最適な方法が採られている。また、めっき液
（４）に添加剤を加える場合においては、その添加剤が
めっきの析出を阻害しないものを選択しなければならな
い。これは、例えば界面活性剤などの添加剤は、粒子
（７）表面だけでなく、めっき表面にも吸着し、めっき
自体を阻害する場合も多いためである。However, these methods are not effective for all combinations of the particles (7) and the plating solution (4), and the optimum method is adopted for each combination. When an additive is added to the plating solution (4), one that does not inhibit the deposition of the plating must be selected. This is because, for example, additives such as surfactants are often adsorbed not only on the surface of the particles (7) but also on the plating surface, and often hinder plating itself.
本発明は、係る課題を解決するためになされたもの
で、界面活性剤などのめっき自体に影響を及ぼす添加剤
を用いずに、粒子（例えば、黒鉛粒子）（７）の表面を
改質し、粒子（黒鉛粒子）（７）とめっき液（例えば、
銀めっき液）（４）との相性が良好で、粒子（黒鉛粒
子）（７）の共析性が良い分散銀めっき液を得ることを
目的とする。The present invention has been made in order to solve the above-mentioned problem, and has been made to modify the surface of particles (eg, graphite particles) (7) without using an additive such as a surfactant which affects the plating itself. , Particles (graphite particles) (7) and a plating solution (for example,
It is an object of the present invention to obtain a dispersed silver plating solution having good compatibility with the silver plating solution (4) and having good eutectoid property of the particles (graphite particles) (7).
［課題を解決するための手段］ すなわち、本発明は銀めっき液中に微細な黒鉛粒子を
分散懸濁させ、その黒鉛粒子を銀めっき皮膜中に共析さ
せる分散銀めっき方法において、前記黒鉛粒子を銀めっ
き液中に混入懸濁させる前に、ゾル−ゲル法によって黒
鉛粒子表面を金属酸化物あるいは金属窒化物で修飾する
ことを特徴とする黒鉛粒子分散銀めっき方法に係る。[Means for Solving the Problems] That is, the present invention relates to a dispersed silver plating method in which fine graphite particles are dispersed and suspended in a silver plating solution and the graphite particles are codeposited in a silver plating film. Before mixing and suspending in a silver plating solution, the surface of graphite particles is modified with a metal oxide or metal nitride by a sol-gel method.
本発明に係る黒鉛粒子分散銀めっき方法は、分散させ
る粒子（黒鉛粒子）（７）をめっき液（銀めっき液）
（４）中に投入する前に、粒子（黒鉛粒子）（７）表面
をゾル−ゲル法によって金属酸化物あるいは金属窒化物
でコーティングした後、めっき液（銀めっき液）（４）
中に投入し、分散銀めっきを行う方法である。The graphite particle-dispersed silver plating method according to the present invention is characterized in that the particles (graphite particles) (7) to be dispersed are plated with a plating solution (silver plating solution).
(4) Before pouring into the particles, particles (graphite particles) (7) After coating the surface with a metal oxide or metal nitride by a sol-gel method, a plating solution (silver plating solution) (4)
It is a method of dispersing silver plating.
ゾル−ゲル法について、「ゾル−ゲル法の科学」（作
花済夫著、アグネ承風社、1988/7/5発行）の８〜９頁に
は、次のように記載されている。ゾル−ゲル法とは、金
属の有機または無機化合物の溶液から酸化物の固体を作
製する方法である。溶液中で上記化合物の加水分解・重
合反応を進ませると、溶液は金属酸化物または水酸化物
の微粒子が溶解したゾルとなる。更に、反応を進ませ
て、そのゾルをゲルとして固定し、できた多孔質のゲル
を加熱すれば酸化物の固体を作成できる。この方法によ
れば、高度に均一で微細な粒子からなる多結晶セラミッ
クを容易に作成できる。The sol-gel method is described as follows in “Science of the sol-gel method” (written by Saio Sakuhana, Agne Shofusha, published on July 5, 1988), pp. 8-9. The sol-gel method is a method for producing an oxide solid from a solution of a metal organic or inorganic compound. When the hydrolysis / polymerization reaction of the above compound proceeds in the solution, the solution becomes a sol in which fine particles of metal oxide or hydroxide are dissolved. Further, the reaction proceeds, the sol is fixed as a gel, and the resulting porous gel is heated to produce an oxide solid. According to this method, a polycrystalline ceramic composed of highly uniform and fine particles can be easily produced.
第６図は上記「ゾル−ゲル法の科学」の11頁に記載さ
れたゾル−ゲル法の概要を示す図である。ゾル−ゲル法
では、出発原料は有機物、無機物のいずれでもよく、ま
た、特定の種類の化合物に限られないが、一般に金属ア
ルコキシドが多く用いられている。FIG. 6 is a diagram showing an outline of the sol-gel method described on page 11 of the above-mentioned “Science of the sol-gel method”. In the sol-gel method, the starting material may be either an organic substance or an inorganic substance, and is not limited to a specific type of compound, but generally a metal alkoxide is often used.
まず、目的とする酸化物に対応する金属アルコキシド
をアルコールに溶解して混合溶液を造る。次に、加水分
解に必要な水、触媒としての酸をアルコール溶液として
添加する。上記の混合溶液を室温〜80℃で撹拌しながら
加水分解と重合反応を進ませると、金属酸化物の粒子が
生じ、溶液はゾルとなり、反応が進むと全体が固まった
ゲルとなる。上記ゲル体を乾燥させ、更に加熱すると、
固定セラミックやガラスを得ることができる。First, a mixed solution is prepared by dissolving a metal alkoxide corresponding to a target oxide in alcohol. Next, water necessary for hydrolysis and an acid as a catalyst are added as an alcohol solution. When the hydrolysis and polymerization reaction are allowed to proceed while stirring the above mixed solution at room temperature to 80 ° C., metal oxide particles are generated, the solution becomes a sol, and as the reaction proceeds, the whole becomes a solidified gel. When the gel body is dried and further heated,
Fixed ceramic and glass can be obtained.
ここでは、金属酸化物のバルク固体の作成法が記載さ
れて要るが、既にある固体の表面上に金属酸化物の皮膜
を形成することも可能である。上記「ゾル−ゲル法の科
学」の85頁には、この皮膜形成法が記載されている。第
７図は皮膜を形成するプロセスを示す図である。まず、
酸化物固体を作製する場合と同様に、金属アルコキシド
−水−酸触媒混合溶液中に皮膜を形成しようとする固体
を浸漬し、ゲルコーティング膜を表面に形成し、その後
加熱すれば所望固体表面に酸化物皮膜を得ることができ
る。この時、窒素雰囲気下で熱処理を行えば、金属窒化
物皮膜を得ることができる。Here, a method for preparing a metal oxide bulk solid is described, but it is also possible to form a metal oxide film on the surface of an existing solid. The above-mentioned "Sol-gel method science", page 85, describes this film formation method. FIG. 7 is a view showing a process of forming a film. First,
As in the case of preparing an oxide solid, a solid to form a film is immersed in a metal alkoxide-water-acid catalyst mixed solution, a gel coating film is formed on the surface, and then heated to a desired solid surface. An oxide film can be obtained. At this time, if heat treatment is performed in a nitrogen atmosphere, a metal nitride film can be obtained.
本発明は上記ゾル−ゲル法により、分散めっき粒子
（黒鉛粒子）（７）表面に金属酸化物あるいは金属窒化
物の皮膜を形成し、その後、めっき液（銀めっき液）
（４）中に投入懸濁させて分散銀めっきを行うものであ
る。The present invention forms a metal oxide or metal nitride film on the surface of the dispersed plating particles (graphite particles) (7) by the above sol-gel method, and then forms a plating solution (silver plating solution).
(4) The dispersion silver plating is carried out by suspending it in the dispersion.
第１図に本発明に係る分散粒子（黒鉛粒子）の概念図
を示す。第１図において、（９）はゾル−ゲル法で粒子
（黒鉛粒子）（７）表面上に形成された金属酸化物また
は金属窒化物を示す。ここでいう金属酸化物や金属窒化
物（９）は特に限定されるものではないが、α−アルミ
ナなどめっき液（銀めっき液）との濡れ性の良好で、め
っき皮膜（８）中への共析性の良好なものが望ましい。FIG. 1 shows a conceptual diagram of the dispersed particles (graphite particles) according to the present invention. In FIG. 1, (9) shows a metal oxide or metal nitride formed on the surface of a particle (graphite particle) (7) by the sol-gel method. The metal oxide or metal nitride (9) used herein is not particularly limited, but has good wettability with a plating solution (silver plating solution) such as α-alumina, and has a good wettability in the plating film (8). Those having good eutectoid properties are desirable.
［作用］ 粒子（黒鉛粒子）（７）表面の電荷やめっき液（銀め
っき液）（４）に対する濡れ性、更にイオンの吸着など
は、粒子（黒鉛粒子）（７）表面の性質や状態に依存す
る。粒子（黒鉛粒子）（７）とめっき液（銀めっき液）
（４）との濡れ性が悪く、良好な分散共析性を示さない
粒子（黒鉛粒子）（７）の場合、第１図に示すように、
粒子（黒鉛粒子）（７）表面上にめっき液（銀めっき
液）（４）との濡れ性やめっき皮膜（８）中への共析性
に優れた表面を有する皮膜（ここでは金属酸化物または
金属窒化物）（９）を形成すれば、良好な分散共析性を
示すようになる。[Action] The charge on the surface of the particles (graphite particles) (7), the wettability to the plating solution (silver plating solution) (4), the adsorption of ions, etc., depend on the properties and state of the surface of the particles (graphite particles) (7). Dependent. Particles (graphite particles) (7) and plating solution (silver plating solution)
In the case of particles (graphite particles) (7) having poor wettability with (4) and exhibiting no good dispersive eutectoid, as shown in FIG.
Particles (graphite particles) (7) A film having a surface having excellent wettability with plating solution (silver plating solution) (4) and eutectoid into plating film (8) on the surface (here, metal oxide Alternatively, when the metal nitride (9) is formed, a good dispersion eutectoid can be exhibited.
［実施例］ 以下に実施例を挙げて本発明を詳細に説明するが、こ
れにより本発明を限定するものではない。[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
第２図は本発明の一実施態様を示す分散させる粒子
（黒鉛粒子）のゾル−ゲル法によるアルミナ形成プロセ
スを示す。FIG. 2 shows an alumina forming process of dispersed particles (graphite particles) according to an embodiment of the present invention by a sol-gel method.
本実施例におけるゾル−ゲル法では、金属アルコキシ
ドとしてアルミニウム−sec−ブトキシドを、また、酸
触媒としてアセト酢酸エチルを用いる。各々ｉ−プロピ
ルアルコールに溶解し混合する。ｉ−プロピルアルコー
ルの量はアルミニウム−sec−ブトキシドが１モルに対
して１〜200倍モル量が望ましい。アセト酢酸エチルは
アルミニウム−sec−ブトキシド１モルに対して0.1〜10
倍モル量添加する。本実施例においては等倍モル量を添
加した。最終的な混合比は（1:1:140）である。この混
合溶液をビーカーの中に入れ、撹拌しながら黒鉛粒子を
加える。ここで使用した黒鉛粒子は粒径約２μｍの黒鉛
粒子である。この混合物を空気中で乾燥させ、溶媒（ｉ
−プロピルアルコール）を蒸発させた後、オーブン中で
熱処理する。この時の熱処理温度は約450℃である。得
られた粉末は再度前記混合溶液中に撹拌しながら加え、
乾燥後、熱処理を行う。この操作は数回繰り返しておこ
なう。繰り返し回数が多い程厚いアルミナ皮膜を形成で
きる。望ましくは１〜10回繰り返すのが良い。なお、実
施例においては３回反復した。In the sol-gel method in this embodiment, aluminum-sec-butoxide is used as the metal alkoxide, and ethyl acetoacetate is used as the acid catalyst. Each is dissolved in i-propyl alcohol and mixed. The amount of i-propyl alcohol is desirably 1 to 200 times mol per mol of aluminum-sec-butoxide. Ethyl acetoacetate is used in an amount of 0.1 to 10 per mol of aluminum-sec-butoxide.
Add twice the molar amount. In this example, the same molar amount was added. The final mixing ratio is (1: 1: 140). This mixed solution is placed in a beaker, and graphite particles are added with stirring. The graphite particles used here are graphite particles having a particle size of about 2 μm. The mixture is dried in air and the solvent (i
-Propyl alcohol) is evaporated and then heat-treated in an oven. The heat treatment temperature at this time is about 450 ° C. The obtained powder is again added to the mixed solution with stirring,
After drying, heat treatment is performed. This operation is repeated several times. As the number of repetitions increases, a thicker alumina film can be formed. Desirably, it should be repeated 1 to 10 times. In addition, in Example, it repeated three times.
上記操作によって、黒鉛粒子の表面上にアルミナが付
着する。この後、アルゴン雰囲気中で約1200℃で熱処理
を行い、付着アルミナをα−アルミナに変質させた。な
お、本実施例におけるゾル−ゲル法では水の添加は行わ
なかったが、必要に応じて0.1〜10倍モル量の水を添加
しても良い。By the above operation, alumina adheres to the surface of the graphite particles. Thereafter, a heat treatment was performed at about 1200 ° C. in an argon atmosphere to convert the attached alumina to α-alumina. In the present embodiment, water was not added in the sol-gel method, but 0.1 to 10 times the amount of water may be added as necessary.
上記のα−アルミナ修飾黒鉛粒子を、硝酸銀50g/l、
硝酸アンモニウム80g/lからなる銀めっき液中に20g/lと
なるように分散懸濁させ、30℃、1A/dm2で分散めっきを
行った。The above α-alumina modified graphite particles, silver nitrate 50g / l,
It was dispersed and suspended at a concentration of 20 g / l in a silver plating solution composed of 80 g / l of ammonium nitrate, and subjected to dispersion plating at 30 ° C. and 1 A / dm 2 .
また、比較例としてゾル−ゲル法で表面修飾しない上
記粒子と同一の黒鉛粒子を同一銀めっき液中に同一量分
散懸濁させ、同一めっき条件でめっきを行った。この結
果を第１表に示す。As a comparative example, the same graphite particles as the above particles whose surface was not modified by the sol-gel method were dispersed and suspended in the same silver plating solution in the same amount and plated under the same plating conditions. Table 1 shows the results.
第１表 α−アルミナ修飾処理 未処理 黒鉛粒子の共析量 ２〜３体積％ 共析なし 共析状態 均一共析 ゾル−ゲル法によってα−アルミナ修飾処理を施した
黒鉛粒子は、処理を行っていない粒子に比べ、銀めっき
液に対する濡れ性が良く、銀めっき液中で均一分散した
懸濁系を造る。 Table 1 α-alumina modification treatment Untreated eutectoid amount of graphite particles 2-3% by volume No eutectoid Eutectoid state Uniform eutectoid Graphite particles which have been subjected to α-alumina modification treatment by the sol-gel method are treated. It has better wettability to the silver plating solution than particles that are not, and produces a suspension system uniformly dispersed in the silver plating solution.
一方、処理を行っていない黒鉛粒子は、銀めっき液中
で凝集し易く、均一な懸濁系を造ることができなかっ
た。更に、処理を行っていない黒鉛粒子は銀めっき皮膜
中にほとんど共析しないのに対し、ゾル−ゲル法によっ
てα−アルミナ修飾処理を施した黒鉛粒子は銀めっき皮
膜中に均一に分散して共析した。On the other hand, untreated graphite particles tended to agglomerate in the silver plating solution, making it impossible to form a uniform suspension. Furthermore, graphite particles that have not been treated hardly eutect into the silver plating film, whereas graphite particles that have been α-alumina-modified by the sol-gel method are uniformly dispersed in the silver plating film. Was analyzed.
第３図に黒鉛粒子表面に付着させたアルミナの付着量
とこのアルミナ被覆黒鉛粒子の銀めっき皮膜中への共析
量との関係を示す。黒鉛粒子上のアルミナ付着量は、ご
く少量でも黒鉛粒子の銀めっき皮膜中への共析に効果が
あり、アルミナの薄い表面被覆が黒鉛粒子の表面改質効
果をもたらしていることは明らかである。FIG. 3 shows the relationship between the amount of alumina attached to the graphite particle surface and the amount of eutectoid in the silver plating film of the alumina-coated graphite particles. Even a very small amount of alumina on graphite particles is effective for eutectoid deposition of graphite particles into the silver plating film, and it is clear that thin surface coating of alumina has a surface modification effect on graphite particles. .
なお、第２図には、金属酸化物皮膜としてアルミナ、
粒子として黒鉛粒子を使用する場合の諸条件を記載した
が、本発明のゾル−ゲル法による金属酸化物または金属
窒化物形成条件並びに材質はこれらに限定されるもので
はない。In FIG. 2, alumina is used as the metal oxide film.
Although the conditions for using graphite particles as the particles have been described, the conditions and materials for forming metal oxides or metal nitrides by the sol-gel method of the present invention are not limited to these.
また、ゾル−ゲル法により前処理を施した黒鉛粒子は
従来の分散銀めっき法と同様の操作に供することができ
る。The graphite particles pretreated by the sol-gel method can be subjected to the same operation as the conventional dispersion silver plating method.
［発明の効果］ 本発明は、以上説明した通り、ゾル−ゲル法によって
めっき液（銀めっき液）（４）に対して濡れ性の良い金
属酸化物または金属窒化物（９）で粒子（黒鉛粒子）
（７）を修飾したので、めっき液（銀めっき液）（４）
に対する粒子（黒鉛粒子）（７）の濡れ性を改善し、め
っき液（銀めっき液）（４）中で均一分散した懸濁系を
造ることができるという効果がある。[Effects of the Invention] As described above, the present invention provides particles (graphite) of metal oxide or metal nitride (9) having good wettability to a plating solution (silver plating solution) (4) by a sol-gel method. particle)
(7) Modified, plating solution (silver plating solution) (4)
This has the effect of improving the wettability of the particles (graphite particles) (7) with respect to, and making it possible to produce a suspension uniformly dispersed in the plating solution (silver plating solution) (4).
更に、めっき皮膜（８）中への共析し難い分散粒子
（黒鉛粒子）（７）の表面を改質できるので、共析し易
くできるし、共析量も増加させることができる。Further, since the surface of the dispersed particles (graphite particles) (7) that are hard to eutect into the plating film (8) can be modified, eutectoid can be easily made and the amount of eutectoid can be increased.
また、本発明に係る別の効果はゾル−ゲル法による粒
子（黒鉛粒子）（７）の表面改質はめっき液（銀めっき
液）（４）中にその成分が溶け出すことがないので、界
面活性剤のようにめっき自体を阻害することがない。Another effect according to the present invention is that the surface modification of the particles (graphite particles) (7) by the sol-gel method does not dissolve the components in the plating solution (silver plating solution) (4). Plating itself is not hindered unlike a surfactant.
第１図は本発明方法により得られる分散粒子（黒鉛粒
子）を示す概念図であり、第２図は本発明の一実施態様
を示すプロセス図であり、第３図は実施例における結果
を示すグラフであり、第４図は従来の分散めっき法の形
態を示す概念図であり、第５図は分散めっき皮膜の断面
の概念図であり、第６図はゾル−ゲル法のプロセスを説
明する概念図であり、第７図はゾル−ゲル法によってコ
ーティングを行うプロセスを示す概念図である。図中、
（４）はめっき液、（７）は分散共析させる粒子、
（８）はめっき皮膜、（９）は金属酸化物あるいは金属
窒化物を示す。なお、各図面中、同一符号は同一または
相当部分を示す。FIG. 1 is a conceptual diagram showing dispersed particles (graphite particles) obtained by the method of the present invention, FIG. 2 is a process diagram showing one embodiment of the present invention, and FIG. 3 shows the results in the examples. FIG. 4 is a conceptual diagram showing a form of a conventional dispersion plating method, FIG. 5 is a conceptual diagram of a cross section of a dispersion plating film, and FIG. 6 illustrates a process of a sol-gel method. FIG. 7 is a conceptual diagram showing a process of performing coating by a sol-gel method. In the figure,
(4) is a plating solution, (7) is particles to be dispersed and eutectoid,
(8) indicates a plating film, and (9) indicates a metal oxide or metal nitride. In the drawings, the same reference numerals indicate the same or corresponding parts.
Claims (1)
させ、その黒鉛粒子を銀めっき皮膜中に共析させる分散
銀めっき方法において、前記黒鉛粒子を銀めっき液中に
混入懸濁させる前に、ゾル−ゲル法によって黒鉛粒子表
面を金属酸化物あるいは金属窒化物で修飾することを特
徴とする黒鉛粒子分散銀めっき方法。1. A dispersion silver plating method in which fine graphite particles are dispersed and suspended in a silver plating solution, and the graphite particles are eutectoidally deposited in a silver plating film, wherein the graphite particles are mixed and suspended in the silver plating solution. A graphite particle-dispersed silver plating method, wherein the surface of graphite particles is modified with a metal oxide or metal nitride by a sol-gel method before the formation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049420A JP2714470B2 (en) | 1990-03-02 | 1990-03-02 | Graphite particle dispersion silver plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049420A JP2714470B2 (en) | 1990-03-02 | 1990-03-02 | Graphite particle dispersion silver plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03253598A JPH03253598A (en) | 1991-11-12 |
| JP2714470B2 true JP2714470B2 (en) | 1998-02-16 |
Family
ID=12830587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2049420A Expired - Lifetime JP2714470B2 (en) | 1990-03-02 | 1990-03-02 | Graphite particle dispersion silver plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2714470B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037144A1 (en) * | 2005-09-29 | 2007-04-05 | Dowa Metaltech Co., Ltd. | Process for producing composite-plated material |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003034508A1 (en) * | 2001-10-12 | 2003-04-24 | Nichia Corporation | Light emitting device and method for manufacture thereof |
| KR101030068B1 (en) | 2002-07-08 | 2011-04-19 | 니치아 카가쿠 고교 가부시키가이샤 | Method of Manufacturing Nitride Semiconductor Device and Nitride Semiconductor Device |
| JP4783954B2 (en) | 2004-06-21 | 2011-09-28 | Ｄｏｗａメタルテック株式会社 | Composite plating material and method for producing the same |
| JP4806808B2 (en) | 2005-07-05 | 2011-11-02 | Ｄｏｗａメタルテック株式会社 | Composite plating material and method for producing the same |
| DE102005057384A1 (en) * | 2005-11-30 | 2007-05-31 | Nanogate Ag | Electrolytically deposited metal layer for coating engine parts comprises embedded particles having a silicon dioxide coating |
| US9562302B2 (en) | 2009-06-29 | 2017-02-07 | Auckland Uniservices Limited | Plating or coating method for producing metal-ceramic coating on a substrate |
| JP7233991B2 (en) | 2019-03-18 | 2023-03-07 | Ｄｏｗａメタルテック株式会社 | Composite plated material and its manufacturing method |
| JP6804597B1 (en) | 2019-08-01 | 2020-12-23 | Ｄｏｗａメタルテック株式会社 | Composite plating material and its manufacturing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01176099A (en) * | 1987-12-29 | 1989-07-12 | Nippon Steel Corp | Composite electroplated steel sheet having high corrosion resistance |
-
1990
- 1990-03-02 JP JP2049420A patent/JP2714470B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01176099A (en) * | 1987-12-29 | 1989-07-12 | Nippon Steel Corp | Composite electroplated steel sheet having high corrosion resistance |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037144A1 (en) * | 2005-09-29 | 2007-04-05 | Dowa Metaltech Co., Ltd. | Process for producing composite-plated material |
| JP2007092141A (en) * | 2005-09-29 | 2007-04-12 | Dowa Holdings Co Ltd | Method for producing composite plated material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03253598A (en) | 1991-11-12 |
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