EP1260615A1 - Metal coating of graphite - Google Patents

Metal coating of graphite Download PDF

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Publication number
EP1260615A1
EP1260615A1 EP20010111708 EP01111708A EP1260615A1 EP 1260615 A1 EP1260615 A1 EP 1260615A1 EP 20010111708 EP20010111708 EP 20010111708 EP 01111708 A EP01111708 A EP 01111708A EP 1260615 A1 EP1260615 A1 EP 1260615A1
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EP
European Patent Office
Prior art keywords
graphite
metal coating
etching bath
alkaline etching
galvanic
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
Application number
EP20010111708
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German (de)
French (fr)
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EP1260615B1 (en
Inventor
Wolf-Dieter Franz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Franz Oberflaechentechnik GmbH and Co KG
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Franz Oberflaechentechnik GmbH and Co KG
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Application filed by Franz Oberflaechentechnik GmbH and Co KG filed Critical Franz Oberflaechentechnik GmbH and Co KG
Priority to DE50100123T priority Critical patent/DE50100123D1/en
Priority to AT01111708T priority patent/ATE234950T1/en
Priority to SI200130012T priority patent/SI1260615T1/en
Priority to EP20010111708 priority patent/EP1260615B1/en
Priority to PCT/EP2002/003116 priority patent/WO2002092884A1/en
Publication of EP1260615A1 publication Critical patent/EP1260615A1/en
Application granted granted Critical
Publication of EP1260615B1 publication Critical patent/EP1260615B1/en
Priority to US10/712,458 priority patent/US20040094424A1/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1896—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by electrochemical pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces

Definitions

  • the present invention relates to a method for the metal coating of Graphite.
  • Graphite has a wide variety of uses as a material. In many Cases must use graphite parts for electrically conductive connections are, often only mechanically clamped and by pressing others electrically conductive parts is contacted (especially by pressing Metal contacts). With numerous technical problems, however required a connection by soldering or other connection techniques, so that the graphite part needs a metallic surface.
  • the invention is based on the technical problem, a method for coating of graphite with metals.
  • the invention is based on the idea that a metal coating of Graphite, i.e. the application to the graphite and not just on top of it Metal layers, for electrical contacting and / or for mechanical Fastening graphite components makes a valuable contribution. To the one can apply other metallic contact pieces to the applied metal layers be pressed, whereby there are comparatively low contact resistances result. Second, the metal layers as Basis for solder connections or other processes for the production of a fixed connection to the component can be used, which has a metal surface provide.
  • the main point is to ensure good liability between the metal layers to be applied and the actual graphite surface.
  • the inventor has found that good adhesion can be achieved if the graphite component is first in an alkaline etching bath in anodic operation is pretreated and activated and then a galvanic coating takes place. Due to the alkaline etching bath in anodic operation the graphite surface is not only thoroughly cleaned but also slightly etched, so the subsequent electroplating is one of foreign contaminants as well as graphite dust largely free and slightly roughened Surface. This allows the metal layer to adhere well to the graphite surface interlock, which significantly benefits the adhesive properties.
  • the alkaline etching bath creates the conditions for a highly adhesive and temperature-resistant coating with metals.
  • the graphite surface before the galvanic metal coating can be germinated with Pd. It can also follow this Pd germination a so-called chemical metal layer can be deposited. This is what it is about is an electroless plating of a metal with a reducing agent.
  • This external currentless deposition is optional, but preferably sets Pd germination ahead.
  • the external currentless Deposition Ni or Cu deposited the two metals also can be present together or in conjunction with other metals.
  • the cleaning effect of the alkaline etching bath can be done by an ultrasound treatment get supported. This helps particles sticking to the surface detach from the surface and also supports mixing and the concentration equalization near the surface.
  • the ultrasound treatment however, has several disadvantages. With some components it is because of mechanical stress on sensitive parts undesirable. Moreover it requires the installation of the parts in a suitable for ultrasound treatment Contraption. To perfect the uniformity of the ultrasound treatment can in particular annular arrangements of the to be treated Batches of components can be selected, but this is relatively expensive in terms of equipment is.
  • the described Ultrasound treatment completely dispensed with and thus the temporal and apparatus expenditure significantly reduced.
  • the treated ones Graphite parts from the alkaline etching bath directly, i.e. in immediate temporal Connection and without further intermediate treatment, in a thin aqueous Solution or immersed in water.
  • the solution residues of the etching bath react with water or a thin solution short and relatively violent what happens notices that the near-surface areas in the water or Foam briefly in the aqueous solution.
  • This foaming has after Observation by the inventor of a cleaning effect comparable to the ultrasonic bath and removes those that have already been etched away or dissolved in the etching bath Impurities effective and easy from the surface.
  • the procedure just described should therefore preferably be used ultrasound treatment in this area of the procedure to leave out entirely.
  • the mentioned galvanic metal coating of the graphite can be on frames and run with appropriate parts geometry in drums.
  • the galvanic Coating can preferably be with Cu, Ni or Sn, a mixture of these Metals or a mixture of one or more of these metals with others Metals.
  • Sn and Sn alloys in particular have good soldering properties, so that the galvanic layer for a later (optional) soldering step forms a good foundation.
  • Preferred parameter ranges of the galvanic coating are a current density of 1-10 A / dm 2 and a treatment time, ie bath and switch-on time of the current, of 5-60 minutes.
  • the alkaline etching bath can preferably be in sodium hydroxide solution (NaOH solution) or Potash lye (KOH solution) or a mixture of the two lyes, for example in a concentration range of 10-60% by weight, particularly preferably 20-50 wt .-% and in the findings of Inventor's best case between 30 and 40 wt .-%.
  • NaOH solution sodium hydroxide solution
  • KOH solution Potash lye
  • the alkaline etching bath can preferably be in sodium hydroxide solution (NaOH solution) or Potash lye (KOH solution) or a mixture of the two lyes, for example in a concentration range of 10-60% by weight, particularly preferably 20-50 wt .-% and in the findings of Inventor's best case between 30 and 40 wt .-%.
  • graphite in this invention is directed to all materials which contains graphite to such an extent and on the relevant surface occurs that the metal coating also of the graphite surfaces is essential even for the technical result. Of course, this includes at first once all pure graphite materials as well as those with minor Additives. However, the invention is preferably also directed to plastic-bound ones Graphite materials, in which graphite particles in a plastic matrix are included. Such material has various technical applications, in which the method according to the invention can be of great advantage can.
  • a component of an electrotechnical made of plastic-bound graphite Device is manufactured in a conventional way to the extent that the final Form is given. Then larger numbers of the component than batch in a commercially available facility for electrolytic etching in 35 % By weight NaOH solution cleaned at 60 ° C for 10 minutes in anodic operation and etched and then directly into a simple water bath Room temperature introduced. There the solution foams in the vicinity of the Components of the batch briefly open, the batch is rinsed further and then in on is known to germinate with Pd. There are commercial ionogens or colloidal Pd solutions are available. The Pd seeds serve as a catalyst for the following metallization steps.
  • Ni layer is then applied to the Pd-germinated graphite components chemically (without external current) deposited. This nickel layer can, because it is very thin, then with chemical nickel, chemical copper, electroplated nickel and / or electroplated copper.
  • An electrolytic Sn alloy can then be applied to the chemical metal layer applied that is so thick (approx. 5-10 ⁇ ) that the solder joints are directly on it can be attached.
  • the soldering process is completely conventional because only the surface of the Sn alloy plays a role.
  • the solder joint can not only be used for excellent electrical contacts to the Graphite component can be used. It also has such good adhesion the graphite component that can also be used for mechanical fastening, so that the graphite component is no longer clamped or through holes in the Screwed graphite component or otherwise in relation to the graphite component must be attached positively or non-positively. It can simply be a suitable one Metal ash can be used as an assembly aid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

Applying a metal coating comprises applying a galvanic metal coating to graphite components after they have been subjected to an alkaline anodic caustic bath. An Independent claim is also included for a process for the production of a solder join with a graphite component. Preferred Features: A lead layer is formed on the graphite components before the metal coating is applied. The lead layer is reinforced by the current-less deposition of nickel or copper. The caustic bath has a temperature of 20-70 degrees C.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Metallbeschichtung von Graphit.The present invention relates to a method for the metal coating of Graphite.

Graphit findet als Werkstoff die unterschiedlichsten Anwendungen. In vielen Fällen müssen Graphitteile für elektrisch leitende Verbindungen eingesetzt werden, wobei häufig nur mechanisch geklemmt und durch Andrücken anderer elektrisch leitfähiger Teile kontaktiert wird (insbesondere durch Anpressen von Metallkontakten). Bei zahlreichen technischen Problemstellungen ist allerdings eine Verbindung durch Löten oder andere Verbindungstechniken gefordert, so dass das Graphitteil eine metallische Oberfläche benötigt.Graphite has a wide variety of uses as a material. In many Cases must use graphite parts for electrically conductive connections are, often only mechanically clamped and by pressing others electrically conductive parts is contacted (especially by pressing Metal contacts). With numerous technical problems, however required a connection by soldering or other connection techniques, so that the graphite part needs a metallic surface.

Der Erfindung liegt das technische Problem zugrunde, ein Verfahren zur Beschichtung von Graphit mit Metallen anzugeben.The invention is based on the technical problem, a method for coating of graphite with metals.

Erfindungsgemäß ist hierzu ein Verfahren zur Metallbeschichtung von Graphit vorgesehen, das gekennzeichnet ist durch folgende Schritte in folgender Reihenfolge: ein alkalisches Ätzbad des Graphits im anodischen Betrieb und eine galvanische Metallbeschichtung des Graphits.According to the invention there is a method for the metal coating of graphite provided, which is characterized by the following steps in the following order: an alkaline etching bath of graphite in anodic operation and one galvanic metal coating of graphite.

Die Erfindung geht von dem Gedanken aus, dass eine Metallbeschichtung von Graphit, also das Aufbringen auf dem Graphit haftender und nicht nur aufliegender Metallschichten, zur elektrischen Kontaktierung und/oder zur mechanischen Befestigung von Graphitbauteilen einen wertvollen Beitrag leistet. Zum einen können auf die aufgebrachten Metallschichten andere metallische Kontaktstücke aufgedrückt werden, wobei sich vergleichsweise niedrige Übergangswiderstände ergeben. Zum zweiten können die Metallschichten als Grundlage für Lötverbindungen oder andere Verfahren zur Herstellung einer festen Verbindung mit dem Bauteil verwendet werden, die eine Metalloberfläche voraussetzen.The invention is based on the idea that a metal coating of Graphite, i.e. the application to the graphite and not just on top of it Metal layers, for electrical contacting and / or for mechanical Fastening graphite components makes a valuable contribution. To the one can apply other metallic contact pieces to the applied metal layers be pressed, whereby there are comparatively low contact resistances result. Second, the metal layers as Basis for solder connections or other processes for the production of a fixed connection to the component can be used, which has a metal surface provide.

Der wesentliche Punkt ist dabei die Sicherstellung einer guten Haftung zwischen den aufzubringenden Metallschichten und der eigentlichen Graphitoberfläche. Der Erfinder hat festgestellt, dass sich eine gute Haftung erzielen lässt, wenn das Graphitbauteil zuerst in einem alkalischen Ätzbad im anodischen Betrieb vorbehandelt und aktiviert wird und anschließend eine galvanische Beschichtung stattfindet. Durch das alkalische Ätzbad im anodischen Betrieb wird die Graphitoberfläche nicht nur gründlich gereinigt sondern auch leicht angeätzt, so dass die nachfolgende galvanische Beschichtung eine von Fremdverunreinigungen sowie Graphitstaub weitgehend freie und leicht angerauhte Oberfläche vorfindet. Dadurch kann sich die Metallschicht gut in der Graphitoberfläche verzahnen, was den Hafteigenschaften wesentlich zugute kommt. Das alkalische Ätzbad schafft die Voraussetzung für eine hochgradig haftfeste und temperaturbeständige Beschichtung mit Metallen.The main point is to ensure good liability between the metal layers to be applied and the actual graphite surface. The inventor has found that good adhesion can be achieved if the graphite component is first in an alkaline etching bath in anodic operation is pretreated and activated and then a galvanic coating takes place. Due to the alkaline etching bath in anodic operation the graphite surface is not only thoroughly cleaned but also slightly etched, so the subsequent electroplating is one of foreign contaminants as well as graphite dust largely free and slightly roughened Surface. This allows the metal layer to adhere well to the graphite surface interlock, which significantly benefits the adhesive properties. The alkaline etching bath creates the conditions for a highly adhesive and temperature-resistant coating with metals.

Optional kann die Graphitoberfläche vor der galvanischen Metallbeschichtung mit Pd bekeimt werden. Außerdem kann nachfolgend zu dieser Pd-Bekeimung eine sog. chemische Metallschicht abgeschieden werden. Dabei handelt es sich um eine außenstromlose Abscheidung eines Metalls mit einem Reduktionsmittel. Diese außenstromlose Abscheidung ist optional, setzt jedoch vorzugsweise die Pd-Bekeimung voraus. Vorzugsweise wird bei der außenstromlosen Abscheidung Ni oder Cu abgeschieden, wobei die beiden Metalle auch gemeinsam oder in Verbindung mit anderen Metallen vorliegen können.Optionally, the graphite surface before the galvanic metal coating can be germinated with Pd. It can also follow this Pd germination a so-called chemical metal layer can be deposited. This is what it is about is an electroless plating of a metal with a reducing agent. This external currentless deposition is optional, but preferably sets Pd germination ahead. Preferably the external currentless Deposition Ni or Cu deposited, the two metals also can be present together or in conjunction with other metals.

Die Reinigungswirkung des alkalischen Ätzbades kann durch eine Ultraschallbehandlung unterstützt werden. Diese hilft, an der Oberfläche haftende Partikel von der Oberfläche abzulösen und unterstützt ferner die Durchmischung und den Konzentrationsausgleich in Oberflächennähe. Die Ultraschallbehandlung hat jedoch verschiedene Nachteile. Bei manchen Bauteilen ist sie wegen der mechanischen Beanspruchung empfindlicher Teile unerwünscht. Außerdem erfordert sie den Einbau der Teile in eine zur Ultraschallbehandlung geeignete Vorrichtung. Zur Perfektionierung der Gleichmäßigkeit der Ultraschallbehandlung können dabei insbesondere ringförmige Anordnungen der zu behandelnden Chargen von Bauteilen gewählt werden, was jedoch apparativ relativ aufwendig ist.The cleaning effect of the alkaline etching bath can be done by an ultrasound treatment get supported. This helps particles sticking to the surface detach from the surface and also supports mixing and the concentration equalization near the surface. The ultrasound treatment however, has several disadvantages. With some components it is because of mechanical stress on sensitive parts undesirable. Moreover it requires the installation of the parts in a suitable for ultrasound treatment Contraption. To perfect the uniformity of the ultrasound treatment can in particular annular arrangements of the to be treated Batches of components can be selected, but this is relatively expensive in terms of equipment is.

Gemäß einem besonders bevorzugten Merkmal der Erfindung wird auf die geschilderte Ultraschallbehandlung gänzlich verzichtet und damit der zeitliche und apparative Aufwand deutlich verringert. Stattdessen werden die behandelten Graphitteile aus dem alkalischen Ätzbad direkt, d.h. in unmittelbarem zeitlichen Zusammenhang und ohne weitere Zwischenbehandlung, in eine dünne wässrige Lösung oder in Wasser getaucht. Dabei entstehen auf den Oberflächen der Teile wegen der dort noch anhaftenden Reste der im Ätzbad verwendeten Lösung große Konzentrationsgradienten. Die Lösungsreste des Ätzbades reagieren mit dem Wasser oder der dünnen Lösung kurz und relativ heftig, was sich daran bemerkbar macht, dass die oberflächennahen Bereiche im Wasser oder in der wässrigen Lösung kurz aufschäumen. Dieses Aufschäumen hat nach Beobachtung des Erfinders eine dem Ultraschallbad vergleichbare Reinigungswirkung und entfernt die zuvor im Ätzbad bereits weggeätzten oder angelösten Verunreinigungen wirksam und einfach von der Oberfläche.According to a particularly preferred feature of the invention, the described Ultrasound treatment completely dispensed with and thus the temporal and apparatus expenditure significantly reduced. Instead, the treated ones Graphite parts from the alkaline etching bath directly, i.e. in immediate temporal Connection and without further intermediate treatment, in a thin aqueous Solution or immersed in water. This creates on the surfaces of the Parts because of the residues of the solution used in the etching bath large concentration gradients. The solution residues of the etching bath react with water or a thin solution short and relatively violent what happens notices that the near-surface areas in the water or Foam briefly in the aqueous solution. This foaming has after Observation by the inventor of a cleaning effect comparable to the ultrasonic bath and removes those that have already been etched away or dissolved in the etching bath Impurities effective and easy from the surface.

Die soeben beschriebene Vorgehensweise sollte also vorzugsweise dazu benutzt werden, eine Ultraschallbehandlung jedenfalls in diesem Bereich des Verfahrens ganz wegzulassen.The procedure just described should therefore preferably be used ultrasound treatment in this area of the procedure to leave out entirely.

Die erwähnte galvanische Metallbeschichtung des Graphits kann auf Gestellen und bei entsprechender Teilegeometrie in Trommeln ablaufen. Die galvanische Beschichtung kann vorzugsweise mit Cu, Ni oder Sn, einer Mischung dieser Metalle oder einer Mischung eines oder mehrerer dieser Metalle mit anderen Metallen erfolgen. Insbesondere Sn und Sn-Legierungen haben gute Löteigenschaften, so dass die galvanische Schicht für einen späteren (optionalen) Lötschritt eine gute Grundlage bildet. The mentioned galvanic metal coating of the graphite can be on frames and run with appropriate parts geometry in drums. The galvanic Coating can preferably be with Cu, Ni or Sn, a mixture of these Metals or a mixture of one or more of these metals with others Metals. Sn and Sn alloys in particular have good soldering properties, so that the galvanic layer for a later (optional) soldering step forms a good foundation.

Somit kann nach dem Ätzvorgang vorzugsweise entweder

  • eine Pd-Bekeimung + chemisch Ni + Cu (oder Ni)
  • oder nach Spülen galvanisch Ni direkt
  • oder nach Spülen galvanisch Cu direkt
    aufgebracht werden; auf diese Schichten erfolgt dann der weitere Schichtaufbau (Sn oder andere Metalle).
Thus, after the etching process, preferably either
  • a Pd nucleation + chemical Ni + Cu (or Ni)
  • or after rinsing galvanically Ni directly
  • or after rinsing galvanically Cu directly
    be applied; The further layer structure (Sn or other metals) then takes place on these layers.

Bevorzugte Parameterbereiche der galvanischen Beschichtung sind eine Stromdichte von 1-10 A/dm2 und eine Behandlungszeit, d.h. Bad und Einschaltzeit des Stromes, von 5-60 Minuten.Preferred parameter ranges of the galvanic coating are a current density of 1-10 A / dm 2 and a treatment time, ie bath and switch-on time of the current, of 5-60 minutes.

Das alkalische Ätzbad kann vorzugsweise in Natronlauge (NaOH-Lösung) oder Kali-Lauge (KOH-Lösung) oder einer Mischung der beiden Laugen erfolgen, und zwar beispielsweise in einem Konzentrationsbereich von 10-60 Gew.-%, besonders bevorzugterweise 20-50 Gew.-% und im nach Feststellungen des Erfinders besten Fall zwischen 30 und 40 Gew.-%. Dabei haben sich Temperaturen von 20°-70°C bewährt, wobei Temperaturen über 30° bzw. 40° und im nach Feststellungen des Erfinders günstigsten Fall über 50° günstiger sind. Der bevorzugte Temperaturbereich liegt zwischen 55° und 65°C.The alkaline etching bath can preferably be in sodium hydroxide solution (NaOH solution) or Potash lye (KOH solution) or a mixture of the two lyes, for example in a concentration range of 10-60% by weight, particularly preferably 20-50 wt .-% and in the findings of Inventor's best case between 30 and 40 wt .-%. There have been temperatures proven from 20 ° -70 ° C, with temperatures above 30 ° or 40 ° and in according to the inventor's best case, more than 50 ° are more favorable. The preferred temperature range is between 55 ° and 65 ° C.

Der Begriff "Graphit" richtet sich bei dieser Erfindung auf alle Materialien, bei denen Graphit in solchem Umfang enthalten ist und auf der relevanten Oberfläche auftritt, daß die Metallbeschichtung eben auch der Graphitoberflächen selbst für das technische Ergebnis wesentlich ist. Dies umfaßt natürlich zunächst einmal alle reinen Graphitmaterialien sowie solche mit geringfügigen Zusätzen. Vorzugsweise richtet sich die Erfindung jedoch auch auf kunststoffgebundene Graphitmaterialien, bei denen Graphitpartikel in einer Kunststoffmatrix enthalten sind. Solches Material hat verschiedene technische Anwendungen, bei denen das erfindungsgemäße Verfahren von großem Vorteil sein kann.The term "graphite" in this invention is directed to all materials which contains graphite to such an extent and on the relevant surface occurs that the metal coating also of the graphite surfaces is essential even for the technical result. Of course, this includes at first once all pure graphite materials as well as those with minor Additives. However, the invention is preferably also directed to plastic-bound ones Graphite materials, in which graphite particles in a plastic matrix are included. Such material has various technical applications, in which the method according to the invention can be of great advantage can.

Konkret kann die Erfindung gemäß folgendem Ausführungsbeispiel realisiert werden, dessen Einzelheiten jedoch nicht beschränkend zu verstehen sind: Specifically, the invention can be implemented according to the following embodiment the details of which, however, are not to be understood as limiting:

Ein aus kunststoffgebundenem Graphit bestehendes Bauteil eines elektrotechnischen Geräts wird in konventioneller Weise soweit hergestellt, dass die endgültige Form gegeben ist. Dann werden größere Zahlen des Bauteils als Charge in einer handelsüblichen Einrichtung für elektrolytische Ätzvorgänge in 35 Gew.-%-iger NaOH-Lösung bei 60°C für 10 Minuten im anodischen Betrieb gereinigt und geätzt und anschließend direkt in ein einfaches Wasserbad bei Zimmertemperatur eingebracht. Dort schäumt die Lösung in der Umgebung der Bauteile der Charge kurz auf, die Charge wird weiter gespült und dann in an sich bekannter Weise mit Pd bekeimt. Dazu stehen kommerzielle ionogene oder kolloidale Pd-Lösungen zur Verfügung. Die Pd-Keime dienen als Katalysator für die folgende Metallisierungsschritte.A component of an electrotechnical made of plastic-bound graphite Device is manufactured in a conventional way to the extent that the final Form is given. Then larger numbers of the component than batch in a commercially available facility for electrolytic etching in 35 % By weight NaOH solution cleaned at 60 ° C for 10 minutes in anodic operation and etched and then directly into a simple water bath Room temperature introduced. There the solution foams in the vicinity of the Components of the batch briefly open, the batch is rinsed further and then in on is known to germinate with Pd. There are commercial ionogens or colloidal Pd solutions are available. The Pd seeds serve as a catalyst for the following metallization steps.

Auf die Pd-bekeimten Graphitbauteile wird dann eine 0,1-2 µm starker Ni-Schicht chemisch (außenstromlos) abgeschieden. Diese Nickelschicht kann, da sie sehr dünn ist, anschließend noch mit chemisch Nickel, chemisch Kupfer, galvanisch Nickel und/oder galvanisch Kupfer verstärkt werden.A 0.1-2 µm thick Ni layer is then applied to the Pd-germinated graphite components chemically (without external current) deposited. This nickel layer can, because it is very thin, then with chemical nickel, chemical copper, electroplated nickel and / or electroplated copper.

Auf die chemische Metallschicht kann dann eine elektrolytische Sn-Legierung aufgebracht werden, die so dick ist (ca. 5-10 µ), dass direkt darauf die Lötstellen angebracht werden können. Der Lötvorgang ist völlig konventionell, weil dabei nur noch die Oberfläche der Sn-Legierung eine Rolle spielt.An electrolytic Sn alloy can then be applied to the chemical metal layer applied that is so thick (approx. 5-10 µ) that the solder joints are directly on it can be attached. The soldering process is completely conventional because only the surface of the Sn alloy plays a role.

Die Lötstelle kann nicht nur für hervorragende elektrische Kontakte zu dem Graphitbauteil verwendet werden. Sie hat außerdem eine so gute Haftung auf dem Graphitbauteil, dass sie auch zur mechanischen Befestigung dienen kann, so dass das Graphitbauteil nicht mehr geklemmt oder durch Bohrungen in dem Graphitbauteil angeschraubt oder anderweitig in bezug auf das Graphitbauteil form- oder kraftschlüssig befestigt werden muss. Es kann einfach eine geeignete Metallasche als Montagehilfe verwendet werden.The solder joint can not only be used for excellent electrical contacts to the Graphite component can be used. It also has such good adhesion the graphite component that can also be used for mechanical fastening, so that the graphite component is no longer clamped or through holes in the Screwed graphite component or otherwise in relation to the graphite component must be attached positively or non-positively. It can simply be a suitable one Metal ash can be used as an assembly aid.

Claims (13)

Verfahren zur Metallbeschichtung von Graphit, gekennzeichnet durch folgende Schritte in folgender Reihenfolge: ein alkalisches Ätzbad des Graphits im anodischen Betrieb, und eine galvanische Metallbeschichtung des Graphits. Process for the metal coating of graphite, characterized by the following steps in the following order: an alkaline etching bath of graphite in anodic operation, and a galvanic metal coating of the graphite. Verfahren nach Anspruch 1, gekennzeichnet durch folgenden Schritt zwischen dem alkalischen Ätzbad und der galvanischen Metallbeschichtung: eine Pd-Bekeimung des Graphits. A method according to claim 1, characterized by the following step between the alkaline etching bath and the galvanic metal coating: Pd nucleation of the graphite. Verfahren nach Anspruch 2, gekennzeichnet durch folgenden Schritt zwischen der Pd-Bekeimung und der galvanischen Metallbeschichtung: eine außenstromlose Metallabscheidung zur Verstärkung der Pd-Schicht. A method according to claim 2, characterized by the following step between the Pd nucleation and the galvanic metal coating: metal electroless plating to strengthen the Pd layer. Verfahren nach Anspruch 3, bei dem bei der außenstromlosen Abscheidung zumindest Ni oder Cu abgeschieden wird.A method according to claim 3, wherein the deposition without external current at least Ni or Cu is deposited. Verfahren nach einem der vorstehenden Ansprüche, gekennzeichnet durch folgenden Schritt zwischen dem alkalischen Ätzbad und dem nachfolgenden Schritt: ein direktes Einbringen des Graphits aus dem alkalischen Ätzbad in Wasser oder eine dünne wässrige Lösung. Method according to one of the preceding claims, characterized by the following step between the alkaline etching bath and the subsequent step: a direct introduction of the graphite from the alkaline etching bath into water or a thin aqueous solution. Verfahren nach Anspruch 5, bei dem zwischen dem alkalischen Ätzbad und der ersten nachfolgenden Metallbeschichtung keine Ultraschallbehandlung durchgeführt wird.A method according to claim 5, wherein between the alkaline etching bath and the first subsequent metal coating no ultrasonic treatment is carried out. Verfahren nach einem der vorstehenden Ansprüche, bei dem bei der galvanischen Metallbeschichtung mit zumindest Cu, Ni oder Sn beschichtet wird. Method according to one of the preceding claims, in which the galvanic metal coating coated with at least Cu, Ni or Sn becomes. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Stromdichte bei der galvanischen Metallbeschichtung zwischen 1 und 10 A/dm2 liegt.Method according to one of the preceding claims, in which the current density in the galvanic metal coating is between 1 and 10 A / dm 2 . Verfahren nach einem der vorstehenden Ansprüche, bei dem die Stromzeit bei der galvanischen Metallbeschichtung zwischen 5 und 60 Minuten liegt.Method according to one of the preceding claims, wherein the current time in the galvanic metal coating between 5 and 60 minutes lies. Verfahren nach einem der vorstehenden Ansprüche, bei dem das alkalische Ätzbad in einer Lösung aus im wesentlichen 10-60 Gew.-%-iger Lösung von NaOH und/oder KOH durchgeführt wird.Method according to one of the preceding claims, in which the alkaline Etching bath in a solution of essentially 10-60% by weight Solution of NaOH and / or KOH is carried out. Verfahren nach Anspruch 10, bei dem das alkalische Ätzbad bei einer Temperatur zwischen 20° und 70°C abläuft.The method of claim 10, wherein the alkaline etching bath at a Temperature between 20 ° and 70 ° C expires. Verfahren nach einem der vorstehenden Ansprüche, bei dem es sich bei dem Graphit um kunststoffgebundene Graphitpartikel handelt.Method according to one of the preceding claims, wherein it is the graphite is plastic-bound graphite particles. Verfahren zum Herstellen einer Lötverbindung mit einem Graphitbauteil, bei dem mit einem Verfahren nach einem der vorstehenden Ansprüche eine Metallbeschichtung auf dem Graphitbauteil aufgebracht wird und danach auf der so hergestellten Metallschicht eine Lötstelle angebracht wird.Method for producing a soldered connection with a graphite component, in which with a method according to any one of the preceding claims a metal coating is applied to the graphite component and then applied a solder joint on the metal layer thus produced becomes.
EP20010111708 2001-05-14 2001-05-14 Metal coating of graphite Expired - Lifetime EP1260615B1 (en)

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DE50100123T DE50100123D1 (en) 2001-05-14 2001-05-14 Metal coating of graphite
AT01111708T ATE234950T1 (en) 2001-05-14 2001-05-14 METAL COATING OF GRAPHITE
SI200130012T SI1260615T1 (en) 2001-05-14 2001-05-14 Metal coating of graphite
EP20010111708 EP1260615B1 (en) 2001-05-14 2001-05-14 Metal coating of graphite
PCT/EP2002/003116 WO2002092884A1 (en) 2001-05-14 2002-03-20 Graphite metal coating
US10/712,458 US20040094424A1 (en) 2001-05-14 2003-11-13 Graphite metal coating

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US6907917B2 (en) * 2003-01-10 2005-06-21 International Business Machines Corporation Graphite-based heat sinks and method and apparatus for the manufacture thereof
US8955580B2 (en) * 2009-08-14 2015-02-17 Wah Hong Industrial Corp. Use of a graphite heat-dissipation device including a plating metal layer
TW201035513A (en) * 2009-03-25 2010-10-01 Wah Hong Ind Corp Method for manufacturing heat dissipation interface device and product thereof
TW201105827A (en) * 2009-08-13 2011-02-16 guo-zhen Zhang Pretreatment method
CN103469182B (en) * 2013-08-30 2015-05-13 西北工业大学 Palladium-free chemical copper-plating method on graphite nanosheet surface

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JPS60208495A (en) * 1984-04-02 1985-10-21 Okuno Seiyaku Kogyo Kk Pretreatment for electroplating to carbon material
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WO2002092884A1 (en) 2002-11-21
SI1260615T1 (en) 2003-12-31

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