DE1916727A1 - Process for dip plating from non-aqueous systems - Google Patents
Process for dip plating from non-aqueous systemsInfo
- Publication number
- DE1916727A1 DE1916727A1 DE19691916727 DE1916727A DE1916727A1 DE 1916727 A1 DE1916727 A1 DE 1916727A1 DE 19691916727 DE19691916727 DE 19691916727 DE 1916727 A DE1916727 A DE 1916727A DE 1916727 A1 DE1916727 A1 DE 1916727A1
- Authority
- DE
- Germany
- Prior art keywords
- metal
- plating
- bath
- solution
- plated
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 238000007654 immersion Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910004534 SiMn Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229910001507 metal halide Inorganic materials 0.000 claims 1
- 150000005309 metal halides Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 16
- 150000002739 metals Chemical class 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 6
- 150000004820 halides Chemical class 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 6
- WJPGSUZQENDAIE-UHFFFAOYSA-L dichloronickel methanol Chemical compound CO.[Ni](Cl)Cl WJPGSUZQENDAIE-UHFFFAOYSA-L 0.000 abstract 1
- 229910001502 inorganic halide Inorganic materials 0.000 abstract 1
- 238000001465 metallisation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 not halides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
- B60Q7/00—Arrangement or adaptation of portable emergency signal devices on vehicles
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1671—Electric field
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
"Verfahren zum Tauchplattieren aus nicht-wäßrigen Systemen""Process for immersion plating from non-aqueous systems"
Die Erfindung betrifft die Aufbringung haftender Überzüge auf Metallgegenständen, insbesondere a.us Aluminium, Beryllium, Titan, Niou und Zirkonium durch Tauchen in ein nicht-wäßriges Jad, also durch elektrochemische Aoscheidung aus einer rnethahollschen Lösung eines Halogenide des abzuscheidenden Metalls, insbesondere die Tauchplattierung von oekrnntlich schwer zu plattierenden Metallen.The invention relates to the application of adhesive coatings to metal objects, in particular a.us aluminum, Beryllium, titanium, niou and zirconium by dipping in a non-aqueous jad, i.e. by electrochemical separation from a Rnethahollschen solution of a halide of the metal to be deposited, in particular dip-plating Of hard-to-plate metals.
Zur Auforingung von Metallüberzügen auf verschiedene Gegenstände jiot es drei Hauptverf'ahren, nämlich die iülektroplf-'ttiorung, die elektrochemische Abscheidung und aas Pt uohverfehren. D;-s wleKtroplattieren geschieht in einer ivlektrolysezelle mit Hilfe von Gleichsbrom zwischen Anode undFor curling metal coatings on various objects There are three main processes, namely the electrochemical deposition and aas Pt uohverfehren. D; - Electroplating takes place in a Electrolysis cell with the help of DC bromine between the anode and
τ 2 -τ 2 -
909845/1Λ28909845 / 1Λ28
BAD ORIGINALBATH ORIGINAL
lA-36lA-36
Kathode innerhalb eines Elektrolyten. Bei der elektrochemischen Plattierung erfolgt durch Reduktion des abzuscheidenden Metalls aus dessen Salzlösung die Beschichtung. Das Bad muß ein Reduktionsmittel zur Beschleunigung der chemischen Reduktion aufweisen. Auch beim Tauchverfahren wird ffti-fc einet» Bad enthaltend eine Lösung des zu' plattierenden Metallsalzes angewandt, die zu plattierenden Gegenstände werden solange in das Bad getaucht, bis die gewünschte Sehichtstärke des zu plattierenden Metalls erreicht ist. Hierbei handelt es sich im Gegense-tz zu der elektrochemischen Plattierung um eine Platzwechselreaktion. Das abzuscheidende Metall muß also in der Spannungsreihe unterhalb Wasserstoff stehen, wohingegen das Metall des zu plattierenden Gegenstandes über Wasserstoff stehen muß, so d?ß ein Austausch von Metall ties zu oeschichtenden Gegenstandes gegen das Piattierungsmetsll in der Lösung stattfinden kenn.Cathode within an electrolyte. In the case of electrochemical plating, the coating is carried out by reducing the metal to be deposited from its salt solution. The bath must contain a reducing agent to accelerate the chemical reduction. Even with the immersion process a bath containing a solution of the material to be plated Metal salt applied, the objects to be plated are immersed in the bath until the desired Visual thickness of the metal to be plated is reached. This is in contrast to the electrochemical one Plating around a change of place reaction. The metal to be deposited must therefore be below in the voltage series Stand hydrogen, whereas the metal of the object to be plated must stand above hydrogen, so d? Ss a Exchange of metal ties to be coated object against the coating metal in the solution know
Die elektrolytische >-.oscheidun£ wird in sehr 'großem Umfsrig zur Herstellung von haftenden Überzügen in jeder gewünschten Schichtstärke angewandt. Dieses Verfahren läßt sich jedoch nicht anwenden euf Kleinteile, wie körniges oder faseriges und besonders f'einteiliges Materiel. Dies beruht auf denElectrolytic treatment is taking place on a very large scale for the production of adhesive coatings in any desired Layer thickness applied. However, this method can do not apply to small parts, such as grainy or fibrous and especially fine-grained material. This is based on the
in Verbindung mit der Schwierigkeiten, uiese Gegenstände oder Produkte/εΆβ Kathode in der Elektrolysezelle zu halten. Aus diesem Grund bevorzugt man die elektrochemische Plattierun^ oder des Tauchverfahren, wenn gleichmäßige Schichten auf sehr kleinen oder dünnen Materialien und Gegenständen engestrebt v/erden.in connection with the difficulty of using these objects or products / εΆβ cathode to keep in the electrolytic cell. For this reason, electrochemical plating or dipping processes are preferred. if even layers on very small or thin ones Striving towards materials and objects.
Trotzdem uie physikalischen Eigenschaften des zu plattierenden Materials oei der Auswahl tier entsprechenden Plt-ttierungs- Nevertheless, the physical properties of the material to be plated without the selection of the appropriate plating
— 5 —- 5 -
909845/1428909845/1428
BAD ORJQ(NALBAD ORJQ (NAL
lA-36 l44 - 3 - LA-36 L44 - 3 -
verfahren von Bedeutung sind, so ist doch der chemische Aufbau des zu plattierenden Grundmaterial von größerer Bedeutung» Einige Grundmaterialien lassen sich nur außerordentlich schwer mit haftenden Überzügen nach einem der drei Hauptv#rfahren versehen. Die sogenannten "Ventilmetalle", wit Aluminium, Tantal, Titan und Niob bilden haftende Oxidsohiahten an der Oberfläche, die einen beträchtlichen elektrischen Widerstand besitzen« Aus diesem Grund lassen sich auoh die Ventilmetalle anodisieren und können dann als Elektroden in elektrolytißohen Kondensatoren angewandt Werden, Wegen ihrer Neigung, Oxidschichten in Wasser oder · in wäßrigem System zu bilden, lassen sich die Ventilmetalle nur außerordentlich schwer plattieren. Befindet sich ganz allgemein gesprochen ein Oxid ruf der Oberfläche dieser Gegenstände, wenn sie plattiert werden, so sind die überzüge nicht haftend» fis ist also notwendig, ein Plattierungsverfahren anzuwenden, welches nicht mit wäßrigen Lösungen arbeitet. Es wurde ein'derartiger Versuch bereits für die Pipttierung von Aluminium mit Gold unternommen (USA-P&tenteöl#lffc 3 281 £64). Danach wird eine Lösung von Goldchlorid im freventlichen in einem Ölträger aufgebürstet. Der Überzug wird denn tsuf eine Temperatur von 8?O Dis 9800C (I600 ois 18CK)0F) erhitzt, dabei wird das Goldchlorid reduziert und der Träger verdampft.processes are important, the chemical structure of the base material to be plated is of greater importance. »Some base materials are extremely difficult to apply with adhesive coatings using one of the three main processes. The so-called "valve metals", such as aluminum, tantalum, titanium and niobium, form adherent oxide adhesive bonds on the surface, which have considerable electrical resistance The valve metals are extremely difficult to clad with a tendency to form oxide layers in water or in an aqueous system. Generally speaking, if there is an oxide on the surface of these objects when they are plated, the coatings are non-adhesive. It is therefore necessary to use a plating process which does not work with aqueous solutions. Such an attempt has already been made for the piptation of aluminum with gold (USA p & tente oil # lffc 3 281 £ 64). After that, a solution of gold chloride is brushed on if necessary in an oil carrier. The coating is for tsuf a temperature of 8? O Dis 980 0 C (I600 ois 18CK) 0 F) is heated, while the gold chloride is reduced and the carrier evaporates.
Ein Tauchverfahren mit einem nicht-wäßrigen''Bad für die Aufbringung von gegenüber dem Grundwerkstoff edleren Metallen iet bereits bekennt (USA-Patentschrift 2 873 214); auch hier sind hohe Temperaturen erforderlich, da man des Bad auf einer Temperatür unterhalb des Söliduspunkts des Grundwerkstoffs, jedoch über dem Liquiduspunkt des Plattierungsmetalls /halten muß,A dipping procedure with a non-aqueous '' bath for the Application of metals that are more noble than the base material iet already acknowledges (U.S. Patent 2,873,214); here too high temperatures are required as one of the bath is on a temperature below the Sölidus point of the base material, but above the liquidus point of the plating metal / must hold
90984S/1A2890984S / 1A28
BAD ORIGINALBATH ORIGINAL
lA-36lA-36
Es ist auch bereits ein weiteres Verfahren (USA-Patentschrift 3 265 526) bekannt, wonach die Abscheidung von Edelmetallen aus einer Lösung der MetalHaaLze in einem organischen Lösungsmittel zusammen mit einem Reduktionsmittel angewandt wurde. Metallgegenstand und Überzug werden dann zur Ausbildung einer fest haftenden Schicht erhitzt. Alle diese drei Verfahren weisen jedoch einen wesentlichen Nachteil auf, nämlich daß eine Wärmebehandlung erforderlich ist, die kostspielig und damit das Plattierungsverfahren belastend ist.Another method (US Pat. No. 3,265,526) is also known, according to which the deposition of Precious metals from a solution of metal halves in one organic solvent was used together with a reducing agent. Metal object and plating become then heated to form a firmly adhering layer. However, all of these three methods have one essential feature Disadvantage, namely that a heat treatment is required, which is expensive and thus the plating process is burdensome.
In dem Buch "Metabi Finishing Guidebook Directory", Metals and Plastics Publications, Inc. of Westwood, New Jersey, Seite ^, 1968, wurde bereits darauf hingewiesen, daß Eisen- und Stahlgegenstände sich durch Tauchplattieren mit Hilfe einer äthanolischen Lösung von Goldchlorid bei Raumtemperatur überziehen lassen. Es zeigte sich jedoch, daß eine solche Lösung für die Tauchplattierung von Metallen wie Beryllium oder Titan nicht geeignet ist, also für Metalle, die durch oberflächliche Oxidschichten die Haftung der Plattierungsschicht verschlechtern können.In the book "Metabi Finishing Guidebook Directory", Metals and Plastics Publications, Inc. of Westwood, New Jersey, page ^, 1968, it has already been pointed out that iron and steel objects are made by dip-plating with the help of an ethanolic solution of gold chloride Let it cover at room temperature. However, it has been found that such a solution is suitable for dip plating of metals such as beryllium or titanium is not suitable, i.e. for metals, which, through superficial oxide layers, prevent the cladding layer from adhering can worsen.
Die Erfindung bringt nun ein Verfahren, welches, unerwarteterweise und bei niederen Temperaturen zu fest haftenden Überzügen auf den bekannterweise schlecht zu plattierenden Metallen, wie Beryllium, Titan, Aluminium, Niob oder Zirkonium, führt. -The invention now provides a method which, unexpectedly and at low temperatures to firmly adhering coatings on metals that are known to be difficult to clad, such as beryllium, titanium, aluminum, niobium or zirconium, leads. -
Nach dem erfindungsgemäßen Verfahren werden die zu plattierenden Gegenstände in ein Bad getaucht, welches zur Beschichtung von Gegenständen aus einem oder mehreren der oben gekannten Metallen ein Halogenid des abzuscheidenden Metalls bei !Raumtemperatur According to the method according to the invention, the objects to be plated are immersed in a bath which is used for coating of objects from one or more of the above Metals a halide of the metal to be deposited at! Room temperature
"9 09845/1428""9 09845/1428"
lA-36lA-36
enthält. Das erfindungsgemäße Verfahren läßt sich bei jeder Temperatur, a.lso auch bei Raumtempera.tür und jeder geeigneten Temperatur, unterhalb des Siedepunkts der Lösung anwenden. Es ist keine Verfahrensstufe bei hoher Temperatur erforderlich. Μεη erhält fest haftende Überzüge auf den zu plattierenden Gegenständen aus z.B. Beryllium, Aluminium, Titan, Niob, Zirkonium und deren Legierungen und festen Lösungen dieser Metalle. Sollte eine Elektroplattierung vorgezogen werden, so eignen sich die erfindungsgemäßen methanolischen Lösungen auch hierzu. Man erreicht unerwartete Ergebnis se gegenüber den üblichen wäßrigen Elektrolysesystemen.contains. The method according to the invention can be used in any temperature, also at room temperature and any suitable temperature, below the boiling point of the solution use. It is not a high temperature process step necessary. Μεη receives firmly adhering coatings on the Objects to be plated made of e.g. beryllium, aluminum, titanium, niobium, zirconium and their alloys and solid solutions of these metals. Electroplating should be preferred the methanolic solutions according to the invention are also suitable for this purpose. You get unexpected results se compared to the usual aqueous electrolysis systems.
Nach dem erfindungsgemäßen Verfahren werden die Gegenstände aus einem oder mehreren der oben genannten Metalle in eine wasserfreie methanolische Lösung des Halogenids des gewünschten Plattierungsmetalls getaucht. Bevorzugt wird als Hrlogenid dr.s Chlorid eines Metalls, welches unterhalb Wi.isserstoff in der SpannungsraLhe steht.According to the method according to the invention, the objects from one or more of the above metals in an anhydrous methanolic solution of the halide des desired plating metal. The preferred Hrlogenid dr.s chloride of a metal, which below Knowledge stands in the field of tension.
Folgende Beispiele erläutern die Erfindung. ß e i spiel 1The following examples illustrate the invention. ß e i game 1
üin Gegenstand ius Titan wird in eine Lösung,· enthaltend etw;, 2 j; wasserfreies Kupferchlorid CuCIp in 100 cnr absolutem Methyl.' Ikohol (p.A.) eingeoracht und nach einigen Minuten .'•un der Lösung genommen, die Oberfläche mit Wasser-, aogespült und. trockengerieben. Msη erhielt einen fest haftenden Kupferüb.erzu. ■ euf dem Titangegerist and. . . . .üin object ius titanium is in a solution, · containing sth ;, 2 j; anhydrous copper chloride CuCIp in 100 cnr absolute methyl. Ikohol (PA) incorporated and after a few minutes. '• The solution is removed, the surface is rinsed with water, ao-rinsed and. rubbed dry. Msη received a firmly adhering copper connector. ■ e on the titanium skeleton and.. . . .
.is zeigte sich, daß bpuren von Wasser durch das Kupferchlorid in u; ü system eingebracht wurden und drß gerade diese gering-It was found that traces of water were caused by the copper chloride in u; ü system were introduced and it is precisely these low-
- 6 9098A5/U2 8- 6 9098A5 / U2 8
BAD ORIGINALBATH ORIGINAL
sten Wassermengen sehr wesentlich zum Erfolg des Verfahrens beitragen. Most amounts of water contribute very significantly to the success of the process.
Bei dem erfindungsgemäßen Verfahren ist es nicht notwendig, vor der Plattierung die Oxidschichten zu entfernen, um haftende Überzüge zu bekommen. Oxidfreie Oberflächen, wie man sie z.B. durch mechanisches Abschleifen erhalten kann, sind jedoch im Hinblick auf schnellere und gleichmäßigere Plattierung wünschenswert. Die chemische Aotragung der Oxidschicht ist auch möglich.In the method according to the invention, it is not necessary to remove the oxide layers prior to plating in order to to get adhesive coatings. Oxide-free surfaces, such as can be obtained e.g. by mechanical grinding, however, are desirable in terms of faster and more uniform plating. The chemical representation of the Oxide layer is also possible.
Ein Berylliumstreifen wurde in ein Bad, enthaltend 0,3 g wasserfreies Kupferchlorid in 100 cnr wasserfreiem Methanol, getaucht. Nach einigen Minuten Tauchzeit konnte ΐηεη einen fest haftenden - Kupferüberzug auf dem Beryllium feststellen. A beryllium strip was immersed in a bath containing 0.3 g of anhydrous copper chloride in 100 cnr of anhydrous methanol. After a few minutes of immersion, ΐηεη was able to determine a firmly adhering copper coating on the beryllium.
Dieser Versuch wurde einige Male mit steigenden Konzentrationen ΰ&\ Kupferchlorid wiederholt, nämlich zwischen 0,3 und 6 g CuCIg in 100 er wasserfreiem Methanol. Es konnte beobachtet werden, daß die Abscheidungs^eschwindigkeit des Kupfers mit der Konzentration schwankt und offensichtlich direkt proportional der Konzentration ist.This experiment was repeated several times with increasing concentrations & ΰ \ copper chloride, namely from 0.3 to 6 g in 100 CuCIg he anhydrous methanol. It could be observed that the rate of deposition of the copper fluctuates with the concentration and is obviously directly proportional to the concentration.
Es wurden mehrere Aluminiumstreifen in ein Bad., enthaltend 3 g Kupferchlorid.in 100 cnr wasserfreiem Methanol getaucht, und zwar ein Streifen 3 rnin, ein Streifen 6 min und ein Strei-Several aluminum strips were placed in a bath., Containing 3 g copper chloride immersed in 100 cnr anhydrous methanol, namely a strip 3 minutes, a strip 6 minutes and a strip
yBADyBAD
909845/U28 ' " 909845 / U28 '"
lA-36 144lA-36 144
fen 30 min.oven 30 min.
Auf metallographischetn Wege wurde die Schichtstärke des Kupfers auf dem Aluminium bestimmt. Dazu wurden die Proben quer aufgeschnitten und die Schnittflächen poliert. Der 3 min plattierte Streifen zeigte eine Schichtstärke von 2,5 bis 5yU, der 6 min plattierte Streifen eine Schicht- ·■ stärke von 7,6 bis IQ κχ und der Streifen mit einer Plattierungszeit von 30 min eine Schichtstärke von etwa 12,7 ;u.The thickness of the copper layer on the aluminum was determined by metallographic methods. For this purpose, the samples were cut open transversely and the cut surfaces were polished. The 3 min-plated strip showed a layer thickness of 2.5 to 5yU, the 6 min-plated strip a layer thickness of 7.6 to IQ κχ and the strip with a plating time of 30 min a layer thickness of about 12.7; u.
Da dem erfindungsgemäßen Bad kein Reduktionsmittel zugesetzt wird, so könnte man das erfindungsgemäße Verfahren eher als Tauchplattierung und nicht so sehr als elektrochemische Plattierung ansprechen. Aus obigen Beispielen könnte man diese Ansicht als bestätigt ansehen, da die Schichtstärke,, wenn auch nicht linear, so doch mit der Zeit zunimmt. Diese Erscheinung steht jedoön im Gegensatz zu den Erwartungen, wonach es sich bei der Plattierung um eine Platzwechselreaktion handelt, die in ihrem Reaktionsνerlauf gegen null tendiert. Mit anderen Worten sind die an der Oberfläche des Gegenstandes liegenden Moleküle oder Atome ausgewechselt, so stehen keine anderen Atome des Grundmetalls mehr zur Verfügung und uie Reaktion hört auf. Eine Erklärung für das erfindungsgemäß auftretende Phänomen dürfte jedoch sein, daß es sich um eine elektrochemische Abscheidung handelt und Methanol als Reduktionsmittel wirkt.Since no reducing agent is added to the bath according to the invention, the method according to the invention could rather than Dip plating rather than electrochemical Address plating. This view could be seen as confirmed from the above examples, since the layer thickness ,, if not linear, it increases with time. However, this appearance is in contradiction to the expectations according to which the plating is a place change reaction, which in its reaction progresses towards zero tends. In other words, the molecules or atoms lying on the surface of the object have been replaced, so no other atoms of the base metal are available any more and the reaction ceases. An explanation for that Phenomenon occurring according to the invention, however, is likely to be that it is an electrochemical deposition and that methanol acts as a reducing agent.
Es zeigte sich, daß andere organische Lösungsmittel, wie Äthanol, nicht zufriedenstellen. So ist Äthanol z.B. vollständig unwirksam eis Lösungsmittel für ein Halogenid zur Abscheidung auf Beryllium oder Titn: und nicht zufriedenstellend für eine Berylliums lurniniurn-Legierung "Lockalloy" It was found that other organic solvents such as Ethanol, unsatisfactory. For example, ethanol is Completely ineffective as a solvent for a halide for deposition on beryllium or titanium: and not satisfactory for a beryllium lurniniurn alloy "Lockalloy"
9098 A 5/ U28 ... ~ c ~ 9098 A 5 / U28 ... ~ c ~
• BAD ORiGlNAt• BAD ORiGlNAt
lA-36 144 - 8 -LA-36 144 - 8 -
Es wurden die verschiedensten Versuche auch mit anderen Salzen, also nicht Halogeniden, durchgeführt, z.B. den Nitraten oder Sulfaten und zwar unter den oben angegebenen Verfahrensbedingungen. Bs zeigte sich jedoch, daß man damit nicht zu zufriedenstellenden Ergebnissen kommt.The most varied attempts were made with others too Salts, i.e. not halides, carried out, e.g. the nitrates or sulfates, among those specified above Procedural conditions. Bs showed, however, that with it does not produce satisfactory results.
Man kann zwar erfindungsgemäß auch Metalle, die in der Spannüngsreihe Über Wasserstoff stehen, abscheiden, jedoch ist "das erfindungsgemäße Verfahren für diese Metalle nicht Übermäßig wirksam, verwendet man z.B. eine methanolische Lösung von Nickelchlorid für die Aufbringung von haftenden NickelÜberzügen auf eines der oben genannten Metalle an; jedoch wird die Plattierungszeit bei Anlegung von elektrischem Strom wesentlich verringert. In einem soleheil Fall wird die methanolische Nickelchloriälösung als Elektrolyt in üblichen Zellen angewandt. Bei* zu plattlerende Gegenstandwird als Kathode geschaltet, Anode sollte Nickel sein. Das erfindungsgemäSe Verfahren ist besonders geeignet zur Aufbringung einer Zwischenschicht^ a»Β. aus Kupfer^ für eine nachfolgende Elektroplattierung, ζ·Β. mit Chrom, welches sich nur unter sehr großen Schwierigkeiten auf verschiedene Werkstoffe plattieren läßt.It is true that, according to the invention, metals that are in the Voltage series Stand above hydrogen, deposit, but "the process according to the invention is not for these metals Overly effective, for example, a methanolic one is used Solution of nickel chloride for the application of adhesive nickel coatings on one of the metals mentioned above; however, the plating time is significantly reduced when an electric current is applied. In a soleheil case the methanolic nickel chloride solution is used as the electrolyte applied in common cells. Object to be flattened at * connected as cathode, anode should be nickel. The method according to the invention is particularly suitable for applying an intermediate layer ^ a »Β. made of copper ^ for a subsequent electroplating, ζ · Β. with chrome, which can only be found with great difficulty different materials can be plated.
Diese Ergebnisse beweisen, daß man nach dem erfindungsgemäßen Verfahren fest haftende Überzüge auf vielen Grundmetallen, wie Titan, Zirkonium, Beryllium, Niob und Aluminium, erhalten kann. Sie können gleichmäßig beschichtet werden, unabhängig von ihrer Form und Größe, auch denn, wenn es sich um Pulver oder Granulate handelt. Es sind keine besonderen Vorbehandlungen erforderlich. Die Plattierung selbst kann bei Raumtemperatur erfolgen.These results prove that after the invention Process firmly adhering coatings on many base metals, such as titanium, zirconium, beryllium, niobium and aluminum, can get. They can be coated evenly, regardless of its shape and size, even if it is powder or granules. There are no special ones Pre-treatments required. The plating itself can take place at room temperature.
909845/U28909845 / U28
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71795068A | 1968-04-01 | 1968-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1916727A1 true DE1916727A1 (en) | 1969-11-06 |
Family
ID=24884186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691916727 Pending DE1916727A1 (en) | 1968-04-01 | 1969-04-01 | Process for dip plating from non-aqueous systems |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3558349A (en) |
| JP (1) | JPS491699B1 (en) |
| DE (1) | DE1916727A1 (en) |
| FR (1) | FR2005332A1 (en) |
| GB (1) | GB1257492A (en) |
| SE (1) | SE352905B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4263342A (en) * | 1979-03-12 | 1981-04-21 | Zakurdaev Anatoly V | Method of manufacturing mercury contact on a beryllium base |
| US11846026B2 (en) | 2021-01-15 | 2023-12-19 | General Electric Company | Coated article for hot hydrocarbon fluid and method of preventing fuel thermal degradation deposits |
-
1968
- 1968-04-01 US US717950A patent/US3558349A/en not_active Expired - Lifetime
-
1969
- 1969-04-01 DE DE19691916727 patent/DE1916727A1/en active Pending
- 1969-04-01 JP JP44025162A patent/JPS491699B1/ja active Pending
- 1969-04-01 GB GB1257492D patent/GB1257492A/en not_active Expired
- 1969-04-01 SE SE04667/69A patent/SE352905B/xx unknown
- 1969-04-01 FR FR6909934A patent/FR2005332A1/fr not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB1257492A (en) | 1971-12-22 |
| SE352905B (en) | 1973-01-15 |
| US3558349A (en) | 1971-01-26 |
| FR2005332A1 (en) | 1969-12-12 |
| JPS491699B1 (en) | 1974-01-16 |
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