DE1621151C3 - Process for the galvanic production of a micro-cracked chrome coating on intermediate nickel layers - Google Patents
Process for the galvanic production of a micro-cracked chrome coating on intermediate nickel layersInfo
- Publication number
- DE1621151C3 DE1621151C3 DE1621151A DER0045725A DE1621151C3 DE 1621151 C3 DE1621151 C3 DE 1621151C3 DE 1621151 A DE1621151 A DE 1621151A DE R0045725 A DER0045725 A DE R0045725A DE 1621151 C3 DE1621151 C3 DE 1621151C3
- Authority
- DE
- Germany
- Prior art keywords
- nickel
- salts
- acid
- ammonium
- bath
- 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.)
- Expired
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052759 nickel Inorganic materials 0.000 title claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 239000011248 coating agent Substances 0.000 title claims description 5
- 238000000576 coating method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002253 acid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 150000001447 alkali salts Chemical class 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- -1 acids chlorides Chemical class 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- XRLUJVFOGKUSMQ-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O XRLUJVFOGKUSMQ-ZVGUSBNCSA-L 0.000 claims description 2
- DPZHKLJPVMYFCU-UHFFFAOYSA-N 2-(5-bromopyridin-2-yl)acetonitrile Chemical compound BrC1=CC=C(CC#N)N=C1 DPZHKLJPVMYFCU-UHFFFAOYSA-N 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- OATWBNIWOJXKAN-UHFFFAOYSA-N butanedioic acid;nickel Chemical compound [Ni].OC(=O)CCC(O)=O OATWBNIWOJXKAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940116232 nickel gluconate Drugs 0.000 claims description 2
- DVQYNXRSNFYQRW-IYEMJOQQSA-L nickel(2+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ni+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O DVQYNXRSNFYQRW-IYEMJOQQSA-L 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- GBIHADTXLFMYDT-UHFFFAOYSA-N nickel;propanedioic acid Chemical compound [Ni].OC(=O)CC(O)=O GBIHADTXLFMYDT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- PURTUPNWTLPILZ-UHFFFAOYSA-N 2-hydroxypropanoic acid;nickel Chemical compound [Ni].CC(O)C(O)=O.CC(O)C(O)=O PURTUPNWTLPILZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- CCIWHAHYUPQNDH-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate 2-hydroxypropane-1,2,3-tricarboxylic acid nickel(3+) Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Ni+3] CCIWHAHYUPQNDH-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-KLVWXMOXSA-N L-gluconic acid Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-KLVWXMOXSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/625—Discontinuous layers, e.g. microcracked layers
-
- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/934—Electrical process
- Y10S428/935—Electroplating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12472—Microscopic interfacial wave or roughness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12847—Cr-base component
- Y10T428/12854—Next to Co-, Fe-, or Ni-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
Die Erfindung betrifft ein Verfahren zur galvanischen Herstellung eines mikrorissigen Chromüberzuges auf Nickelzwischenschichten, die gegebenenfalls auf eine vorher galvanisch abgeschiedene Metallschicht aufgebracht sind, wobei vor dem Verchromen galvanisch bei einer Badhöchsttemperatur von 35° C und einer zwischen 1 und 15 A/dm2 liegenden Stromdichte eine Nickelzwischenschicht mit Hilfe eines in dem Hauptbestandteil Nickelchlorid, Nickelsulfamat oder Nickelfluoborat für sich bekannten wässerigen, sauren Nickelbades aufgebracht wird, welches zusätzlich Essigsäure, Nickelacetat, Glukonsäure, Nickelglukonat, Weinsteinsäure, Nickeltartrat, Ameisensäure, Nickelformiat, Malonsäure, Nickelmalonat, Milchsäure, Nickellactat, Zitronensäure, Nickelzitrat, Bernsteinsäure, Nickelsuccinat, Ammoniumacetat oder Mischungen davon enthält, nach Patent 14 96 9745.The invention relates to a method for the galvanic production of a micro-cracked chrome coating on intermediate nickel layers, which are optionally applied to a previously galvanically deposited metal layer, with a galvanic galvanic at a maximum bath temperature of 35 ° C and a current density between 1 and 15 A / dm 2 prior to chrome plating Nickel intermediate layer is applied with the aid of an aqueous, acidic nickel bath, which is known for its main component nickel chloride, nickel sulfamate or nickel fluorate, which additionally contains acetic acid, nickel acetate, gluconic acid, nickel gluconate, tartaric acid, nickel tartrate, formic acid, nickel formate, malonic acid, nickel malonate, lactic acid, citric acid Nickel citrate, succinic acid, nickel succinate, ammonium acetate or mixtures thereof, according to patent 14 96 9745.
Nach der Lehre des Hauptpatents enthalten die Bäder für rissig werdende Nickelschichten im wesentlichen ein Nickelsalz einer starken Säure, etwa Nickelchlorid, und ein Nickelsalz einer schwachen Säure, etwa der Essig-, Glukon-, Weinstein-, Ameisen-, Malon-, Zitronen- oder Bernsteinsäure. Um die Herstellungskosten solcher Bäder zu verringern und den Kostenaufwand für verschleppte Badbestandteile zu vermindern, hat man versucht, eine billigere Zusammensetzung dieser Bäder zu erreichen.According to the teaching of the main patent, the baths contain essentially cracked nickel layers a nickel salt of a strong acid, such as nickel chloride, and a nickel salt of a weak one Acid, such as acetic, gluconic, tartaric, formic, malonic, citric or succinic acid. To the To reduce manufacturing costs of such baths and the cost of dragged-out bath components to reduce, attempts have been made to achieve a cheaper composition of these baths.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß im Nickelbad die Nickelsalze der starken Säuren zu einem Teil und die Nickelsalze der schwachen Säuren ganz oder zum Teil durch Ammonium- oder Alkalisalze der entsprechenden Säuren substituiert sind.According to the invention, this object is achieved in that the nickel salts of the strong acids are added to the nickel bath a part and the nickel salts of the weak acids in whole or in part by ammonium or alkali salts the corresponding acids are substituted.
Vorteilhaft werden als Ammonium- oder AlkalisalzeAre advantageous as ammonium or alkali salts
ίο der starken Säuren Chloride, Fluoborate, Sulfamate und Sulfate des Natriums, Kaliums und Ammoniums oder Gemische von mindestens zweien dieser Salze gewählt. Die Ammonium- oder Alkalisalze der schwachen Säuren sind vorteilhafte Natrium-, Kalium- und Ammoniumsalze der Glukon-, Weinstein-, Malon-, Ameisen-, Milch-, Zitronen- und Bernsteinsäure sowie die Natrium- und Kaliumsalze der Essigsäure oder Gemische von mindestens zweien dieser Salze.ίο the strong acids chlorides, fluoborates, sulfamates and Sulphates of sodium, potassium and ammonium or mixtures of at least two of these salts are selected. The ammonium or alkali salts of the weak acids are beneficial sodium, potassium and Ammonium salts of gluconic, tartaric, malonic, formic, lactic, citric and succinic acids as well the sodium and potassium salts of acetic acid or mixtures of at least two of these salts.
Es ist bemerkenswert, daß durch Verändern der Konzentration der Komponenten des Bades, insbesondere
des Anteils und der Art der schwachen Säure, je nach Wunsch ein engerer oder weiterer Verband der
Netze zu erreichen ist, zu denen sich die Risse j zusammensetzen. Die Dichte der Risse läßt sich *
außerdem durch Verändern des pH-Wertes des Bades und der Badtemperatur variieren. Ferner gestattet die
Veränderung des Gehaltes an gelöstem Nickel veränderliche Werte der Stromdichte zu erreichen, so daß in
Abhängigkeit von den vorhandenen Einrichtungen und der Gestalt der zu behandelnden Teile das wirtschaftlichste
Bad für die Erzeugung der mit Mikrorissen versehenen Chromschichten zusammengestellt werden
kann.
Aus der US-PS 23 51966 ist ein Elektrolytbad bekannt, das Nickelchlorid und Nickelacetat enthält. Mit
Hilfe dieses Bades soll bei einer Badtemperatur von vorzugsweise zwischen 55 und 65°C eine Nickelschicht
feinen Korngefüges, guten Aussehens und hoher Zähigkeit niedergeschlagen werden. Damit bestehen zu
vorliegender Erfindung keine Berührungspunkte. Einerseits werden mit dem bekannten Elektrolytbad keine
rissigen Nickelzwischenschichten niedergeschlagen und andererseits wird nicht die Lehre gegeben, aus Gründen
der Wirtschaftlichkeit die Nickelsalze teilweise durch Ammonium- oder Alkalisalze zu ersetzen.It is noteworthy that, by changing the concentration of the components of the bath, in particular the proportion and type of weak acid, a closer or wider association of the networks to which the cracks j are composed can be achieved, as desired. The density of the cracks can also be varied by changing the pH of the bath and the bath temperature. Furthermore, changing the content of dissolved nickel allows variable values of the current density to be achieved, so that the most economical bath for the production of the micro-cracked chrome layers can be put together depending on the equipment available and the shape of the parts to be treated.
From US-PS 23 51966 an electrolyte bath is known which contains nickel chloride and nickel acetate. With the help of this bath, a nickel layer with a fine grain structure, good appearance and high toughness should be deposited at a bath temperature of preferably between 55 and 65 ° C. There are thus no points of contact with the present invention. On the one hand, no cracked intermediate nickel layers are deposited with the known electrolyte bath and, on the other hand, the teaching is not given to replace some of the nickel salts with ammonium or alkali salts for reasons of economy.
Das Ersetzen von Ammonium- oder Alkalisalzen starker oder schwacher Säuren durch Nickelsalze gleicher Säuren istinGray/Dettner »Neuzeitliche galvanische Metallabscheidung«, 1957, Seite 280, Abs. 3 und 4, beschrieben. Es findet also eine zu vorliegender Erfindung umgekehrte Substitution statt, wobei es allein um die Zugabe von Chloridionen ins Bad geht. Diesen Chloridionen fällt die Aufgabe wie Verbesserung der Anodenlöslichkeit, höhere zulässige kathodische Stromdichte, glattere, feinkörnigere, härtere und stärkere Niederschläge, geringere Neigung zur Bildung von Poren, Nadeln usw. zu. Gerade die Angabe »geringere Neigung zur Bildung von Poren« zeigt, daß ein der vorliegenden Erfindung entgegengesetzter Zweck angestrebt wird.The replacement of ammonium or alkali salts of strong or weak acids with nickel salts same acids is in Gray / Dettner "Modern Electroplating Metal Deposition", 1957, page 280, paragraph 3 and 4. There is thus a reverse substitution to the present invention, with it alone is about adding chloride ions to the bathroom. These chloride ions have the task of improving the Anode solubility, higher permissible cathodic current density, smoother, finer-grained, harder and stronger Precipitation, less tendency to form pores, needles, etc. too. Especially the statement »lesser The tendency towards the formation of pores shows that a purpose contrary to the present invention is being sought will.
Schließlich wird auf die FR-PS 8 30 993 verwiesen, die ein Elektrolytbad beschreibt, das Nickelchlorid, Ameisensäure und Natriumchlorid enthält. Auch hier ist man bestrebt, dicke, homogene und spannungsfreie Überzugs ge zu erzeugen. Man erhält dieses Resultat, indem man das Elektrolytbad mittels organischer Säuren, wie beispielsweise Ameisensäure, schwach sauer hält. Außerdem liegt die Badtemperatur nahe der Siedetem-Finally, reference is made to FR-PS 8 30 993, which describes an electrolyte bath, the nickel chloride, formic acid and contains sodium chloride. Here, too, the aim is to have a thick, homogeneous and tension-free coating ge to generate. This result is obtained by adding organic acids to the electrolyte bath, such as For example, formic acid, is weakly acidic. In addition, the bath temperature is close to the boiling point
peratur.temperature.
Beispiele für Badzusammensetzungen und Verfahrensbedingungen für die galvanische Herstellung eines mikrorissigen Chromüberzuges auf Nickelzwischenschichten sind nachfolgend aufgeführt, wobei die angegebenen Zahlen als Näherungswerte anzusehen sind:Examples of bath compositions and process conditions for electroplating a micro-cracked chrome coating on intermediate nickel layers are listed below, with the The figures given are to be regarded as approximate values:
Beispiel IIIExample III
NickelchloridNickel chloride
AmmoniumacetatAmmonium acetate
AmmoniumchloridAmmonium chloride
pH-WertPH value
StromdichteCurrent density
Temperaturtemperature
Dauerduration
Dichte der RisseDensity of cracks
Beispiel IVExample IV
NickelchloridNickel chloride
AmmoniumacetatAmmonium acetate
AmmoniumchloridAmmonium chloride
pH-WertPH value
StromdichteCurrent density
Temperaturtemperature
Dichte der RisseDensity of cracks
NickelchloridNickel chloride
NatriumacetatSodium acetate
NatriumchloridSodium chloride
pH-WertPH value
StromdichteCurrent density
Temperaturtemperature
Dichte der RisseDensity of cracks
150 g/l150 g / l
50 g/l50 g / l
120 g/l120 g / l
3,5 bis3.5 to
Ibis 10 A/dm2 Ibis 10 A / dm 2
25° C25 ° C
1 Min.1 min.
etwa 700 Risse je cmabout 700 cracks per cm
150 g/l150 g / l
50 g/l50 g / l
120 g/l120 g / l
3,5 bis3.5 to
1 bis 15 A/dm2 1 to 15 A / dm 2
35° C35 ° C
etwa 500 Risse je cmabout 500 cracks per cm
150 g/l150 g / l
50 g/l50 g / l
150 g/l150 g / l
Ibis 10 A/dm2 Ibis 10 A / dm 2
25° C25 ° C
etwa 300 Risse je cmabout 300 cracks per cm
Alle genannten Bäder sind verträglich mit geeigneten Glanzbildner, wie sie bereits im Hauptpatent angegeben sind.All the baths mentioned are compatible with suitable brighteners, as already indicated in the main patent are.
Claims (3)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR991133A FR1447970A (en) | 1964-10-12 | 1964-10-12 | Corrosion resistant decorative chrome deposits |
| FR996104A FR88318E (en) | 1964-10-12 | 1964-11-24 | Corrosion resistant decorative chrome deposits |
| FR3489A FR89217E (en) | 1964-10-12 | 1965-01-27 | Corrosion resistant decorative chrome deposits |
| FR11348A FR89657E (en) | 1964-10-12 | 1965-03-31 | Corrosion resistant decorative chrome deposits |
| FR57477A FR90417E (en) | 1964-10-12 | 1966-04-13 | Corrosion resistant decorative chrome deposits |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1621151A1 DE1621151A1 (en) | 1970-07-16 |
| DE1621151B2 DE1621151B2 (en) | 1978-03-23 |
| DE1621151C3 true DE1621151C3 (en) | 1978-11-23 |
Family
ID=27514668
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1965R0041715 Granted DE1496974B2 (en) | 1964-10-12 | 1965-10-07 | PROCESS FOR THE ELECTRICAL PRODUCTION OF A MICRO-CRACKED CHROME COATING ON NICKEL INTERLAYERS |
| DE1621151A Expired DE1621151C3 (en) | 1964-10-12 | 1967-04-10 | Process for the galvanic production of a micro-cracked chrome coating on intermediate nickel layers |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1965R0041715 Granted DE1496974B2 (en) | 1964-10-12 | 1965-10-07 | PROCESS FOR THE ELECTRICAL PRODUCTION OF A MICRO-CRACKED CHROME COATING ON NICKEL INTERLAYERS |
Country Status (13)
| Country | Link |
|---|---|
| US (3) | US3388049A (en) |
| JP (2) | JPS5024248B1 (en) |
| AT (1) | AT276893B (en) |
| BE (2) | BE670116A (en) |
| BR (1) | BR6788420D0 (en) |
| CH (1) | CH445999A (en) |
| DE (2) | DE1496974B2 (en) |
| ES (1) | ES339183A2 (en) |
| FR (5) | FR1447970A (en) |
| GB (2) | GB1122795A (en) |
| NL (2) | NL140902B (en) |
| OA (1) | OA117E (en) |
| SE (2) | SE327875B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
| US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
| US3474010A (en) * | 1966-10-26 | 1969-10-21 | M & T Chemicals Inc | Method of electroplating corrosion resistant coating |
| US3866289A (en) * | 1969-10-06 | 1975-02-18 | Oxy Metal Finishing Corp | Micro-porous chromium on nickel-cobalt duplex composite plates |
| GB1541118A (en) * | 1976-12-03 | 1979-02-21 | Bnf Metals Tech Centre | Nickel plating |
| JPS54119436U (en) * | 1978-02-09 | 1979-08-21 | ||
| US4416738A (en) * | 1980-01-28 | 1983-11-22 | The Boeing Company | Chromium plating |
| US4384929A (en) * | 1981-07-06 | 1983-05-24 | Occidental Chemical Corporation | Process for electro-depositing composite nickel layers |
| US4432843A (en) * | 1982-07-29 | 1984-02-21 | Omi International Corporation | Trivalent chromium electroplating baths and processes using thiazole addition agents |
| JPH02116220U (en) * | 1989-03-04 | 1990-09-18 | ||
| DE69607130T2 (en) * | 1995-12-29 | 2000-10-19 | At & T Corp., New York | Electroplating nickel on nickel ferrite devices |
| EP2975162B1 (en) * | 2014-07-18 | 2018-09-05 | FRANZ Oberflächentechnik GmbH & Co KG | Method for providing a workpiece with a protective coating |
| US10138884B2 (en) * | 2014-12-22 | 2018-11-27 | Weatherford Technology Holdings, Llc | Nickel corrosion barrier under chrome for sucker rod pumps |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2678908A (en) * | 1951-07-26 | 1954-05-18 | Eastman Kodak Co | Method of forming ferrotyping surfaces |
| DE1176956B (en) * | 1958-08-27 | 1964-08-27 | Bosch Gmbh Robert | Process for the multi-stage galvanic deposition of shiny nickel coatings |
| GB871276A (en) * | 1959-02-26 | 1961-06-28 | Hanson Van Winkle Munning Co | Improvements in electrodeposition of nickel |
| NL271860A (en) * | 1961-11-27 | |||
| NL275167A (en) * | 1962-02-23 | |||
| GB1091526A (en) * | 1963-07-24 | 1967-11-15 | Canning & Co Ltd W | Improvements in electrodeposition of chromium |
| US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
-
1964
- 1964-10-12 FR FR991133A patent/FR1447970A/en not_active Expired
- 1964-11-24 FR FR996104A patent/FR88318E/en not_active Expired
-
1965
- 1965-01-27 FR FR3489A patent/FR89217E/en not_active Expired
- 1965-03-15 US US440019A patent/US3388049A/en not_active Expired - Lifetime
- 1965-03-31 FR FR11348A patent/FR89657E/en not_active Expired
- 1965-09-24 BE BE670116D patent/BE670116A/xx not_active IP Right Cessation
- 1965-09-28 CH CH1335465A patent/CH445999A/en unknown
- 1965-10-04 GB GB41936/65A patent/GB1122795A/en not_active Expired
- 1965-10-07 DE DE1965R0041715 patent/DE1496974B2/en active Granted
- 1965-10-11 SE SE13121/65A patent/SE327875B/xx unknown
- 1965-10-11 JP JP40062000A patent/JPS5024248B1/ja active Pending
- 1965-10-12 NL NL656513216A patent/NL140902B/en not_active IP Right Cessation
-
1966
- 1966-04-13 FR FR57477A patent/FR90417E/en not_active Expired
-
1967
- 1967-03-24 BE BE696105D patent/BE696105A/xx unknown
- 1967-03-29 NL NL6704452A patent/NL6704452A/xx unknown
- 1967-03-30 US US626938A patent/US3620936A/en not_active Expired - Lifetime
- 1967-04-04 GB GB05291/67A patent/GB1187843A/en not_active Expired
- 1967-04-06 OA OA52895A patent/OA117E/xx unknown
- 1967-04-10 AT AT338167A patent/AT276893B/en not_active IP Right Cessation
- 1967-04-10 DE DE1621151A patent/DE1621151C3/en not_active Expired
- 1967-04-11 BR BR188420/67A patent/BR6788420D0/en unknown
- 1967-04-12 SE SE05064/67A patent/SE335935B/xx unknown
- 1967-04-12 ES ES339183A patent/ES339183A2/en not_active Expired
- 1967-04-12 JP JP42022950A patent/JPS4827183B1/ja active Pending
-
1971
- 1971-09-27 US US00184251A patent/US3759802A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB1187843A (en) | 1970-04-15 |
| FR1447970A (en) | 1966-08-05 |
| CH445999A (en) | 1967-10-31 |
| JPS5024248B1 (en) | 1975-08-14 |
| SE335935B (en) | 1971-06-14 |
| FR90417E (en) | 1967-12-08 |
| BE696105A (en) | 1967-09-01 |
| NL6704452A (en) | 1967-10-16 |
| US3620936A (en) | 1971-11-16 |
| DE1496974A1 (en) | 1969-12-18 |
| BE670116A (en) | 1966-01-17 |
| NL140902B (en) | 1974-01-15 |
| AT276893B (en) | 1969-12-10 |
| OA117E (en) | 1970-12-15 |
| DE1496974B2 (en) | 1971-11-04 |
| DE1621151A1 (en) | 1970-07-16 |
| DE1621151B2 (en) | 1978-03-23 |
| ES339183A2 (en) | 1968-04-16 |
| SE327875B (en) | 1970-08-31 |
| US3759802A (en) | 1973-09-18 |
| US3388049A (en) | 1968-06-11 |
| FR89217E (en) | 1967-05-26 |
| GB1122795A (en) | 1968-08-07 |
| FR88318E (en) | 1967-01-20 |
| BR6788420D0 (en) | 1973-07-10 |
| NL6513216A (en) | 1966-04-13 |
| JPS4827183B1 (en) | 1973-08-20 |
| FR89657E (en) | 1967-07-28 |
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