DE1796110B2 - AQUATIC BATH FOR GALVANIC DEPOSITION OF GLAZING AND PORE-FREE PALLADIUM COATINGS - Google Patents
AQUATIC BATH FOR GALVANIC DEPOSITION OF GLAZING AND PORE-FREE PALLADIUM COATINGSInfo
- Publication number
- DE1796110B2 DE1796110B2 DE19681796110 DE1796110A DE1796110B2 DE 1796110 B2 DE1796110 B2 DE 1796110B2 DE 19681796110 DE19681796110 DE 19681796110 DE 1796110 A DE1796110 A DE 1796110A DE 1796110 B2 DE1796110 B2 DE 1796110B2
- Authority
- DE
- Germany
- Prior art keywords
- palladium
- bath
- pore
- complex
- glazing
- 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
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 42
- 229910052763 palladium Inorganic materials 0.000 title claims description 21
- 230000008021 deposition Effects 0.000 title claims description 6
- 239000004202 carbamide Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- -1 sulfite compound Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- KHJWSKNOMFJTDN-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHJWSKNOMFJTDN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
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)
Description
Die vorliegende Erfindung betrifft ein wäßriges Bad mit einem pH-Wert höher als 8 zur galvanischen Abscheidung glänzender und porenfreier Palladiumüberzüge, dem das Palladium in Form eines eine Stickstoffverbindung enthaltenden Komplexes zugegeben istThe present invention relates to an aqueous bath with a pH higher than 8 for electroplating Deposition of shiny and pore-free palladium coatings, to which the palladium in the form of a one Nitrogen compound-containing complex is added
Derartige Bäder ermöglichen die Abscheidung von metallischem Palladium mit hoher Reinheit Die üblicherweise verwendeten Palladium-Salze sind das Palladium-tetrammino-dinitrat und das Palladium-diamminodinitrit, das unter dem Namen Palladium-Salz »P« bekannt istSuch baths enable the deposition of metallic palladium with a high degree of purity Palladium salts commonly used are palladium tetrammino dinitrate and palladium diamminodinitrite, which is known as the palladium salt "P"
Aus der DT-AS 12 39159 ist ein Bad zum galvanischen Abscheiden von Palladium bekannt das Palladium in Form eines stickstoffhaltigen Komplexes, Palladium-diammino-dinitrit und Ammoniumsalz einer schwachen organischen Säure, Äthylendiamintetraessigsäure, enthält Es hat sich gezeigt, daß die abgeschiedenen Schichten bei den allgemein üblichen Schichtstärken 2,5 bis 5 μπι teilweise porig sind.A bath for the galvanic deposition of palladium is known from DT-AS 12 39 159 Palladium in the form of a nitrogen-containing complex, palladium-diammino-dinitrite and an ammonium salt weak organic acid, ethylenediaminetetraacetic acid, has been shown to contain the deposited layers are partially porous with the generally customary layer thicknesses of 2.5 to 5 μm.
Aufgabe der vorliegenden Erfindung ist es, ein galvanisches Palladiumbad mit einem pH-Wert höher als 8, das Palladium in Form eines eine Stickstoffverbindung enthaltenden Komplexes gelöst enthält, zur Verfügung zu stellen, das beständig ist und mit dem glänzende und porenfreie Schichten abgeschieden werden können, und zwar mit einer Schichtstärke, wie sie im allgemeinen für Kontakte, Verbinder, gedruckte Schaltungen, Platten usw. verwendet wird sowie, falls notwendig, für höhere Schichtstärken.The object of the present invention is to provide a galvanic palladium bath with a higher pH value than 8, which contains palladium dissolved in the form of a complex containing a nitrogen compound, for To provide that is permanent and deposited with the shiny and pore-free layers can be, with a layer thickness as is generally used for contacts, connectors, printed Circuits, plates, etc. is used and, if necessary, for higher layer thicknesses.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Komplex ein Harnstoffkomplex istAccording to the invention, this object is achieved in that the complex is a urea complex
Den Palladium-Harnstoff-Komplex erhält man durch Reaktion von Palladiumchlorid oder Palladiumchlorid und Natriumchlorid oder anderen palladiumhaltigen Salzen mit einer einen schwachen Harnstoffüberschuß enthaltenden Lösung. Dabei setzt sich ein Salz ab, das ca. 36% Palladiummetall enthält und das in einer alkalischen Harnstofflösung löslich istThe palladium-urea complex is obtained by reacting palladium chloride or palladium chloride and sodium chloride or other palladium-containing salts with a slight excess of urea containing solution. A salt is deposited that contains approx. 36% palladium metal and that in one alkaline urea solution is soluble
Bei Steuerung des pH-Wertes durch Ammoniak enthält das Bad vorteilhaft eine Sulfitverbindung mit einer Konzentration von 1,5 bis 70 g/l, wodurch besonders weiße Palladiumüberzüge erzeugt werden lcftnnen.If the pH is controlled by ammonia, the bath advantageously contains a sulfite compound a concentration of 1.5 to 70 g / l, whereby particularly white palladium coatings are produced open.
Ferner ist es zweckmäßig, daß die Lösung komplex- oder chelatbildende Verbindungen, z. B. äthylendiamintetraessigsaures Natrium, enthält um eine Verunreinigung des Bades durch vom zu galvanisierenden Werkstück stammende MetaUionen zu unterbinden.It is also useful that the solution complex or chelate compounds, for. B. ethylenediaminetetraacetic acid Sodium, contains a contamination of the bath by from the to be electroplated To prevent metaUions originating from the workpiece.
Der in einer harnsioffhaltigen Lösung gelöste Palladium-Harnstoff-Komplex kann direkt für die galvanische Palladiumabscheidung verwendet werden. Die Lösung muß alkalisch sein, was durch einen Zusatz von Ammoniumhydroxyd leicht zu erreichen ist Es ist jedoch ratsam, daß das Bad seine Leitfähigkeit erhöhende Salze gelöst enthält Solche Salze sind z. B. Phosphate, die bei der Reaktion mit den Palladium-Ionen oder dem Harnstoff keinen Niederschlag hervorrufen.The palladium-urea complex dissolved in a solution containing urea can be used directly for the galvanic palladium deposition can be used. The solution must be alkaline, which is indicated by an additive of ammonium hydroxide is easy to reach, however, it is advisable that the bath check its conductivity contains dissolving increasing salts. Such salts are z. B. Phosphates, which react with the palladium ions or urea do not cause precipitation.
In der Mehrzahl der Fälle, in denen man Palladium auf Kupfer, Kupferlegierungen, oder Nickel und Nickellegierungen abscheidet erfolgt auch eine bestimmte Zuführung von vom zu galvanisierenden Werkstück stammenden störenden MetaUionen die durch Äthylendiamintetraessigsäure (ÄDTE) und durch ähnliche Verbindungen cheliert werden, wodurch die Mitabscheidung des Werkstückmetalls zusammen mit dem Palladium verhindert wird.In the majority of cases where you get palladium on Copper, copper alloys, or nickel and nickel alloys also deposit a certain amount Supply of interfering metals from the workpiece to be electroplated, caused by ethylenediaminetetraacetic acid (ÄDTE) and are chelated by similar compounds, thereby co-deposition of the workpiece metal together with the palladium is prevented.
Der pH-Wert wird durch Hinzufügung von Ammoniumhydroxyd über 8 gehalten.The pH is adjusted by adding ammonium hydroxide held over 8.
Die nachstehenden Beispiele dienen der näheren Erläuterung des erfindungsgemäßen Bades.The following examples serve to explain the bath according to the invention in more detail.
Es wurde ein Bad folgender Zusammensetzung hergestellt:A bath of the following composition was made:
bis zu einem pH-Wert von 9,5up to a pH of 9.5
Bei einer Temperatur von 500C und einer Stromdichte von 0,3 A/dm2 erhält man glänzende Palladiumüberzüge. Glossy palladium coatings are obtained at a temperature of 50 ° C. and a current density of 0.3 A / dm 2.
Zu der in Beispiel 1 beschriebenen Lösung, ohne Natriumniirit, wurden 25 g Natriumsulfit (wasserfrei) hinzugefügt.To the solution described in Example 1, without sodium nitrate, 25 g of sodium sulfite (anhydrous) added.
Bei einer Stromdichte von 0,5 A/dm2 erhält man glänzende und nicht poröse Überzüge einer Stärke von 2 bis 10 μπι. Die so erhaltenen Überzüge waren weißer als die in Beispiel 1 erzielten.At a current density of 0.5 A / dm 2 , glossy and non-porous coatings with a thickness of 2 to 10 μm are obtained. The coatings obtained in this way were whiter than those obtained in Example 1.
Es wurde ein Bad folgender Zusammensetzung hergestellt:A bath of the following composition was made:
bis zu einem pH-Wert von 8,5up to a pH of 8.5
Dieses Bad lieferte glänzende und weiße Überzüge bei einer Stromdichte von 0,1 A/dm2 bei einer Temperatur von 55° C.This bath gave glossy and white coatings at a current density of 0.1 A / dm 2 at a temperature of 55 ° C.
Die Natriumsulfitmenge wurde auf 75 g/l gebracht und die Palladium-Harnstoff-Verbindung wurde bis zur Grenze ihrer Löslichkeit beigefügt Unter diesen Bedingungen erhielt man glänzende Überzüge bei Stromdichten über 1,0 A/dm2.The amount of sodium sulfite was brought to 75 g / l and the palladium-urea compound was added up to the limit of its solubility. Under these conditions, glossy coatings were obtained with current densities above 1.0 A / dm 2 .
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1261267 | 1967-09-08 | ||
| CH1261267A CH479715A (en) | 1967-09-08 | 1967-09-08 | Process for electrolytic plating of palladium, and bath for carrying out this process |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1796110A1 DE1796110A1 (en) | 1972-02-24 |
| DE1796110B2 true DE1796110B2 (en) | 1977-04-21 |
| DE1796110C3 DE1796110C3 (en) | 1977-12-15 |
Family
ID=
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1289451B (en) * | 1964-05-25 | 1969-02-13 | Buehler Ltd | Portable polisher for metallurgical examination |
| DE19803818A1 (en) * | 1997-11-15 | 1999-05-27 | Doduco Gmbh | Electrolytic bath for the deposition of palladium and alloys of palladium |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1289451B (en) * | 1964-05-25 | 1969-02-13 | Buehler Ltd | Portable polisher for metallurgical examination |
| DE19803818A1 (en) * | 1997-11-15 | 1999-05-27 | Doduco Gmbh | Electrolytic bath for the deposition of palladium and alloys of palladium |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS475401B1 (en) | 1972-02-16 |
| CH479715A (en) | 1969-10-15 |
| GB1171734A (en) | 1969-11-26 |
| DE1796110A1 (en) | 1972-02-24 |
| US3637474A (en) | 1972-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| EHJ | Ceased/non-payment of the annual fee |