EP0149029A1 - Palladium bath - Google Patents
Palladium bath Download PDFInfo
- Publication number
- EP0149029A1 EP0149029A1 EP84112868A EP84112868A EP0149029A1 EP 0149029 A1 EP0149029 A1 EP 0149029A1 EP 84112868 A EP84112868 A EP 84112868A EP 84112868 A EP84112868 A EP 84112868A EP 0149029 A1 EP0149029 A1 EP 0149029A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- added
- bath
- pyridine
- bath according
- 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.)
- Withdrawn
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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
Definitions
- the invention relates to a bath for the rapid galvanic deposition of shiny, highly ductile, crack and pore-free palladium layers, which contains palladium in the form of a palladium salt.
- Palladium layers are required for both decorative and 7 ⁇ m technical use. In technical use, it is used in particular as a substitute for gold. In decorative use, slight cracking or pore formation can still be accepted, but not in technical use.
- the palladium layers must be absolutely free of cracks and pores and generally also highly ductile in order to meet the requirements placed on these palladium layers.
- the sulfad-based palladium baths are almost always aggressive and attack a number of base metals. This aggressiveness also causes rapid contamination by foreign metal ions. Since they also usually separate powdery precipitates, these known palladium baths only meet subordinate requirements.
- the alkaline baths listed under b) also only give imperfect precipitation with more or less strong pores, which are shiny even in relatively thin layers.
- the palladium baths belonging to the last group are preferred in practice, platinum or platinized titanium generally being used as the insoluble anode material.
- platinum or platinized titanium generally being used as the insoluble anode material.
- the relatively good yield of such baths is offset by the disadvantages that it is difficult to achieve pore-free coatings, that the constantly evaporating ammonia creates uncomfortable operating conditions and requires extensive suction devices, and that the pH of such baths is also unstable and therefore very difficult to maintain constant can be held.
- ea has also become known to use an aqueous neutral or alkaline solution with a palladium compound and an ammonium salt of a weak organic acid which does not form an insoluble compound with the palladium compound for the deposition of palladium coatings.
- a bath for depositing tough palladium coatings on electrical contacts has already become known, which contains palladium in the form of a nitrogen-containing complex, the complex consisting of an aqueous alkaline-ammoniacal solution of tetramine-palladium-bromide.
- the invention specifies a palladium bath which deposits the shiny, highly ductile, crack- and pore-free palladium layers to be deposited quickly, that is to say with a high limiting current density. This is achieved in the manner according to the invention by adding pyridine or a pyridine derivative as a complexing agent.
- the bath according to the invention As was found when using the bath according to the invention, with high current efficiency and accordingly high limiting current density, correspondingly rapid deposits result in shiny, highly ductile, crack-free and pore-free palladium layers, the gloss also being retained even with thick layers. There are none pleasant side effects, especially if good suction is provided when adding pyridine, such as in baths with ammoniacal medium.
- the hardness of the precipitation can be set between a hardness of 100 to 500 HV. It is noteworthy that even the soft precipitation is extremely resistant to abrasion.
- Di-ammonium hydrogenphosphate which is also a good buffer / conducting salt system, has proven itself quite well for this.
- Potassium sodium tartrate can be used in a similar way.
- Salts of organic polyhydroxy acids, such as, for example, gluconic acid sodium salt have proven useful as organic buffer systems.
- these organic buffer systems can also be complexing agents for palladium at the same time, similar to, for example, (NH 4 ) 2 HPO 4 .
- Suitable sulfur-containing additives can also be added to the bath to modify the mechanical precipitation properties, in particular to adjust the desired hardness.
- these sulfur-containing additives are expediently added in the form of organic sulfur compounds, in particular as sulfonic acid, as sulfonate or as sulfonamide.
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- 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)
Abstract
Description
Die Erfindung betrifft ein Bad zum schnellen galvanischen Abcheiden von qlänzenden, hochduktilen, riß- und porenfreien Palladiumschichten, das Palladium in Form eines Palladiumsalzes enthält.The invention relates to a bath for the rapid galvanic deposition of shiny, highly ductile, crack and pore-free palladium layers, which contains palladium in the form of a palladium salt.
Palladiumschichten werden sowohl zum dekorativen als auch 7um technischen Einsatz benötigt. Im technischen Einsatz wird es insbesondere als Substitut für Gold eingesetzt. Im dekorativen Einsatz kann zwar noch eine geringfügige Riß-oder Porenbildung in Kauf genommen werden, jedoch nicht im technischen Einsatz. Hier müssen die Pallndiumschichten absolut riß- und porenfrei und im allgemeinen auch hochduktil sein, um den an diese Palladiumschichten gestellten Forderungen zu genügen.Palladium layers are required for both decorative and 7 µm technical use. In technical use, it is used in particular as a substitute for gold. In decorative use, slight cracking or pore formation can still be accepted, but not in technical use. Here, the palladium layers must be absolutely free of cracks and pores and generally also highly ductile in order to meet the requirements placed on these palladium layers.
Bei Palladiumbädern kann man unterscheiden:
- a) Bäder auf Sulfatbasis, die auch mit löslichen Palladiumanoden betrieben werden,
- b) alkalische Bäder auf der Basis des Palladiumhydroxokomplexes,
- c) Bäder auf Chloridbasis oder auf der Basis der Nitratbeziehungsweise Nitritkomplexe in neutralem oder ammoniakalischem Medium.
- a) sulfate-based baths which are also operated with soluble palladium anodes,
- b) alkaline baths based on the palladium hydroxo complex,
- c) Baths based on chloride or on the basis of nitrate or nitrite complexes in neutral or ammoniacal medium.
Die Palladiumbäder auf Sulfadbasis sind fast durchweg aggresiv und greifen eine Reihe von Grundmetallen an. Auch wird durch diese Aggressivität eine schnelle Verunreinigung durch Fremdmetall-Ionen herbeigeführt. Da sie zudem meistens pulvrige Niederschläge abscheiden, genügen diese bekannten Palladiumbäder nur untergeordneten Anforderungen.The sulfad-based palladium baths are almost always aggressive and attack a number of base metals. This aggressiveness also causes rapid contamination by foreign metal ions. Since they also usually separate powdery precipitates, these known palladium baths only meet subordinate requirements.
Auch die unter b) angeführten alkalischen Bäder ergeben nur unvollkommene Niederschläge mit mehr oder weniger starken Poren, die auch nur in verhältnismäßig dünnen Schichten glänzend sind.The alkaline baths listed under b) also only give imperfect precipitation with more or less strong pores, which are shiny even in relatively thin layers.
Die zur letzten Gruppe zählenden Palladiumbäder werden in der Praxis bevorzugt, wobei als unlösliches Anodenmaterial im allgemeinen Platin oder platiniertes Titan zum Einsatz kommt. Der verhältnismäßig guten Ausbeute derartiger Bäder stehen jedoch die Nachteile gegenüber, daß kaum porenfreie Überzüge zu erzielen sind, daß das ständig verdampfende Ammoniak unangenehme Betriebsbedingungen schafft und umfangreiche Absaugvorrichtungen erfordert, und daß auch der pH-Wert solcher Bäder instabil ist und daher nur sehr schwierig konstant gehalten werden kann.The palladium baths belonging to the last group are preferred in practice, platinum or platinized titanium generally being used as the insoluble anode material. However, the relatively good yield of such baths is offset by the disadvantages that it is difficult to achieve pore-free coatings, that the constantly evaporating ammonia creates uncomfortable operating conditions and requires extensive suction devices, and that the pH of such baths is also unstable and therefore very difficult to maintain constant can be held.
Um trotzdem porenfreie Überzüge zu erzielen ist ea auch schon bekanntgeworden, zum Abscheiden von Palladiumüberzügen eine wäßrige neutrale oder alkalische Lösung mit einer Palladiumverbindung und einem Ammoniumsalz einer schwachen organischen Säure, die keine unlösliche Verbindung mit der Palladiumverbindung bildet, zu verwenden. So ist bereits ein Bad zum Abscheiden von zähen Palladiumüberzügen auf elektrischen Kontakten bekanntgeworden, das Palladium in Form eines Stickstoff enthaltenden Komplexes enthält, wobei der Komplex aus einer wäßrigen alkalisch-ammoniakalischpn Lösung von Tetramin-Palladium-Bromid besteht. Obwohl hierdurch eine Verbesserung erreicht werden konnte, gelingt es auch damit nicht, dicke, vollkommen porenfreie Überzüge mit Palladium zu erzielen; außerdem bleibt nach wie vor die Notwendigkeit des Absaugens der Ammoniakdämpfe bestehen.In order to nevertheless achieve pore-free coatings, ea has also become known to use an aqueous neutral or alkaline solution with a palladium compound and an ammonium salt of a weak organic acid which does not form an insoluble compound with the palladium compound for the deposition of palladium coatings. A bath for depositing tough palladium coatings on electrical contacts has already become known, which contains palladium in the form of a nitrogen-containing complex, the complex consisting of an aqueous alkaline-ammoniacal solution of tetramine-palladium-bromide. Although an improvement was achieved in this way, it is also not possible to achieve thick, completely non-porous coatings with palladium; in addition, the need to extract ammonia vapors remains.
Festzustellen ist auch, daß infolge der Wasserstoffaufnahme des Palladiums bei der kathodischen Abscheidung aus den bekannten Bädern trotz geringer Stromausbeute, also mit niedriger Grenstromdichte, die Duktilität im allgemeinen unter der Anforderung verbleibt und auch die innere Spannung der Niederschläge verhältnismäßig hoch ist.It should also be noted that as a result of the hydrogen absorption of the palladium during cathodic deposition from the known baths, in spite of the low current yield, that is to say the low current density, the ductility generally remains below the requirement and the internal tension of the precipitates is also relatively high.
Die Erfindung gibt ein Palladiumbad an, das schnell, also mit hoher Grenzstromdichte, die zu fordernden glänzenden, hochduktilen, riß- und porenfreien Pnlladiumschichten abscheidet. Dies gelingt in erfindungsgemäßer Weise durch die Beifügung von Pyridin oder einem Pyridinderivats als Komplexbildner.The invention specifies a palladium bath which deposits the shiny, highly ductile, crack- and pore-free palladium layers to be deposited quickly, that is to say with a high limiting current density. This is achieved in the manner according to the invention by adding pyridine or a pyridine derivative as a complexing agent.
Wie beim Einsatz des erfindungsgemäßen Bades festgestellt werden konnte, ergeben sich bei hoher Stromausbeute und demgemäß hoher Grenzstromdichte entsprechend schnelle Abscheidungen tatsächlich glänzende, hochduktile, riß- und porenfreie Palladiumschichten, wobei der Glanz auch noch bei dicken Schichten erhalten bleibt. Es treten keine unangenehmen Begleiterscheinungen auf, insbesondere wenn bei Pyridinzugabe eine gut wirkende Absaugung vorgesehen wird, wie beispielsweise bei den Bädern mit ammoniakalischem Medium. Außerdem ist die Härte des Niederschlags einstellbar etwa zwischen einer Härte von 100 bis 500 HV. Bemerkenswert ist, daß auch die weichen Niederschläge trotzdem äußerst abriebfest sind.As was found when using the bath according to the invention, with high current efficiency and accordingly high limiting current density, correspondingly rapid deposits result in shiny, highly ductile, crack-free and pore-free palladium layers, the gloss also being retained even with thick layers. There are none pleasant side effects, especially if good suction is provided when adding pyridine, such as in baths with ammoniacal medium. In addition, the hardness of the precipitation can be set between a hardness of 100 to 500 HV. It is noteworthy that even the soft precipitation is extremely resistant to abrasion.
Besonders gute Ergebnisse lassen sich dann erzielen, wenn die Seitengruppe des Pyridinderivats in 3er-Position steht. Bevorzugt wird hierbei Pyridilessigsäure zugegeben.Particularly good results can be achieved if the side group of the pyridine derivative is in the 3-position. Pyridilacetic acid is preferably added here.
Für spezielle Bedingungen empfiehlt es sich, dem Rad noch sekundäre Komplexbildner und organische Puffersysteme beizufügen. Recht gut bewährt hierzu hat sich di-Ammoniumhydrogenphosphat, das außerdem noch ein gutes Puffer-/Leitsalzsystem darstellt. Ähnlich kann auch Kalium-natrium-tartrat eingesetzt werden. Als organische Puffersysteme haben sich Salze organischer Polyhydroxysäuren, wie beispielsweise Gluconsäure-Natrium-Salz, bewährt. Selbstverständlich können diese organischen Puffersysteme auch gleichzeitig Komplexbildner für Palladium sein, ähnlich wie beispielsweise (NH4)2HPO4.For special conditions, it is advisable to add secondary complexing agents and organic buffer systems to the wheel. Di-ammonium hydrogenphosphate, which is also a good buffer / conducting salt system, has proven itself quite well for this. Potassium sodium tartrate can be used in a similar way. Salts of organic polyhydroxy acids, such as, for example, gluconic acid sodium salt, have proven useful as organic buffer systems. Of course, these organic buffer systems can also be complexing agents for palladium at the same time, similar to, for example, (NH 4 ) 2 HPO 4 .
Zur Modifizierung der mechanischen Niederschlagseigenschaften, insbesondere zur Einstellung der gewünschten Härte, können dem Bad weiterhin geeignete schwefelhaltige Zusätze zugegeben werden. Nach der Erfindung werden diese schwefelhaltigen Zusätze zweckmäßigerweise in Form organischer Schwefelverbindungen beigefügt, insbesondere als Sulfonsäure, als Sulfonat oder als Sulfonamid.Suitable sulfur-containing additives can also be added to the bath to modify the mechanical precipitation properties, in particular to adjust the desired hardness. According to the invention, these sulfur-containing additives are expediently added in the form of organic sulfur compounds, in particular as sulfonic acid, as sulfonate or as sulfonamide.
Ansatz: 20...60 g/1 K-Na-tartrat
- 10...50 g/1 (NH 4)2 H P0 4
- 2...19 g/1 Polyoxisäure
- 10...40 g/1 Pyridinessigsäure
- 10...20 g/1 Pd2+
- pH = 12
- Temperatur = 10...50 °C
- i = 0,5 - 3 A/dm2 im Standbad = 95 - 100 %
- t = 0,5 - 1 µm/min (Standbad)
- 10 ... 50 g / 1 ( NH 4 ) 2 H P0 4
- 2 ... 19 g / 1 polyoxyacid
- 10 ... 40 g / 1 pyridine acetic acid
- 10 ... 20 g / 1 Pd 2+
- pH = 12
- Temperature = 10 ... 50 ° C
- i = 0.5 - 3 A / dm 2 in the standing bath = 95 - 100%
- t = 0.5 - 1 µm / min (standing bath)
Niederschlag: Rißfrei und glänzend. Die Rißfreiheit bleibt auch nach dem Wärmetest (Erwärmung auf 150 °C über 60 min, danach abschreckn in kaltem Wasser) erhalten.Precipitation: Crack-free and shiny. The absence of cracks remains even after the heat test (heating to 150 ° C for 60 min, then quenching in cold water).
Außerordentlich erwähnenswert ist, daß die Haftung der Schicht, insbesondere auf Nickel und auf Buntmetallen, sehr gut ist.It is extremely worth mentioning that the adhesion of the layer, especially on nickel and on non-ferrous metals, is very good.
Claims (9)
durch die Beifügung von Pyridin oder einem Pyridinderivat als Kompexbildner.1. Bath for the rapid electrodeposition of shiny, highly ductile, crack and pore-free palladium layers, which contains palladium in the form of a palladium salt
by adding pyridine or a pyridine derivative as a complexing agent.
dadurch gekennzeichnet,
daß die Seitengruppe des Pyridinderivates in 3er-Position steht.2. Bath according to claim 1,
characterized,
that the side group of the pyridine derivative is in the 3-position.
dadurch gekennzeichnet,
daß das Pyridin als Pyridilessigsäure zugegeben wird.3. bath according to claim 1 or 2,
characterized,
that the pyridine is added as pyridilacetic acid.
der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß weitere sekundäre Komplexbildner und organische Puffersysteme beigefügt werden.4. Bad after one or more
of the preceding claims,
characterized,
that additional secondary complexing agents and organic buffer systems are added.
dadurch gekennzeichnet,
daß als sekundärer Koplexbildner di-Ammoniumhydrogenphosphat beigefügt wird.5. Bath according to claim 4,
characterized,
that di-ammonium hydrogen phosphate is added as a secondary coplexing agent.
dadurch gekennzeichnet,
daß als sekundärer Komplexbildner Kalium-natrium-tartrat beigefügt wird.6. Bath according to claim 4,
characterized,
that potassium sodium tartrate is added as a secondary complexing agent.
dadurch gekennzeichnet,
daß als organischer Puffer Polyhydroxysäure beigefügt wird.7. Bath according to claim 4,
characterized,
that polyhydroxy acid is added as an organic buffer.
der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß neben den Komplexbildnern organische Schwefelverbindungen, insbesondere Sulfonsäuren, Sulfonate und Sulfonamide beigefügt werden.8. Bad after one or more
of the preceding claims,
characterized,
that organic sulfur compounds, in particular sulfonic acids, sulfonates and sulfonamides, are added in addition to the complexing agents.
der vorhergehenden Ansprüche,
gekennzeichnet durch
20...60 g/1 K-Na-tartrat, 10...50 g/1 (NH4)2 H PO4, 2...19 g/1 Polyoxisäure, 10...40 g/l Pyridinessigsäure, 10...20 g/l Pd2+, pH = 12, Temperatur = 10...50 °C, i = 0,5 - 3 A/dm2 im Standbad9. Bad after one or more
of the preceding claims,
marked by
20 ... 60 g / 1 K-Na-tartrate, 10 ... 50 g / 1 (NH 4 ) 2 H PO 4 , 2 ... 19 g / 1 polyoxyacid, 10 ... 40 g / l pyridine acetic acid , 10 ... 20 g / l Pd 2+ , pH = 12, temperature = 10 ... 50 ° C, i = 0.5 - 3 A / dm 2 in the standing bath
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3347384 | 1983-12-29 | ||
DE19833347384 DE3347384A1 (en) | 1983-12-29 | 1983-12-29 | PALLADIUM BATH |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0149029A1 true EP0149029A1 (en) | 1985-07-24 |
Family
ID=6218336
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84112868A Withdrawn EP0149029A1 (en) | 1983-12-29 | 1984-10-25 | Palladium bath |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0149029A1 (en) |
JP (1) | JPS60243296A (en) |
DE (1) | DE3347384A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0225422A1 (en) * | 1985-12-12 | 1987-06-16 | LeaRonal, Inc. | Alkaline baths and methods for electrodeposition of palladium and palladium alloys |
DE4428966A1 (en) * | 1993-08-16 | 1995-02-23 | Enthone Omi Inc | Electroplating bath and process for white palladium |
CN102168291A (en) * | 2011-03-16 | 2011-08-31 | 上海中子星化工科技有限公司 | Palladium plating solution |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4741818A (en) * | 1985-12-12 | 1988-05-03 | Learonal, Inc. | Alkaline baths and methods for electrodeposition of palladium and palladium alloys |
JP2539394B2 (en) * | 1986-10-29 | 1996-10-02 | 株式会社日立製作所 | Palladium electroplating solution |
DE4425110C1 (en) * | 1994-07-15 | 1995-10-26 | Heraeus Gmbh W C | Aq. plating bath for electrodeposition of palladium |
CN105441998A (en) * | 2015-10-30 | 2016-03-30 | 无锡市嘉邦电力管道厂 | Palladium plating containing sodium nitrite and tetra-n-propylammonium bromide and plating method thereof |
CN105332023A (en) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing tetra-n-propylammonium bromide and electroplating method thereof |
CN105316722A (en) * | 2015-11-20 | 2016-02-10 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing tetraphenylarsonium bromide and electroplating method of palladium electroplating solution |
CN105332021A (en) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing sodium nitrite and tetraphenylarsonium bromide and electroplating method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3285754A (en) * | 1962-07-05 | 1966-11-15 | Johnson Matthey Co Ltd | Deposition of palladium |
US3972787A (en) * | 1974-06-14 | 1976-08-03 | Lea-Ronal, Inc. | Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners |
FR2364980A1 (en) * | 1976-09-17 | 1978-04-14 | Parker Ste Continentale | Electrodeposition of palladium alloys for jewellery - or protective coatings, using bath contg. organic cpds. and brighteners |
DE3307174A1 (en) * | 1982-03-08 | 1983-09-15 | Technic Inc., Providence, R.I. | GALVANIC PALLADIUM BATH |
-
1983
- 1983-12-29 DE DE19833347384 patent/DE3347384A1/en not_active Withdrawn
-
1984
- 1984-10-25 EP EP84112868A patent/EP0149029A1/en not_active Withdrawn
- 1984-12-25 JP JP27217184A patent/JPS60243296A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3285754A (en) * | 1962-07-05 | 1966-11-15 | Johnson Matthey Co Ltd | Deposition of palladium |
US3972787A (en) * | 1974-06-14 | 1976-08-03 | Lea-Ronal, Inc. | Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners |
FR2364980A1 (en) * | 1976-09-17 | 1978-04-14 | Parker Ste Continentale | Electrodeposition of palladium alloys for jewellery - or protective coatings, using bath contg. organic cpds. and brighteners |
DE3307174A1 (en) * | 1982-03-08 | 1983-09-15 | Technic Inc., Providence, R.I. | GALVANIC PALLADIUM BATH |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0225422A1 (en) * | 1985-12-12 | 1987-06-16 | LeaRonal, Inc. | Alkaline baths and methods for electrodeposition of palladium and palladium alloys |
DE4428966A1 (en) * | 1993-08-16 | 1995-02-23 | Enthone Omi Inc | Electroplating bath and process for white palladium |
GB2283498A (en) * | 1993-08-16 | 1995-05-10 | Enthone Omi Inc | Metallic additive-free white palladium electroplating bath |
GB2283498B (en) * | 1993-08-16 | 1997-06-25 | Enthone Omi Inc | Electroplating bath and process for white palladium |
DE4428966C2 (en) * | 1993-08-16 | 2000-01-13 | Enthone Omi Inc | Process for depositing a white palladium metal coating |
CN102168291A (en) * | 2011-03-16 | 2011-08-31 | 上海中子星化工科技有限公司 | Palladium plating solution |
CN102168291B (en) * | 2011-03-16 | 2013-05-01 | 上海中子星化工科技有限公司 | Palladium plating solution |
Also Published As
Publication number | Publication date |
---|---|
DE3347384A1 (en) | 1985-07-11 |
JPS60243296A (en) | 1985-12-03 |
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Legal Events
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---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE CH FR GB LI NL SE |
|
17P | Request for examination filed |
Effective date: 19850805 |
|
17Q | First examination report despatched |
Effective date: 19860909 |
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Effective date: 19870120 |
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Inventor name: SCHNEIDER, THOMAS |