EP0081788B1 - Non-additive fast depositing galvanic palladium bath - Google Patents
Non-additive fast depositing galvanic palladium bath Download PDFInfo
- Publication number
- EP0081788B1 EP0081788B1 EP82111270A EP82111270A EP0081788B1 EP 0081788 B1 EP0081788 B1 EP 0081788B1 EP 82111270 A EP82111270 A EP 82111270A EP 82111270 A EP82111270 A EP 82111270A EP 0081788 B1 EP0081788 B1 EP 0081788B1
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- EP
- European Patent Office
- Prior art keywords
- bath
- palladium
- electrolyte
- phosphoric acid
- ammonia
- 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.)
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 87
- 229910052763 palladium Inorganic materials 0.000 title claims description 40
- 238000000151 deposition Methods 0.000 title claims description 17
- 239000000654 additive Substances 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 54
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims 2
- -1 amine compounds Chemical class 0.000 description 4
- 101100028920 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cfp gene Proteins 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- 101100522123 Caenorhabditis elegans ptc-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009736 wetting Methods 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
Definitions
- the invention relates to a method for producing an additive-free, fast-depositing electroplating bath for depositing shiny and crack-free palladium layers and a method for the electroplating of shiny and crack-free palladium layers using such a bath.
- the palladium baths working in the acidic range are usually characterized by low stability of the palladium complex, a low deposition rate (1 to 8 ⁇ m per min) and high packaging costs. However, they have the advantage that they allow a 100% current yield and the coatings are therefore usually crack-free.
- the known alkaline palladium baths are based on ammonia complexes or amine compounds. With these baths it is usually very difficult to keep the pH constant. Another disadvantage of these baths is that only a low deposition rate between 0.25 and 1 ⁇ m can be achieved.
- the coatings tend to crack, either through the use of glossy images, which lead to residual stresses, or through a non-100% current efficiency, since the hydrogen produced during the deposition is built into the layer; As is well known, hydrogen is very strongly absorbed by palladium.
- the constantly evaporating ammonia in the case of ammoniacal baths requires extensive suction devices because of the odor load.
- palladium compounds such as PdC1 2 , Pd (OH) 2 , K 2 Pd (N0 2 ) 4 , Pd (NH 2 S0 3 ) 2 , Pd (NH 3 ) 2 C1 2 and Pd (NH 3 ) 2 (N0 2 ) 2 are used.
- EP-A-0 076 523 discloses a quick-depositing galvanic palladium bath for depositing shiny, crack-free palladium layers, which contains an ammoniacal solution of a palladium tetraamino complex and a phosphate anion or carbonate anion.
- This bath should be free of quaternized pyridinium additives.
- the addition of palladium in the form of palladium tetraamine chloride is preferred.
- the invention has for its object to provide a palladium bath for the deposition of shiny, crack-free palladium layers, which only requires low manufacturing costs and high deposition rates of at least 10 to 25 microns / min with a 100% current yield. Furthermore, it should be possible to dispense with any addition of gloss and a high bath stability should be guaranteed. In order to achieve permanent corrosion resistance, the deposited layer should not contain any sulfur.
- This object is achieved in a process for producing a generic bath by adding phosphoric acid, ammonia to the neutralization of the phosphoric acid and palladium in the form of palladium chloride in succession in distilled water heated to 90 ° C., then the use pH adjusted with ammonia or phosphoric acid and the bath is replenished to the final volume with distilled water.
- the palladium bath according to the invention is also particularly advantageous because it is based on palladium chloride, one of the cheapest palladium salts.
- the process for the galvanic deposition of shiny, crack-free palladium layers using such a bath is characterized in that the bath temperatures in the range from 20 to 80 ° C., with current densities in the range from 40 to 180 A / dm 2 and with an electrolyte movement, which is defined by a rotating disk electrode with an outer diameter of 10 mm and a disk diameter of 2 mm at a rotational speed of 3600 to 10,000 rpm.
- the layers are of excellent quality. Even with an enlargement up to 15000, no cracks could be detected.
- the free ammonia content is so low that there is no fear of odor and no corrosion of the treated material and the system.
- the pH stability is better than with the other known alkaline baths. In the bath according to the invention the palladium does not tend to self-reduction, so that the bath is highly stable.
- the palladium bath according to the invention is advantageously used in continuously operating electroplating systems, possibly also for the partial coating of components, such as Connectors or the like., Which are connected together to form a band.
- the increased electrolyte movement is preferably achieved by spraying the electrolyte onto the workpiece with the aid of nozzles.
- the nozzles form the anode, while the strip is contacted cathodically.
- the free ends of the parts sprayed with electrolyte are preferably continuously wetted with electrolyte by an arrangement of a channel or the like.
- the bath produces glossy and crack-free layers at a temperature of 60 ° C and a current density of 75 A / dm 2 when the rotating disk electrode is operated at 5000 rpm.
- the bath produces glossy and crack-free layers at a temperature of 65 ° C and an electrolyte movement over spray nozzles at a current density of 140 A / dm 2 and with an electrolyte quantity of 2.8 ml / sec per nozzle.
- the bath gives a shiny and crack-free palladium layer at a temperature of 60 ° C and a current density of 60 A / dm 2 and an electrolyte movement over spray nozzles with an amount of electrolyte of 1.7 ml / sec and per nozzle.
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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)
- Electroplating Methods And Accessories (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines zusatzfreien, schnellabscheidenden galvanischen Bades zum Abscheiden von glänzenden und rissfreien Palladiumschichten und ein Verfahren zum galvanischen Abscheiden von glänzenden und rissfreien Palladiumschichten unter Verwendung eines derartigen Bades.The invention relates to a method for producing an additive-free, fast-depositing electroplating bath for depositing shiny and crack-free palladium layers and a method for the electroplating of shiny and crack-free palladium layers using such a bath.
Grundsätzlich unterscheidet man zwischen alkalischen und sauren Palladiumbädern. Meist werden diesen Bädern Zusätze zur Glanzbildung beigegeben. Durch die Badzusammensetzung und diese Zusätze besteht die Gefahr, dass in der abgeschiedenen Palladiumschicht Fremdkomponenten, z. B. Schwefel, eingebaut werden, was Anlass zur Rissbildung und schlechter Korrosionsbeständigkeit geben kann.A basic distinction is made between alkaline and acidic palladium baths. Additions to the shine are usually added to these baths. Due to the bath composition and these additives there is a risk that foreign components, e.g. As sulfur, are installed, which can give rise to cracking and poor corrosion resistance.
Die im sauren Bereich arbeitenden Palladiumbäder sind meist gekennzeichnet durch geringe Stabilität des Palladiumkomplexes, eine niedrige Abscheiderate (1 bis 8 µm pro min) und hohe Konfektionierungskosten. Sie haben jedoch den Vorteil, dass sie eine 100%ige Stromausbeute erlauben und die Überzüge daher meistens rissfrei sind.The palladium baths working in the acidic range are usually characterized by low stability of the palladium complex, a low deposition rate (1 to 8 µm per min) and high packaging costs. However, they have the advantage that they allow a 100% current yield and the coatings are therefore usually crack-free.
Die bekannten alkalischen Palladiumbäder sind auf der Basis von Ammoniakkomplexen oder Aminverbindungen aufgebaut. Bei diesen Bädern ist es meist sehr schwierig, den pH-Wert konstant zu halten. Ein weiterer Nachteil dieser Bäder ist, dass nur eine geringe Abscheiderate zwischen 0,25 bis 1 µm erzielbar ist.The known alkaline palladium baths are based on ammonia complexes or amine compounds. With these baths it is usually very difficult to keep the pH constant. Another disadvantage of these baths is that only a low deposition rate between 0.25 and 1 µm can be achieved.
Ausserdem neigen die Überzüge zu Rissbildung, entweder durch die Verwendung von Glanzbildern, welche zu Eigenspannungen führen, oder durch eine nicht 100%ige Stromausbeute, da der bei der Abscheidung entstehende Wasserstoff in die Schicht eingebaut wird; Wasserstoff wird bekanntlich durch das Palladium sehr stark absorbiert. Ausserdem verlangt das ständig verdampfende Ammoniak im Falle ammoniakalischer Bäder wegen der Geruchsbelastung umfangreiche Absaugvorrichtungen.In addition, the coatings tend to crack, either through the use of glossy images, which lead to residual stresses, or through a non-100% current efficiency, since the hydrogen produced during the deposition is built into the layer; As is well known, hydrogen is very strongly absorbed by palladium. In addition, the constantly evaporating ammonia in the case of ammoniacal baths requires extensive suction devices because of the odor load.
Durch die DE-A-26 57 925 ist ein ammoniakfreies, wässriges Bad bekanntgeworden, bei dem zum Ansetzen u.a. auch Palladiumchlorid (PdC12) verwendet wird. Infolge sehr geringer Stromdichten (bis 1 A/dm2) ergeben sich aber nur sehr geringe Abscheideraten.From DE-A-26 57 925 an ammonia-free, aqueous bath has become known in which, among other things, palladium chloride (PdC1 2 ) is also used for the preparation. As a result of very low current densities (up to 1 A / dm 2 ), there are only very low deposition rates.
Ferner ist es beispielsweise durch die DE-A-29 39 920 bekannt, dass man zum Ansetzen des Bades Palladiumverbindungen wie PdC12, Pd(OH)2, K2 Pd(N02)4, Pd(NH2S03)2, Pd(NH3)2C12 und Pd(NH3)2(N02)2 verwendet.Furthermore, it is known, for example from DE-A-29 39 920, that for preparing the bath, palladium compounds such as PdC1 2 , Pd (OH) 2 , K 2 Pd (N0 2 ) 4 , Pd (NH 2 S0 3 ) 2 , Pd (NH 3 ) 2 C1 2 and Pd (NH 3 ) 2 (N0 2 ) 2 are used.
Aus der SU-A-454 280 ist ein galvanisches Bad zum Abscheiden von Palladium/Platin-Legierungen bekannt, das in wässriger Lösung H2PtC16 6H20, PdCI2· 2H20, (NH4)2 HP04 und Na2 HP04 12H20 enthält. Ein Vergleich eines derartigen Legierungsbades mit reinen Palladiumbädern ist jedoch nicht möglich, da die Mitabscheidung anderer Metalle grundsätzlich anderen Bedingungen genügt und auch im Hinblick auf den Glanz und die Rissfreiheit zu anderen Ergebnissen führt.From SU-A-454 280 a galvanic bath for the deposition of palladium / platinum alloys is known which contains H 2 PtC1 6 6H20, PdCI2.2H20, (NH 4 ) 2 HP0 4 and Na 2 HP04 12H20 in aqueous solution. However, a comparison of such an alloy bath with pure palladium baths is not possible, since the co-deposition of other metals basically satisfies other conditions and also leads to different results with regard to the gloss and freedom from cracks.
Aus einer älteren, nicht veröffentlichten europäischen Patentanmeldung entsprechend der EP-A-0 076 523 geht ein schnellabscheidendes galvanisches Palladiumbad zum Abscheiden von glänzenden, rissfreien Palladiumschichten hervor, welches eine ammoniakalische Lösung eines Palladiumtetraaminokomplexions und einem Phosphatanion oder Carbonatanion enthält. Dieses Bad soll frei von quaternierten Pyridinium-Glanzzusätzen sein. Beim Ansatz des Bades wird die Zugabe von Palladium in Form von Palladiumtetraaminchlorid bevorzugt.An older, unpublished European patent application corresponding to EP-A-0 076 523 discloses a quick-depositing galvanic palladium bath for depositing shiny, crack-free palladium layers, which contains an ammoniacal solution of a palladium tetraamino complex and a phosphate anion or carbonate anion. This bath should be free of quaternized pyridinium additives. When preparing the bath, the addition of palladium in the form of palladium tetraamine chloride is preferred.
Der Erfindung liegt die Aufgabe zugrunde, ein Palladiumbad zum Abscheiden von glänzenden, rissfreien Palladiumschichten zu schaffen, das nur geringe Konfektionierungskosten erfordert und hohe Abscheideraten von mindestens 10 bis 25 µm/min erlaubt bei 100%iger Stromausbeute. Ferner soll auf jeglichen Glanzzusatz verzichtet werden können und eine hohe Badstabilität gewährleistet sein. Zur Erzielung einer dauerhaften Korrosionsbeständigkeit soll die abgeschiedene Schicht keinen Schwefel enthalten.The invention has for its object to provide a palladium bath for the deposition of shiny, crack-free palladium layers, which only requires low manufacturing costs and high deposition rates of at least 10 to 25 microns / min with a 100% current yield. Furthermore, it should be possible to dispense with any addition of gloss and a high bath stability should be guaranteed. In order to achieve permanent corrosion resistance, the deposited layer should not contain any sulfur.
Diese Aufgabe wird bei einem Verfahren zur Herstellung eines gattungsgemässen Bades dadurch gelöst, dass in bis auf 90°C aufgeheiztes, destilliertes Wasser nacheinander Phosphorsäure, Ammoniak bis zur Neutralisation der Phosphorsäure und Palladium in Form von Palladiumchlorid zugegeben werden, dann der Gebrauchs-pH-Wert mittels Ammoniak oder Phosphorsäure eingestellt und das Bad bis zum Endvolumen mit destilliertem Wasser ergänzt wird.This object is achieved in a process for producing a generic bath by adding phosphoric acid, ammonia to the neutralization of the phosphoric acid and palladium in the form of palladium chloride in succession in distilled water heated to 90 ° C., then the use pH adjusted with ammonia or phosphoric acid and the bath is replenished to the final volume with distilled water.
Als besonders vorteilhaft hat es sich erwiesen, wenn zu 600 ml bis auf 90°C aufgeheizten destillierten Wasser 10 bis 100 ml Phosphorsäure einer Dichte von 1,71, 25%ige Ammoniaklösung bis zur Neutralisation der Phosphorsäure und 5 bis 40 g Palladium in Form von Palladiumchlorid zugegeben werden, dann der Gebrauchs-pH-Wert mittels Ammoniak oder Phosphorsäure auf 6,5 bis 8,5 eingestellt wird und das Bad auf 1 Liter mit destilliertem Wasser ergänzt wird.It has proven particularly advantageous if 10 to 100 ml of phosphoric acid with a density of 1.71, 25% strength ammonia solution to neutralize the phosphoric acid and 5 to 40 g of palladium in the form of to 600 ml of distilled water heated to 90 ° C. Palladium chloride are added, then the use pH is adjusted to 6.5 to 8.5 using ammonia or phosphoric acid and the bath is made up to 1 liter with distilled water.
Das erfindungsgemässe Palladiumbad ist auch deshalb besonders vorteilhaft, weil es auf der Basis von Palladiumchlorid angesetzt ist, einem der billigsten Palladiumsalze.The palladium bath according to the invention is also particularly advantageous because it is based on palladium chloride, one of the cheapest palladium salts.
Das Verfahren zum galvanischen Abscheiden von glänzenden, rissfreien Palladiumschichten unter Verwendung eines solchen Bades ist dadurch gekennzeichnet, dass bei Badtemperaturen im Bereich von 20 bis 80°C, mit Stromdichten im Bereich von 40 bis 180 A/dm2 und mit einer Elektrolytbewegung gearbeitet wird, welche durch eine rotierende Scheibenelektrode mit einem Aussendurchmesser von 10 mm und einem Scheibendurchmesser von 2 mm bei einer Umdrehungsgeschwindigkeit von 3600 bis 10 000 UpM definiert ist.The process for the galvanic deposition of shiny, crack-free palladium layers using such a bath is characterized in that the bath temperatures in the range from 20 to 80 ° C., with current densities in the range from 40 to 180 A / dm 2 and with an electrolyte movement, which is defined by a rotating disk electrode with an outer diameter of 10 mm and a disk diameter of 2 mm at a rotational speed of 3600 to 10,000 rpm.
Bei einer im Durchlaufverfahren arbeitenden Sprühzellenanordnung wird vorteilhaft mit einer Elektrolytbewegung gearbeitet, die entsteht, wenn durch jede Düse mit einem Düsendurchmesser von 2 mm eine Elektrolytmenge von 1 bis 15 ml/ sec fliesst. Eine für diese Zwecke brauchbare Sprühzellenanordnung ist beispielsweise in der älteren Patentanmeldung entsprechend der DE-A-31 08 358 beschrieben.In the case of a spray cell arrangement operating in a continuous process, an electrolyte movement is advantageously used, which occurs when each nozzle has a nozzle diameter an electrolyte amount of 1 to 15 ml / sec flows from 2 mm. A spray cell arrangement that can be used for these purposes is described, for example, in the older patent application corresponding to DE-A-31 08 358.
Es hat sich gezeigt, dass auf diese Weise eine vorzügliche Qualität der Schichten entsteht. Sogar bei einer Vergrösserung bis 15000 konnten keine Risse nachgewiesen werden. Bei einem bevorzugten pH-Wert von 7,3 ist der Gehalt an freiem Ammoniak so gering, dass keine Geruchsbelastung und keine Korrosion des behandelten Gutes sowie der Anlage zu befürchten ist. Ausserdem ist die pH-Stabilität besser als bei den anderen bekannten alkalischen Bädern. Im erfindungsgemässen Bad neigt das Palladium nicht zur Selbstreduktion, so dass eine hohe Stabilität des Bades gegeben ist.It has been shown that the layers are of excellent quality. Even with an enlargement up to 15000, no cracks could be detected. At a preferred pH value of 7.3, the free ammonia content is so low that there is no fear of odor and no corrosion of the treated material and the system. In addition, the pH stability is better than with the other known alkaline baths. In the bath according to the invention the palladium does not tend to self-reduction, so that the bath is highly stable.
Das erfindungsgemässe Palladiumbad wird mit Vorteil in kontinuierlich arbeitenden Galvanisieranlagen eingesetzt, ggf. auch für die partielle Beschichtung von Bauteilen, wie z.B. Steckverbindern oder dgl., die miteinander zu einem Band verbunden sind. Vorzugsweise wird die erhöhte Elektrolytbewegung durch Spritzen des Elektrolyten auf das Werkstück mit Hilfe von Düsen erzielt. Hierbei bilden die Düsen die Anode, während das Band kathodisch kontaktiert ist. Vorzugsweise sind bei einer im Durchlaufverfahren arbeitenden Sprühzellenanordnung die freien Enden der mit Elektrolyt besprühten Teile durch eine Anordnung einer Rinne oder dgl. ständig mit Elektrolyt benetzt. Durch die ständige Benetzung der unteren Enden der zu beschichtenden Teile wird eine Verarmung des Elektrolyten an Ionen verhindert, was somit zum Verbrennen bzw. Abscheiden von nichtglänzenden Schichten führen würde. Anstelle einer Rinne genügt meist auch die Anordnung einer Schiene unter dem Bad, derart, dass sich ein geringer Elektrolytstau auf der Schiene bildet, in dem die Enden der zum Band vereinigten Teile eintauchen.The palladium bath according to the invention is advantageously used in continuously operating electroplating systems, possibly also for the partial coating of components, such as Connectors or the like., Which are connected together to form a band. The increased electrolyte movement is preferably achieved by spraying the electrolyte onto the workpiece with the aid of nozzles. Here, the nozzles form the anode, while the strip is contacted cathodically. In a spray cell arrangement operating in a continuous process, the free ends of the parts sprayed with electrolyte are preferably continuously wetted with electrolyte by an arrangement of a channel or the like. The permanent wetting of the lower ends of the parts to be coated prevents depletion of the electrolyte by ions, which would thus lead to the burning or deposition of non-glossy layers. Instead of a channel, it is usually sufficient to arrange a rail under the bath in such a way that a small amount of electrolyte builds up on the rail, in which the ends of the parts combined to form the strip are immersed.
Durch sinnvolles Abstimmen von Anoden-Kathoden-Abstand, Elektrolytbewegung und Stromdichte können glänzende, porenfreie Schichten leicht erzielt werden. Auch die Badführung ist relativ einfach, weil lediglich der pH-Wert und der Palladiumgehalt kontrolliert und geregelt zu werden brauchen.By carefully coordinating the anode-cathode distance, electrolyte movement and current density, shiny, non-porous layers can be easily achieved. Bath management is also relatively easy because only the pH value and the palladium content need to be checked and regulated.
Um die Erfindung weiter zu veranschaulichen, werden nachstehend einige spezielle Beispiele beschrieben. Die angegebenen Mengen der einzelnen Bestandteile beziehen sich jeweils auf einen Liter wässrige Lösung; die einzelnen Bestandteile sind: Phosphorsäure (H3P04) d = 1,71, Ammoniak (NH40H) 25%, Palladiumchlorid (PdC12) 99,9% und destilliertes Wasser.To further illustrate the invention, some specific examples are described below. The stated amounts of the individual components each relate to one liter of aqueous solution; the individual components are: phosphoric acid (H 3 P0 4 ) d = 1.71, ammonia (NH 4 0H) 25%, palladium chloride (PdC1 2 ) 99.9% and distilled water.
Zur Definition der Elektrolytbewegung wurde entweder eine rotierende Scheibenelektrode mit einem Durchmesser von 10 mm und einem Scheibendurchmesser von 2 mm oder eine Sprühzellenanordnung mit einem Düsendurchmesser von 2 mm verwendet. Eine solche ist beispielsweise in der älteren Patentanmeldung entsprechend der DE-A-31 08 358 beschrieben. Bei allen Beispielen beträgt die Stromausbeute 100% und werden glänzende bis seidenmattglänzende, rissfreie Schichten erzielt.Either a rotating disc electrode with a diameter of 10 mm and a disc diameter of 2 mm or a spray cell arrangement with a nozzle diameter of 2 mm was used to define the electrolyte movement. Such is described for example in the older patent application according to DE-A-31 08 358. In all examples, the current efficiency is 100% and glossy to satin matt, crack-free layers are achieved.
600 ml destilliertes Wasser werden auf 60 bis 65°C erhitzt und nacheinander zugegeben:
- 20 ml Phosphorsäure, 220 ml Ammoniak und 30 g Palladium als Palladiumchlorid, wobei der pH-Wert auf 7,3 mittels Ammoniak oder Phosphorsäure eingestellt wird, und das Bad mit destilliertem Wasser auf ein Liter ergänzt wird.
- 20 ml of phosphoric acid, 220 ml of ammonia and 30 g of palladium as palladium chloride, the pH being adjusted to 7.3 using ammonia or phosphoric acid, and the bath being made up to one liter with distilled water.
Das Bad ergibt bei einer Temperatur von 60°C und einer Stromdichte von 75 A/dm2 glänzende und rissfreie Schichten, wenn die rotierende Scheibenelektrode mit 5000 upM betrieben wird.The bath produces glossy and crack-free layers at a temperature of 60 ° C and a current density of 75 A / dm 2 when the rotating disk electrode is operated at 5000 rpm.
600 ml destilliertes Wasser werden auf 60 bis 65°C erhitzt und nacheinander zugegeben:
- 20 ml Phosphorsäure, 220 ml Ammoniak und 30 g Palladium als Palladiumchlorid, wobei der pH-Wert auf 7,3 mittels Ammoniak oder Phosphorsäure eingestellt wird, und das Bad mit destilliertem Wasser auf ein Liter ergänzt wird.
- 20 ml of phosphoric acid, 220 ml of ammonia and 30 g of palladium as palladium chloride, the pH being adjusted to 7.3 using ammonia or phosphoric acid, and the bath being made up to one liter with distilled water.
Das Bad ergibt bei einer Temperatur von 65 °C und einer Elektrolytbewegung über Spritzdüsen bei einer Stromdichte von 140 A/dm2 und bei einer Elektrolytmenge von 2,8 ml/sec je Düsen glänzende und rissfreie Schichten.The bath produces glossy and crack-free layers at a temperature of 65 ° C and an electrolyte movement over spray nozzles at a current density of 140 A / dm 2 and with an electrolyte quantity of 2.8 ml / sec per nozzle.
600 ml destilliertes Wasser werden auf 60 bis 65 °C erhitzt und nacheinander zugegeben:
- 20 ml Phosphorsäure, 220 ml Ammoniak und 30 g Palladium als Palladiumchlorid, wobei der pH-Wert auf 7,3 mittels Ammoniak oder Phosphorsäure eingestellt wird und das Bad mit destilliertem Wasser auf ein Liter ergänzt wird.
- 20 ml of phosphoric acid, 220 ml of ammonia and 30 g of palladium as palladium chloride, the pH being adjusted to 7.3 using ammonia or phosphoric acid and the bath being made up to one liter with distilled water.
Das Bad ergibt bei einer Temperatur von 60°C und einer Stromdichte von 60 A/dm2 und einer Elektrolytbewegung über Spritzdüsen bei einer Elektrolytmenge von 1,7 ml/sec und je Düse glänzende und rissfreie Palladiumschichten.The bath gives a shiny and crack-free palladium layer at a temperature of 60 ° C and a current density of 60 A / dm 2 and an electrolyte movement over spray nozzles with an amount of electrolyte of 1.7 ml / sec and per nozzle.
600 ml destilliertes Wasser werden auf 60 bis 65°C erhitzt und nacheinander zugegeben:
- 20 ml Phosphorsäure, 220 ml Ammoniak und 10 g Palladium als Palladiumchlorid, wobei der pH-Wert auf 7,8 mittels Ammoniak oder Phosphorsäure eingestellt wird, und das Bad mit destilliertem Wasser auf ein Liter ergänzt wird.
- 20 ml of phosphoric acid, 220 ml of ammonia and 10 g of palladium as palladium chloride, the pH being adjusted to 7.8 using ammonia or phosphoric acid, and the bath made up to one liter with distilled water.
Bei einer Temperatur von 70°C und einer Stromdichte von 40 A/dm2 ergeben sich seidenmatte bis matte, rissfreie Schichten, wenn die rotierende Scheibenelektrode mit 10 000 UpM betrieben wird.At a temperature of 70 ° C and a current density of 40 A / dm 2 , silk-matt to matt, crack-free layers result when the rotating disc electrode is operated at 10,000 rpm.
600 ml destilliertes Wasser werden auf 60 bis 65°C erhitzt und nacheinander zugegeben:
- 20 ml Phosphorsäure, 150 ml Ammoniak und 10 g Palladium als Palladiumchlorid, wobei der pH-Wert auf 7,3 mittels Ammoniak und Phosphorsäure eingestellt wird, und das Bad mit destilliertem Wasser auf ein Liter ergänzt wird.
- 20 ml of phosphoric acid, 150 ml of ammonia and 10 g of palladium as palladium chloride, the pH being 7.3 using ammonia and phosphorus acid is adjusted, and the bath is made up to one liter with distilled water.
Bei einer Temperatur von 65°C und einer Stromdichte von 10 A/dm2 ergeben sich glänzende und rissfreie Palladiumschichten, wenn die rotierende Scheibenelektrode mit 4000 UpM betrieben wird.At a temperature of 65 ° C and a current density of 10 A / dm 2 , shiny and crack-free palladium layers result when the rotating disc electrode is operated at 4000 rpm.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3148788 | 1981-12-09 | ||
| DE3148788A DE3148788C2 (en) | 1981-12-09 | 1981-12-09 | Aqueous bath and process for the galvanic deposition of shiny and crack-free palladium layers and process for the production of the bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0081788A1 EP0081788A1 (en) | 1983-06-22 |
| EP0081788B1 true EP0081788B1 (en) | 1987-09-16 |
Family
ID=6148299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82111270A Expired EP0081788B1 (en) | 1981-12-09 | 1982-12-06 | Non-additive fast depositing galvanic palladium bath |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4451336A (en) |
| EP (1) | EP0081788B1 (en) |
| JP (1) | JPS58107492A (en) |
| DE (2) | DE3148788C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622110A (en) * | 1981-10-06 | 1986-11-11 | Learonal, Inc. | Palladium plating |
| US4545868A (en) * | 1981-10-06 | 1985-10-08 | Learonal, Inc. | Palladium plating |
| DE3443420A1 (en) * | 1984-11-26 | 1986-05-28 | Siemens AG, 1000 Berlin und 8000 München | Electroplating bath for the rapid deposition of palladium alloys |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0076523A1 (en) * | 1981-10-06 | 1983-04-13 | LeaRonal, Inc. | A method of high speed electroplating palladium and palladium electroplating solution therefor |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US330149A (en) * | 1885-11-10 | Gaston pilbt and clement cabby | ||
| SU454280A1 (en) * | 1972-10-17 | 1974-12-25 | Киевский Ордена Ленина Политехнический Институт Им.50-Летия Великой Октябрьской Социалистической Революции | Electrolyte to precipitate platinum-palladium alloy |
| US3925170A (en) * | 1974-01-23 | 1975-12-09 | American Chem & Refining Co | Method and composition for producing bright palladium electrodepositions |
| US3972787A (en) * | 1974-06-14 | 1976-08-03 | Lea-Ronal, Inc. | Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners |
| DE2551988A1 (en) * | 1975-11-17 | 1977-05-26 | Schering Ag | PROCESS FOR THE SELECTIVE GALVANIC DEPOSITION OF METALS AND DEVICE FOR CARRYING OUT THE PROCESS |
| DE2657925A1 (en) * | 1976-12-21 | 1978-06-22 | Siemens Ag | AMMONIA-FREE, AQUATIC BATH FOR GALVANIC DEPOSITION OF PALLADIUM OR. PALLADIUM ALLOYS |
| FR2403399A1 (en) * | 1977-09-19 | 1979-04-13 | Oxy Metal Industries Corp | SHINY PALLADIUM ELECTROLYTIC COATING BATHS |
| GB2028870B (en) * | 1978-07-26 | 1982-11-03 | Effluent Treatment Ltd | Electrolysis method and apparatus for treating solutions |
| NL7812196A (en) * | 1978-12-15 | 1980-06-17 | Galentan Ag | DEVICE FOR ELECTROLYTIC APPLICATION OF METAL COATINGS. |
| DE2939920C2 (en) * | 1979-10-02 | 1982-09-23 | W.C. Heraeus Gmbh, 6450 Hanau | Use of an amine in a bath for the electrodeposition of palladium |
| US4392921A (en) * | 1980-12-17 | 1983-07-12 | Occidental Chemical Corporation | Composition and process for electroplating white palladium |
| DE3108358C2 (en) * | 1981-03-05 | 1985-08-29 | Siemens AG, 1000 Berlin und 8000 München | Device for the partial electroplating of electrically conductive bands, strips or the like. Parts combined in a continuous process |
-
1981
- 1981-12-09 DE DE3148788A patent/DE3148788C2/en not_active Expired
-
1982
- 1982-11-19 US US06/443,011 patent/US4451336A/en not_active Expired - Fee Related
- 1982-12-06 DE DE8282111270T patent/DE3277311D1/en not_active Expired
- 1982-12-06 EP EP82111270A patent/EP0081788B1/en not_active Expired
- 1982-12-06 JP JP57214552A patent/JPS58107492A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0076523A1 (en) * | 1981-10-06 | 1983-04-13 | LeaRonal, Inc. | A method of high speed electroplating palladium and palladium electroplating solution therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0341556B2 (en) | 1991-06-24 |
| JPS58107492A (en) | 1983-06-27 |
| DE3148788A1 (en) | 1983-07-21 |
| US4451336A (en) | 1984-05-29 |
| DE3148788C2 (en) | 1986-08-21 |
| DE3277311D1 (en) | 1987-10-22 |
| EP0081788A1 (en) | 1983-06-22 |
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