EP1244827B1 - Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same - Google Patents

Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same Download PDF

Info

Publication number
EP1244827B1
EP1244827B1 EP00990767A EP00990767A EP1244827B1 EP 1244827 B1 EP1244827 B1 EP 1244827B1 EP 00990767 A EP00990767 A EP 00990767A EP 00990767 A EP00990767 A EP 00990767A EP 1244827 B1 EP1244827 B1 EP 1244827B1
Authority
EP
European Patent Office
Prior art keywords
sulfate
whitening agent
compound
atoms
rhodium
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 - Lifetime
Application number
EP00990767A
Other languages
German (de)
French (fr)
Other versions
EP1244827A1 (en
Inventor
Uwe Manz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore Galvanotechnik GmbH
Original Assignee
Umicore Galvanotechnik GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Publication of EP1244827A1 publication Critical patent/EP1244827A1/en
Application granted granted Critical
Publication of EP1244827B1 publication Critical patent/EP1244827B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/236—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids specially adapted for aerating or carbonating beverages
    • B01F23/2361—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids specially adapted for aerating or carbonating beverages within small containers, e.g. within bottles
    • B01F23/23611—Portable appliances comprising a gas cartridge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
    • B01F23/2376—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media characterised by the gas being introduced
    • B01F23/23761—Aerating, i.e. introducing oxygen containing gas in liquids

Definitions

  • the invention relates to a galvanic bath for the deposition of high-gloss white rhodium coatings and a whitening agent for this purpose.
  • Rhodium coatings are e.g. deposited as a tarnish protection on silver and should have high gloss and the brightest possible, white color, similar to that of silver.
  • electrolytes are composed on the basis of rhodium sulfate, phosphate or sulfamate, sulfuric acid, phosphoric acid, alkanesulfonic acid or amidosulfuric acid.
  • these usually contain certain organic compounds as brightener additives.
  • Typical, very frequently used brightener additives are, as described, for example, in EP 0 056 590, the compounds pyridine-3-sulfonic acid and naphthalene-trisulfonic acid.
  • a wetting agent and / or a phosphonic acid may additionally be contained in such a bath.
  • a disadvantage of the existing systems lies in the fact that the very bright, white color of silver is not achieved and that with increasing layer thickness increasingly hazy deposition occurs.
  • the whiteners according to formula I are selected compounds from the class of alkyl sulfates (first embodiment) or from the class of alkyl sulfates or alkyl sulfonates (second embodiment).
  • R is a straight- or branched-chain or cyclic alkyl group having up to 20 C atoms.
  • These compounds are sufficiently water-soluble and compatible with the electroplating bath.
  • the compounds have surfactant properties wherein the corresponding effect is reduced to less than 4 for a total number of C atoms, and generally no sufficient solubility is given for a total number of C atoms greater than 20.
  • Preferred brightener additives are compounds of the formula I in which R represents straight-chain or branched-chain or cyclic alkyl groups having 5 to 12 C atoms and in particular branched-chain alkyl groups having 6 to 10 C atoms.
  • Branched-chain compounds are particularly useful in processes and equipment where there is a high degree of foaming, e.g. in air-agitated electrolytes, in drum processing, in high-speed separation equipment (spray equipment) and in selective deposition equipment, e.g. Diving cells.
  • Typical whiteners according to the invention are Hexyl sulfate (first and second embodiments) Hexylsulfonate (second embodiment) 2-ethylhexyl sulfate (first and second embodiments) Heptyl sulfate (first and second embodiments) Octyl sulfate (first and second embodiments) Octylsulfonate (second embodiment) Decyl sulfate (first and second embodiments) Decyl sulfonate (second embodiment) Dodecyl sulfate (first and second embodiments) 7-ethyl-2-methyl-4-undecanol sulfate (first and second embodiments) Cyclohexylsulfate (First and Second Embodiments) and their isomers.
  • the application of the whitening agent according to the invention in baths for the electrodeposition of rhodium layers is expediently carried out in a concentration range from 0.01 to 10 g / l.
  • Baths according to the invention which contain the whitening agent according to formula I in a concentration of 0.1 to 6 g / l are particularly advantageous.
  • the galvanic rhodium baths according to the invention typically contain about 0.1-20 g / l Rhodium as rhodium sulfate, phosphate, alkanesulfonate or sulfamate, 10-200 g / l Sulfuric acid, phosphoric acid, amidosulfuric acid or mixtures of these acids, 0 - 5 g / l Pyridine-3-sulfonic acid as brightener, 0.01-2 g / l wetting agent 0.1-10 g / l Compound of the formula I as a whitening agent according to the invention.
  • the baths are usually operated at current densities of 0.5-5 A / dm 2 (rack operation) and temperatures up to 60 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Chemically Coating (AREA)
  • Physical Vapour Deposition (AREA)
  • Paper (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention concerns a bath for the electrochemical deposition of high-gloss white rhodium coatings and a whitening agent for the same. The brightness or degree of whiteness of the deposited coatings is significantly increased by means of compounds having the formula R-SOm-H, wherein m is the numbers 3 or 4 and R is a straight-chain or branched chain or cyclic alkyl group having up to 20 C atoms, as a whitening agent. The thickness of the coating that can be deposited without a bloom is also significantly increased.

Description

Die Erfindung betrifft ein galvanisches Bad für die Abscheidung von hochglänzenden weißen Rhodiumüberzügen und einen Weißmacher hierfür.The invention relates to a galvanic bath for the deposition of high-gloss white rhodium coatings and a whitening agent for this purpose.

Rhodiumüberzüge werden z.B. als Anlaufschutz auf Silber abgeschieden und sollen Hochglanz und einen möglichst hellen, weißen Farbton, ähnlich dem von Silber, aufweisen.Rhodium coatings are e.g. deposited as a tarnish protection on silver and should have high gloss and the brightest possible, white color, similar to that of silver.

Handelsübliche Elektrolyte sind zusammengesetzt auf der Basis Rhodiumsulfat, -phosphat oder -sulfamat, Schwefelsäure, Phosphorsäure, Alkansulfonsäure oder Amidoschwefelsäure.Commercially available electrolytes are composed on the basis of rhodium sulfate, phosphate or sulfamate, sulfuric acid, phosphoric acid, alkanesulfonic acid or amidosulfuric acid.

Damit aus solchen Bädern schleierfreie Überzüge abgeschieden werden enthalten diese üblicherweise bestimmte organische Verbindungen als Glanzzusätze. Typische, sehr häufig eingesetzte Glanzzusätze sind, wie beispielsweise in EP 0 056 590 beschrieben, die Verbindungen Pyridin-3-sulfonsäure und Naphthalin-tri-sulfonsäure. Um das Festhaften von Wasserstoff an der Kathode zu verhindern kann in einem derartigen Bad zusätzlich ein Netzmittel und/oder eine Phosphonsäure enthalten sein.So that fog-free coatings are deposited from such baths, these usually contain certain organic compounds as brightener additives. Typical, very frequently used brightener additives are, as described, for example, in EP 0 056 590, the compounds pyridine-3-sulfonic acid and naphthalene-trisulfonic acid. In order to prevent the sticking of hydrogen to the cathode, a wetting agent and / or a phosphonic acid may additionally be contained in such a bath.

Ein Nachteil der bestehenden Systeme liegt nun darin, daß die sehr helle, weisse Farbe von Silber nicht erreicht wird und daß mit ansteigender Schichtstärke verstärkt schleierige Abscheidung auftritt.A disadvantage of the existing systems lies in the fact that the very bright, white color of silver is not achieved and that with increasing layer thickness increasingly hazy deposition occurs.

Es war daher Aufgabe der Erfindung, eine Optimierung derartiger Rhodiumbäder in der Hinsicht vorzunehmen, daß sich die Überzüge signifikant weißer abscheiden lassen und die Helligkeit bzw. der Weißheitsgrad dem Silber deutlich weiter angenähert werden. Außerdem sollte die schleierfrei abscheidbare Schichtdicke erhöht werden. Überraschend wurde nun gefunden, daß dies erreicht werden kann, wenn derartigen Bäder zur Abscheidung von Rhodiumschichten als Weißmacher mindestens eine Verbindung der allgemeinen Formel I

        R - SO m -H     (I)

zugefügt wird, worin

m
die Zahlen 3 oder 4 und
R
eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen,
ist.It was therefore an object of the invention to carry out an optimization of such rhodium baths in the sense that the coatings can be deposited significantly whiter white and the brightness or whiteness of the silver are approached significantly further. In addition, the film thickness which can be deposited without haze should be increased. Surprisingly, it has now been found that this can be achieved if such baths for the deposition of rhodium layers as whiteners at least one compound of the general formula I.

R - SO m -H (I)

is added, in which
m
the numbers 3 or 4 and
R
a straight- or branched-chain or cyclic alkyl group having up to 20 carbon atoms,
is.

Gegenstand einer ersten Ausführungsform der Erfindung ist somit ein Bad zur galvanischen Abscheidung von hochglänzenden weißen Rhodiumschichten, enthaltend Rhodium in gelöster Form, gegebenenfalls mit einer organische Verbindung als Glanzzusatz, wobei das Bad als Weißmacher mindestens eine Verbindung der allgemeinen Formel

        R - SO m -H     (I)

enthält, worin

m
die Zahl 4 und
R
eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen,
ist.The subject of a first embodiment of the invention is thus a bath for the electrodeposition of high-gloss white rhodium layers containing rhodium in dissolved form, optionally with an organic compound as brightener additive, wherein the bath as whitener at least one compound of the general formula

R - SO m -H (I)

contains, in which
m
the number 4 and
R
a straight- or branched-chain or cyclic alkyl group having up to 20 carbon atoms,
is.

Die erste Ausführungsform betrifft weiterhin die Verwendung von Verbindungen der allgemeinen Formel

        R-SO m -H     (I)

worin

m
die Zahl 4 und
R
eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen, ist
als Weißmacher in Bädern zur galvanischen Abscheidung von glänzenden Rhodiumschichten, enthaltend Rhodium in gelöster Form, sowie gegebenenfalls eine organische Verbindung als Glanzzusatz und ein Netzmittel.The first embodiment further relates to the use of compounds of the general formula

R-SO m -H (I)

wherein
m
the number 4 and
R
a straight- or branched-chain or cyclic alkyl group having up to 20 C atoms
as a whitener in baths for the electrodeposition of shiny rhodium layers, containing rhodium in dissolved form, and optionally an organic compound as a brightener and a wetting agent.

Gegenstand einer zweiten Ausführungsform der Erfindung ist ein Bad zur galvanischen Abscheidung von hochglänzenden weißen Rhodiumschichten, enthaltend Rhodium in gelöster Form mit einer organischen Verbindung als Glanzzusatz, wobei die organische Verbindung aus Pyridin-3-sulfonsäure und Naphthalin-tri-sulfonsäure ausgewählt ist, wobei
das Bad als Weißmacher mindestens eine Verbindung der allgemeinen Formel

        R - SO m -H     (I)

enthält, worin

m
die Zahlen 3 oder 4 und
R
eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen,
ist.The subject of a second embodiment of the invention is a bath for the electrodeposition of high-gloss white rhodium layers containing rhodium in dissolved form with an organic compound as brightener, wherein the organic compound of pyridine-3-sulfonic acid and naphthalene-trisulfonic acid is selected
the bath as whitener at least one compound of the general formula

R - SO m -H (I)

contains, in which
m
the numbers 3 or 4 and
R
a straight- or branched-chain or cyclic alkyl group having up to 20 carbon atoms,
is.

Die zweite Ausführungsform betrifft weiterhin die Verwendung von Verbindungen der allgemeinen Formel

        R-SO m -H     (I)

worin

m
die Zahlen 3 oder 4 und
R
eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen, ist
als Weißmacher in Bädern zur galvanischen Abscheidung von glänzenden Rhodiumschichten, enthaltend Rhodium in gelöster Form, sowie eine organische Verbindung als Glanzzusatz und gegebenenfalls ein Netzmittel, wobei die organische Verbindung aus Pyridin-3-sulfonsäure und Naphthalin-tri-sulfonsäure ausgewählt ist.The second embodiment further relates to the use of compounds of the general formula

R-SO m -H (I)

wherein
m
the numbers 3 or 4 and
R
a straight- or branched-chain or cyclic alkyl group having up to 20 C atoms
as a whitener in baths for the electrodeposition of bright rhodium layers containing rhodium in dissolved form, and an organic compound as a brightener and optionally a wetting agent, wherein the organic compound of pyridine-3-sulfonic acid and naphthalene-trisulfonic acid is selected.

Die Weißmacher gemäß Formel I sind ausgewählte Verbindungen aus der klasse der Alkylsulfate (erste Ausführungsform) bzw aus der Klasse der Alkylsulfate oder Alkylsulfonate (zweite Ausführungsform). In Formel I bedeutet R eine gerad- oder verzweigtkettige oder cyclische Alkylgruppe mit bis zu 20 C-Atomen.The whiteners according to formula I are selected compounds from the class of alkyl sulfates (first embodiment) or from the class of alkyl sulfates or alkyl sulfonates (second embodiment). In formula I, R is a straight- or branched-chain or cyclic alkyl group having up to 20 C atoms.

Die Verbindungen der Formel I sind an sich bekannt und ohne weiteres verfügbar.The compounds of the formula I are known per se and readily available.

Diese Verbindungen sind ausreichend wasserlöslich und mit dem Galvanikbad kompatibel. Die Verbindungen haben Tensideigenschaften, wobei die entsprechende Wirkung bei einer Gesamtzahl an C-Atomen weniger als 4 verringert ist, und bei einer Gesamtzahl an C-Atomen von mehr als 20 im allgemeinen keine ausreichende Löslichkeit mehr gegeben ist.These compounds are sufficiently water-soluble and compatible with the electroplating bath. The compounds have surfactant properties wherein the corresponding effect is reduced to less than 4 for a total number of C atoms, and generally no sufficient solubility is given for a total number of C atoms greater than 20.

Bevorzugte Glanzzusätze sind Verbindungen der Formel I in denen. R für gerad- oder verzweigtkettige oder cyclische Alkylgruppen mit 5 bis 12 C-Atomen und insbesondere für verzweigtkettige Alkylgruppen mit 6 bis 10 C-Atomen steht.Preferred brightener additives are compounds of the formula I in which R represents straight-chain or branched-chain or cyclic alkyl groups having 5 to 12 C atoms and in particular branched-chain alkyl groups having 6 to 10 C atoms.

Verzweigtkettige Verbindungen eignen sich aufgrund der nur gering ausgeprägten Schaumneigung besonders in Verfahren und Anlagen, bei denen eine starke Schaumbildung stört, z.B. in luftbewegten Elektrolyten, bei der Trommelbearbeitung, in Anlagen zur Hochgeschwindigkeitsabscheidung (Spritzanlagen) und in Anlagen zur selektiven Abscheidung, wie z.B. Tauchzellen.Branched-chain compounds are particularly useful in processes and equipment where there is a high degree of foaming, e.g. in air-agitated electrolytes, in drum processing, in high-speed separation equipment (spray equipment) and in selective deposition equipment, e.g. Diving cells.

Typische erfindungsgemäße Weißmacher sind
Hexylsulfat (erste und zweite Ausführungsform)
Hexylsulfonat (zweite Ausführungsform)
2-Ethylhexylsulfat (erste und zweite Ausführungsform)
Heptylsulfat (erste und zweite Ausführungsform)
Octylsulfat (erste und zweite Ausführungsform)
Octylsulfonat (zweite Ausführungsform)
Decylsulfat (erste und zweite Ausführungsform)
Decylsulfonat (zweite Ausführungsform)
Dodecylsulfat (erste und zweite Ausführungsform)
7-Ethyl-2-methyl-4-undecanolsulfat (erste und zweite Ausführungsform)
Cyclohexylsulfat (erste und zweite Ausführungsform)
und deren Isomere.Typical whiteners according to the invention are
Hexyl sulfate (first and second embodiments)
Hexylsulfonate (second embodiment)
2-ethylhexyl sulfate (first and second embodiments)
Heptyl sulfate (first and second embodiments)
Octyl sulfate (first and second embodiments)
Octylsulfonate (second embodiment)
Decyl sulfate (first and second embodiments)
Decyl sulfonate (second embodiment)
Dodecyl sulfate (first and second embodiments)
7-ethyl-2-methyl-4-undecanol sulfate (first and second embodiments)
Cyclohexylsulfate (First and Second Embodiments)
and their isomers.

Diese Verbindungen können auch in Form ihrer Salze vorliegen.These compounds may also be present in the form of their salts.

Die Anwendung des erfindungsgemäßen Weißmachers in Bädern zur galvanischen Abscheidung von Rhodiumschichten erfolgt zweckmäßigerweise in einem Konzentrationsbereich von 0,01 bis 10 g/l. Besonders vorteilhaft sind erfindungsgemäße Bäder, die den Weißmacher gemäß Formel I in einer Konzentration von 0,1 bis 6 g/l enthalten.The application of the whitening agent according to the invention in baths for the electrodeposition of rhodium layers is expediently carried out in a concentration range from 0.01 to 10 g / l. Baths according to the invention which contain the whitening agent according to formula I in a concentration of 0.1 to 6 g / l are particularly advantageous.

Durch den erfindungsgemäßen Einsatz der Verbindungen der Formel I als Weißmacher in galvanischen Rhodiumbädern von ansonsten üblicher Zusammensetzung wird in unerwarteter Weise die Helligkeit bzw. der Weißheitsgrad der abgeschiedenen Überzüge signifikant gesteigert. Ebenso wird die maximale Schichtdicke, bei welcher noch hochglänzend abgeschieden wird, deutlich erhöht.The use according to the invention of the compounds of the formula I as whiteners in galvanic rhodium baths of otherwise customary composition significantly increases the brightness or whiteness of the deposited coatings in an unexpected manner. Likewise, the maximum layer thickness, at which high gloss is deposited, is significantly increased.

Zur Herstellung der erfindungsgemäßen Rhodiumbäder kann von vielen gängigen und handelsüblichen galvanischen Rhodiumbädern ausgegangen werden, in dem diesen die entsprechende Menge an Verbindung der Formel I zugegeben wird.To prepare the rhodium baths according to the invention, one can start from many common and commercially available galvanic rhodium baths, in which the corresponding amount of compound of the formula I is added.

Die erfindungsgemäßen galvanischen Rhodiumbäder enthalten typischerweise etwa 0,1 - 20 g/l Rhodium als Rhodiumsulfat, -phosphat, -alkansulfonat oder -sulfamat, 10 - 200 g/l Schwefelsäure, Phosphorsäure, Amidoschwefelsäure oder Gemische dieser Säuren, 0 - 5 g/l Pyridin-3-sulfonsäure als Glanzbildner, 0,01 - 2 g/l Netzmittel 0,1 - 10 g/l Verbindung der Formel I als erfindungsgemäßen Weißmacher. The galvanic rhodium baths according to the invention typically contain about 0.1-20 g / l Rhodium as rhodium sulfate, phosphate, alkanesulfonate or sulfamate, 10-200 g / l Sulfuric acid, phosphoric acid, amidosulfuric acid or mixtures of these acids, 0 - 5 g / l Pyridine-3-sulfonic acid as brightener, 0.01-2 g / l wetting agent 0.1-10 g / l Compound of the formula I as a whitening agent according to the invention.

Die Bäder werden üblicherweise bei Stromdichten von 0,5 - 5 A/dm2 (Gestellbetrieb) und Temperaturen bis 60 °C betrieben.The baths are usually operated at current densities of 0.5-5 A / dm 2 (rack operation) and temperatures up to 60 ° C.

Die Erfindung soll anhand der folgenden Beispiele erläutert werden:

Anmerkung:
Alle Helligkeitwerte (L*) wurden im CIE-L*a*b*-System (1976) mit einem Farbmessgerät SP68S der Fa. X-Rite gemessen.
The invention will be explained with reference to the following examples:
Annotation:
All brightness values (L *) were measured in the CIE-L * a * b * system (1976) using a color measuring device SP68S from X-Rite.

Beispiel 1:Example 1:

In einem Rhodiumelektrolyten mit

  • 2 g/l Rhodium in Form von Rhodiumphosphat
  • 32 g/l Schwefelsäure
  • 0,2 g/l Pyridin-3-sulfonsäure
  • pH <1
  • Temperatur 40 °C
wird auf vorvernickelten Blechen der Größe 25 x 40 mm (Versuchsaufbau: 1 Liter Becherglas, platinierte Titananode, ohne Bewegung, bei einer Stromdichte von 1 A/dm2 Überzüge mit einer Stromausbeute von 12,8 % und der Helligkeit L*=88,7 erreicht. Die Überzüge aus diesem Elektrolyten sind bis maximal 0,3 µm schleierfrei abscheidbar.In a rhodium electrolyte with
  • 2 g / l rhodium in the form of rhodium phosphate
  • 32 g / l sulfuric acid
  • 0.2 g / l of pyridine-3-sulfonic acid
  • pH <1
  • Temperature 40 ° C
on pre-nickel-plated sheets of size 25 x 40 mm (experimental setup: 1 liter beaker, platinum-plated titanium anode, without movement, at a current density of 1 A / dm 2 coatings with a current efficiency of 12.8% and brightness L * = 88.7 The coatings from this electrolyte can be separated without fogging up to a maximum of 0.3 μm.

Durch den Zusatz von 2 g/l Octylsulfonat sinkt die Stromausbeute bei 1 A/dm2 nur unwesentlich auf 12,1 % (1 A/dm2), aber die Helligkeit steigt auf L*=89,8 an. Die Überzüge aus diesem Bad lassen sich nun bis 0,5 µm schleierfrei abscheiden.With the addition of 2 g / l octylsulfonate, the current efficiency at 1 A / dm 2 drops only insignificantly to 12.1% (1 A / dm 2 ), but the brightness increases to L * = 89.8. The coatings from this bath can now be deposited without haze up to 0.5 μm.

Beispiel 2:Example 2:

In einem Rhodiumelektrolyten mit

  • 2 g/l Rhodium in Form von Rhodiumsulfat
  • 30 g/l Schwefelsäure
  • 0,2 g/l Pyridin-3-sulfonsäure
  • 20 mg/l Netzmittel (Fluortensid)
  • pH <1
  • Temperatur 40 °C
wird auf vorvernickelten Blechen der Größe 25 x 40 mm (Versuchsaufbau: 1 Liter Becherglas, platinierte Titananode, Badbewegung 200 U/min durch Magnetrührstab 60 mm, Warenbewegung 5 cm/s, bei einer Stromdichte von 1 A/dm2 Überzüge mit einer Stromausbeute von 37,8 % und der Helligkeit L*=87,2 erreicht. Bei 2 A/dm2 beträgt die Stromausbeute noch 26,3 % und die Helligkeit erreicht einen Wert von L*=86,3. Die Überzüge aus diesem Elektrolyten sind bis maximal 0,3 µm schleierfrei abscheidbar.In a rhodium electrolyte with
  • 2 g / l rhodium in the form of rhodium sulfate
  • 30 g / l sulfuric acid
  • 0.2 g / l of pyridine-3-sulfonic acid
  • 20 mg / l wetting agent (fluorosurfactant)
  • pH <1
  • Temperature 40 ° C
is on pre - nickel - plated sheets of size 25 x 40 mm (experimental setup: 1 liter beaker, platinized titanium anode, bath movement 200 rpm by magnetic stir bar 60 mm, goods movement 5 cm / s, at a current density of 1 A / dm 2 coatings with a current efficiency of At 2 A / dm 2 , the current efficiency is still 26.3% and the brightness reaches a value of L * = 86.3 The coatings from this electrolyte are up to 37.8% and the brightness L * = 87.2 0.3 μm can be deposited without fogging.

Durch den Zusatz von 2 g/l 2-Ethylhexylsulfat sinkt die Stromausbeute nur unwesentlich auf 37,1 % (1 A/dm2) bzw. 26,0 % (2 A/dm2) aber die Helligkeit steigt auf L*=89,5 (1 A/dm2) und L*=90,0 (2 A/dm2) an. Außerdem lassen sich aus diesem Bad Überzüge von 0,7 µm schleierfrei abscheiden. Der Elektrolyt arbeitet sehr schaumarm und ist daher für den Trommelbetrieb ausgezeichnet geeignet.By the addition of 2 g / l 2-ethylhexyl sulfate, the current efficiency decreases only insignificantly to 37.1% (1 A / dm 2 ) or 26.0% (2 A / dm 2 ) but the brightness increases to L * = 89 , 5 (1 A / dm 2 ) and L * = 90.0 (2 A / dm 2 ). In addition, coatings of 0.7 μm can be deposited without haze from this bath. The electrolyte works very low foaming and is therefore excellently suitable for drum operation.

Claims (10)

  1. A bath for electrochemically depositing a highly lustrous white rhodium coating, containing rhodium in dissolved form optionally with an organic compound as a brightening additive, wherein the bath contains as a whitening agent at least one compound having the general formula

            R-SOm-H     (I),

    wherein
    m is the number 4, and
    R is a straight-chain or branched or cyclic alkyl group having up to 20 C atoms.
  2. The electroplating bath according to claim 1, wherein it contains as a whitening agent at least one compound having the formula I, wherein
    R is a straight-chain or branched alkyl group having 5 to 12 C atoms, preferably a branched alkyl group having 6 to 10 C atoms.
  3. The electroplating bath according to claim 1 or 2, wherein it contains as a whitening agent the compounds hexyl sulfate, 2-ethylhexyl sulfate, heptyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, 7-ethyl-2-methyl-4-undecanol sulfate, cyclohexyl sulfate or isomers thereof.
  4. The electroplating bath according to claims 1 to 3, wherein it contains 0.01 to 10 g/l, preferably 0.1 to 6 g/l, of the compound having the formula I.
  5. Use of a compound having the general formula

            R - SOm - H     (I),

    wherein
    m is the number 4, and
    R is a straight-chain or branched or cyclic alkyl group having up to 20 C atoms,
    as a whitening agent in a bath for electrochemically depositing a lustrous rhodium coating, containing rhodium in dissolved form, and optionally an organic compound as a brightening additive and a wetting agent.
  6. A bath for electrochemically depositing a highly lustrous white rhodium coating, containing rhodium in dissolved form with an organic compound as a brightening additive, wherein the organic compound is selected from pyridine-3-sulfonic acid and naphthalene-tri-sulfonic acid, wherein the bath contains as a whitening agent at least one compound having the general formula

            R-SOm-H     (I),

    wherein
    m is the number 3 or 4, and
    R is a straight-chain or branched or cyclic alkyl group having up to 20 C atoms.
  7. The electroplating bath according to claim 6, wherein it contains as a whitening agent at least one compound having the formula I, wherein
    R is a straight-chain or branched alkyl group having 5 to 12 C atoms, preferably a branched alkyl group having 6 to 10 C atoms.
  8. The electroplating bath according to claim 6 or 7, wherein it contains as a whitening agent the compounds hexyl sulfate, hexyl sulfonate, 2-ethylhexyl sulfate, heptyl sulfate, octyl sulfate, octyl sulfonate, decyl sulfate, decyl sulfonate, dodecyl sulfate, 7-ethyl-2-methyl-4-undecanol sulfate, cyclohexyl sulfate or isomers thereof.
  9. The electroplating bath according to claims 6 to 8, wherein it contains 0.01 to 10 g/l, preferably 0.1 to 6 g/l, of the compound having the formula I.
  10. Use of a compound having the general formula

            R - SOm - H     (I),

    wherein
    m is the number 3 or 4, and
    R is a straight-chain or branched or cyclic alkyl group having up to 20 C atoms,
    as a whitening agent in a bath for electrochemically depositing a lustrous rhodium coating, containing rhodium in dissolved form and an organic compound as a brightening additive, and optionally a wetting agent, wherein the organic compound is selected from pyridine-3-sulfonic acid and naphthalene-tri-sulfonic acid.
EP00990767A 1999-12-23 2000-12-15 Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same Expired - Lifetime EP1244827B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19962839 1999-12-23
DE19962839 1999-12-23
PCT/EP2000/012796 WO2001048273A1 (en) 1999-12-23 2000-12-15 Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same

Publications (2)

Publication Number Publication Date
EP1244827A1 EP1244827A1 (en) 2002-10-02
EP1244827B1 true EP1244827B1 (en) 2006-04-19

Family

ID=7934370

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00990767A Expired - Lifetime EP1244827B1 (en) 1999-12-23 2000-12-15 Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same

Country Status (9)

Country Link
US (1) US6878411B2 (en)
EP (1) EP1244827B1 (en)
JP (1) JP4545367B2 (en)
CN (1) CN1181226C (en)
AT (1) ATE323789T1 (en)
DE (1) DE50012619D1 (en)
HK (1) HK1054057B (en)
TW (1) TW573074B (en)
WO (1) WO2001048273A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20032218A1 (en) * 2003-11-14 2005-05-15 Calegaro Di Luigi Di Francesc O Calegaro S P Flli METHOD OF SURFACE FINISH OF THE SILVER AND ITS ALLOYS
US20070012575A1 (en) * 2005-07-12 2007-01-18 Morrissey Ronald J Bright rhodium electrodeposition
CN101949043B (en) * 2010-09-08 2011-11-02 深圳大学 Formulation for electroplating black rhodium layer and method thereof
US9248416B2 (en) 2012-09-14 2016-02-02 Marc C. Striebinger Apparatus for the pressurization and evacuation of a container
CN107687008A (en) * 2017-08-28 2018-02-13 立美珠宝服务（深圳）有限公司 Electric Jinsui River and preparation method thereof
CN109778262A (en) * 2017-11-10 2019-05-21 丹阳市金地生态园林发展有限公司 A kind of metal alloy containing epoxychloropropane brightens electroplate liquid
CN111850631B (en) * 2020-07-30 2021-10-08 金川集团股份有限公司 High-gloss decorative rhodium-plated layer electroplating solution
IT202100027197A1 (en) 2021-10-22 2023-04-22 Berkem Srl GALVANIC BATH FOR THE ELECTROCHEMICAL DEPOSITION OF RHODIUM-RUTHENIUM ALLOYS HAVING A COLOR SIMILAR TO PURE RHODIUM AND HIGH MECHANICAL RESISTANCE AND DEPOSIT SO OBTAINED

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3780198A (en) * 1971-06-07 1973-12-18 Crown Cork & Seal Co System for carbonating beverages
FR2293968A1 (en) * 1974-12-13 1976-07-09 Cem Comp Electro Mec Nozzle for producing gas in liquid emulsion - injects gas into spray formed by impinging liquid on surface
JPS5224131A (en) * 1975-08-14 1977-02-23 Dowa Mining Co Luster* thick rhodium plating method
DE2644378A1 (en) * 1976-10-01 1978-04-06 Fuellpack Dipl Brauerei Ing Di METHOD FOR ADMISSION OF GAS, IN PARTICULAR CARBON DIOXIDE GAS, INTO A LIQUID FLOWING IN A LINE, IN PARTICULAR A BEVERAGE, AND EQUIPMENT FOR CARRYING OUT THE METHOD
JPS604920B2 (en) * 1981-03-30 1985-02-07 日本鉱業株式会社 Method for manufacturing black rhodium plated articles with good wear resistance
JPS5757883A (en) * 1980-09-25 1982-04-07 Nippon Mining Co Ltd Production of black or blue rhodium coated articles and plating bath for this
US4402802A (en) * 1981-01-03 1983-09-06 Dequssa Aktiengesellschaft Electrolytic bath for the deposition of rhodium coatings
DE3100997C2 (en) * 1981-01-15 1986-08-14 Degussa Ag, 6000 Frankfurt Bath for the galvanic deposition of rhodium coatings
JPS63206492A (en) * 1987-02-23 1988-08-25 Ishifuku Kinzoku Kogyo Kk Bright rhodium plating solution
US5329975A (en) * 1993-09-22 1994-07-19 Heitel Robert G Apparatus for pressurizing containers and carbonating liquids
DE9404731U1 (en) * 1994-03-21 1994-09-01 Negele, Helfried, 86916 Kaufering Device for feeding carbon dioxide into tap water
JPH1150295A (en) * 1997-07-28 1999-02-23 Daiwa Kasei Kenkyusho:Kk Plating bath
TR199801497U (en) * 1998-08-03 2000-03-21 Çağlar Şeref Innovation in soda machines.

Also Published As

Publication number Publication date
WO2001048273A1 (en) 2001-07-05
JP4545367B2 (en) 2010-09-15
TW573074B (en) 2004-01-21
HK1054057A1 (en) 2003-11-14
US20030111352A1 (en) 2003-06-19
HK1054057B (en) 2005-07-29
CN1181226C (en) 2004-12-22
CN1420948A (en) 2003-05-28
ATE323789T1 (en) 2006-05-15
US6878411B2 (en) 2005-04-12
JP2003518559A (en) 2003-06-10
DE50012619D1 (en) 2006-05-24
EP1244827A1 (en) 2002-10-02

Similar Documents

Publication Publication Date Title
DE2255584C2 (en) Acid copper plating bath
DE69127394T2 (en) Tin electroplating at high speed
DE4126502C1 (en)
DE3836521A1 (en) WAESSER SOUR BATHROOM FOR GALVANIC SEPARATION OF GLAZING AND CROSS-FREE COPPER COVER AND USE OF THIS BATH
DE2255728A1 (en) ELECTROCHEMICAL PREPARATIONS AND PROCEDURES
DE1062079B (en) Cyanide bath and process for the galvanic deposition of copper coatings
EP1408141B1 (en) Process and electrolyte for the galvanic deposition of bronze
DE4023444C2 (en) A method of electrodepositing copper from an aqueous, alkaline, cyanide-free bath using both a soluble and an insoluble anode
DE3428277A1 (en) AQUEOUS BATH AND A METHOD FOR GALVANICALLY DEPOSITING A ZINC-IRON ALLOY
EP1244827B1 (en) Bath for electrochemically depositing highly lustrous white rhodium coatings and whitening agent for the same
DE3012168C2 (en)
DE3447813A1 (en) AQUEOUS ACID BATH AND A METHOD FOR GALVANIC DEPOSITION OF ZINC OR ZINC ALLOYS
DE3854551T2 (en) Tin, lead and tin-lead alloy electrolytes for high-speed electroplating.
DE10025552C1 (en) Acidic electroplating nickel bath and process for depositing a satin nickel or nickel alloy coating
EP1192297B1 (en) Acidic bath for galvanic deposition of lustrous gold and gold alloy layers and lustring additive therfor
DE2630980C2 (en)
DE2537065C2 (en)
DE2835539C2 (en)
WO2015000010A1 (en) Electrolyte bath and objects or articles coated with the aid of the bath
DE602004011520T2 (en) AQUEOUS, SOFT SOLUTION AND METHOD FOR THE ELECTROLYTIC DECOMPOSITION OF COPPER COATS AND THE USE OF THE SOLUTION
DE2215737C3 (en) Aqueous acid galvanic semi-bright nickel bath
DE3611627A1 (en) CONNECTION, COMPOSITION AND METHOD FOR ELECTROPLATING
DE2450133A1 (en) PROCESS AND GALVANIC BATH FOR DEPOSITING NICKEL / IRON AND NICKEL / COBALT / IRON ALLOYS
DE2032867B2 (en) Galvanic gold bath and process for the deposition of even, thick gold coatings
DE4032864A1 (en) ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20020718

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20021218

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UMICORE GALVANOTECHNIK GMBH

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 50012619

Country of ref document: DE

Date of ref document: 20060524

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060719

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060919

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
ET Fr: translation filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20061107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061231

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070122

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BERE Be: lapsed

Owner name: UMICORE GALVANOTECHNIK G.M.B.H.

Effective date: 20061231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20121120

Year of fee payment: 13

Ref country code: GB

Payment date: 20121212

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20121127

Year of fee payment: 13

Ref country code: FR

Payment date: 20130107

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20131107

Year of fee payment: 14

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 323789

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131215

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131215

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131215

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131215

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141215

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20191203

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 50012619

Country of ref document: DE