EP1244827A1 - 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

Info

Publication number
EP1244827A1
EP1244827A1 EP00990767A EP00990767A EP1244827A1 EP 1244827 A1 EP1244827 A1 EP 1244827A1 EP 00990767 A EP00990767 A EP 00990767A EP 00990767 A EP00990767 A EP 00990767A EP 1244827 A1 EP1244827 A1 EP 1244827A1
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EP
European Patent Office
Prior art keywords
sulfate
bath
rhodium
whitening agent
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00990767A
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German (de)
French (fr)
Other versions
EP1244827B1 (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
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Degussa Galvanotechnik GmbH
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Publication of EP1244827A1 publication Critical patent/EP1244827A1/en
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Classifications

    • 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
    • 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
    • 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 galvanic bath for the deposition of high-gloss white rhodium coatings and a whitening agent therefor.
  • Rhodium coatings are e.g. deposited as a contactor on silver and should have a high gloss and as bright a white color as possible, similar to that of silver.
  • electrolytes are composed of rhodium sulfate, phosphate or sulfamate, sulfuric acid, phosphoric acid, alkanesulfonic acid or amidosulfuric acid.
  • haze-free coatings are deposited from such baths, they usually contain certain organic compounds as gloss additives.
  • Typical, very frequently used gloss additives are, as described, for example, in EP 0 056 590, the compounds pyridine-3-sulfonic acid and naphthalene-t ⁇ -sulfonic acid.
  • a bath may additionally contain a wetting agent and / or a phosphonic acid.
  • a disadvantage of the existing systems is that the very bright, white color of silver is not achieved and that with an increasing layer thickness, more haze deposition occurs.
  • R is a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms
  • the invention thus relates to a bath for the electrodeposition of high-gloss white rhodium layers, containing rhodium in dissolved form, optionally with an organic compound as a gloss additive, characterized in that the bath as a whitening agent comprises at least one compound of the general formula
  • R is a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms
  • the whitening agents according to formula I are selected compounds from the class of the alkyl sulfates or alkyl sulfonates.
  • R denotes a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms.
  • the compounds of the formula I are known per se and are readily available. These compounds are sufficiently water soluble and compatible with the electroplating bath. The compounds have surfactant properties, the corresponding action being reduced by less than 4 for a total number of carbon atoms and generally no longer providing adequate solubility if the total number of carbon atoms is more than 20.
  • Preferred gloss additives are compounds of the formula I in which R represents straight-chain or branched-chain or cyclic alkyl groups having 5 to 12 carbon atoms and in particular branched-chain alkyl groups having 6 to 10 carbon atoms.
  • branched-chain connections are particularly suitable in processes and systems in which strong foam formation interferes, e.g. in air-moving electrolytes, in drum processing, in systems for high-speed separation (spraying systems) and in systems for selective separation, e.g. Diving cells.
  • Typical whiteners according to the invention are:
  • the use of the whitener according to the invention in baths for the electrodeposition of rhodium layers is expediently carried out in a concentration range of 0.01 to 10 g / l.
  • Bathers 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 brightness or the degree of whiteness of the deposited coatings is significantly increased in an unexpected manner.
  • the maximum layer thickness at which high-gloss deposition is still applied is also significantly increased.
  • the galvanic rhodium baths according to the invention typically contain approximately
  • the baths are usually operated at current densities of 0.5 - 5 A / dm 2 (rack operation) and temperatures up to 60 ° C.

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  • 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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paper (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

Bad zur galvanischen Abscheidung von hochglänzenden weißen Rhodiumüberzügen und Weißmacher hierfürBath for the electrodeposition of high-gloss white rhodium coatings and whitener therefor
Beschreibung:Description:
Die Erfindung betrifft ein galvanisches Bad für die Ab- scheidung von hochglanzenden weißen Rhodiumuberzugen und einen Weißmacher hierfür.The invention relates to a galvanic bath for the deposition of high-gloss white rhodium coatings and a whitening agent therefor.
Rhodiumuberzuge werden z.B. als Anlaufschütz auf Silber abgeschieden und sollen Hochglanz und einen möglichst hellen, weißen Farbton, ahnlich dem von Silber, aufweisen.Rhodium coatings are e.g. deposited as a contactor on silver and should have a high gloss and as bright a white color as possible, similar to that of silver.
Handelsübliche Elektrolyte sind zusammengesetzt auf der Basis Rhodiumsulfat, -phosphat oder -sulfamat, Schwefelsaure, Phosphorsaure, Alkansulfonsaure oder Amidoschwefelsaure .Commercial electrolytes are composed of rhodium sulfate, phosphate or sulfamate, sulfuric acid, phosphoric acid, alkanesulfonic acid or amidosulfuric acid.
Damit aus solchen Badern schleierfreie Überzüge abgeschieden werden enthalten diese üblicherweise bestimmte organische Verbindungen als Glanzzusatze . Typische, sehr häufig eingesetzte Glanzzusatze sind, wie beispielsweise in EP 0 056 590 beschrieben, die Verbindungen Pyridιn-3- sulfonsaure und Naphthalin-tπ-sulfonsaure . Um das Festhaften von Wasserstoff an der Kathode zu verhindern kann in einem derartigen Bad zusätzlich ein Netzmittel und/oder eine Phosphonsaure enthalten sein.So that haze-free coatings are deposited from such baths, they usually contain certain organic compounds as gloss additives. Typical, very frequently used gloss additives are, as described, for example, in EP 0 056 590, the compounds pyridine-3-sulfonic acid and naphthalene-tπ-sulfonic acid. In order to prevent hydrogen from adhering to the cathode, such a bath may additionally contain a wetting agent and / or a phosphonic acid.
Ein Nachteil der bestehenden Systeme liegt nun darin, daß die sehr helle, weisse Farbe von Silber nicht erreicht wird und daß mit ansteigender Schichtstarke verstärkt schleieri- ge Abscheidung auftritt.A disadvantage of the existing systems is that the very bright, white color of silver is not achieved and that with an increasing layer thickness, more haze deposition occurs.
Es war daher Aufgabe der Erfindung, eine Optimierung derartiger Rhodiumbader in der Hinsicht vorzunehmen, daß sich die Überzüge signifikant weißer abscheiden lassen und die Helligkeit bzw. der Weißheitsgrad dem Silber deutlich wei- ter 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 IIt was therefore an object of the invention to optimize such rhodium baths in such a way that the coatings can be deposited significantly whiter and the brightness or the degree of whiteness are approximated significantly further to that of silver. In addition, the layer thickness that can be deposited without fog should be increased. Surprisingly, it has now been found that this can be achieved if such baths for the deposition of rhodium layers as whitening agents have at least one compound of the general formula I.
R - SOm-H (I)R - SO m -H (I)
zugefügt wird, worinis added in which
m die Zahlen 3 oder 4 undm the numbers 3 or 4 and
R eine gerad- oder verzweigtkettige oder cyklische Alkylgruppe mit bis zu 20 C-Atomen,R is a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms,
ist.is.
Gegenstand 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, dadurch gekenn- zeichnet, daß das Bad als Weißmacher mindestens eine Verbindung der allgemeinen FormelThe invention thus relates to a bath for the electrodeposition of high-gloss white rhodium layers, containing rhodium in dissolved form, optionally with an organic compound as a gloss additive, characterized in that the bath as a whitening agent comprises at least one compound of the general formula
R - SOm-H (I)R - SO m -H (I)
enthält, worincontains what
m die Zahlen 3 oder 4 undm the numbers 3 or 4 and
R eine gerad- oder verzweigtkettige oder cyklische Alkylgruppe mit bis zu 20 C-Atomen,R is a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms,
ist .is.
Die Weißmacher gemäß Formel I sind ausgewählte Verbindungen aus der Klasse der Alkylsulfate oder Alkylsulfonate . In Formel I bedeutet R eine gerad- oder verzweigtkettige oder cyklische Alkylgruppe mit bis zu 20 C-Atomen.The whitening agents according to formula I are selected compounds from the class of the alkyl sulfates or alkyl sulfonates. In formula I, R denotes a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms.
Die Verbindungen der Formel I sind an sich bekannt und ohne weiteres verfügbar. Diese Verbindungen sind ausreichend wasserlöslich und mit dem Galvanikbad kompatibel. Die Verbindungen haben Tensi- deigenschaften, 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.The compounds of the formula I are known per se and are readily available. These compounds are sufficiently water soluble and compatible with the electroplating bath. The compounds have surfactant properties, the corresponding action being reduced by less than 4 for a total number of carbon atoms and generally no longer providing adequate solubility if the total number of carbon atoms is more than 20.
Bevorzugte Glanzzusätze sind Verbindungen der Formel I in denen R für gerad- oder verzweigtkettige oder cyklische Alkylgruppen mit 5 bis 12 C-Atomen und insbesondere für verzweigtkettige Alkylgruppen mit 6 bis 10 C-Atomen steht.Preferred gloss additives are compounds of the formula I in which R represents straight-chain or branched-chain or cyclic alkyl groups having 5 to 12 carbon atoms and in particular branched-chain alkyl groups having 6 to 10 carbon 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 Trommel- bearbeitung, in Anlagen zur Hochgeschwindigkeitsabscheidung (Spritzanlagen) und in Anlagen zur selektiven Abscheidung, wie z.B. Tauchzellen.Because of their low tendency to foam, branched-chain connections are particularly suitable in processes and systems in which strong foam formation interferes, e.g. in air-moving electrolytes, in drum processing, in systems for high-speed separation (spraying systems) and in systems for selective separation, e.g. Diving cells.
Typische erfindungsgemäße Weißmacher sindTypical whiteners according to the invention are
Hexylsulfat HexylsulfonatHexyl sulfate hexyl sulfonate
2-Ethylhexylsulfat2-ethyl hexyl
HeptylsulfatHeptylsulfat
Octylsulfatoctyl
Octylsulfonat DecylsulfatOctyl sulfonate decyl sulfate
DecylsulfonatDecylsulfonat
Dodecylsulfatdodecyl sulfate
7-Ethyl-2-methyl-4-undecanolsulfat7-ethyl-2-methyl-4-undecanolsulfat
Cyclohexylsulfat und deren Isomere. Diese Verbindungen können auch in Form ihrer Salze vorliegen.Cyclohexyl sulfate and its isomers. These compounds can also be in the form of their salts.
Die Anwendung des erfindungsgemaßen Weißmachers in Badern zur galvanischen Abscheidung von Rhodiumschichten erfolgt zweckmaßigerweise in einem Konzentrationsbereich von 0,01 bis 10 g/1. Besonders vorteilhaft sind erfindungsgemaße Bader, die den Weißmacher gemäß Formel I in einer Konzentration von 0,1 bis 6 g/1 enthalten.The use of the whitener according to the invention in baths for the electrodeposition of rhodium layers is expediently carried out in a concentration range of 0.01 to 10 g / l. Bathers 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 erfindungsgemaßen Einsatz der Verbindungen der Verbindungen der Formel I als Weißmacher in galvanischen Rhodiumbadern 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 hochglan- zend abgeschieden wird, deutlich erhöht.Through the use according to the invention of the compounds of the compounds of the formula I as whitening agents in galvanic rhodium baths of otherwise customary composition, the brightness or the degree of whiteness of the deposited coatings is significantly increased in an unexpected manner. The maximum layer thickness at which high-gloss deposition is still applied is also significantly increased.
Zur Herstellung der erfindungsgemaßen Rhodiumbader kann von vielen gangigen und handelsüblichen galvanischen Rhodiumbadern ausgegangen werden, in dem diesen die entsprechende Menge an Verbindung der Formel I zugegeben wird.To produce the rhodium baths according to the invention, it is possible to start from many common and commercially available galvanic rhodium baths by adding the corresponding amount of compound of the formula I to them.
Die erfindungsgemaßen galvanischen Rhodiumbader enthalten typischerweise etwaThe galvanic rhodium baths according to the invention typically contain approximately
0,1 - 20 g/1 Rhodium als Rhodiumsulfat, -phosphat, -alkansulfonat oder -sulfamat,0.1-20 g / 1 rhodium as rhodium sulfate, phosphate, alkane sulfonate or sulfamate,
10 - 200 g/1 Schwefelsaure, Phosphorsaure, Ami- doschwefelsaure oder Gemische dieser10 - 200 g / 1 sulfuric acid, phosphoric acid, amidosulfuric acid or mixtures of these
Sauren,acidic,
0 - 5 g/1 Pyridin-3-sulfonsaure als Glanzbildner,0 - 5 g / 1 pyridine-3-sulfonic acid as brightener,
0,01 - 2 g/1 Netzmittel0.01 - 2 g / 1 wetting agent
0,1 - 10 g/1 Verbindung der Formel I als erfmdungs- gemäßen Weißmacher. Die Bäder werden üblicherweise bei Stromdichten von 0,5 - 5 A/dm2 (Gestellbetrieb) und Temperaturen bis 60 °C betrieben.0.1 - 10 g / 1 compound of formula I as 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.
Die Erfindung soll anhand der folgenden Beispiele erläutert werden:The following examples are intended to illustrate the invention:
Anmerkung: Alle Helligkeitwerte (L*) wurden im CIE-L*a*b*- System (1976) mit einem Farbmessgerät SP68S der Fa. X-Rite gemessen.Note: All brightness values (L *) were measured in the CIE-L * a * b * system (1976) with a color measuring device SP68S from X-Rite.
Beispiel 1:Example 1:
In einem Rhodiumelektrolyten mitIn a rhodium electrolyte with
2 g/1 Rhodium in Form von Rhodiumphosphat2 g / 1 rhodium in the form of rhodium phosphate
32 g/1 Schwefelsäure32 g / 1 sulfuric acid
0,2 g/1 Pyridin-3-sulfonsaure0.2 g / 1 pyridine-3-sulfonic acid
pH <1pH <1
Temperatur 40 °CTemperature 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.is on pre-nickel-plated sheets of size 25 x 40 mm (experimental setup: 1 liter beaker, platinum-coated titanium anode, without movement, with a current density of 1 A / dm 2 coatings with a current efficiency of 12.8% and the brightness L * = 88.7 The coatings from this electrolyte can be deposited free of fog up to a maximum of 0.3 μm.
Durch den Zusatz von 2 g/1 Octylsulfonat sinkt die Strom- ausbeute 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. Beispiel 2:With the addition of 2 g / 1 octyl sulfonate, the current yield at 1 A / dm 2 drops only slightly to 12.1% (1 A / dm 2 ), but the brightness increases to L * = 89.8. The coatings from this bath can now be deposited up to 0.5 μm free of fog. Example 2:
In einem Rhodiumelektrolyten mitIn a rhodium electrolyte with
2 g/1 Rhodium in Form von Rhodiumsulfat2 g / 1 rhodium in the form of rhodium sulfate
30 g/1 Schwefelsäure30 g / 1 sulfuric acid
0,2 g/1 Pyridin-3-sulfonsaure0.2 g / 1 pyridine-3-sulfonic acid
20 mg/1 Netzmittel (Fluortensid)20 mg / 1 wetting agent (fluorosurfactant)
pH <1pH <1
Temperatur 40 °CTemperature 40 ° C
wird auf vorvernickelten Blechen der Größe 25 x 40 mm (Ver- suchsaufbau: 1 Liter Becherglas, platinierte Titananode,is on pre-nickel-plated sheets of size 25 x 40 mm (test setup: 1 liter beaker, platinum-coated titanium anode,
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 vonBath movement 200 rpm by magnetic stirring bar 60 mm, movement of goods 5 cm / s, with a current density of 1 A / dm 2 coatings with a current efficiency of 37.8% and the brightness L * = 87.2 achieved. At 2 A / dm 2 , the current yield is still 26.3% and the brightness reaches a value of
L*=86,3. Die Überzüge aus diesem Elektrolyten sind bis maximal 0,3 μm schleierfrei abscheidbar.L * = 86.3. The coatings made of this electrolyte can be deposited without fog up to a maximum of 0.3 μm.
Durch den Zusatz von 2 g/1 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/dmz) 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 adding 2 g / 1 2-ethylhexyl sulfate, the current yield drops only slightly 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 z ) and L * = 90.0 (2 A / dm 2 ). In addition, coatings of 0.7 μm can be deposited from this bath free of fog. The electrolyte works with very little foam and is therefore ideally suited for drum operation.

Claims

Bad zur galvanischen Abscheidung von hochglänzenden weißen Rhodiumüberzügen und Weißmacher hierfürPatentansprüche : Bath for the galvanic deposition of high-gloss white rhodium coatings and whitening agents therefor
1. Bad zur galvanischen Abscheidung von hochglänzenden weißen Rhodiumschichten, enthaltend Rhodium in gelöster Form gegebenenfalls mit einer organischen Verbindung als Glanzzusatz, dadurch gekennzeichnet, daß das Bad als Weißmacher mindestens eine Verbindung der allgemeinen Formel1. Bath for the electrodeposition of high-gloss white rhodium layers containing rhodium in dissolved form, optionally with an organic compound as a gloss additive, characterized in that the bath as a whitening agent contains at least one compound of the general formula
R - SOm-H (I)R - SO m -H (I)
enthält, worincontains what
m die Zahlen 3 oder 4 undm the numbers 3 or 4 and
R eine gerad- oder verzweigtkettige oder cyklische Alkylgruppe mit bis zu 20 C-Atomen,R is a straight-chain or branched-chain or cyclic alkyl group with up to 20 C atoms,
ist .is.
2. Galvanisches Bad nach Anspruch 1, dadurch gekennzeichnet, daß es als Weißmacher mindestens eine Verbindung der Formel I enthält, worin2. Galvanic bath according to claim 1, characterized in that it contains at least one compound of formula I as whitening agent, wherein
m die Zahlen 3 oder 4 undm the numbers 3 or 4 and
R eine gerad- oder verzweigtkettige Alkylgruppe mit 5 bis 12 C-Atomen, vorzugsweise eine verzweigtkettige Alkylgruppe mit 6 bis 10 C- AtomenR is a straight or branched chain alkyl group with 5 to 12 C atoms, preferably a branched chain alkyl group with 6 to 10 C atoms
ist. ois. O
3. Galvanisches Bad nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es als Weißmacher die Verbindungen Hexylsulfat, He- xylsulfonat, 2-Ethylhexylsulfat , Heptylsulfat , Octyl- sulfat, Octylsulfonat, Decylsulfat, Decylsulfonat , Do- decylsulfat, 7-Ethyl-2-methyl-4-undecanolsulfat , Cyclo- hexylsulfat oder deren Isomere enthält.3. Galvanic bath according to claim 1 or 2, characterized in that it contains the compounds hexyl sulfate, hexyl sulfonate, 2-ethylhexyl sulfate, heptyl sulfate, octyl sulfate, octyl sulfonate, decyl sulfate, decyl sulfonate, do- decyl sulfate, 7-ethyl-2 contains -methyl-4-undecanol sulfate, cyclohexyl sulfate or their isomers.
4. Galvanisches Bad nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß es 0,01 bis 10 g/1, vorzugsweise 0,1 bis 6 g/1, an Verbindung der Formel I enthält.4. Galvanic bath according to claims 1 to 3, characterized in that it contains 0.01 to 10 g / 1, preferably 0.1 to 6 g / 1, of compound of formula I.
5. Verwendung von Verbindungen der allgemeinen Formel5. Use of compounds of the general formula
R - SOm-H (I)R - SO m -H (I)
worinwherein
m die Zahlen 3 oder 4 undm the numbers 3 or 4 and
R eine gerad- oder verzweigtkettige oder cykli- schen Alkylgruppe mit bis zu 20 C-Atomen, istR is a straight or branched chain or cyclic alkyl group with up to 20 carbon atoms
als Weißmacher in Bädern zur galvanischen Abscheidung von glänzenden Rhodiumschichten, enthaltend Rhodium in gelöster Form, sowie gegebenenfalls einer organischen Verbindung als Glanzzusatz und ein Netzmittel. as whitener in baths for the galvanic deposition of shiny rhodium layers containing rhodium in dissolved form, and optionally an organic compound as a shine additive and a wetting agent.
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)

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

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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)

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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
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
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
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.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0148273A1 *

Also Published As

Publication number Publication date
HK1054057A1 (en) 2003-11-14
JP4545367B2 (en) 2010-09-15
US6878411B2 (en) 2005-04-12
DE50012619D1 (en) 2006-05-24
JP2003518559A (en) 2003-06-10
EP1244827B1 (en) 2006-04-19
TW573074B (en) 2004-01-21
US20030111352A1 (en) 2003-06-19
WO2001048273A1 (en) 2001-07-05
ATE323789T1 (en) 2006-05-15
CN1420948A (en) 2003-05-28
CN1181226C (en) 2004-12-22
HK1054057B (en) 2005-07-29

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