CA2662238A1 - A novel additive for chromium electrolytes - Google Patents
A novel additive for chromium electrolytes Download PDFInfo
- Publication number
- CA2662238A1 CA2662238A1 CA002662238A CA2662238A CA2662238A1 CA 2662238 A1 CA2662238 A1 CA 2662238A1 CA 002662238 A CA002662238 A CA 002662238A CA 2662238 A CA2662238 A CA 2662238A CA 2662238 A1 CA2662238 A1 CA 2662238A1
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- Prior art keywords
- additive
- chromic acid
- chromium
- long
- acids
- 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.)
- Abandoned
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- 239000000654 additive Substances 0.000 title claims abstract description 66
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 26
- 239000011651 chromium Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims description 60
- 239000003792 electrolyte Substances 0.000 title claims description 24
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims abstract description 26
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 16
- 150000007513 acids Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000009499 grossing Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000013533 biodegradable additive Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 5
- -1 perfluoro Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011937 reductive transformation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- PLQISZLZPSPBDP-UHFFFAOYSA-M sodium;pentadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCS([O-])(=O)=O PLQISZLZPSPBDP-UHFFFAOYSA-M 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Primary Cells (AREA)
- Chemically Coating (AREA)
Abstract
The fluoride surfactant-free, long-term stable and biodegradable additive for chromic acid solutions lowers the surface tension and thus enhances the separation process of the chromium, particularly when used with electrolytic chroming. Preferred additives are CH3(CH2)nSO3H and the salts thereof wherein n = 10 to 18.
Description
GT64732PC D'usseldorf, September 11, 2006 -----------------------------------------------------------------------Goldschmidt TIB GmbH
----------------------------------------------------------------------A novel additive for chromium electrolytes -----------------------------------------------------------------------The present invention relates to the field of additives for chromium electrolytes, especially to the field of the additive surfactants for chromium electrolytes, and to the field of the additives for polymer metallizations.
For electrochemical chromium-plating, which typically takes place in chromium electrolytes at high concentration of aggressive chromic acid, a wide variety of different additives are proposed in order to prevent the formation of aggressive spray mists. However, it has been found to be difficult in practice to find compounds which, on the one hand, have favourable properties but, on the other hand, survive the aggressive conditions in the chromium-plating.
Particularly suitable for the reduction of spray mist are foam-forming wetting agents which, by lowering the surface tension, not only reduce the spray losses but also greatly reduce the entrainment of the chromium electrolyte. For this purpose, a wide variety of different products have been proposed, for example perfluoroalkylsulphonic acids (PFOAs). These products are also stable to the highly oxidative properties of chromic acid. However, their use is problematic and already banned in many applications. These fluorine surfactants are not biodegradable, since they do not undergo any photolytic, hydrolytic, oxidative or reductive transformation whatsoever. They are biodegraded neither aerobically nor anaerobically. Owing to their physicochemical properties, perfluoro alkylsulphonic acids remain as end metabolites and are not degraded any further.
DE 1034945 has proposed alkylmethylsulphonates as additives, which are said to have the properties of a surfactant and simultaneously bring about process-improving influences with regard to the smoothing of the chromium layer.
However, these additives are unsuitable in practice, since they decompose in the course of chromium-plating within a very short time.
It is therefore an object of the present invention to find an additive for chromium electrolytes which reduces the disadvantages detailed above.
----------------------------------------------------------------------A novel additive for chromium electrolytes -----------------------------------------------------------------------The present invention relates to the field of additives for chromium electrolytes, especially to the field of the additive surfactants for chromium electrolytes, and to the field of the additives for polymer metallizations.
For electrochemical chromium-plating, which typically takes place in chromium electrolytes at high concentration of aggressive chromic acid, a wide variety of different additives are proposed in order to prevent the formation of aggressive spray mists. However, it has been found to be difficult in practice to find compounds which, on the one hand, have favourable properties but, on the other hand, survive the aggressive conditions in the chromium-plating.
Particularly suitable for the reduction of spray mist are foam-forming wetting agents which, by lowering the surface tension, not only reduce the spray losses but also greatly reduce the entrainment of the chromium electrolyte. For this purpose, a wide variety of different products have been proposed, for example perfluoroalkylsulphonic acids (PFOAs). These products are also stable to the highly oxidative properties of chromic acid. However, their use is problematic and already banned in many applications. These fluorine surfactants are not biodegradable, since they do not undergo any photolytic, hydrolytic, oxidative or reductive transformation whatsoever. They are biodegraded neither aerobically nor anaerobically. Owing to their physicochemical properties, perfluoro alkylsulphonic acids remain as end metabolites and are not degraded any further.
DE 1034945 has proposed alkylmethylsulphonates as additives, which are said to have the properties of a surfactant and simultaneously bring about process-improving influences with regard to the smoothing of the chromium layer.
However, these additives are unsuitable in practice, since they decompose in the course of chromium-plating within a very short time.
It is therefore an object of the present invention to find an additive for chromium electrolytes which reduces the disadvantages detailed above.
This object is achieved by an additive according to Claim 1. Accordingly, an additive, especially a smoothing additive for chromium electrolytes, is provided, characterized in that a chromic acid solution which contains 0.1 g/1 of additive and 250 g/l of chromic acid has a surface tension of <_ 30 mN/m, and 0.1 g/1 of additive, at 45 C and 6000 Ah of charge passage, in a chromic acid solution which contains 270 g/I of chromic acid, has a stability of _ 4 h.
It should be noted that the term "additive" within the present invention can relate either to an individual substance or to a substance mixture; for reasons of readability and clarity, however, "additive" is only referred to in the singular within the present invention. If the additive used is a substance mixture, what is meant in each case is that the substance mixture has the properties described, but the individual components of the mixture may also have the properties described.
In the context of the present invention, "stability" means especially the lasting efficacy of the additive with regard to the surface tension under the chemically demanding conditions of a chromium electrolyte.
In particular, in the context of the present invention, "stability" over a certain period means that the surface tension increases by not more than 5 mN/m over this time.
In particular, in the context of the present invention, "chromium electrolytes"
and/or "chromic acid solution operations" are understood to mean chromium electrolytes or chromic acid solutions which comprises catalysts and/or further acids.
It has been found that, surprisingly, when such an additive is added to chromic acid solutions in chromium-plating operations, in most applications of the present invention, at least one, usually more than one, of the following advantages can be achieved:
- The use of the inventive additive improves the operation of the chromium electrolytes in a lasting manner.
- The use of the additive leads to the formation of significantly smaller gas bubbles, which is associated with a drastic reduction in the emission nuisance.
- It is likewise possible to considerably reduce entrainment losses.
- Depending on the process, when the additive is used, the dispersibility of the electrolytes in many applications is improved.
- The additive does not adversely affect the properties of the layer, not even with regard to layer properties such as hardness, crack network, structure, etc.
A chromic acid solution which contains 0.1 g/l of additive and 250 g/l of chromic acid preferably has a surface tension of <_ 28 mN/m, even more preferably <_ 25 mN.
A chromic acid solution which contains 0.1 g/l of additive and 400 g/1 of chromic acid preferably has a surface tension of <_ 35 mN/m, even more preferably <_ mN/m.
0.1 g/l of additive at 45 C in a chromium electrolyte which contains 270 g/l of chromic acid preferably has a stability of _ 8 h, even more preferably of _ 12 h.
In a preferred embodiment of the present invention, the additive is free of fluorine surfactants. This is understood to mean especially that the additive does not contain any organofluorine compound, or that the proportion of organofluorine compounds in the additive is below the detection limit.
In a preferred embodiment of the present invention, the additive is biodegradable.
This is understood to mean especially that, according to OECD criteria, _ 99.5%, preferably _ 99.8%, of the additive has degraded in the screening test after 8 days.
In many applications, such an additive contributes to minimizing expenditure with regard to preventing the contamination of the environment, or even to making it entirely superfluous.
A chromium electrolyte which contains 0.1 g/l of additive and 250 g/1 of chromic acid preferably has a current density of _ 30 A/dm2 to < 60 A/dm2, even more preferably _ 40 A/dm2 to_ 50 A/dm2.
A chromium electrolyte which contains 0.2 g/1 of additive and 350 to 400 g/l of chromic acid preferably has a current density of _ 5 A/dmz to <_ 25 A/dmz, even more preferably _ 8 A/dm2 to S 20 A/dm2.
In a preferred embodiment of the present invention, the additive comprises a material selected from the group of long-chain alkylmonosulphonic acids, long-chain alkyldisulphonic acids, long-chain alkylpolysulphonic acids, salts of the long-chain alkylmonosulphonic acids, salts of the long-chain alkyldisulphonic acids, salts of the long-chain alkylpolysulphonic acids and mixtures thereof.
In this context, "long-chain" is understood to mean C4 and greater. The long-chain alkyl radicals are preferably unbranched, but it is also possible to use branched alkylmono-, -di- and -polysulphonic acids and salts thereof.
The salts used in a preferred embodiment of the present invention are alkali metal salts, alkaline earth metal salts, NH4+ salts, NR4+ salts (where R = alkyl) and mixtures thereof.
In a preferred embodiment of the present invention, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 10 and n<_ 18. In practice, these compounds often have a particularly elevated stability and are preferred in this respect.
More preferably, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 12 and n<_ 17; even more preferably, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H
or salts thereof, where n> 14 and n< 16.
The present invention also relates to use of the inventive additive as a smoothing agent in chromium electrolytes. In a preferred embodiment of the present invention, the concentration of additive is between 0.05 g/1 and <_ 20 g/l, more preferably _ 0.1 g/I and <_ 10 g/l, and most preferably ? 1 g/I and <_ 3 g/l.
The present invention also relates to use of the inventive additive as an additive in polymer mordants. The inventors have found that, surprisingly, the inventive additive can be used not only in chromium electrolytes but also in the pretreatment of polymer metallizations. In these mordants, the additive has a wetting effect and lowers the surface tension of the chromic acid-containing mordants. The positive influence on chromic acid mist formation and entrainment is comparable to the effects described above for chromium electrolytes.
The present invention also relates to use of an additive which comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 10 and n< 18, more preferably n> 12 and n 5 17, even more preferably n _ 14 and n<_ 16, or mixtures thereof, as an additive in polymer mordants.
The aforementioned components to be used in accordance with the invention, and those claimed and described in the working examples, are not subject to any particular exceptional conditions in their size, three-dimensional configuration, material selection and technical design, such that the selection criteria known in the field of use can be used without restriction.
Further details, features and advantages of the subject-matter of the invention are evident from the subclaims and from the description of an inventive example which follows, in which - in a purely illustrative and non-restrictive manner -one use of an inventive additive is detailed.
Example I:
In a bath containing 400 g/l of chromic acid, 5 g/l of phosphoric acid, 3 g/1 of potassium nitrate, 3 g/l of rare earth fluorides (e.g. cerium, lanthanum) and, as the inventive additive, 2 g/l of sodium pentadecanesulphonate, at a temperature of 20-25 C and a current density of 20 A/dm2, a black chromium coating was performed.
It was possible to lower the surface tension to a value of 29.8 mN/m by the addition of the inventive additive.
In the subsequent studies, it was found that the chromium layer deposited had a very uniform appearance. In particular, the dispersibility of the electrolyte was improved. The testing of several sheets gave a dispersion of the chromium layer which was improved by an average of 1.0-1.5 cm according to corresponding tests in a Hull cell.
It should be noted that the term "additive" within the present invention can relate either to an individual substance or to a substance mixture; for reasons of readability and clarity, however, "additive" is only referred to in the singular within the present invention. If the additive used is a substance mixture, what is meant in each case is that the substance mixture has the properties described, but the individual components of the mixture may also have the properties described.
In the context of the present invention, "stability" means especially the lasting efficacy of the additive with regard to the surface tension under the chemically demanding conditions of a chromium electrolyte.
In particular, in the context of the present invention, "stability" over a certain period means that the surface tension increases by not more than 5 mN/m over this time.
In particular, in the context of the present invention, "chromium electrolytes"
and/or "chromic acid solution operations" are understood to mean chromium electrolytes or chromic acid solutions which comprises catalysts and/or further acids.
It has been found that, surprisingly, when such an additive is added to chromic acid solutions in chromium-plating operations, in most applications of the present invention, at least one, usually more than one, of the following advantages can be achieved:
- The use of the inventive additive improves the operation of the chromium electrolytes in a lasting manner.
- The use of the additive leads to the formation of significantly smaller gas bubbles, which is associated with a drastic reduction in the emission nuisance.
- It is likewise possible to considerably reduce entrainment losses.
- Depending on the process, when the additive is used, the dispersibility of the electrolytes in many applications is improved.
- The additive does not adversely affect the properties of the layer, not even with regard to layer properties such as hardness, crack network, structure, etc.
A chromic acid solution which contains 0.1 g/l of additive and 250 g/l of chromic acid preferably has a surface tension of <_ 28 mN/m, even more preferably <_ 25 mN.
A chromic acid solution which contains 0.1 g/l of additive and 400 g/1 of chromic acid preferably has a surface tension of <_ 35 mN/m, even more preferably <_ mN/m.
0.1 g/l of additive at 45 C in a chromium electrolyte which contains 270 g/l of chromic acid preferably has a stability of _ 8 h, even more preferably of _ 12 h.
In a preferred embodiment of the present invention, the additive is free of fluorine surfactants. This is understood to mean especially that the additive does not contain any organofluorine compound, or that the proportion of organofluorine compounds in the additive is below the detection limit.
In a preferred embodiment of the present invention, the additive is biodegradable.
This is understood to mean especially that, according to OECD criteria, _ 99.5%, preferably _ 99.8%, of the additive has degraded in the screening test after 8 days.
In many applications, such an additive contributes to minimizing expenditure with regard to preventing the contamination of the environment, or even to making it entirely superfluous.
A chromium electrolyte which contains 0.1 g/l of additive and 250 g/1 of chromic acid preferably has a current density of _ 30 A/dm2 to < 60 A/dm2, even more preferably _ 40 A/dm2 to_ 50 A/dm2.
A chromium electrolyte which contains 0.2 g/1 of additive and 350 to 400 g/l of chromic acid preferably has a current density of _ 5 A/dmz to <_ 25 A/dmz, even more preferably _ 8 A/dm2 to S 20 A/dm2.
In a preferred embodiment of the present invention, the additive comprises a material selected from the group of long-chain alkylmonosulphonic acids, long-chain alkyldisulphonic acids, long-chain alkylpolysulphonic acids, salts of the long-chain alkylmonosulphonic acids, salts of the long-chain alkyldisulphonic acids, salts of the long-chain alkylpolysulphonic acids and mixtures thereof.
In this context, "long-chain" is understood to mean C4 and greater. The long-chain alkyl radicals are preferably unbranched, but it is also possible to use branched alkylmono-, -di- and -polysulphonic acids and salts thereof.
The salts used in a preferred embodiment of the present invention are alkali metal salts, alkaline earth metal salts, NH4+ salts, NR4+ salts (where R = alkyl) and mixtures thereof.
In a preferred embodiment of the present invention, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 10 and n<_ 18. In practice, these compounds often have a particularly elevated stability and are preferred in this respect.
More preferably, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 12 and n<_ 17; even more preferably, the additive comprises, as at least one component, the compound CH3(CH2)nSO3H
or salts thereof, where n> 14 and n< 16.
The present invention also relates to use of the inventive additive as a smoothing agent in chromium electrolytes. In a preferred embodiment of the present invention, the concentration of additive is between 0.05 g/1 and <_ 20 g/l, more preferably _ 0.1 g/I and <_ 10 g/l, and most preferably ? 1 g/I and <_ 3 g/l.
The present invention also relates to use of the inventive additive as an additive in polymer mordants. The inventors have found that, surprisingly, the inventive additive can be used not only in chromium electrolytes but also in the pretreatment of polymer metallizations. In these mordants, the additive has a wetting effect and lowers the surface tension of the chromic acid-containing mordants. The positive influence on chromic acid mist formation and entrainment is comparable to the effects described above for chromium electrolytes.
The present invention also relates to use of an additive which comprises, as at least one component, the compound CH3(CH2)nSO3H or salts thereof, where n _ 10 and n< 18, more preferably n> 12 and n 5 17, even more preferably n _ 14 and n<_ 16, or mixtures thereof, as an additive in polymer mordants.
The aforementioned components to be used in accordance with the invention, and those claimed and described in the working examples, are not subject to any particular exceptional conditions in their size, three-dimensional configuration, material selection and technical design, such that the selection criteria known in the field of use can be used without restriction.
Further details, features and advantages of the subject-matter of the invention are evident from the subclaims and from the description of an inventive example which follows, in which - in a purely illustrative and non-restrictive manner -one use of an inventive additive is detailed.
Example I:
In a bath containing 400 g/l of chromic acid, 5 g/l of phosphoric acid, 3 g/1 of potassium nitrate, 3 g/l of rare earth fluorides (e.g. cerium, lanthanum) and, as the inventive additive, 2 g/l of sodium pentadecanesulphonate, at a temperature of 20-25 C and a current density of 20 A/dm2, a black chromium coating was performed.
It was possible to lower the surface tension to a value of 29.8 mN/m by the addition of the inventive additive.
In the subsequent studies, it was found that the chromium layer deposited had a very uniform appearance. In particular, the dispersibility of the electrolyte was improved. The testing of several sheets gave a dispersion of the chromium layer which was improved by an average of 1.0-1.5 cm according to corresponding tests in a Hull cell.
MATERIALS AND METHODS
The surface tension was measured with a K8 tensiometer from Kruss Hamburg.
The unit works by the Du Nouy ring method. The force of a liquid lamella drawn up by the ring is measured. The liquid is raised until there is contact of the ring with the surface. With the aid of a torsion balance, the force required to raise the platinum ring is measured. The further the ring is pulled out of the liquid, the greater this is. At the point of the highest force applied, when the liquid lamella breaks off, there is a force equilibrium from which the surface tension of the liquid can be calculated. The ring geometry is taken into account by means of an instrument-specific calibration by the manufacturer.
The current density is determined by means of a measurement of the currents with an amperemeter and reference to the known surface geometry of the components to be chromium-plated.
The dispersibility of an electrolyte is determined by the evaluation of sheets after tests with the electrolyte in a Hull cell. The dispersion of the chromium layer is determined by measuring the expansion of the coated surface on the sheet after it has passed through the test run. The measurement is effected with a ruler. In general, several sheets are coated and measured under the same conditions in order to obtain reliable averages.
The surface tension was measured with a K8 tensiometer from Kruss Hamburg.
The unit works by the Du Nouy ring method. The force of a liquid lamella drawn up by the ring is measured. The liquid is raised until there is contact of the ring with the surface. With the aid of a torsion balance, the force required to raise the platinum ring is measured. The further the ring is pulled out of the liquid, the greater this is. At the point of the highest force applied, when the liquid lamella breaks off, there is a force equilibrium from which the surface tension of the liquid can be calculated. The ring geometry is taken into account by means of an instrument-specific calibration by the manufacturer.
The current density is determined by means of a measurement of the currents with an amperemeter and reference to the known surface geometry of the components to be chromium-plated.
The dispersibility of an electrolyte is determined by the evaluation of sheets after tests with the electrolyte in a Hull cell. The dispersion of the chromium layer is determined by measuring the expansion of the coated surface on the sheet after it has passed through the test run. The measurement is effected with a ruler. In general, several sheets are coated and measured under the same conditions in order to obtain reliable averages.
Claims (9)
1. Additive, especially a smoothing additive for chromium electrolytes, characterized in that a chromic acid solution which contains 0.1 g/l of additive and 250 g/l of chromic acid has a surface tension of <= 30 mN/m, and 0.1 g/l of additive, at 45°C and 6000 Ah of charge passage, in a chromic acid solution which contains 270 g/l of chromic acid, has a stability of >= 4 h.
2. Additive according to Claim 1, characterized in that the additive is free of fluorine surfactants.
3. Additive according to Claim 1 or 2, characterized in that the additive is biodegradable.
4. Additive according to one of Claims 1 to 3, characterized in that a chromic acid solution which contains 0.1 g/l of additive and 250 g/l of chromic acid has a current density of >= 30 A/dm 2 to <= 60 A/dm2.
5. Additive according to one of Claims 1 to 4, comprising a material selected from the group of long-chain alkylmonosulphonic acids, long-chain alkyldisulphonic acids, long-chain alkylpolysulphonic acids, salts of the long-chain alkylmonosulphonic acids, salts of the long-chain alkyldisulphonic acids, salts of the long-chain alkylpolysulphonic acids and mixtures thereof.
6. Additive according to one of Claims 1 to 5, comprising CH3(CH2)n SO3H or salts thereof, where n >= 10 and n <= 18.
7. Use of an additive according to one or more of Claims 1 to 6 as a smoothing agent in chromium electrolytes.
8. Use according to Claim 7, wherein the concentration of the additive is between >= 0.05 g/l and <= 20 g/l.
9. Use of an additive according to one or more of Claims 1 to 6 as an additive in polymer mordants for pretreating polymer metallizations.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006042076.4 | 2006-09-05 | ||
| DE102006042076A DE102006042076A1 (en) | 2006-09-05 | 2006-09-05 | A new additive for chromium electrolytes |
| PCT/EP2007/059308 WO2008028932A1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2662238A1 true CA2662238A1 (en) | 2008-03-13 |
Family
ID=38596409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002662238A Abandoned CA2662238A1 (en) | 2006-09-05 | 2007-09-05 | A novel additive for chromium electrolytes |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US20080142372A1 (en) |
| EP (1) | EP2061916A1 (en) |
| JP (1) | JP5588677B2 (en) |
| KR (1) | KR20090075677A (en) |
| AU (1) | AU2007293648A1 (en) |
| BR (1) | BRPI0716255A2 (en) |
| CA (1) | CA2662238A1 (en) |
| DE (1) | DE102006042076A1 (en) |
| EA (1) | EA016032B1 (en) |
| IL (1) | IL197411A0 (en) |
| MX (1) | MX2009002410A (en) |
| NO (1) | NO20091361L (en) |
| RS (1) | RS20090102A (en) |
| SG (1) | SG174763A1 (en) |
| WO (1) | WO2008028932A1 (en) |
| ZA (1) | ZA200901539B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011102052A1 (en) * | 2011-05-19 | 2012-11-22 | Anke Gmbh & Co. Kg | Wetting agent for electrolytic application and its use |
| US9771661B2 (en) * | 2012-02-06 | 2017-09-26 | Honeywell International Inc. | Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates |
| TWI456093B (en) * | 2012-06-26 | 2014-10-11 | Dexnano Chemicals Co Ltd | Method for black chromium oxide and black chromium oxide electroplating layer thereof |
| ES2766775T3 (en) * | 2013-09-05 | 2020-06-15 | Macdermid Enthone Inc | Aqueous electrolyte composition that has reduced air emission |
| US10087540B2 (en) | 2015-02-17 | 2018-10-02 | Honeywell International Inc. | Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same |
| CN105177640A (en) * | 2015-08-04 | 2015-12-23 | 重庆立道表面技术有限公司 | Efficient high-performance and high-hardness chromium plating process |
| CN110565124A (en) * | 2019-08-05 | 2019-12-13 | 宣城金诺模塑科技有限公司 | Chromium plating solution for automobile ornaments and electroplating method thereof |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1012463B (en) * | 1954-10-05 | 1957-07-18 | Friedrich Kessler | 5, 0 to 50, 0 m roll tape mass with automatic rolling device |
| DE1034945B (en) * | 1956-05-15 | 1958-07-24 | Riedel & Co | Smoothing agent and bath for electrolytic chrome plating from an aqueous hexavalent chromic acid solution |
| US3041257A (en) * | 1960-08-25 | 1962-06-26 | Westinghouse Electric Corp | Chromium electroplating |
| US3745097A (en) * | 1969-05-26 | 1973-07-10 | M & T Chemicals Inc | Electrodeposition of an iridescent chromium coating |
| CN87100440B (en) * | 1987-01-27 | 1988-05-11 | 中国人民解放军装甲兵工程学院 | Process of metal brush-plating on non-conductive material |
| DE3723198A1 (en) * | 1987-07-14 | 1989-02-16 | Bayer Ag | FOAM-RESISTANT ADDITIVE IN ACID SOURS AND GALVANIC BATHS |
| US4997686A (en) * | 1987-12-23 | 1991-03-05 | Surface Technology, Inc. | Composite electroless plating-solutions, processes, and articles thereof |
| EP0452471B1 (en) * | 1989-11-06 | 1997-03-12 | Atotech Usa, Inc. | Protection of lead-containing anodes during chromium electroplating |
| US5453175A (en) * | 1989-11-06 | 1995-09-26 | Elf Atochem N. A., Inc. | Protection of lead-containing anodes during chromium electroplating |
| WO1994004722A1 (en) * | 1992-08-14 | 1994-03-03 | Blasberg Oberflächentechnik GmbH | Anode for use in electrolytic chrome-plating |
| DE4328883C2 (en) * | 1993-08-27 | 1996-08-14 | Bayer Ag | Process for the preparation of molded polyamide parts for the subsequent electroless metallization |
| DE4436391A1 (en) * | 1994-10-12 | 1996-04-18 | Bayer Ag | Process for direct galvanic through-plating of two-layer printed circuit boards and multilayers |
| EP0860519A1 (en) * | 1997-02-12 | 1998-08-26 | LUIGI STOPPANI S.p.A. | Chromium plating from baths catalyzed with alkanedisulfonic-alkanesulfonic compounds with inhibitors such as aminoalkanesulfonic acids and heterocyclic bases |
| DE19828545C1 (en) * | 1998-06-26 | 1999-08-12 | Cromotec Oberflaechentechnik G | Galvanic bath for forming a hard chromium layer on machine parts |
| DE10033433A1 (en) * | 2000-07-10 | 2002-01-24 | Basf Ag | Process for electrolytic galvanizing from electrolytes containing alkanesulfonic acid |
| DE10124631C1 (en) * | 2001-05-18 | 2002-11-21 | Atotech Deutschland Gmbh | Direct electrolytic metallization of insulating substrate surface, used in circuit board production, e.g. for metallizing fine holes, uses pretreatment with water-soluble polymer and acid solutions of permanganate and thiophen compound |
| DE10255853A1 (en) * | 2002-11-29 | 2004-06-17 | Federal-Mogul Burscheid Gmbh | Manufacture of structured hard chrome layers |
| JP2005240180A (en) * | 2004-01-30 | 2005-09-08 | Riken Corp | Sliding member having composite chrome plating film and method for manufacturing the same |
| DE102004019370B3 (en) * | 2004-04-21 | 2005-09-01 | Federal-Mogul Burscheid Gmbh | Production of optionally coated structurized hard chrome layer, used e.g. for decoration, protection or functional coating on printing roller or stamping, embossing or deep drawing tool uses aliphatic sulfonic acid in acid plating bath |
| DE102004026489B3 (en) * | 2004-05-27 | 2005-09-29 | Enthone Inc., West Haven | Process for the metallization of plastic surfaces |
-
2006
- 2006-09-05 DE DE102006042076A patent/DE102006042076A1/en not_active Ceased
-
2007
- 2007-09-04 US US11/849,491 patent/US20080142372A1/en not_active Abandoned
- 2007-09-05 MX MX2009002410A patent/MX2009002410A/en unknown
- 2007-09-05 EA EA200970249A patent/EA016032B1/en not_active IP Right Cessation
- 2007-09-05 CA CA002662238A patent/CA2662238A1/en not_active Abandoned
- 2007-09-05 BR BRPI0716255-3A patent/BRPI0716255A2/en not_active IP Right Cessation
- 2007-09-05 EP EP07803268A patent/EP2061916A1/en not_active Withdrawn
- 2007-09-05 RS RSP-2009/0102A patent/RS20090102A/en unknown
- 2007-09-05 SG SG2011063302A patent/SG174763A1/en unknown
- 2007-09-05 KR KR1020097006769A patent/KR20090075677A/en not_active Application Discontinuation
- 2007-09-05 AU AU2007293648A patent/AU2007293648A1/en not_active Abandoned
- 2007-09-05 WO PCT/EP2007/059308 patent/WO2008028932A1/en active Application Filing
- 2007-09-05 JP JP2009527138A patent/JP5588677B2/en active Active
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2009
- 2009-03-04 ZA ZA2009/01539A patent/ZA200901539B/en unknown
- 2009-03-05 IL IL197411A patent/IL197411A0/en unknown
- 2009-04-02 NO NO20091361A patent/NO20091361L/en not_active Application Discontinuation
-
2011
- 2011-06-14 US US13/160,292 patent/US20110290658A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| NO20091361L (en) | 2009-05-28 |
| EA200970249A1 (en) | 2009-08-28 |
| DE102006042076A1 (en) | 2008-03-20 |
| EA016032B1 (en) | 2012-01-30 |
| US20110290658A1 (en) | 2011-12-01 |
| KR20090075677A (en) | 2009-07-08 |
| JP5588677B2 (en) | 2014-09-10 |
| RS20090102A (en) | 2010-08-31 |
| BRPI0716255A2 (en) | 2013-09-03 |
| MX2009002410A (en) | 2009-05-28 |
| AU2007293648A1 (en) | 2008-03-13 |
| ZA200901539B (en) | 2010-02-24 |
| EP2061916A1 (en) | 2009-05-27 |
| JP2010502836A (en) | 2010-01-28 |
| IL197411A0 (en) | 2009-12-24 |
| SG174763A1 (en) | 2011-10-28 |
| US20080142372A1 (en) | 2008-06-19 |
| WO2008028932A1 (en) | 2008-03-13 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |
Effective date: 20130905 |