WO2008028932A1 - Additive for chromic acid applications - Google Patents
Additive for chromic acid applications Download PDFInfo
- Publication number
- WO2008028932A1 WO2008028932A1 PCT/EP2007/059308 EP2007059308W WO2008028932A1 WO 2008028932 A1 WO2008028932 A1 WO 2008028932A1 EP 2007059308 W EP2007059308 W EP 2007059308W WO 2008028932 A1 WO2008028932 A1 WO 2008028932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- additive
- chromic acid
- acids
- long
- chain
- Prior art date
Links
- 239000000654 additive Substances 0.000 title claims abstract description 58
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 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 title claims abstract description 32
- 230000000996 additive effect Effects 0.000 title claims description 51
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011651 chromium Substances 0.000 claims abstract description 35
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 18
- 150000007513 acids Chemical class 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 4
- 238000009499 grossing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- -1 aliphatic sulfonic acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 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
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- JHDXAQHGAJXNBY-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JHDXAQHGAJXNBY-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 235000021110 pickles Nutrition 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
- CAXRKYFRLOPCAB-UHFFFAOYSA-N propane-1,1-disulfonic acid Chemical compound CCC(S(O)(=O)=O)S(O)(=O)=O CAXRKYFRLOPCAB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011937 reductive transformation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—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
Definitions
- the present invention relates to the field of additives for chromium electrolytes, in particular to the field of additive surfactants for chromium electrolytes, and to the field of additives for chromic acid solutions used in plastic metallizations.
- Foaming wetting agents are particularly suitable for the reduction of spray mist, which, in addition to reducing the spray losses, greatly reduce the drag-out of the chromium electrolyte by lowering the surface tension.
- PFOS Perfiuoralkylsulfonklaren
- PFOS Perfiuoralkylsulfon Acid
- fluorosurfactants are not biodegradable because they are not subject to any photolytic, hydrolytic, oxidative or reductive transformation. They are neither biodegraded aerobically nor anaerobically. Because of their chemical-physical properties, perfiuoralkylsulfonic acids remain as end-metabolites and are not further degraded.
- DE-C 39 33 896 describes the addition of saturated, aliphatic sulfonic acids or their salts or halogen derivatives with a maximum of 2 C atoms and a maximum of 6
- Fluorine compounds are mentioned.
- the working current density is 10 to 1200 A / dm 2 .
- CrO 3 and 1.3% are H 2 SO 4 at 300 g / l
- wetting agent 10 mg / 1 Ammoniumfluoroctansulfonat used the current density is 50 A / dm 2 and the temperature at 55 0 C;
- the additional additive is a saturated aliphatic sulfonic acid having 1 C and 1 sulfonic acid group (3.2 g / L).
- the galvanic chromium baths of DE-A 43 05 732 contain at a content per 1 of 150 to 400 g CrO 3 and 1 to 4 wt .-% H 2 SO 4 (based on CrO 3 ) 0.4 to 10 g 1.3 Propanedisulfonic acid 2-sulfinic acid and / or propan-l, 2,3-trisulfonic acid or salts thereof. In the specific example, working at 55 0 C and a current density of 50 A / dm 2 with 3 to 5 g of additive.
- the galvanic chromium bath of DE-C 44 30 923 contains, as an additive to CrO 3, 2 to 10 g / l of methanesulfonic acid and 2 to 20 g / l of MgSiF 6 .
- the bath also contains 0.1 ml / 1 tetraethylammonium perfluorooctane sulfonate and 1 g / l sugar.
- the chrome plating is carried out at 40 0 C and a current density of 1.82 A / dm 2 over 1 h.
- a chromium bath is known, which in addition to 100 to 600 g / l CrO 3 and sulfate ions in a proportion of Cr 6+ to SO 4 2 " from 90 to 120 to 1 in addition 0.01 to 3, 0 g / l Na-2-hydroxyethanesulfonate or the free acid
- the chromium plating is carried out in 3 stages at 44 to 57 0 C for> 1 h.
- the hard chrome layers of DE-A 102 55 853 are produced in an electrolyte containing 50 to 600 g / l CrO 3 , 0.5 to 10 g / l H 2 SO 4 , 1 to 20 g / l of an aliphatic sulfonic acid with 1 to 6 C atoms and 10 to 200 g / l of a molybdate, vanadate or zirconate.
- the electrolyte contains 250 g / l CrO 3 , 2.5 g / l H 2 SO 4 , 4 g / l methanesulfonic acid and 100 g / l (NH 4 ) 8 Mo 7 O 24 • 4H 2 O; the electrolysis is carried out at 55 0 C and a current density of 40 A / dm 2 at 30 min or 50 A / dm 2 at 120 min.
- the electrolyte of DE-B 10 2004 019 370 contains - compared with the solution described above - just no molybdate, vanadate or zirconate.
- Methanesulfonic acid (as a 70% solution) in an amount of 9 ml / 1 at 60 to 70 0 C for 30 min at a current density of 30 to 80 A / dm 2 is used.
- the current efficiency is ⁇ 12% (as in the previous solution).
- an additive for aqueous chromic acid solutions which is fluorosurfactant-free and biodegradable and has a surface tension of ⁇ 35mN / m in a chromic acid solution containing this additive, and when used in electrolytic chrome plating, determined at 45 ° C and 6000 Ah charge cycle in this containing the additive chromic acid solution, a stability of> 4 h.
- additive may refer to both a single substance and a mixture of substances
- Substance mixture is used, it is generally meant that the substance mixture has the properties described, but optionally, only the individual components of the mixture have the properties described.
- the term "stability" is understood as meaning the continuous effectiveness of the additive with respect to the surface tension under the chemically demanding conditions of a chromic acid solution when used in electrolytic chromium plating. the surface tension does not increase by more than 5 mN / m over the specified period of time.
- chromium electrolyte (s) and / or “chromic acid solution (s)” is understood to mean chromium electrolytes or chromic acid solutions which, in addition to chromic acid and water, may also contain catalysts and / or further acids.
- the content of chromic acid in the solution or the electrolyte - based on CrO 3 - is generally in the range of 120 to 450 g / l. It has been found that with the addition of an inventive additive to chromic acid solutions in most applications, but especially in electrolytic chromium plating, at least one, usually even more, of the following advantages can be achieved:
- the mode of operation of the chromium electrolytes is sustainably improved.
- the use of the additive leads to the formation of significantly smaller gas bubbles, which is accompanied by a drastic reduction of the emission load.
- the throwing power of the electrolyte is improved in many applications when using the additive.
- the additive does not adversely affect the properties of the resulting chromium layer, not even with regard to the important layer properties such as hardness, crack network or structure.
- a chromic acid solution e.g. 0.1 g / l of additive and 250 g / l of chromic acid, has a surface tension of ⁇ 28 mN / m, more preferably still ⁇ 25 mN / m.
- a chromic acid solution e.g. 0.1 g / l of additive and 400 g / l of chromic acid, has a surface tension of ⁇ 35 mN / m, more preferably of ⁇ 30 mN / m.
- an inventive additive at 45 ° C in a chromium electrolyte containing 0.1 g / l to 250 g / l chromic acid, a stability of> 8 h, in particular of> 12 h.
- the additive is fluorosurfactant free.
- this is understood to mean that it contains no organofluorine-containing surface-active compound or that its proportion in the additive is below the detection limit.
- the additive is biodegradable. This is understood to mean that according to OECD criteria> 99.5%, preferably> 99.8% of the additive in the screening test are degraded after 8 days.
- An inventive additive thus contributes in many applications, expenses relating to the Prevent contamination of the environment to minimize or even completely redundant.
- a chromium electrolyte which contains, for example, 0.1 g / l of additive and 250 g / l of chromic acid has, in particular, a current density of 30 A / dm 2 to 60 A / dm 2 , in particular of 40 A / dm 2 to 50 A / dm 2 on.
- a chromium electrolyte containing, for example, 0.2 g / l of additive and 350 to 400 g / l of chromic acid has, in particular, a current density of 5 A / dm 2 to 25 A / dm 2 , in particular 8 A / dm 2 to 20 A / dm 2 on.
- the additive contains at least one surfactant from the group of long-chain alkylmonosulphonic acids, long-chain alkyldisulphonic acids, long-chain alkylpolysulfonic acids, salts of long-chain alkylmonosulfonic acids, salts of long-chain alkyldisulfonic acids and salts of long-chain alkylpolysulfonic acids.
- the surfactant additive comprises at least one CH 3 (CH 2) n SO 3 H or salts thereof, wherein n is 10 to 18.
- these compounds often have a particularly high stability and are preferred in this respect.
- the additive contains such surfactants with n from 12 to 17, even more preferably with n from 14 to 16.
- the present invention also relates to a use of the additive according to the invention as a smoothing agent in chromium electrolytes.
- concentration of additive is generally between 0.05 g / l and 20 g / l, preferably 0.1 g / l to 10 g / l, and most preferably 1 g / l to 3 g / l.
- the present invention also relates to a use of the additive according to the invention as an additive in plastic pickling. It was surprisingly found that the additive according to the invention is not only used in chromium electrolytes but also in this kind of pretreatment for plastic metallizations. The additive also wetting in these mordants and thus lowers the surface tension of the chromic acid-containing mordant. The positive influence of chromic acid mist formation and pickling during pickling is comparable to the effects previously described for chromium electrolytes.
- the proportions of surfactant in a chromic acid-based pickle are substantially the same as those in the chromium electrolyte.
- a black chromium coating was carried out at a temperature of 20 to 25 0 C and a current density of 20 A / dm 2 .
- the surface tension could be lowered by the addition of the additive according to the invention to a value of 29.8 mN / m.
- the chromic acid solution was still stable even after 4 h of electrolytic chrome-plating, i. the surface tension has increased only by significantly less than 5 mN / m.
- the surface tension was measured using a K8 tensiometer from Krüss GmbH in Hamburg.
- the device works according to the Du Noüy ring method.
- the force of a liquid lamella pulled up by the ring is measured.
- the liquid is lifted until the ring makes contact with the surface.
- With the help of a torsion scale the force required to raise the platinum ring is measured. This is the greater the further the ring is pulled out of the liquid.
- the ring geometry is taken into account by a device-specific calibration of the manufacturer.
- the current density was determined by measuring the amperage with an ammeter and referring to the known surface geometry of the components to be chromed.
- the determination of the throwing power of an electrolyte is carried out by the evaluation of sheets after tests with the electrolyte in a Hull cell.
- the scattering of the chromium layer is determined by measuring the extent of the coated surface on the sheet after it has completed the test run. The measurement is done with a ruler. As a rule, several sheets are coated and measured under the same conditions in order to obtain more reliable average values.
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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
- Primary Cells (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RSP-2009/0102A RS20090102A (en) | 2006-09-05 | 2007-09-05 | A novel additive for chromium electrolytes |
MX2009002410A MX2009002410A (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications. |
BRPI0716255-3A BRPI0716255A2 (en) | 2006-09-05 | 2007-09-05 | Additive for Applications of Chromic Acid |
CA002662238A CA2662238A1 (en) | 2006-09-05 | 2007-09-05 | A novel additive for chromium electrolytes |
JP2009527138A JP5588677B2 (en) | 2006-09-05 | 2007-09-05 | New additives for chromium electrolytes |
EA200970249A EA016032B1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic electrolytes |
EP07803268A EP2061916A1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications |
AU2007293648A AU2007293648A1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications |
ZA2009/01539A ZA200901539B (en) | 2006-09-05 | 2009-03-04 | A novel additive for chromium electrolytes |
IL197411A IL197411A0 (en) | 2006-09-05 | 2009-03-05 | A novel additive for chromium electrolytes |
NO20091361A NO20091361L (en) | 2006-09-05 | 2009-04-02 | Additives for chromic acid use |
Applications Claiming Priority (2)
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008028932A1 true WO2008028932A1 (en) | 2008-03-13 |
Family
ID=38596409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/059308 WO2008028932A1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications |
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) |
Cited By (1)
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 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP2845928B1 (en) * | 2013-09-05 | 2019-11-06 | MacDermid Enthone Inc. | Aqueous electrolyte composition having a reduced airborne 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 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US3745097A (en) * | 1969-05-26 | 1973-07-10 | M & T Chemicals Inc | Electrodeposition of an iridescent chromium coating |
EP0287753A1 (en) * | 1987-01-27 | 1988-10-26 | Armour Force Engineering Institute Of The Chinese People's Liberation Army | Process for electroless plating a metal on non-conductive materials |
WO1994004722A1 (en) * | 1992-08-14 | 1994-03-03 | Blasberg Oberflächentechnik GmbH | Anode for use in electrolytic chrome-plating |
DE4328883A1 (en) * | 1993-08-27 | 1995-03-02 | Bayer Ag | Process for preparing polyamide mouldings for subsequent currentless metallisation |
US5453175A (en) * | 1989-11-06 | 1995-09-26 | Elf Atochem N. A., Inc. | Protection of lead-containing anodes during chromium electroplating |
WO1998036108A1 (en) * | 1997-02-12 | 1998-08-20 | Luigi Stoppani S.P.A. | Chromium plating from baths catalyzed with alkanedisulfonic-alkanesulfonic compounds with inhibitors such as aminealkanesulfonic and heterocyclic bases |
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 |
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 |
EP1600528A2 (en) * | 2004-05-27 | 2005-11-30 | Enthone, Inc. | Method for the metallisation of plastic surfaces |
Family Cites Families (9)
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 |
US3041257A (en) * | 1960-08-25 | 1962-06-26 | Westinghouse Electric Corp | Chromium electroplating |
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 |
SG52702A1 (en) * | 1989-11-06 | 1998-09-28 | Atotech Usa Inc | Protection of lead-containing anodes during chromium electroplating |
DE4436391A1 (en) * | 1994-10-12 | 1996-04-18 | Bayer Ag | Process for direct galvanic through-plating of two-layer printed circuit boards and multilayers |
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 |
JP2005240180A (en) * | 2004-01-30 | 2005-09-08 | Riken Corp | Sliding member having composite chrome plating film and method for manufacturing the same |
-
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 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
- 2007-09-05 SG SG2011063302A patent/SG174763A1/en unknown
- 2007-09-05 KR KR1020097006769A patent/KR20090075677A/en not_active Application Discontinuation
- 2007-09-05 RS RSP-2009/0102A patent/RS20090102A/en unknown
- 2007-09-05 CA CA002662238A patent/CA2662238A1/en not_active Abandoned
- 2007-09-05 MX MX2009002410A patent/MX2009002410A/en unknown
- 2007-09-05 BR BRPI0716255-3A patent/BRPI0716255A2/en not_active IP Right Cessation
- 2007-09-05 EA EA200970249A patent/EA016032B1/en not_active IP Right Cessation
- 2007-09-05 EP EP07803268A patent/EP2061916A1/en not_active Withdrawn
-
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
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US3745097A (en) * | 1969-05-26 | 1973-07-10 | M & T Chemicals Inc | Electrodeposition of an iridescent chromium coating |
EP0287753A1 (en) * | 1987-01-27 | 1988-10-26 | Armour Force Engineering Institute Of The Chinese People's Liberation Army | Process for electroless plating a metal on non-conductive materials |
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 |
DE4328883A1 (en) * | 1993-08-27 | 1995-03-02 | Bayer Ag | Process for preparing polyamide mouldings for subsequent currentless metallisation |
WO1998036108A1 (en) * | 1997-02-12 | 1998-08-20 | Luigi Stoppani S.P.A. | Chromium plating from baths catalyzed with alkanedisulfonic-alkanesulfonic compounds with inhibitors such as aminealkanesulfonic and heterocyclic bases |
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 |
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 |
EP1600528A2 (en) * | 2004-05-27 | 2005-11-30 | Enthone, Inc. | Method for the metallisation of plastic surfaces |
Cited By (2)
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 |
WO2012156102A2 (en) | 2011-05-19 | 2012-11-22 | Anke Gmbh & Co. Kg | Wetting agent for electrolytic applications and use thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2662238A1 (en) | 2008-03-13 |
EA016032B1 (en) | 2012-01-30 |
JP2010502836A (en) | 2010-01-28 |
MX2009002410A (en) | 2009-05-28 |
IL197411A0 (en) | 2009-12-24 |
JP5588677B2 (en) | 2014-09-10 |
RS20090102A (en) | 2010-08-31 |
EP2061916A1 (en) | 2009-05-27 |
DE102006042076A1 (en) | 2008-03-20 |
EA200970249A1 (en) | 2009-08-28 |
US20080142372A1 (en) | 2008-06-19 |
NO20091361L (en) | 2009-05-28 |
KR20090075677A (en) | 2009-07-08 |
BRPI0716255A2 (en) | 2013-09-03 |
US20110290658A1 (en) | 2011-12-01 |
ZA200901539B (en) | 2010-02-24 |
SG174763A1 (en) | 2011-10-28 |
AU2007293648A1 (en) | 2008-03-13 |
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