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EP2061916A1 - Additif pour applications d'acide chromique - Google Patents

Additif pour applications d'acide chromique

Info

Publication number
EP2061916A1
EP2061916A1 EP07803268A EP07803268A EP2061916A1 EP 2061916 A1 EP2061916 A1 EP 2061916A1 EP 07803268 A EP07803268 A EP 07803268A EP 07803268 A EP07803268 A EP 07803268A EP 2061916 A1 EP2061916 A1 EP 2061916A1
Authority
EP
European Patent Office
Prior art keywords
additive
chromic acid
acids
long
chain
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.)
Withdrawn
Application number
EP07803268A
Other languages
German (de)
English (en)
Inventor
Lorenz Läser
Matthias Weiss
Frank Honselmann
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.)
TIB Chemicals AG
Original Assignee
TIB Chemicals AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TIB Chemicals AG filed Critical TIB Chemicals AG
Publication of EP2061916A1 publication Critical patent/EP2061916A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—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)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Primary Cells (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un additif sans tensio-actifs fluorés, stable à longue durée et biodégradable pour des solutions d'acide chromique agissant en réduisant la tension de surface et améliorant ainsi le processus de déposition du chrome, particulièrement lors de l'emploi pour le chromage électrolytique. Les additifs préférés sont CH<SUB>3</SUB>(CH<SUB>2</SUB>)<SUB>n</SUB>SO<SUB>3</SUB>H et leurs sels, avec n = 10 à 18.
EP07803268A 2006-09-05 2007-09-05 Additif pour applications d'acide chromique Withdrawn EP2061916A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006042076A DE102006042076A1 (de) 2006-09-05 2006-09-05 Ein neues Additiv für Chromelektrolyte
PCT/EP2007/059308 WO2008028932A1 (fr) 2006-09-05 2007-09-05 Additif pour applications d'acide chromique

Publications (1)

Publication Number Publication Date
EP2061916A1 true EP2061916A1 (fr) 2009-05-27

Family

ID=38596409

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07803268A Withdrawn EP2061916A1 (fr) 2006-09-05 2007-09-05 Additif pour applications d'acide chromique

Country Status (16)

Country Link
US (2) US20080142372A1 (fr)
EP (1) EP2061916A1 (fr)
JP (1) JP5588677B2 (fr)
KR (1) KR20090075677A (fr)
AU (1) AU2007293648A1 (fr)
BR (1) BRPI0716255A2 (fr)
CA (1) CA2662238A1 (fr)
DE (1) DE102006042076A1 (fr)
EA (1) EA016032B1 (fr)
IL (1) IL197411A0 (fr)
MX (1) MX2009002410A (fr)
NO (1) NO20091361L (fr)
RS (1) RS20090102A (fr)
SG (1) SG174763A1 (fr)
WO (1) WO2008028932A1 (fr)
ZA (1) ZA200901539B (fr)

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DE102011102052A1 (de) 2011-05-19 2012-11-22 Anke Gmbh & Co. Kg Netzmittel für elektrolytische Anwendung und dessen Verwendung
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 (zh) * 2012-06-26 2014-10-11 Dexnano Chemicals Co Ltd 形成黑色三價氧化鉻鍍層之電化學方法及其黑色三價氧化鉻鍍層
EP2845928B1 (fr) * 2013-09-05 2019-11-06 MacDermid Enthone Inc. Composition d'électrolyte aqueux ayant une émission aérienne réduite
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 (zh) * 2015-08-04 2015-12-23 重庆立道表面技术有限公司 一种高效高性能高硬镀铬工艺
CN110565124A (zh) * 2019-08-05 2019-12-13 宣城金诺模塑科技有限公司 一种汽车饰件用镀铬溶液及其电镀方法

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Also Published As

Publication number Publication date
BRPI0716255A2 (pt) 2013-09-03
RS20090102A (en) 2010-08-31
EA200970249A1 (ru) 2009-08-28
AU2007293648A1 (en) 2008-03-13
DE102006042076A1 (de) 2008-03-20
KR20090075677A (ko) 2009-07-08
NO20091361L (no) 2009-05-28
SG174763A1 (en) 2011-10-28
JP5588677B2 (ja) 2014-09-10
MX2009002410A (es) 2009-05-28
US20110290658A1 (en) 2011-12-01
US20080142372A1 (en) 2008-06-19
IL197411A0 (en) 2009-12-24
JP2010502836A (ja) 2010-01-28
EA016032B1 (ru) 2012-01-30
ZA200901539B (en) 2010-02-24
WO2008028932A1 (fr) 2008-03-13
CA2662238A1 (fr) 2008-03-13

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