EP1114206B1 - Wässriges alkalisches cyanidfreies bad zur galvanischen abscheidung von zink- oder zinklegierungsüberzügen - Google Patents

Wässriges alkalisches cyanidfreies bad zur galvanischen abscheidung von zink- oder zinklegierungsüberzügen Download PDF

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Publication number
EP1114206B1
EP1114206B1 EP99936607A EP99936607A EP1114206B1 EP 1114206 B1 EP1114206 B1 EP 1114206B1 EP 99936607 A EP99936607 A EP 99936607A EP 99936607 A EP99936607 A EP 99936607A EP 1114206 B1 EP1114206 B1 EP 1114206B1
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Prior art keywords
zinc
bath
bath according
amount
coatings
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP99936607A
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German (de)
English (en)
French (fr)
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EP1114206A1 (de
Inventor
Birgit Sonntag
Udo Grieser
Barrie Sydney James
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • Cyanide-free zinc electrolyte baths can be used divide into two bath types, namely into weakly acidic zinc electrolytes (containing zinc chloride or zinc sulfate) and alkaline Zinkatelektrolyte.
  • the ratio of zinc layer thickness in the high current density range to the zinc layer thickness in the low current density range is called layer thickness distribution and should ideally 1.
  • Zinc and zinc alloy baths always have to meet higher demands. Accordingly, a Zinc coating on the object to be coated everywhere have the same layer thickness and a high gloss.
  • a good layer thickness distribution can be achieved by lowering the current yield in the high current density range, while the current efficiency in the low current density range is maintained.
  • the additives proposed so far are disadvantageous however, the tendency that the galvanically generated Flake off zinc layers.
  • the formation of zinc or zinc alloy flaking of the coated substrate, often too referred to as blistering when using Cyanide-free, alkaline baths are a serious problem represents, although no confirmed knowledge regarding the influence of the additives used on the blistering available.
  • the appearance of the blistering works turned out to be particularly disadvantageous because it often takes weeks occurs and therefore often complaints to the coating industry can lead.
  • US Pat. No. 4,030,987 also describes a diallylammonium sulfur dioxide copolymer as an additive for zinc and zinc alloy plating baths described which one of the zinc layers should give uniform layer thickness.
  • the invention is therefore based on the object, the shortcomings to overcome the prior art and in particular a aqueous cyanide-free alkaline bath for galvanic deposition to provide zinc and zinc alloy coatings, obtained with the coatings of zinc or zinc alloys can be in which even after long storage none There is a tendency to form flaking.
  • the soluble polymer of the general formula A contained in the bath according to the invention can be obtained by reacting N, N'-bis [3- (dialkylamino) alkyl] ureas with 1, ⁇ -dihaloalkanes.
  • This reaction can be represented by the following reaction scheme, the radicals R 1 -R 4 , X and m and n being as defined above:
  • the implementation of the starting products can, for example, in aqueous solution and carried out at temperatures of 20 to 100 ° C. become.
  • the invention used polymers of formula A are obtained in which the amino urea units by hydrocarbon bridges are connected.
  • the degree of polymerization of these polymers is 2-80.
  • the starting materials of the general formulas D and E are known per se.
  • the diaminoureas of the formula D. are described for example in JP 04-198160.
  • the other starting products for the production of the invention are 1, ⁇ -dihaloalkanes general formula E. Individual examples of these 1, ⁇ -dihaloalkanes are 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane.
  • the polymer of formula A is in the bath according to the invention in an amount of 0.1 to 50 g / l, preferably 0.25 to 10 g / l, contain.
  • the degree of polymerization of polymer A plays a role in avoiding blistering and improving Layer thickness distribution is irrelevant; only the required Solubility of the polymer in the galvanic bath sets an upper limit on the degree of polymerization.
  • the bath contains, as a further additive, a quaternary derivative of a pyridine-3-carboxylic acid of the formula B and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula C.
  • R 6 represents a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
  • the amount of this additional additive in the invention Bath is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.
  • quaternary derivatives of a pyridine-3-carboxylic acid Formula 3 or C are known compounds and for example in B. S. James, M Phil thesis, Aston Univ. 1979 or DE 40 38 721.
  • the production of these derivatives is generally carried out by reacting nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.
  • the addition of the further additive B and / or C results in a further improvement of the layer thickness distribution.
  • Another Advantage of adding the derivatives B and C mentioned to the bath according to the invention is to improve the gloss call.
  • baths according to the invention can additionally the additives A, B and / or C mentioned above also other polymers, such as that in the above-mentioned documents mentioned polymers contain.
  • Zinc baths the usual aqueous alkaline cyanide-free baths, as used to deposit zinc or zinc alloy coatings can be used on different substrates. Standard baths of this type are described, for example, in DE 25 25 264 and US 3,884,774.
  • the baths according to the invention contain the usual sources of zinc ions, such as zinc metal, zinc salts and Zinc oxide, but zinc oxide is preferred, that in alkaline Solution is present as zincate.
  • the concentration of zinc in the baths according to the invention is in the usual range for such baths from 0.2 to 20 g / l, preferably 5 to 20 g / l.
  • zinc alloy coatings from the baths according to the invention to be separated then contain the baths a source of additional metal ions.
  • additional metal ions preferably come Cobalt, nickel, manganese and / or iron ions in Consideration.
  • Suitable salts are nickel sulfate, iron sulfate, Cobalt sulfate and manganese chloride.
  • the concentration of metal ions in the invention Baths can vary and amount within a wide range preferably 0.01 to 100 g / l. Because with different Alloy types also have a different alloy content is necessary, for example, to prevent corrosion improve, this concentration is from metal ion to metal ion different.
  • the baths preferably contain zinc in one Amount of 0.2 to 20 g / l, cobalt in an amount of 10 up to 120 mg / l, nickel in an amount of 0.3 to 3 g / l, manganese in an amount of 10 to 100 g / l and iron in an amount from 10 to 120 mg / l. These concentrations refer to the amount of metal ions contained in the bath. Appropriate Conversions provide the quantities of those to be used Salts of these metals.
  • the additional above Contain metal ions If the baths according to the invention the additional above Contain metal ions, then it is useful to the baths complexing agents also matched to these additional metal ions add to the deposition potential control and a common reduction with the existing ones To allow zinc ions.
  • Chelating agents are preferred as such complexing agents.
  • suitable chelating agents are hydroxycarboxylates, such as sodium gluconate, amino alcohols, such as triethanolamine, Polyamines, such as polyethylene diamine, aminocarboxylates, such as EDTA, Aminophosphonates such as amino-tris (methylenephosphonic acid), and polyhydric alcohols, such as sorbitol or sucrose.
  • the chelating agent can be used individually or as a mixture in the invention Baths may be included, the amount of which is preferably in the range is from 2 to 200 g / l.
  • the baths according to the invention contain - like the corresponding ones Prior art baths - a source of hydroxide ions, preferably an alkali hydroxide.
  • a source of hydroxide ions preferably an alkali hydroxide.
  • potassium hydroxide an increase in the gloss of the zinc layer.
  • the baths according to the invention known levelers, such as 3-mercapto-1,2,4-triazole and / or thiourea, with thiourea being preferred.
  • concentration leveling is the usual concentration of zinc baths and is, for example, 0.01 to 0.50 g / l.
  • Other additives aromatic aldehydes are for the baths according to the invention or their bisulfite adducts.
  • Preferred aromatic aldehydes are selected from the group 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures selected from it.
  • These additives their concentration in the range from 0.005 to 1.0 g / l, preferably from 0.01 to 0.50 g / l, lies, act in a manner known per se as brighteners.
  • a particularly preferred example of such Vanillin is the brightener.
  • the invention Bad as a brightener also other substances, such as Substances selected from the group of sulfur compounds, Aldehydes, ketones, amines, polyvinyl alcohol, polyvinyl pyrrolidone, Proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof, contain.
  • the baths according to the invention can also be water-softening Contain funds, because the addition of such Sensitivity of the bath according to the invention to foreign metal ions, especially calcium and magnesium from tap water, is reduced.
  • water softening Agents are EDTA, sodium silicates and tartaric acid.
  • customary conductive metal substrates coated with zinc or be provided with a zinc alloy Using the baths according to the invention, customary conductive metal substrates coated with zinc or be provided with a zinc alloy.
  • Another object of the invention is therefore a method for the galvanic deposition of zinc coatings or zinc alloy coatings on conventional substrates, which is characterized in that a bath with the above composition is used as the bath.
  • the coatings are preferably deposited at a current density in the range from 0.01 to 10 A / dm 2 and at a temperature in the range from 15 to 45 ° C.
  • the method according to the invention can be used for mass parts for example as a drum electroplating process and Deposition on larger workpieces as a rack plating process be performed.
  • Anodes are used which can be soluble, such as zinc anodes, which also serve as a source of zinc ions, so that on the Zinc deposited by dissolution of zinc on the cathode Anode is recovered.
  • Anodes such as iron anodes, are used, the zinc ions extracted from the electrolyte to others Need to be added again, e.g. under use a zinc dissolving container.
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.
  • a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and 30 ° C for 30 minutes.
  • the steel sheet was rinsed and in a commercially available Blue chromating (Corrotriblue, Atotech) chromated.
  • the Chromated sheet had a standard commercially available.
  • the zinc layer showed no tendency to blister, even tempering in a circulating air cabinet at 220 ° C for 30 minutes and then Quenching in tap water at room temperature resulted not chipping.
  • the Hull cell sheet was rinsed and in a commercially available Yellow chromating (Tridur Yellow Liquid, Atotech) chromated.
  • the chromated sheet had a slight iridescence and standard.
  • the layer thickness distribution was according to that described above Test measured, it was 1.30.
  • the zinc layer showed no signs of blistering, not even after tempering in the recirculating air cabinet for 30 minutes 220 ° C and then quenching in tap water from Room temperature.
  • Steel screws were galvanized in a drum at a current density of 0.1-1 A / dm 2 and room temperature.
  • the shiny zinc layer was very even on the screws spread and showed no tendency to blister, not even in the drying cabinet for 30 minutes at 220 ° C and then quenching in water which Room temperature.
  • a steel sheet (5 cm x 5 cm) was deposited at 3 A / dm 2 and 30 ° C for 30 minutes.
  • a uniform, shiny zinc-nickel layer was deposited.
  • the zinc-nickel layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • the Hull cell sheet was rinsed and in a commercially available Black chromating for zinc-iron layers (Tridur Black Liquid ZnFe, Atotech) chromated.
  • the chromated sheet had a very good black color.
  • the layer thickness distribution was according to that described above Test measured, it was 1.50.
  • the zinc-iron layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • a steel sheet (5 cm x 5 cm) was deposited at 2 A / dm 2 and room temperature for 30 minutes.
  • a uniform, shiny zinc-iron-cobalt layer was deposited.
  • the zinc-iron-cobalt layer showed no signs of blistering, not even after tempering in the air circulation cabinet for 30 minutes at 220 ° C and then quenched in tap water from room temperature.
  • a Hull cell sheet was deposited at 1 ampere and room temperature for 15 minutes. The Hull cell sheet was rinsed and lightened in 0.3 vol% HNO 3 for 10 s.
  • the layer thickness distribution was according to that described above Test measured; it was 1.41.
  • the manganese incorporation was measured with XRF at the same positions at which the layer thickness was also measured. At 2.8 A / dm 2 , the manganese content was 5.65%; at 0.5 A / dm 2 the manganese content was 7.81%.
  • the layer thickness is measured at two points 3 cm from the lower edge and 2.5 cm from the right and left side edge at high (2.8 A / dm 2 ) and low current density (0.5 A / dm 2 ).
  • XRF is used to measure at four points at the respective position in order to keep the measurement error as low as possible.
  • the layer thickness distribution corresponds to the ratio of the measured values for the layer thickness at high (hcd) and low current density (lcd).
  • Layer thickness distribution hcd: lcd
  • a coated Zn anode serves as the anode. It works with strong air injection (1 l / min), which flows out of an L-shaped plastic tube with 6 small holes (3 on each side) below the inserted cathode.
  • the cathode sheet (18.5 cm x 5 cm) is bent at the lower end and coated at 2.8 A for 35 min.
  • the bath should be at a temperature of 20 ° C, as bubbles occur especially at low temperatures.
  • the sheet is rinsed off, lightened in 0.3% by volume HNO 3 for 10 s, rinsed again and dried under compressed air. Then the sheet is carefully bent straight until it takes on an elongated shape and stored at room temperature. It must be checked daily for blisters.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP99936607A 1998-09-02 1999-07-26 Wässriges alkalisches cyanidfreies bad zur galvanischen abscheidung von zink- oder zinklegierungsüberzügen Expired - Lifetime EP1114206B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19840019 1998-09-02
DE19840019A DE19840019C1 (de) 1998-09-02 1998-09-02 Wäßriges alkalisches cyanidfreies Bad zur galvanischen Abscheidung von Zink- oder Zinklegierungsüberzügen sowie Verfahren
PCT/EP1999/005318 WO2000014305A1 (de) 1998-09-02 1999-07-26 Wässriges alkalisches cyanidfreies bad zur galvanischen abscheidung von zink- oder zinklegierungsüberzügen

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EP1114206A1 EP1114206A1 (de) 2001-07-11
EP1114206B1 true EP1114206B1 (de) 2003-02-26

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US (1) US6652728B1 (es)
EP (1) EP1114206B1 (es)
JP (1) JP4263363B2 (es)
AT (1) ATE233329T1 (es)
CA (1) CA2342219C (es)
DE (2) DE19840019C1 (es)
ES (1) ES2193728T3 (es)
PT (1) PT1114206E (es)
WO (1) WO2000014305A1 (es)

Cited By (3)

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WO2007147603A3 (de) * 2006-06-21 2008-05-15 Atotech Deutschland Gmbh Wässriges alkalisches, cyanidfreies bad zur galvanischen abscheidung von zink- und zinklegierungsüberzügen
EP2175048A1 (en) 2008-10-13 2010-04-14 Atotech Deutschland Gmbh Metal plating composition for deposition of tin-zinc alloys onto a substrate
WO2011029781A1 (en) 2009-09-08 2011-03-17 Atotech Deutschland Gmbh Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths

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CN111733433A (zh) * 2020-06-15 2020-10-02 武汉钢铁有限公司 低铁含量镀层的碱性电镀锌铁合金镀液添加剂及其应用

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JP2002524662A (ja) 2002-08-06
US6652728B1 (en) 2003-11-25
PT1114206E (pt) 2003-07-31
ES2193728T3 (es) 2003-11-01
CA2342219C (en) 2008-09-23
WO2000014305A1 (de) 2000-03-16
ATE233329T1 (de) 2003-03-15
JP4263363B2 (ja) 2009-05-13
CA2342219A1 (en) 2000-03-16
WO2000014305A9 (de) 2000-08-24
EP1114206A1 (de) 2001-07-11
DE59904390D1 (de) 2003-04-03
DE19840019C1 (de) 2000-03-16

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