WO2020120388A1 - Électrolyte à base de zinc sans acide borique ni ammoniaque pour une séparation galvanique de dépôts de zinc - Google Patents

Électrolyte à base de zinc sans acide borique ni ammoniaque pour une séparation galvanique de dépôts de zinc Download PDF

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Publication number
WO2020120388A1
WO2020120388A1 PCT/EP2019/084199 EP2019084199W WO2020120388A1 WO 2020120388 A1 WO2020120388 A1 WO 2020120388A1 EP 2019084199 W EP2019084199 W EP 2019084199W WO 2020120388 A1 WO2020120388 A1 WO 2020120388A1
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Prior art keywords
electrolyte
concentration
zinc
acetate
glycine
Prior art date
Application number
PCT/EP2019/084199
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German (de)
English (en)
Inventor
Ralph Krauß
Vera Lipp
Ingo Messerschmid
Original Assignee
Dr.-Ing. Max Schlötter Gmbh & Co. Kg
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.)
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Application filed by Dr.-Ing. Max Schlötter Gmbh & Co. Kg filed Critical Dr.-Ing. Max Schlötter Gmbh & Co. Kg
Priority to US17/312,812 priority Critical patent/US20220064814A1/en
Publication of WO2020120388A1 publication Critical patent/WO2020120388A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the invention relates to a boric acid and ammonium-free aqueous electrolyte for the electrodeposition of zinc coatings, a method for producing the electrolyte and a method for producing a component with zinc coating by electrodeposition from the electrolyte.
  • Zinc coatings are used in many technical areas
  • the zinc coatings can be formed by galvanic (electrochemical) deposition from a zinc electrolyte on the metallic component.
  • the deposition is preferably carried out from weak acid
  • Electrolytes because these generally allow much higher deposition rates than alkaline electrolytes. A good deposition speed is important for an economical coating of components, for example accessories for automobile production.
  • Boric acid is also characterized by a low price, electrochemical stability, process compatibility and unproblematic wastewater treatment.
  • EP 2 706 132 A1 describes the use of a boric acid-free, weakly acidic zinc-nickel electrolyte, which in particular uses a mixture of adipic acid, succinic acid, glutaric acid, sulfosuccinic acid and propionic acid to replace boric acid.
  • a zinc-nickel electrolyte also requires stronger complexing agents (e.g. DETA or EDA) for the nickel, so that sufficient nickel (typically 12 to 15% by weight) can be incorporated into the zinc-nickel layer.
  • complexing agents typically 12 to 15% by weight
  • ammonium chloride and other ammonium salts are environmentally problematic, because ammonium or ammonia should not get into the wastewater.
  • ammonia is a very good ligand for various heavy metals and increases their mobility.
  • essential zinc chloride ammonium chloride or potassium chloride.
  • Succinic acid, acetic acid, lactic acid, malonic acid, adipic acid, tartaric acid and citric acid or their salts can also be present.
  • the pH is preferably between 3 and 4.
  • Ammonium chloride requires complex process wastewater treatment, as already described above.
  • the low pH values in these electrolytes lead to a high solubility of the zinc anodes (anode solubility).
  • the high anode solubility means that
  • CMR substances i.e. substances that are carcinogenic, mutagenic or
  • Ammonium chloride should be for ecological reasons due to the
  • Waste water problems can be avoided. There is therefore a need for a zinc electrolyte that does not require boric acid or ammonium chloride and yet can be operated economically and is largely harmless from a health and ecological point of view.
  • the electrolyte should be the
  • the invention has for its object to provide a zinc electrolyte for the galvanic deposition of zinc coatings, which does not contain boric acid and
  • the zinc electrolyte is said to be able to be operated in particular at high current densities and to use buffer substances which are ecological and
  • the electrolyte is intended in particular to deposit shiny zinc coatings with an advantageous visual impression
  • the present invention relates in particular to the following:
  • the electrolyte has a pH of 4.5 to 6.5.
  • Concentration of CI is 120 to 190 g / L.
  • Concentration of acetate is 7.5 to 30 g / L.
  • Concentration of acetate is 10 to 20 g / L, preferably 12 g / L.
  • the total concentration of glycine and / or alanine is in the range from 0.5 to 20 g / L.
  • the total concentration of glycine and / or alanine is in the range from 1.0 to 10 g / L.
  • the total concentration of glycine and / or alanine is in the range from 1.5 to 5 g / L, preferably 2.5 g / L.
  • Nicotinic acid in a concentration of 0.01 to 2.0 g / L.
  • Nicotinic acid in a concentration of 0.5 to 1.0 g / L.
  • Nicotinic acid in a concentration of 0.08 to 0.5 g / L, preferably 0.1 g / L.
  • Potassium hydroxide and / or sodium hydroxide which can be added as a solid or in the form of an aqueous solution.
  • Electrolyte for the galvanic deposition of zinc coatings also referred to herein as “electrolyte” or “zinc electrolyte”
  • the electrolyte includes:
  • the electrolyte has a pH of 4.5 to 6.5.
  • Alanine is also present in protonated and / or deprotonated form.
  • Combination of acetate with glycine and / or alanine in the concentrations given above does not require the addition of boric acid or the addition of ammonium to provide versatile zinc electrolyte for the galvanic deposition of zinc coatings.
  • Acetate and glycine or alanine serve, among other things, as buffer substances in order to keep the pH in the electrolyte constant.
  • Acetate and the amino acids glycine and alanine are, of course, completely harmless from both a health and ecological point of view and can be disposed of via waste water without any problems.
  • acetate, glycine and alanine are inexpensive and available almost indefinitely and therefore represent a particularly advantageous substitute for the use of boric acid or related boron compounds as well as ammonium compounds such as ammonium chloride.
  • zinc coatings can be deposited over a practical current density range such as 0.2 to 8 A / dm 2 . Especially at high
  • deposited zinc coatings in the form of the optical impression, that is to say a homogeneous gloss and reduction in burns compared to zinc electrolytes without these substances.
  • "Burn-ons” are generally understood to mean mis-colored, dark, amorphous or coarsely crystalline, mostly powdery areas, as a result of which the zinc coating can become unusable for many applications.
  • the electrolyte is suitable for metallic components
  • Concentration ranges are used and the temperature can be varied over a wide range such as 15 to 50 ° C.
  • the electrolyte is also suitable for common ones
  • Buffer compounds in the form of iron (III) hydroxide (Fe (OH) 3) are precipitated and removed. Furthermore, the
  • Buffer compounds do not increase anode solubility (usually zinc anodes) when the electrolyte is not in use. This is beneficial because the concentrations are not
  • water-soluble zinc salts such as Zinc sulfate
  • Zinc methanesulfonate, zinc acetate and zinc chloride are used. It goes without saying that all types of salts, for example anhydrous salts or salts with
  • Crystal water can be used.
  • Zinc acetate and / or zinc chloride are preferably used because the anions are acetate and chloride for the buffering action or
  • the zinc concentration can vary over a wide range and so can the electrolyte
  • the concentration of Zn 2+ in the electrolyte is 15 to 70 g / L.
  • the concentration of Zn 2+ is in particular 20 to 60 g / L, preferably 25 to 50 g / L, more preferably 30 to 40 g / L and most preferably 35 g / L. If the zinc concentration is too low, it increases
  • the electrolyte in addition to zinc, which is of course required for the formation of the zinc coating, also contains one or more conductive salts.
  • Conductive salts increase the conductivity of the electrolyte, which is important in order to be able to coat with zinc at high current densities and with a good deposition rate.
  • Potassium chloride and / or sodium chloride are used in particular as conductive salts. Is preferred
  • the conductive salt is naturally dissolved in the electrolyte, which is why the concentrations of the respective ions are given here.
  • the concentration of CI in the electrolyte is 100 to 200 g / L.
  • the concentration of CI can in particular be 120 to 190 g / L, preferably 130 to 180 g / L and more preferably 160 g / L.
  • the concentration of CI can in particular be 120 to 190 g / L, preferably 130 to 180 g / L and more preferably 160 g / L.
  • Electrolyte are operated well. (4) The cations K + and / or Na + can get into the electrolyte from different reagents. On the one hand, K + and / or Na + come from the conductive salt described above. Furthermore, these ions can also be introduced into the electrolyte as a component of other salts. For example, acetate, glycine or alanine and other weak acids can also be in the form of the corresponding potassium salt and / or
  • Sodium salt can be used for the formation of the electrolyte.
  • Potassium and sodium are naturally harmless from a health and ecological point of view and do not interfere with
  • the electrolyte can, but does not have to, contain other cations in addition to Zn 2+ and K + and / or Na + .
  • Zn 2+ , K + and Na + preferably make up at least 95% by weight, more preferably at least 98% by weight, most preferably at least 99% by weight or 100% by weight of all cations in the electrolyte.
  • the electrolyte preferably contains Zn 2+ and K + .
  • Zn 2+ and K + can make up at least 90% by weight, more preferably at least 95% by weight, most preferably at least 99% by weight or 100% by weight of all cations in the electrolyte.
  • Electrolyte is in the range of 0.75 to 6.0 mol / L. Because of the different masses of K + and Na + , the
  • the electrolyte preferably contains K + and optionally Na + , the concentration of K + being 0.75 to 6.0 mol / L, in particular 2.7 to 4.8 mol / L, preferably 3.3 to 4.1 mol / L, is.
  • the concentration of Na + is preferred
  • 0.5 mol / L or less and more preferably 0.2 mol / L or less, which includes 0 mol / L (i.e. 0 to 0.5 mol / L or 0 to 0.2 mol / L).
  • the electrolyte contains acetate as a buffer substance.
  • AcCr and AcOH form a conjugated acid-base pair, or the deprotonated and protonated form of the acetate.
  • Acetate reagent ie as a source for the acetate in the electrolyte, at least one of potassium acetate, sodium acetate and acetic acid, preferably potassium acetate, can be used.
  • the statement of the concentration of the acetate relates to the mass of the acetate ion (AcO), that is to say the mass of the
  • the acetate serves as a buffer substance to keep the pH of the electrolyte constant. Furthermore, the acetate helps to produce shiny and tempered zinc coatings. In particular at high current densities, acetate turned out to be essential for the operation of the electrolyte. If the acetate concentration (which includes the conjugate acid as described above) is too low, the desired effects are insufficiently obtained. Solubility problems may occur at higher concentrations. The economics of the electrolyte and the quality of the zinc coatings are best in the preferred areas.
  • the electrolyte also contains glycine and / or alanine in addition to acetate, which also serve as buffer substances.
  • Glycine and / or a water-soluble salt thereof can be used as the source of the glycine.
  • Alanine and / or a can be used as the source of the alanine water-soluble salt thereof can be used.
  • At least one of glycine, potassium salt of glycine is preferred
  • Glycine has two pK values, so may be a function of the pH from 4.5 to 6.5, glycine in equilibrium in several species in the electrolyte. Glycine can
  • Electrolyte can be present.
  • protonated and / or deprotonated form can express that acetate, glycine or alanine in all protonated, deprotonated or externally neutral species occurring at pH values from 4.5 to 6.5
  • the species automatically form in equilibrium in the electrolyte at the corresponding pH, as is typical for weak acids and is known to the person skilled in the art.
  • the concentration of glycine or alanine is
  • glycine H 2 N-CH 2 -C0 2 H
  • alanine H 2 N-CHCH 3 - CO2H
  • the concentration of glycine and / or alanine can in particular be 0.5 to 20 g / L, preferably 1.0 to 10 g / L, more preferably 1.5 to 5 g / L and most preferably 2.5 g / L, be. If the electrolyte contains too little glycine or alanine, the desired effects are only insufficiently obtained. Solubility problems may occur if the amounts are too large.
  • Electrolytes 4.5 to 6.5. It can preferably be 4.5 to 6.0 and more preferably 4.8 to 5.3. At these pH values, good separation rates and low
  • the electrolyte also contains one or more further buffer substances.
  • the further buffer substance is in particular at least one
  • Buffer substance selected from the group consisting of succinic acid, adipic acid, malic acid, 2- (N-morpholino) ethanesulfonic acid, tris (hydroxymethyl) aminomethane, triethanolamine, taurine, b-alanine, glutamic acid,
  • Citric acid and salts thereof are especially potassium and / or sodium salts.
  • the additional buffer substance is therefore optional and can be used in a concentration of 0.1 to 40 g / L.
  • the electrolyte contains:
  • the electrolyte contains:
  • the electrolyte contains:
  • Electrolyte additionally (g) nicotinic acid and / or (h) ethoxylated thiodiglycol.
  • the electrolyte particularly preferably contains nicotinic acid and ethoxylated thiodiglycol.
  • Nicotinic acid as such or water-soluble salts thereof, in particular the potassium and / or sodium salt thereof, can be used as the source of nicotinic acid. Simply nicotinic acid is preferably used.
  • nicotinic acid is a weak acid, it can balance the protonated and deprotonated form at pH 4.5 to 6.5 in the electrolyte
  • Nicotinic acid can therefore be present in the form of the conjugate base and / or the conjugate acid analogously to the acetate and glycine or alanine.
  • the concentration is calculated in relation to the mass of nicotinic acid (C 6 H 5 NO 2) as such.
  • Nicotinic acid in the electrolyte is in particular 0.01 to 2.0 g / L, preferably 0.05 to 1.0 g / L, more preferably 0.08 to 0.5 g / L, most preferably 0.1 g / L L.
  • temperable zinc coatings in particular their tempering ability is further improved. Even at high current densities, temperable zinc coatings can be produced which, after tempering, have little or no defects such as bubbles and have a very advantageous optical impression, that is to say a homogeneous gloss without clouding or fog.
  • the concentration is on
  • nicotinic acid If nicotinic acid is too high, the formation of fog or clouding in the zinc coating can increase again.
  • Ethoxylated thiodiglycol is an oligomeric or polymeric compound that results from the addition reaction of Thiodiglycol (HO-CH2-CH2-S-CH2-CH2-OH) with ethylene oxide
  • a suitable ethoxylated thiodiglycol has an average of at least 20
  • Structural units derived from ethylene oxide Structural units derived from ethylene oxide.
  • Structural units derived from ethylene oxide With fewer structural units derived from ethylene oxide, the beneficial effects could not be observed to the same extent.
  • Ethoxylated thiodiglycol can be in the form of an aqueous
  • ethoxylated thiodiglycol for example as 70%
  • aqueous solution available, such as CHE ED 7127 70% (from Erbslöh) or Aduxol TDG-027 70% (from Schrer & Schläpfer).
  • an average of at least 20 structural units derived from ethylene oxide in the electrolyte can be 0.3 to 10 g / L, preferably 0.5 to 5 g / L, more preferably 1.0 to 3.5 g / L and most preferably 2 , 1 g / L.
  • the electrolyte contains (g) Nicotinic acid in a concentration of 0.05 to 1.0 g / L, and / or
  • the electrolyte therefore preferably contains nicotinic acid and ethoxylated thiodiglycol, in particular those specified above
  • the electrolyte can also contain one or more conventional additives for zinc electrolytes in suitable amounts, as is known per se to the person skilled in the art.
  • the electrolyte can, for example, at least one additive from the group consisting of
  • wetting agents e.g. alkoxylated ß-naphthol
  • base gloss e.g. sodium benzoate
  • solubilizers or hydrotropes e.g. sodium cumene sulfonate
  • brighteners e.g.
  • wetting agents serve to lower the surface tension of the electrolyte and ensure good wetting of the surface to be coated.
  • Solubilizers or hydrotropes ensure a sufficiently good solubility for
  • Suitable additives are commercially available. For example, at Schlotter SLOTANIT BSF 1668 (an additive for zinc electrolytes, which wetting agents and Contains basic gloss) and SLOTANIT BSF 1662 (an additive for zinc electrolytes, which contains solubilizers and brighteners). These additives can be used in customary amounts according to the corresponding use and
  • the process includes the steps:
  • Solid or in the form of an aqueous solution can be added.
  • step A in particular (a ') to (c')
  • Temperature can be cooled.
  • the pH of the electrolyte from 4.5 to 6.5 can result solely from the composition of the components. It is also possible to adjust the pH in an optional step B)
  • Solid or in the form of an aqueous solution Solid or in the form of an aqueous solution.
  • 50% potassium hydroxide solution (KOH) can be used.
  • Hydrochloric acid, potassium hydroxide and sodium hydroxide are particularly suitable because they do not introduce any additional ions into the electrolyte.
  • a method for producing a component with a zinc coating comprises the galvanic deposition of zinc on a metallic component from an electrolyte according to one of the embodiments described above.
  • any metallic substrate can be used that is suitable for the galvanic deposition of zinc.
  • the component preferably comprises iron or an iron alloy or consists entirely of it.
  • accessories for the automotive industry can be coated with zinc.
  • the process can also be used, for example, for the galvanic deposition of zinc coatings on components made of cast materials such as
  • the component e.g. a steel sheet, first 1) degreased in a hot cleaning solution, 2) pickled in acid (e.g. semi-concentrated hydrochloric acid), 3) electrolytically degreased and then 4) picked up with dilute hydrochloric acid. After steps 1) to 4), rinsing with water is carried out.
  • acid e.g. semi-concentrated hydrochloric acid
  • the pH can be adjusted during the process.
  • the procedure can be analogous to step B) described above.
  • Iron can optionally precipitated as iron (III) hydroxide and removed.
  • Stirring devices circulation pumps (also in combination with Venturi nozzles) or air injections can be used.
  • the metallic component is switched as a cathode and divalent zinc ions are reduced to metallic zinc on its surface, as a result of which the zinc coating is formed.
  • Zinc is usually used as the anode.
  • the component with a zinc coating is subjected to a passivation treatment after the electrodeposition.
  • the component with a zinc coating is coated with a suitable one
  • Passivations typically contain chromium (III) - and
  • SLOTOPAS Z 20 Blue or the passivation concentrate SLOTOPAS Z 21 Blue which are available from Schlotter. It can be carried out according to the manufacturer's instructions for use.
  • the passivation treatment takes place after the galvanic deposition.
  • the components are usually coated with zinc First rinse the coating with water. If the components are annealed with zinc coating, the passivation treatment can always be carried out before or after
  • the component with a zinc coating is annealed after the electrodeposition.
  • Annealing expels the hydrogen absorbed during the electroplating process in order to counteract the risk of subsequent embrittlement of the component by the hydrogen.
  • the temperature is usually heated to 180 to 230 ° C., preferably 200 to 230 ° C. Heat is usually applied over a longer period of time, for example 2 to 24 hours.
  • the component Before annealing, the component is usually rinsed with water and dried.
  • the annealing is basically optional and can be carried out regardless of whether a passivation treatment is carried out. If a passivation treatment is carried out, this can take place both before and after the tempering.
  • Fig. 1 shows a schematic experimental setup for the galvanic deposition of zinc on an angled
  • FIG. 2 shows a schematic experimental setup for the galvanic deposition of zinc on a straight line
  • the electrolytes were prepared at room temperature by adding and stirring the other components to deionized water. The dissolution of the solids was accelerated by heating to 60 ° C. After the solution was formed, it was cooled to 25 ° C.
  • Potassium chloride was used in technical quality.
  • Zinc chloride HP from Schlotter was used as zinc chloride.
  • SLOTANIT BSF 1668 basic additive
  • SLOTANIT BSF 1662 blueener additive
  • Glycine was used in "pure" quality.
  • Nicotinic acid was used in technical quality.
  • cathodic current density 3 to 6 A / dm 2 for 2 min at 25 ° C and subsequent rinsing with water.
  • Electrolyte volume 3.0 L.
  • pH of the electrolyte 5.2.
  • Electrolyte temperature 25 ° C.
  • the electrolyte (1) is in a beaker (10) and was by means of a magnetic stirrer (15) and a magnetic one
  • Constant (rectifier) (20) from Gossen Metrawatt type SLP 240-40. A current of 3.0 A and a voltage of 2.5 V are illustrated by way of example.
  • Fine zinc anodes 99.99% Zn according to DIN EN 1179 were used as anode material (length: 10 cm, width: 5 cm, thickness: 1 cm). The anodes were immersed 9 cm deep in the electrolyte.
  • the cathode sheet (3) was placed in the center of the two anodes in the beaker. The distance from the anodes to the front and back of the cathode sheet is 6 cm. The cathode sheet is so deep in the electrolyte
  • the coated sheets were galvanized
  • Test A Burns on the angle plate
  • the deposited layer thicknesses were 10 gm.
  • the sheets were then passivated as described above.
  • Electrolytes El to E6 are used (see Table 2 and Table 3). The current density was varied and was 0.25, 1.0, 2.0, 4.0, 6.0 and 8.0 A / dm 2 . The deposited layer thicknesses were 10 pm.
  • the electrolyte E3 which contains potassium acetate and glycine, could be used for zinc coatings of very good temperature at common current densities between 0.25 and 2 A / dm 2
  • Electrolytes E4 and E5 found in Examples 6 and 7, which contained ethoxylated thiodiglycol (E4) and nicotinic acid (E5), respectively.
  • E4 and E5 ethoxylated thiodiglycol (E4) and nicotinic acid (E5), respectively.
  • the procedure described was pretreated and then coated at a current density of 3.0 A / dm 2 .
  • the electrolytes E1 to E6 were used for comparative examples 5 and 6 (VB5 and VB6) and for examples 9 to 12 (see table 4). The secluded
  • the sheets were dried for 15 min at 80 ° C. in a forced air oven and, after cooling to room temperature, the adhesive strength was checked again visually
  • Adhesive strips (tesa ® film crystal clear from Tesa SE) are glued to the metal sheets and removed after 60 s. The zinc coatings were checked for damage.
  • ammonium-free electrolyte adhesive-resistant zinc coatings can be produced.

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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)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un électrolyte aqueux sans acide borique ni ammoniaque servant à la séparation galvanique de dépôts de zinc et un procédé pour sa production. L'électrolyte est composé de : (a) Zn2+ avec une concentration de 15 à 70 g/L ; (b) Cl- avec une concentration de 100 à 200 g/L ; (c) K+ et/ou Na+ au total avec une concentration de 0,75 à 6,0 mol/L ; (d) acétate avec une concentration de 5,0 à 45 g/L ; (e) glycine et/ou alanine au total avec une concentration de 0,5 à 30 g/L ; et (f) eau. L'électrolyte présente une valeur de pH de 4,5 à 6,5. Dans une variante préférée, l'électrolyte contient (g) de l'acide nicotinique et/ou (h) du thiodiglycol éthoxylé. La présente invention concerne en outre un procédé de fabrication d'un composant avec un dépôt de zinc, qui emploie l'électrolyte.
PCT/EP2019/084199 2018-12-12 2019-12-09 Électrolyte à base de zinc sans acide borique ni ammoniaque pour une séparation galvanique de dépôts de zinc WO2020120388A1 (fr)

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US17/312,812 US20220064814A1 (en) 2018-12-12 2019-12-09 Zinc electrolyte devoid of boric acid and ammonium for the electrodeposition of zinc coatings

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EP18211972.7 2018-12-12
EP18211972.7A EP3666929A1 (fr) 2018-12-12 2018-12-12 Électrolyte de zinc sans acide borique et sans ammonium pour le dépôt galvanique des revêtements de zinc

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US4832802A (en) * 1988-06-10 1989-05-23 Mcgean-Rohco, Inc. Acid zinc-nickel plating baths and methods for electrodepositing bright and ductile zinc-nickel alloys and additive composition therefor
US4877497A (en) 1986-05-26 1989-10-31 Nkk Corporation Acidic electro-galvanizing solution
SU1585390A1 (ru) * 1988-06-29 1990-08-15 Предприятие П/Я М-5288 Электролит цинковани
US20030085130A1 (en) * 2001-09-21 2003-05-08 Enthone Inc. Zinc-nickel electrolyte and method for depositing a zinc-nickel alloy therefrom
EP2706132A1 (fr) 2012-09-10 2014-03-12 Dr. Hesse GmbH & Cie KG Electrolyte zinc-nickel sans acide borique
CN102877099B (zh) * 2012-06-12 2015-01-07 浙江吉利汽车研究院有限公司杭州分公司 一种提高基层结合力的复合镀膜工艺

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