US3340073A - Regeneration of chemical plating baths - Google Patents

Regeneration of chemical plating baths Download PDF

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Publication number
US3340073A
US3340073A US599344A US59934466A US3340073A US 3340073 A US3340073 A US 3340073A US 599344 A US599344 A US 599344A US 59934466 A US59934466 A US 59934466A US 3340073 A US3340073 A US 3340073A
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US
United States
Prior art keywords
bath
chloride
plating
litre
magnesium
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Expired - Lifetime
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US599344A
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English (en)
Inventor
Zirngiebl Eberhard
Klein Heinz-Gunter
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Bayer AG
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Bayer AG
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Publication date
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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1617Purification and regeneration of coating baths

Definitions

  • Chemical plating baths which contain as a reducing agent boron hydrides with one to four hydrogen atoms linked directly to boron. These baths work at a satisfactory plating rate and reduction yield until about 75% of the nickel applied has been withdrawn from the bath by plating. The reduction yield and plating rate then decrease considerably whereupon a further use of the bath becomes uneconomical.
  • the precipitates thus formed are difficult to filter, and metal residues still present in the plating bath, acting as decomposition catalysts, result in, on addition of boron hydrides with one to four hydrogen atoms directly linked to boron, the spontaneous decomposition 40 of the baths.
  • the object of the invention is to provide a process for the regeneration of chemical plating baths, containing as a reducing agent boron hydrides with one to four hydrogen atoms directly linked to boron, characterised by reacting the used baths with water-soluble alkaline earth metal compounds, preferably with magnesium chloride, and filtering off the precipitates thereby formed. The filtrates are then treated once more with the salt of the plating metal and a complex former or reducing agent. The working up can be carried out with alkaline earth metal compounds in the solid state or in solution.
  • Suitable water-soluble alkaline earth metal compounds according to the invention are, for example, magnesium chloride, magnesium sulphate, magnesium acetate, calcium chloride, strontium chloride, barium chloride.
  • the working up of the used chemical plating baths working only at a slow plating rate and with a poor reduction yield, is carried out by stirring them with the water-soluble alkaline earth metal compounds and subsequent filtration.
  • the excess of soluble alkaline earth metal compounds in the baths can be removed, if desired, by the addition of suitable precipitation agents.
  • suitable precipitation agents for example, an excess of Ca+ is suitably precipitated with oxalates, an excess of Ba++ with sulphates.
  • the working up of the chemical plating baths is effected continuously: during plating a supplementary metal salt solution and a solution of the reducing agent containing sodium hydroxide is continuously run into the plating bath in operation.
  • concentrations of both solutions are adjusted in such a way that the composition of the plating bath remains unchanged.
  • overflow a quantity of bath liquid corresponding to the increase in volume is removed from the plating bath, and this, after regeneration and adjustment to the concentration of the supplementary metal salt solution, is again fed back into the plating bath.
  • the regeneration is carried out as follows: The overflow liquid is put into the circuit as an afterplating bath so that the residual reducing agent is used up. Subsequently a quantity of magnesium chloride is added which corresponds to the alkali metal and borate content of the solution; the mixture is filtered off from the precipitate, the residue is Washed with a little water, the filtrate is adjusted again to the concentration of the supplementary metal 'salt solution by the addition of metal salt and, if desired, of complex former.
  • the interfering alkali metal salts are kept by the bath regeneration according to the invention at a concentration which does not influence the chemical plating process, it is possible to maintain the working capacity of a bath for a practically unlimited period of time.
  • Example 1 1 litre of a chemical plating bath of the composition Nickel chloride (NiCl .6H O) g./litre 30 Ethylene diamine (96-98%) g./litre 62 Sodium hydroxide g./litre 42 Thiodiglycollic acid g/litre 1 Lead chloride mg./litre 10 Sodium boranate mg./litre 0.6
  • the adjustment of the bath to the concentration of the supplementary metal salt solution can only be carried out by the addition of the nickel salt as a solid or in solution to the filtrate.
  • the ethylene diamine content is equally adjusted to the initial concentration.
  • Example 2 Foils of polyglycol-terephthalate were consecutively pretreated in the following baths:
  • Nickel sulphate g./litre 20 Cobalt sulphate g./litre 20 Concentrated aqueous ammonia cc./litre N-dimethylborazane g./litre 1.5
  • the temperature of the bath was 40 C., the period of immersion between 5 and 10 minutes.
  • the bath was checked analytically and the initial concentration was re established every 5 hours. After about 20 hours running time the bath stopped plating.
  • Regeneration was carried out by the addition of 50 g. of magnesium sulphate to the plating bath while stirring. Subsequently the precipitate formed was filtered off, the residue was washed with a little water and the filtrate was adjusted to the initial concentration of the plating bath by adding the metal salts, the complex former and the reducing agent.
  • the bath now worked again without any disturbance.
  • Silvery coatings were obtained on the polyglycol-terephthalate foils, with a resistance of between 0.4 and 0.6 ohm./ cm.
  • Example 3 2 litres of a chemical plating bath of the following compositions:
  • a process for regenerating a chemical plating bath containing as reducing agent a boron hydrogen compound having 1 to 4 hydrogen atoms linked directly with the boron atom, an alkali metal hydroxide or ammonia, a nickel and/or cobalt metal salt and a complex former selected from the group consisting of ammonia and organic complex forming agents the step which comprises adding to the exhausted plating bath at least one water soluble alkaline earth metal compound selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium acetate, calcium chloride, strontium chloride and barium chloride, and removing from the bath the precipitated borates and hydroxides thereby formed.
  • said alkaline earth metal compound is magnesium chloride.
  • Process according to claim 1 which comprises removing the excess of soluble alkaline earth metal compound in said bath by the addition to the bath of a suitable precipitating agent whereby the cationic fraction of said compound is precipitated and can be removed.
  • a process for the regeneration of a chemical plating bath containing as reducing agent a boron hydrogen compound having 1 to 4 hydrogen atoms linked directly to the boron atom, alkali metal hydroxide or ammonia, nickel and/ or cobalt metal salt and a complex former selected from the group consisting of ammonia and organic complex forming agents the steps which comprise adding to the exhausted plating bath at least one water soluble alkaline earth metal compound selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium acetate calcium chloride, strontium chloride and barium chloride, removing the precipitated borates and hydroxides thereby formed and adding to the bath liquid at least that amount of the bath components required to re-establish the initial content thereof in said bath.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
US599344A 1961-05-27 1966-12-02 Regeneration of chemical plating baths Expired - Lifetime US3340073A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF34032A DE1242970B (de) 1961-05-27 1961-05-27 Verfahren zum Regenerieren eines erschoepften Bades zur chemischen Abscheidung einesborhaltigen Metallueberzugs

Publications (1)

Publication Number Publication Date
US3340073A true US3340073A (en) 1967-09-05

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ID=7095377

Family Applications (1)

Application Number Title Priority Date Filing Date
US599344A Expired - Lifetime US3340073A (en) 1961-05-27 1966-12-02 Regeneration of chemical plating baths

Country Status (5)

Country Link
US (1) US3340073A (fr)
BE (1) BE618098A (fr)
CH (1) CH414301A (fr)
DE (1) DE1242970B (fr)
GB (1) GB932903A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038085A (en) * 1976-03-03 1977-07-26 Chromium Industries, Inc. Method of treating electroless nickel plating bath
US5269838A (en) * 1992-04-20 1993-12-14 Dipsol Chemicals Co., Ltd. Electroless plating solution and plating method with it
US5576053A (en) * 1993-05-11 1996-11-19 Murata Manufacturing Co., Ltd. Method for forming an electrode on an electronic part

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1237399B (de) * 1963-07-22 1967-03-23 Bayer Ag Verfahren zum kontinuierlichen, chemischen Abscheiden borhaltiger Nickel- und Kobalt-ueberzuege

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2434191A (en) * 1942-02-02 1948-01-06 Du Pont Removing organic impurities from copper-cyanide electroplating baths
US2886451A (en) * 1958-01-17 1959-05-12 Gen Am Transport Processes of regenerating chemical nickel plating solutions
GB836480A (en) * 1957-01-15 1960-06-01 Du Pont Improvements in or relating to alloy plate
CA654202A (en) * 1962-12-18 Budininkas Pranas Recovery of depleted chemical nickel plating baths

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1219249A (fr) * 1958-01-17 1960-05-16 Gen Am Transport Perfectionnements aux procédés de nickelage chimique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA654202A (en) * 1962-12-18 Budininkas Pranas Recovery of depleted chemical nickel plating baths
US2434191A (en) * 1942-02-02 1948-01-06 Du Pont Removing organic impurities from copper-cyanide electroplating baths
GB836480A (en) * 1957-01-15 1960-06-01 Du Pont Improvements in or relating to alloy plate
US2886451A (en) * 1958-01-17 1959-05-12 Gen Am Transport Processes of regenerating chemical nickel plating solutions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038085A (en) * 1976-03-03 1977-07-26 Chromium Industries, Inc. Method of treating electroless nickel plating bath
US5269838A (en) * 1992-04-20 1993-12-14 Dipsol Chemicals Co., Ltd. Electroless plating solution and plating method with it
US5576053A (en) * 1993-05-11 1996-11-19 Murata Manufacturing Co., Ltd. Method for forming an electrode on an electronic part

Also Published As

Publication number Publication date
CH414301A (de) 1966-05-31
BE618098A (fr) 1962-09-17
GB932903A (en) 1963-07-31
DE1242970B (de) 1967-06-22

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