US3454475A - Electroplating bath and process - Google Patents

Electroplating bath and process Download PDF

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Publication number
US3454475A
US3454475A US471753A US3454475DA US3454475A US 3454475 A US3454475 A US 3454475A US 471753 A US471753 A US 471753A US 3454475D A US3454475D A US 3454475DA US 3454475 A US3454475 A US 3454475A
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United States
Prior art keywords
bath
alanine
grams
zinc
poly
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Expired - Lifetime
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US471753A
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English (en)
Inventor
John D Rushmere
William H Todd
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids

Definitions

  • This invention relates to the electrodeposition of zinc and, more particularly, to electrodepositing zinc from alkaline cyanide plating baths containing a polymeric brightening agent.
  • the primary object of this invention is to provide a new polymeric material useful for depositing bright zinc from alkaline cyanide baths.
  • a further object is to provide an additive which may be used effectively in small quantities and which has a relatively low cost.
  • the objects of this invention are accomplishd by the use of a low molecular weight, water-soluble homopolymer of fi-alanine.
  • These polymers are linear, straight chain polymers having repeating units which may be represented by the fomula:
  • the polymers can be prepared by the process described in US. Patent 2,734,081 or by another process which will be described later herein.
  • the preferred polymers are completely miscible in water and are represented by those in which n is an integer from 5 to 10.
  • n is an integer from 5 to 10.
  • the principal requirement resides in the polymers having at least some solubility in the cyanide plating bath. Since the polymers are highly active brightening agents, the required solubility may be very low, i.e., 0.01 weight percent or less.
  • a small quantity of the Si-alanine homopolymer is introduced into a plating bath containing zinc cyanide.
  • the homopolymer is preferably introduced into the bath from a stock solution.
  • the solution may be aqueous or contain a water-miscible organic solvent such as methyl Cellosolve, isopropanol, or other organic solvent which is inert, i.e., non-reactive, with respect to the homopolymer and bath constituents.
  • the amount of the polymer used is not critical but should generally be sufiicient to provide from about 0.1 to 20 grams/liter in the bath.
  • a plating bath containing zinc cyanide, sodium hydroxide, sodium cyanide, sodium carbonate and sodium sulfide is prepared by dissolving the 3,454,475 Patented July 8, 1969 "ice constituents in water.
  • the poly-fi-alanine is then added separately from a concentrated aqueous brightener solution.
  • the concentrate may contain from about 5 to 25% by Weight of the polymer.
  • the poly-B-alanine used in Example I was prepared by refiuxing 100 grams of ethylene cyanohydrin, 40 grams of cyclohexane, 18 grams of 1,2- dimethoxyethane and 2 grams of potassium hydroxide. After polymerization, which required about two hours, 55 grams of solvent were decanted. The poly-,B-alanine residue was a hard, sticky yellow mass.
  • EXAMPLE I An aqueous plating bath having the following composition was used to plate a steel panel in a Hull cell.
  • EXAMPLE II methyl Cellosolve solution was successively increased in stages as follows: 0.8 milliliter/liter, 1.6 milliliters/liter, 2.4 milliliters/liter, 3.2 milliliters/liter. After bright dipping in dilute nitric acid solution to remove stains, the quality of the zinc plate showed a successive improvement over the plate obtained in the absence of the additive. At the highest concentration, 3.2 milliliters/liter, the zinc plate was very bright on all surfaces of the crank hole cover and had the appearance of a product obtainable from the best known commercially available brighteners.
  • EXAMPLE III In this example, methyl Cellosolve was used in preparing the poly-B-alanine and a barrel plating operation was carried out.
  • the poly-B-alanine was prepared by refluxing 100 grams of ethylene cyanohydrin, 20 grams of methyl Cellosolve and 2 grams of sodium cyanide. The resulting reflux, which contained approximately 80 weight percent of poly-,B-alanine, was added directly to the bath.
  • 100 grams of No. 8 by %-inch steel screws were barrel plated in a bath having the composition described in Example I containing 4.5 milliliters/liter of the poly-5- alanine/methyl Cellosolve solution. The screws were plated for minutes in a Daniels Type 3H minibarrel using a current of 5 amps. After washing and bright dipping in 0.5 weight percent nitric acid, the screws were found to have a blue-white color and were bright and lustrous.
  • EXAMPLE IV In this example, isopropanol was used as a solvent in preparing poly-,B-alanine and a still plating operation was carried out.
  • the poly-B-alanine was prepared by refluxing 100 grams of ethylene cyanohydrin, 40 grams of isopropanol and 2 grams of potassium hydroxide. To the cold reflux, 160 grams of cold water was added to form a yellow stock solution having a specific gravity of 1.05. A bath having the composition of that described in Example I and containing 1.5 grams/liter of stock solution was prepared.
  • a six link length of steel chain (each link 1-inch long by %-inch wide made from -inch rod) was suspended in the bath and plated for 15 minutes using a zinc oxide, rather than zinc" cyanide, may be used in the baths. Details for preparing and using the baths are, of course, well known to those skilled in the art.
  • the bright zinc deposits provided by the present invention are responsive to treatment with protective agents. Excellent results are obtained using a variety of available commercial products such as chromate conversion coating preparations.
  • An aqueous, alkaline, cyanide zinc electroplating bath containing as a brightening agent therefor a Watersoluble homopolymer of 3-alanine, said homopolymer being present in an amount sufficient to yield a zinc electrodeposit of improved brightness.
  • n is an integer from 5 to 10.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US471753A 1965-07-13 1965-07-13 Electroplating bath and process Expired - Lifetime US3454475A (en)

Applications Claiming Priority (1)

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US47175365A 1965-07-13 1965-07-13

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US3454475A true US3454475A (en) 1969-07-08

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NL (1) NL6607127A (forum.php)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4717458A (en) * 1986-10-20 1988-01-05 Omi International Corporation Zinc and zinc alloy electrolyte and process

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2451426A (en) * 1943-11-25 1948-10-12 Du Pont Bright zinc plating
US2589209A (en) * 1948-09-04 1952-03-18 Hanson Van Winkle Munning Co Dithiocarbamate-aldehyde condensation polymers
US2680712A (en) * 1951-08-07 1954-06-08 Hanson Van Winkle Munning Co Alkaline zinc plating baths
US2691643A (en) * 1950-11-15 1954-10-12 Transparent Package Company Preparation of polypeptides of beta-alanine
US2734081A (en) * 1956-02-07 Preparation of
US2791554A (en) * 1954-09-22 1957-05-07 Ann F Hull Method of electrodepositing zinc
US2798040A (en) * 1955-09-15 1957-07-02 Dow Chemical Co Electrowinning of metals
US2860089A (en) * 1956-08-09 1958-11-11 R O Hull & Company Inc Method of electro depositing zinc
US2989449A (en) * 1960-04-06 1961-06-20 Du Pont Electrodeposition of zinc

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734081A (en) * 1956-02-07 Preparation of
US2451426A (en) * 1943-11-25 1948-10-12 Du Pont Bright zinc plating
US2589209A (en) * 1948-09-04 1952-03-18 Hanson Van Winkle Munning Co Dithiocarbamate-aldehyde condensation polymers
US2691643A (en) * 1950-11-15 1954-10-12 Transparent Package Company Preparation of polypeptides of beta-alanine
US2680712A (en) * 1951-08-07 1954-06-08 Hanson Van Winkle Munning Co Alkaline zinc plating baths
US2791554A (en) * 1954-09-22 1957-05-07 Ann F Hull Method of electrodepositing zinc
US2798040A (en) * 1955-09-15 1957-07-02 Dow Chemical Co Electrowinning of metals
US2860089A (en) * 1956-08-09 1958-11-11 R O Hull & Company Inc Method of electro depositing zinc
US2989449A (en) * 1960-04-06 1961-06-20 Du Pont Electrodeposition of zinc

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4717458A (en) * 1986-10-20 1988-01-05 Omi International Corporation Zinc and zinc alloy electrolyte and process

Also Published As

Publication number Publication date
NL6607127A (forum.php) 1967-01-16

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