US3841982A - Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath - Google Patents

Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath Download PDF

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Publication number
US3841982A
US3841982A US00333927A US33392773A US3841982A US 3841982 A US3841982 A US 3841982A US 00333927 A US00333927 A US 00333927A US 33392773 A US33392773 A US 33392773A US 3841982 A US3841982 A US 3841982A
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US
United States
Prior art keywords
bath
zinc
hydrogen
group
alkyl
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.)
Expired - Lifetime
Application number
US00333927A
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English (en)
Inventor
G Southfield
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.)
OMI International Corp
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Oxy Metal Finishing Corp
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 Oxy Metal Finishing Corp filed Critical Oxy Metal Finishing Corp
Priority to US00333927A priority Critical patent/US3841982A/en
Priority to NL7304246A priority patent/NL7304246A/xx
Priority to FR7311420A priority patent/FR2180708B1/fr
Priority to DE2318984A priority patent/DE2318984C2/de
Priority to IT49467/73A priority patent/IT983031B/it
Priority to CA169,009A priority patent/CA1009178A/en
Priority to GB1826373A priority patent/GB1387529A/en
Priority to AR247599A priority patent/AR197894A1/es
Priority to JP48042757A priority patent/JPS4917324A/ja
Application granted granted Critical
Publication of US3841982A publication Critical patent/US3841982A/en
Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION
Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • X is S- or A is independently selected from the group consisting n is or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of l to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
  • Zincate plating baths have been used as a means of electrodepositing zinc without employing cyanide ions due to the difficulty in disposing of cyanide ions in waste efiluent.
  • Some conventional zinc brighteners produce a bright deposit but only over a narrow current density range.
  • the high current density areas generally resulted in a spongy or burnt deposit. It has been found through the combination of brighteners employed in the present case to obtain not only a bright deposit, but also a deposit over a wide current density area.
  • a method for obtaining a bright zinc electrodeposit over a wide current density area from a zincate electroplating bath by employing a combination of additives, the first being a polyethyleneimine and the second one being a heterocyclic nitrogen containing compound.
  • X is S or I NR,
  • A is independently selected from the group consisting n is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
  • Zincate plating baths are those which generally contain zinc oxide and caustic, such as sodium hydroxide.
  • the amount of sodium hydroxide that may be employed ranges from 50 to 250 grams/liter, preferably from about to about 200 grams/liter, while the amount of zinc oxide ranges from 5 to 50 grams/liter, preferably from about 8 to about 30 grams/liter.
  • the processing parameters are such that normally atmospheric temperature and pressure is employed, although temperatures up to 55 C. may also be employed, and even more preferably 15 to about 45 C.
  • the cathode current density ranges from about 5 to 25 amps per sq. ft. while the anode current density ranges from about 10 to 35 amps per sq. ft. where the zinc deposition can occur with agitation.
  • agents may also be present in the bath, such as those described in the above patents.
  • suitable agents may be anisaldehyde, glue, polyvinyl alcohol and the glycerol ester of polyvinyl alcohol wherein these alcohols have a molecular weight of 5,000 to 20.- 000.
  • Other polymers that may be employed are gelatin, peptone, and the like.
  • chelating agents or agents which can form a complex with the metal zinc in the bath may also be employed, such as nitrilotriacetic acid and the various alkali metal salts, such as the sodium salt, ethylenediaminetetraacetic acid, and its water soluble salts, such as sodium, and the like.
  • the polyethyleneimine that may be used in the present case has a molecular weight ranging from 1,000 to 400,- 000, preferably 600 to 60,000 where the percentage of primary, secondary and tertiary nitrogen atoms is about 25, 50, and 25% respectively.
  • a zincate bath that may be employed in the present invention is as follows:
  • the bath pH may be adjusted by adding NaOl-I.
  • Some of the nitrogen heterocylic compounds that may be employed in the present invention are as follows.
  • water solubilizing group any substituent on the six membered carbocyclic ring which will improve the water solubility of the compound.
  • Such groups are hydroxy, alkoxy, such as methoxy or ethoxy and the like, carboxy, amino, and the like.
  • R may be other groups which are not detrimental to the electrodeposition of zinc such as chloro, bromo, cyano (CN), nitro and the like.
  • EXAMPLE 1 A zincate plating bath was formulated containing the following components and was used to electrodeposit zinc onto a steel substrate at a cathode current density of ASP and a temperature of 75 F.
  • the initial bath pH is about 14.
  • EXAMPLE 2 Zincate plating bath similar to the above was also prepared but further including 0.1 g./l. of polyvinyl alcohol. A bright zinc deposit was obtained over a broad current density range following the procedure of Example #1.
  • Example 3 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde with equivalent results being obtained.
  • Example 4 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde and 0.1 grams/liter of polyvinyl alcohol with equivalent results being obtained.
  • An aqueous alkaline electroplating bath comprising inc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration of 0.2 to grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
  • A is independently selected from the group consisting of 11 is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is O, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbons, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
  • a method of depositing bright zinc from a zincate electroplating bath comprising electrolyzing the bath of Claim 1 for a period of time suflicient to form a bright zinc deposit onto a cathodic surface.
  • a cyanide free alkaline zincate electroplating bath comprising zinc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration from 0.2 to 100 grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
  • X is S- or l lR and A is independently selected from the group consisting of n is O or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.

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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)
US00333927A 1972-04-17 1973-02-20 Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath Expired - Lifetime US3841982A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US00333927A US3841982A (en) 1972-04-17 1973-02-20 Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath
NL7304246A NL7304246A (enrdf_load_stackoverflow) 1972-04-17 1973-03-27
FR7311420A FR2180708B1 (enrdf_load_stackoverflow) 1972-04-17 1973-03-29
DE2318984A DE2318984C2 (de) 1972-04-17 1973-04-14 Wäßriges alkalisches Bad und Verfahren zur Abscheidung von glänzenden Zinküberzügen
CA169,009A CA1009178A (en) 1972-04-17 1973-04-16 Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath
GB1826373A GB1387529A (en) 1972-04-17 1973-04-16 Method to improve the brightness of zinc from an alkaline zincate electrode-position bath
IT49467/73A IT983031B (it) 1972-04-17 1973-04-16 Metodo per depositare elettroliti camente zinco brillante e bagni in esso impiegati
AR247599A AR197894A1 (es) 1972-04-17 1973-04-17 Bano de electrochapado alcalino acuoso
JP48042757A JPS4917324A (enrdf_load_stackoverflow) 1972-04-17 1973-04-17

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24493872A 1972-04-17 1972-04-17
US00333927A US3841982A (en) 1972-04-17 1973-02-20 Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath

Publications (1)

Publication Number Publication Date
US3841982A true US3841982A (en) 1974-10-15

Family

ID=26936902

Family Applications (1)

Application Number Title Priority Date Filing Date
US00333927A Expired - Lifetime US3841982A (en) 1972-04-17 1973-02-20 Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath

Country Status (9)

Country Link
US (1) US3841982A (enrdf_load_stackoverflow)
JP (1) JPS4917324A (enrdf_load_stackoverflow)
AR (1) AR197894A1 (enrdf_load_stackoverflow)
CA (1) CA1009178A (enrdf_load_stackoverflow)
DE (1) DE2318984C2 (enrdf_load_stackoverflow)
FR (1) FR2180708B1 (enrdf_load_stackoverflow)
GB (1) GB1387529A (enrdf_load_stackoverflow)
IT (1) IT983031B (enrdf_load_stackoverflow)
NL (1) NL7304246A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084542A (en) * 1990-05-31 1992-01-28 E. I. Du Pont De Nemours And Company Epoxy/isocyanate crosslinked coatings containing 1,3-disubstituted imidazole-2-thione catalysts
US6656606B1 (en) 2000-08-17 2003-12-02 The Westaim Corporation Electroplated aluminum parts and process of production
WO2013056996A1 (de) * 2011-10-19 2013-04-25 Basf Se Formulierungen, ihre verwendung als oder zur herstellung von geschirrspülmitteln und ihre herstellung
CN103842559A (zh) * 2011-10-04 2014-06-04 杰富意钢铁株式会社 电镀锌钢板的制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5332771B2 (enrdf_load_stackoverflow) * 1973-12-10 1978-09-09

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1480997A (fr) * 1966-05-25 1967-05-12 Schering Ag Bain de brillantage zincique alcalin, ne contenant pas de cyanures
DE1935821B2 (de) * 1969-07-15 1972-03-16 Riedel & Co, 4800 Bielefeld Verfahren zur herstellung eines glanzzusatzes fuer alkalische cyanidfreie zinkbaeder

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084542A (en) * 1990-05-31 1992-01-28 E. I. Du Pont De Nemours And Company Epoxy/isocyanate crosslinked coatings containing 1,3-disubstituted imidazole-2-thione catalysts
US6656606B1 (en) 2000-08-17 2003-12-02 The Westaim Corporation Electroplated aluminum parts and process of production
US6692630B2 (en) 2000-08-17 2004-02-17 The Westaim Corporation Electroplated aluminum parts and process for production
CN103842559A (zh) * 2011-10-04 2014-06-04 杰富意钢铁株式会社 电镀锌钢板的制造方法
CN103842559B (zh) * 2011-10-04 2016-11-09 杰富意钢铁株式会社 电镀锌钢板的制造方法
WO2013056996A1 (de) * 2011-10-19 2013-04-25 Basf Se Formulierungen, ihre verwendung als oder zur herstellung von geschirrspülmitteln und ihre herstellung
US8574374B2 (en) 2011-10-19 2013-11-05 Basf Se Formulations, their use as or for producing dishwashing compositions and their preparation
KR20140088566A (ko) * 2011-10-19 2014-07-10 바스프 에스이 제형, 식기세척 세제로서의 또는 이를 제조하기 위한 이의 용도, 및 이의 제조
RU2607085C2 (ru) * 2011-10-19 2017-01-10 Басф Се Составы, их применение в качестве или для приготовления средств для мытья посуды и получение составов
KR101884618B1 (ko) 2011-10-19 2018-08-02 바스프 에스이 제형, 식기세척 세제로서의 또는 이를 제조하기 위한 이의 용도, 및 이의 제조

Also Published As

Publication number Publication date
GB1387529A (en) 1975-03-19
DE2318984C2 (de) 1982-11-11
NL7304246A (enrdf_load_stackoverflow) 1973-10-19
FR2180708B1 (enrdf_load_stackoverflow) 1977-04-29
IT983031B (it) 1974-10-31
AR197894A1 (es) 1974-05-15
CA1009178A (en) 1977-04-26
FR2180708A1 (enrdf_load_stackoverflow) 1973-11-30
DE2318984A1 (de) 1973-11-08
JPS4917324A (enrdf_load_stackoverflow) 1974-02-15

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AS Assignment

Owner name: OXY METAL INDUSTRIES CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084

Effective date: 19741220

AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP.

Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885

Effective date: 19801222

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Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827

Effective date: 19830915

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Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY

Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733

Effective date: 19830930