US3806431A - Zinc electroplating bath having low cyanide content - Google Patents
Zinc electroplating bath having low cyanide content Download PDFInfo
- Publication number
- US3806431A US3806431A US00249628A US24962872A US3806431A US 3806431 A US3806431 A US 3806431A US 00249628 A US00249628 A US 00249628A US 24962872 A US24962872 A US 24962872A US 3806431 A US3806431 A US 3806431A
- Authority
- US
- United States
- Prior art keywords
- zinc
- alkanolamine
- aldehyde
- bath
- cyanide
- 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
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052725 zinc Inorganic materials 0.000 abstract description 24
- 239000011701 zinc Substances 0.000 abstract description 24
- 239000007859 condensation product Substances 0.000 abstract description 18
- 238000009713 electroplating Methods 0.000 abstract description 16
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 10
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000737 periodic effect Effects 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical group [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal cyanide Chemical class 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 0.000 description 1
- 208000034155 RAS-associated autoimmune leukoproliferative disease Diseases 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 201000009200 autoimmune lymphoproliferative syndrome type 4 Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
Definitions
- a bath for electroplating zinc containing in aqueous solution a zinc salt, an alkali metal cyanide, an alkali metal hydroxide, an aldehyde-alkanolamine condensation product, a water soluble polyvinyl alcohol and optionally salts of metals of Groups VII-B or VIII of the Periodic Table of Elements and further tricrotonylene tetramine and trithione (3-thio-3H-l,2-dithiole), said bath having a low cyanide content, yields highly brilliant zinc coatings with very good throwing power and metal distribution.
- Preferred aldehyde-alkanolarnine condensation products are condensation products of a mono-alkanolamine with an aromatic aldehyde of the general formula CHO wherein R is hydroxyl and/or lower alkoxy having from 1 to 4 carbon atoms and x is zero, one, or two.
- the invention BACKGROUND OF THE INVENTION
- the invention relates to a zinc electroplating bath having a low cyanide content.
- cyanide containing electroplating baths for depositing zinc on, e.g., iron.
- the zinc deposits obtained with the known baths may have good throwing power, brilliance and a good metal distribution.
- the addition of brighteners to the electroplating baths is required.
- As brighteners for this purpose aldehyde-alkanolamine condensation products, water soluble polyvinyl alcohol and salts of metals of Group VII-B or Group VIII of the Periodic Table are known. Since the problem of water pollution and the costly measures of freeing waste water from poisonous substances gain growing importance the use of cyanide containing electroplating baths recently has decreased considerably. At present increasingly weak acid or alkaline zinc electroplating baths with no cyanide or having a low cyanide content are used which, however, usually do not provide the brilliance of cyanide containing zinc electroplating baths.
- the cyanide content of the bath of the invention may be lowered from the normal content of 80 g. to 150 g./l. to a level of from g. to 25 g./l. without adversely affecting the zinc deposit obtained.
- It is a further object of the present invention to provide an alkaline zinc electroplating bath comprising in aqueous solution a zinc salt, one or more aldehyde-alkanolarnine condensation products, water soluble polyvinyl alcohol and optionally salts of a metal of Groups VII- B or VIII of the Periodic Table of Elements and, in addition, tricrotonylene tetramine and trithione (3-thio-3H-l,2-dithiole).
- additives such as additional brighteners may be used.
- the zinc electroplating bath according to the invention preferably contains 0.1 g. to 1.0 g./l. of tricrotonylene tetramine. Most preferred is an amount of 0.1 g. to 0.5 g. of tricrotonylene tetramine per liter of the zinc bath.
- the preferred amounts of trithione in the zinc bath are 0.01 g. to 0.05 g./l., in particular 0.01 g. to 0.02 g./l.
- Preferred aldehyde-alkanolamine condensation products are condensation products of a lower mono-alkanolamine, such as mono-ethanolamine and of an aldehyde of the formula OHO - (R); wherein R is hydroxyl and/or lower alkoxy having 1 to 4 carbon atoms, in particular methoxy, and x is zero, one, or two.
- Preferred aldehydes are salicylaldehyde, anisaldehyde, vanillin, or veratraldehyde.
- unsaturated aromatic aldehydes such as cinnamic aldehyde, or formaldehyde can also be used.
- the amount of the aldehyde-alkanolamine condensation product is preferably between 0.2 g. and 2 g./l. of the bath, in particular between 0.3 g. and 1 g./l., as the salt of a metal of Group VII-B or Group VIII of the Periodic Table, a salt of manganese, cobalt or nickel is preferred.
- Said salt is used in amounts between 0.01 g. and 0.1 g./l. preferably between 0.01 g. and 0.05 g./l.
- Polyvinyl alcohol is preferably used in an amount between 0.01 g. and 0.5 g./l., in particular between 0.1 g. and 0.5 g./l. of the bath.
- EXAMPLE II 0.5 g./l. of a condensation product of mono-ethanolamine and vanillin, 0.2-0.4 'g./l. of tricrotonylene tetramine, 0.01-0.05 g./l. of trithione,
- EXAMPLE III Smooth and bright zinc coatings on iron having good throwing power and metal distribution were obtained by using an electroplating bath of the following composition:
- a zinc electroplating bath comprising, in aqueous solution,
- a zinc salt in an amount equivalent to between about 7 g./l. and about 15 g./l. of zinc oxide
- the zinc electroplating bath of claim 1 in which the condensation product of an aldehyde with an alkanolamine is the condensation product of a lower mono alkanolamine and an aromatic aldehyde of the formula OHO ('R) z in which R is a member selected from the group consisting of hydroxyl and lower alkoxy with 1 to 4 carbon atoms, and x is one of the numerals 0, 1, and 2.
- a zinc electroplating bath comprising, in aqueous solutions,
- a zinc salt in an amount equivalent to between about 7 g./l. and about 15 g./l. of zinc oxide
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (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)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DENDAT2123108 DE2123108A1 (OSRAM) | 1972-05-02 | ||
| US00249628A US3806431A (en) | 1972-05-02 | 1972-05-02 | Zinc electroplating bath having low cyanide content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00249628A US3806431A (en) | 1972-05-02 | 1972-05-02 | Zinc electroplating bath having low cyanide content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3806431A true US3806431A (en) | 1974-04-23 |
Family
ID=22944319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00249628A Expired - Lifetime US3806431A (en) | 1972-05-02 | 1972-05-02 | Zinc electroplating bath having low cyanide content |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3806431A (OSRAM) |
| DE (1) | DE2123108A1 (OSRAM) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915815A (en) * | 1972-11-15 | 1975-10-28 | Reinhard Koch | Alkaline zinc electroplating bath |
| US4169772A (en) * | 1978-11-06 | 1979-10-02 | R. O. Hull & Company, Inc. | Acid zinc plating baths, compositions useful therein, and methods for electrodepositing bright zinc deposits |
-
0
- DE DENDAT2123108 patent/DE2123108A1/de active Pending
-
1972
- 1972-05-02 US US00249628A patent/US3806431A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915815A (en) * | 1972-11-15 | 1975-10-28 | Reinhard Koch | Alkaline zinc electroplating bath |
| US4169772A (en) * | 1978-11-06 | 1979-10-02 | R. O. Hull & Company, Inc. | Acid zinc plating baths, compositions useful therein, and methods for electrodepositing bright zinc deposits |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2123108A1 (OSRAM) |
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