GB2064585A - Acid Zinc Electroplating Solutions and Method Utilizing Ethoxylated/Propoxylated Polyhydric Alcohols - Google Patents
Acid Zinc Electroplating Solutions and Method Utilizing Ethoxylated/Propoxylated Polyhydric Alcohols Download PDFInfo
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- GB2064585A GB2064585A GB8036594A GB8036594A GB2064585A GB 2064585 A GB2064585 A GB 2064585A GB 8036594 A GB8036594 A GB 8036594A GB 8036594 A GB8036594 A GB 8036594A GB 2064585 A GB2064585 A GB 2064585A
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- zinc
- acid
- plating solution
- aqueous
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- 239000011701 zinc Substances 0.000 title claims abstract description 99
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 99
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 18
- 238000009713 electroplating Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 22
- 238000007747 plating Methods 0.000 claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 238000007670 refining Methods 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 24
- 235000011187 glycerol Nutrition 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005282 brightening Methods 0.000 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000006353 oxyethylene group Chemical group 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 235000010356 sorbitol Nutrition 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 claims description 5
- 229930008407 benzylideneacetone Natural products 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical group CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- JJKVMNNUINFIRK-UHFFFAOYSA-N 4-amino-n-(4-methoxyphenyl)benzamide Chemical compound C1=CC(OC)=CC=C1NC(=O)C1=CC=C(N)C=C1 JJKVMNNUINFIRK-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 239000003752 hydrotrope Substances 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- -1 oxyethylene, glycerin Chemical class 0.000 claims 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims 2
- MHGOKSLTIUHUBF-UHFFFAOYSA-N 2-ethylhexyl sulfate Chemical compound CCCCC(CC)COS(O)(=O)=O MHGOKSLTIUHUBF-UHFFFAOYSA-N 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 235000000346 sugar Nutrition 0.000 claims 1
- 150000008163 sugars Chemical group 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 4
- 239000011260 aqueous acid Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- 239000011248 coating agent Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 150000002314 glycerols Chemical group 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- MHGOKSLTIUHUBF-UHFFFAOYSA-M 2-ethylhexyl sulfate(1-) Chemical compound CCCCC(CC)COS([O-])(=O)=O MHGOKSLTIUHUBF-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002557 polyglycidol polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical class [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- 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)
- Electroplating Methods And Accessories (AREA)
Abstract
The problem of low "cloud point" and of foaming associated with the conventional grain-refining agents used in aqueous acid zinc electroplating solutions are reduced or avoided by employing as the grain- refining agent a polyhydric alcohol having three or more hydroxyl groups substituted with one or more oxyalkylene groups and which is soluble in the zinc plating solution. The use of these grain-refining agents also permits continuous operation at higher bath temperatures than is presently possible without deterioration or clouding of the plating solutions, and plating at lower temperatures than is presently possible.
Description
SPECIFICATION
Acid Zinc Plating Solutions and Method
Utilizing Ethoxylated/Propoxylated Polyhydric
Alcohols
Technical Field
This invention relatesto the field of electroplating, or electrodepositing, zinc and, in preferred embodiments, to novel acid zinc plating solutions which are capable of providing a high quality bright and lustrous zinc deposit on a conductive workpiece utilizing conventional electroplating apparatus. The invention also provides an improved method for electroplating high quality zinc coatings from the novel acid zinc plating solutions of the invention. Either bright and lustrous, or semibright, zinc platings, having excellent adhesion and a high degree of ductility can be produced in accordance with the invention.
Background
It is well known in the art that bright and lustrous metallic zinc deposits can be electroplated on a metallic substrate from aqueous acid zinc plating solutions, or baths.
However, difficulties persist in commercially producing uniform and reliable zinc coatings with sufficiently high levels of brightness and luster.
For example, the temperature of the plating solution must be controlled generally within a range of about 600 to 900F (150 to 300C).
Particularly at higher temperatures, difficulties are experienced with "clouding", or instability of the plating solutions, particularly with solution components which are hydrophobic or contain hydrophobic su bstituents. At lower temperatures, difficulties are encountered in obtaining uniform and acceptable zinc coatings, particularly with regard to avoidance of streaking and like surface imperfections.
In conventional acid zinc plating baths, grainrefining agents are utilized to produce a commercially acceptable bright and lustrous zinc coating. Without grain-refining agents, the zinc coatings produced by conventional baths may not exhibit uniformly smooth and refined surfaces over the full range of current densities normally encountered in commercial applications. In the prior art, grain-refining agents have typically been polyethers which contain substantial quantities of hydrophobic substituents, exhibit substantial surface-active properties and are classified as surfactants.
Due to the presence of substantial quantities of hydrophobic substituents, the solubility of the prior art grain-refining agents in an aqueous, acid zinc plating bath has been of critical importance.
Such baths typically exhibit a low "cloud point", which is the point at which the surfactant or hydrophobic materials begin to separate from the aqueous plating solution.
It is also desirable to utilize agitation in a zinc plating bath, which is typically provided by bubbling air through the plating solution.
However, the presence of conventional grainrefining agents, which are surfactants, leads to excess foaming that must be controlled, usually by addition of further additives, such as defoaming agents or the like.
Illustrative of aqueous, acid zinc plating systems utilizing such prior art grain-refining agents are those disclosed in U. S. Patents No.
3,920,528; No.3,928,149; No.4,014,761; No.
4,075,066; No. 4,119,502; No. 4,137,133; and No.4,138,394. U.S Patent No.3,891,520 discloses use of polymers of polyethylene glycol, which are dihydric alcohols, while U.S. Patent No.
4,070,256 indicates that aliphatic monohydric alcohols can be utilized. However, both the monohydric and dihydric alcohols used in the prior art are surface-active agents (i.e., surfactants) and are foamers in the acid zinc plating baths in which they are utilized. U.S.
Patent No. 3,945,894 discloses use of water soluble polyglycidols and derivatives thereof, which exhibit poor throwing and covering power, and cause formation of unacceptable bands or interference in the mid-current density ranges.
In all of these acid zinc plating baths of the prior art, there remains a need for a grain-refining agent which makes little, if any, contribution to the cloud point of the bath, and which does not foam in the operating zinc plating solutions.
The improved zinc acid plating solutions and method of the invention provide both a wide latitude of operational utility, particularly with respect to the operable temperatures of the plating bath. They also do not contribute to foaming. They are particularly useful and advantageous because they allow for continuous operation at higher bath temperatures than is presently possible, without deterioration or clouding of the plating solutions. In addition, they allow for commercially acceptable plating to proceed at much lower temperatures than is presently possible. This eliminates the need for preliminary heat up of the plating baths before plating can be started.
Summary of Invention
In accordance with the invention, it has been discovered that aqueous, acid zinc plating solutions for electrodeposition of zinc coatings can be provided utilizing a grain-refining agent comprising a non-surfactant substituted polyhydric alcohol having three or more ethoxylated and/or propoxylated hydroxyl groups.
Typically, the aqueous, acid zinc plating solutions of the invention contain a source of zinc ions, an electrolyte which provides electrolytically charged ions which are capable of conducting an electric current, at least one organic brightener or luster forming agent, and an organic acid or salt thereof, in addition to the novel grain-refining agents of the invention. Preferably, these plating solutions may also contain a buffering agent, as well as other optional additives which do not adversely effect the solubility or stability of the zinc plating solution. Semi-bright zinc coatings can likewise be produced by variation, elimination, of the amount of brightener used in these plating solutions.
The plating solutions of the invention can be effectively operated at a temperature ranging from about 50 to 1000F (100 to 490C) and at a pH ranging from between about 4.5 to 6.5. These plating solutions effectively have no significant cloud point and substantially no foam is generated by the grain-refining agents of the invention in the plating solution, even when air agitation is utilized.
An improved method for electroplating zinc coatings, preferably having a bright and lustrous appearance, is also provided in accordance with the invention, whereby the novel aqueous, acid zinc plating solution of the invention is utilized for electroplating.
Zinc coatings can be produced in accordance with the invention which exhibit excellent grain refinement and high quality brightness and luster over a wide range of current densities and plating conditions. If less brightener is used, a semi-bright zinc plate having excellent adhesion and a high degree of ductility can be produced.
Accordingly, it is an object of the invention to provide improved aqueous, acid zinc plating solutions which contain grain-refining agents and permit electro-deposition of commercially acceptable bright and lustrous, or semi-bright, zinc coatings over a wider range of plating conditions, most notably temperature, than is possible with conventional acid zinc plating baths.
It is a further object of the invention to provide an improved aqueous, acid zinc plating solution which does not foam when air agitation or the like is utilized during electroplating of bright and lustrous zinc coatings.
It is yet a further object of the invention to provide an improved method of electroplating zinc coatings over the widest possible range of plating conditions, particularly temperature, and without foaming.
Other objects and advantages of the novel aqueous, acid zinc plating solution and method of the invention will be readily apparent to those skilled in the art through study of the following description of the preferred embodiments and the appended claims.
Description of Preferred Embodiments
An improved aqueous, acid zinc plating solution capable of electroplating bright and lustrous zinc coatings is provided in accordance with a preferred embodiment of the invention.
Such an aqueous acid zinc plating bath contains a source of zinc ions in solution. Any conventional source of zinc ions can be utilized. For example, zinc chloride, zinc sulfate, zinc sulfamate, zinc acetate, zinc fluoborate or mixtures thereof can be dissolved in aqueous solution. Nevertheless, it is fully within the purview of the invention that any compound or material capable of providing a source of zinc ions in aqueous solution, which does not otherwise interfere with the stability or operability of the resultant aqueous plating solution, can be utilized.
An electrolyte is provided in the aqueous plating solution to provide electrically charged ions capable of conducing an electrical current.
For example, an electrolyte may be selected from any soluble alkali salt of hydrochloric acid, sulfuric acid, sulfamate acid, fluoboric acid, or acetic acid, or from ammonium chloride, ammonium sulfate, ammonium sulfa mate, ammonium acetate, ammonium fluoborate or mixtures thereof. It is fully within the purview of the invention that other suitable electrolytes may be utilized, provided they do not interfere either with the stability or operability of the resultant aqueous zinc plating bath.
Since the preferred embodiment of the novel zinc plating solution of the invention is to be operable to provide a bright or lustrous zinc coating, at least one brightening agent is added to the bath. The amount of such brightening agent may be varied to control the degree of brightness required. For example, conventional brightening agents such as benzylidene acetone or ochlorobenzaldehyde may be utilized. Of course, if a semi-bright or dull zinc coating is desired, a reduced amount of brightener may be utilized or the brightening agent omitted from the plating bath all together. Such modification of the specific composition of the novel zinc plating solution of the invention is fully within the skill of one in the art.
The zinc plating bath of the invention also contains an organic acid, or salt of an organic acid. Preferably, benzoic acid or sodium benzoate are utilized.
The aqueous zinc plating solution of the invention further contains a novel and improved grain-refining agent comprising a polyhydric alcohol having three or more hydroxyl groups substituted with one or more oxyalkylene groups.
Preferably, a polyhydric alcohol such as glycerin, sorbitol, mannitol or the like is utilized, having hydroxyl groups substituted with either oxyethylene or oxypropylene groups, or combinations thereof.
It is within the purview of the invention that the number of oxyalkylene groups substituted on a polyhydric alcohol which can be used as improved grain-refining agent of the invention may be varied over a broad range. The number depends upon the particular polyhydric alcohol which is substituted, the specific oxyalkylene group selected and variables of the zinc plating solution, such as pH, operating temperature and solubility.
Accordingly, the number of oxyalkylene groups is not a limiting factor of the invention, provided the substituted polyhydic alcohol is soluble, and remains substantially soluble, in the zinc plating solutions of the invention.
Preferably, when the grain-refining agent of the invention is glycerin substituted with oxyethylene groups, between 5 to 30 moles of ethylene oxide are substituted for hydroxyl groups. Glycerin substituted with oxypropylene groups preferably has between 3 and 1 5 moles of propylene oxide substituted for hydroxyl groups.
When the grain-refining agent of the invention is an oxyethylene substituted sorbitol, preferably between 6 and 100 moles of ethylene oxide are substituted for hydroxyl groups. Sorbitol substituted with oxypropylene groups preferably has between 1 and 20 moles of propylene oxide substituted for hydroxyl groups.
It is fully within the purview of the invention that such polyhydric alcohols may have less than all available hydroxyl sites substituted. However, it is preferred that all available hydroxyl groups shouid be substituted with an oxyalkylene group.
Furthermore, while oxyalkylene groups normally terminate with a hydroxyl group, the terminal hydrogen may be substituted with any radical group which does not interfere with, or adversely effect, the solubility or performance of the grain-refining agent in the zinc plating solution.
It is also fully within the purview of the
invention that the substituted polyhydric alcohols
utilized as grain-refining agents in accordance
with the invention may contain one or more
different oxyalkylene groups. For example,
glyceric having some hydroxyl sites substituted
with oxyethylene and other hydroxyl sites
substituted with oxypropylene can be utilized in
accordance with the invention. Furthermore,
grain-refining agents in accordance with the
present invention may contain blends of various
different polyhydric alcohols substituted with various different oxyalkylene groups.
Preferably, an anionic surfactant is also
included in a zinc plating solution of the invention.
For example, alkyl sulfates or sulfonates or alkyl
aryl sulfonates can be advantageously utilized.
Most preferred is the sodium sat of 2-ethyl hexyl sulfate.
Optionally, it may also be desirable to
incorporate a buffering agent, such as boric acid
or salts thereof, in the novel zinc plating solution
of the invention. Other conventional types of
additives and agents, which are not incompatible
with the solubility or performance of the zinc
plating solutions of the invention, may be also
incorporated, if desired. For example, it is fully
within the purview of the invention that
hydrotropes or like additives can be optionally
included in zinc plating solutions of the invention.
In accordance with the preferred embodiment
of the method of the invention, an aqueous, acid
zinc plating solution of the invention is used to
electroplate a bright and lustrous zinc coating.
The temperature of the zinc plating solution is
maintained between about 5O0Fto 120by (100C to 490C), and preferably between 650 and 900F (1 80--33 OC), with a pH ranging from between
about 4.5 to 6.5 and preferably between 4.9 and
5.3. Current density ranging from about 1 to 120 amps per square foot (amps/ft2) can be applied between a zinc anode and an immersed metallic workpiece.
In accordance with the method of the invention utilizing the improved aqueous, acid zinc plating solution, platings of zinc which are bright and lustrous over the entire range of current density are obtained. If semi-bright or dull zinc coatings are desired, and less brightening agent incorporated in the zinc plating solution, a semibright or dull zinc coating will be produced having excellent adhesion and a high degree of ductility.
While the thickness of the zinc coatings obtained in accordance with the invention is not limited, it usually ranges from between 0.1 and 0.6 mils (0.0001 to 0.0006 inches) and, preferably, about 0.25 mils (0.00025 inches).
In order to illustrate more fully the improved aqueous, acid zinc plating solutions and method of the invention, the following Examples are set forth, but are not intended to limit the scope of the invention.
Example 1
An aqueous, acid zinc chloride plating solution was prepared by admixture of the following:
Zinc chloride 34 g/l
Potassium chloride 210 g/l
Boric acid 26 g/l
2-ethyl hexyl sulfate
sodium salt 21 g/l
Benzoic acid, sodium salt 3.7 g/l
Benzylidene acetone 0.26 g/l
o-chlorobenzaldehyde 0.07 g/l
Glycerin ethoxylated with
17 moles of ethylene
oxide 8.5 g/l
This zinc plating solution had a pH between 4.9 and 5.3 and a temperature of 750F (23.9 or). A steel panel was prepared in the conventional manner and placed in a standard Hull cell. Two amps of electrical current was applied across the electrodes of the cell for 5 minutes, so as to produce a current density ranging from about 1 to 120 amps/ft.2. Solution agitation was provided by mechanical motion.
After 5 minutes, the flow of current was terminated and panel removed for examination.
The panel was coated with a bright and lustrous plating of zinc over the entire range of current densities.
Example 2
Example 1 was repeated, with the exception that glycerin ethyoxylated with 26 moles of ethylene oxide (commercially available under the trade name Macol ETG-26) was used as the
grain-refining agent.
The resultant panel exhibited a bright and
lustrous plating of zinc over the entire range of
current densities.
Example 3
Example 1 was repeated, except that glycerin
ethoxylated with 5 moles of ethylene oxide was
used as the grain-refining agent.
The resultant panel exhibited a bright and lustrous plating over the entire range of current density.
Example 4
Example 1 was repeated, except that glycerin ethoxylated with 30 moles of ethylene oxide was used as the grain-refining agent.
The resultant panel exhibited a zinc plating which was bright and lustrous over the entire range of current density.
Example 5
Example 1 was repeated, except that plating was conducted at an elevated temperature which ranged between 1200 and 1250F (48.90 to 51.70C).
The resultant zinc coating on the panel exhibited a bright and lustrous appearance over the entire range of current density.
Example 6
For purposes of comparison with the performance of a grain-refining agent of the prior art. Example 5 was repeated, except that a conventional grain-refining agent comprising cetyl-stearyl alcohol ethoxylated with 26 moles of ethylene oxide was used in place of the substituted glycerin material of the invention.
The zinc plating solution clouded and the grainrefining agent partially separated from solution forming an oily film. The resultant zinc plating on the panel exhibited poor grain refinement and an oily surface, and was commercially unacceptable.
Example 7
Example 1 was repeated, except that glycerin having hydroxyl groups substituted with 30 moles of ethylene oxide and 1.5 moles of propylene oxide was utilized as the grain-refining agent of the invention.
The resultant zinc coating on the panel was bright and lustrous over the entire range of current density.
Example 8
Example 1 was repeated, except that glycerin having hydroxyl groups substituted with 12 moles of propylene oxide (commercially available under the trade name Macol ETG-12) was used as the grain-refining agent.
The resultant zinc coating on the panel was bright and lustrous over the entire range of current densities.
Example 9
Example 1 was again repreated, except that sorbitol ethoxylated with 50 moles of ethylene oxide was utilized as the grain-refining agent.
The resultant zinc coating on the panel was bright and lustrous over the entire range of current density,
Although the preceding specific examples are presented solely for purposes of illustration, it is to be understood that such zinc plating solutions and methods of electroplating zinc utilizing the same in accordance with the invention maybe altered, varied or modified without departing from the spirit or scope of the invention as defined by the appended claims.
Claims (22)
1. An aqueous, acid zinc plating solution for electrodeposition of zinc coatings consisting of:
(a) a source of zinc ions;
(b) an electrolyte which provides electrolytically charged ions capable of conducting an electric current;
(c) an organic acid or salt of an organic acid; and
(d) a grain-refining agent comprising a polyhydric alcohol having three or more hydroxyl groups substituted with one or more oxyalkylene groups.
2. The aqueous, acid zinc plating solution of claim 1 further including at least one organic brightening agent.
3. The aqueous, acid zinc plating solution of claim 2 wherein said brightening agent is selected from benzylidene acetone and ochlorobenzaldehyde.
4. The aqueous, acid zinc plating solution of
claim 1, claim 2 or claim 3 where said source of zinc ions is a zinc salt selected from zinc chloride, zinc sulfate, zinc sulfamate, zinc acetate, zinc fluoborate or mixtures thereof and said electrolyte is selected from a soluble alkali salt of hydrochloric acid, sulfuric acid, sulfamic acid, fluoboric acid, or acetic acid, and ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium acetate, ammonium fluoborate or mixtures thereof.
5. The aqueous, acid zinc plating solution of any one of claims 1 to 4, further including an anionic surfactant.
6. The aqueous, acid zinc plating solution of any one of claims 1 to 5 further including one or more additives selected from buffering agents, selected from boric acid or salts thereof, or hydrotropes.
7. The aqueous, acid zinc plating solution of any one of claims 1 to 6 wherein said polyhydric alcohol is selected from glycerin, sorbitol, mannitol or other polyhydric alcohols substituted with at least one mole of oxyalkylene per available hydroxyl group, said oxyalkylene being selected from oxyethylene or oxypropylene.
8. The aqueous, acid zinc plating solution of claim 7 wherein said polyhydric alcohol is selected from glycerin having hydroxyl groups substituted with 1 7 moles of oxyethylene, glycerin having hydroxyi groups substituted with
12 moles of oxypropylene, glycerin having hydroxyl groups substituted with 30 moles of oxyethylene and 1.5 moles of oxypropylene, or sorbitol having hydroxyl groups substituted with 50 moles of ethylene oxide.
9. An aqueous, acid zinc plating solution comprising:
(a) zinc chloride;
(b) potassium chloride;
(c) boric acid;
(d) 2-ethyl hexyl sulfate, sodium salt;
(e) benzoic acid, sodium sait;
(f) benzylidene acetone;
(g) o-chlorobenzaldehyde; and
(h) glycerin ethoxylated with 1 7 moles of ethylene oxide.
10. An aqueous, acid zinc plating solution as claimed in claim 1, substantially as hereinbefore described with particular reference to the examples.
11. An aqueous, acid zinc plating solution as claimed in claim 1 substantially as shown in any one of Example 1 to 5 and 7 to 9.
12. An improved method for electroplating bright and lustrous zinc comprising:
(a) providing an aqueous, acid zinc plating solution comprising zinc ions, electrolytic ions, an organic acid or salt thereof, and a grain-refining agent comprising a polyhydric alcohol having three or more hydroxyl groups substituted with one or more oxyalkylene groups,
(b) maintaining said plating solution at a temperature ranging between about 500F to 1 200F and a pH of between about 4.5 to 6.5,
(c) immersing a metallic workpiece and a zinc anode in said plating solution, and
(d) applying a voltage across said metallic workpiece and anode cause electroplating of zinc to occur on said metallic workpiece.
13. The method of claim 12 further including in said plating solution at least one brightening agent.
14. The method of claim 13 wherein said brightening agent is selected from benzylidene acetone or o-chlorobenzaldehyde.
1 5. The method of claim 12, 13 or 14 wherein said source of zinc ions is a zinc salt selected from zinc chloride, zinc sulfate, zinc sulfamate, zinc acetate, zinc fluoborate or mixtures thereof and said electrolyte is selected from a soluble alkali salt of hydrochloric acid, sulfuric acid, sulfamic acid, fluoboric acid, or acetic acid, and ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium acetate, ammonium fluoborate or mixtures thereof.
16. The method of any one of claims 12 to 15 further including in said plating solution an anionic surfactant.
17. The method of any one of claims 12 to 16 wherein said zinc plating solution further includes one or more additives selected from buffering agents, selected from boric acid or salts thereof, or hydrotropes.
1 8. The method of any one of claims 12 to 17 wherein said polyhydric alcohol is selected from glycerin, sorbitol, mannitol or other sugars substituted with at least one mole of oxyalkylene per hydroxyl group, said oxyalkylene being selected from oxyethylene or oxypropylene.
1 9. The method of claim 18 wherein said polyhydric alcohol is selected from glycerin having hydroxyl groups substituted with 1 7 moles of oxyethylene, glycerin having hydroxyl groups substituted with 1 2 moles of oxypropylene, glycerin having hydroxyl groups substituted with 30 moles of oxyethylene and 1.5 moles of oxypropylene, or sorbitol having hydroxyl groups substituted with 50 moles of ethylene oxide.
20. A method as claim in claim 12, substantially as hereinbefore described with particular reference to the Examples.
21. A method as claimed in claim 12, substantially as shown in any one of Examples 1 to 5 and 7 to 9.
22. Zinc plated articles when prepared by the method claimed in any one of claims 12 to 21 or using the zinc plating solution claimed in any one of claims 1 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9548379A | 1979-11-19 | 1979-11-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2064585A true GB2064585A (en) | 1981-06-17 |
| GB2064585B GB2064585B (en) | 1983-11-09 |
Family
ID=22252215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8036594A Expired GB2064585B (en) | 1979-11-19 | 1980-11-14 | Acid zinc electro plating solutions and methods utilizing ethoxylated/propoxylated polyhydric alcohols |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5841357B2 (en) |
| AU (1) | AU536353B2 (en) |
| BE (1) | BE886216A (en) |
| BR (1) | BR8007548A (en) |
| CH (1) | CH647009A5 (en) |
| ES (1) | ES496940A0 (en) |
| FR (1) | FR2470169B1 (en) |
| GB (1) | GB2064585B (en) |
| IT (1) | IT1142191B (en) |
| SE (1) | SE8008081L (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2557892A1 (en) * | 1984-01-09 | 1985-07-12 | Omi Int Corp | ACID SOLUTION FOR ELECTROLYTIC COATING OF ZINC AND ZINC ALLOY, AND METHOD FOR USING THE SAME |
| FR2595102A1 (en) * | 1986-03-03 | 1987-09-04 | Omi Int Corp | POLYOXYALKYL POLYHYDROXYL COMPOUNDS AS ADDITIVES IN ZINC ALLOY ELECTROLYTES |
| GB2266894A (en) * | 1992-05-15 | 1993-11-17 | Zinex Corp | Modified tin brightener for tin-zinc alloy electroplating bath |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5775077B2 (en) * | 2009-07-30 | 2015-09-09 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Metal plating composition containing an inhibitor for filling submicron structures without voids |
| US20110108115A1 (en) * | 2009-11-11 | 2011-05-12 | International Business Machines Corporation | Forming a Photovoltaic Device |
| JP5552042B2 (en) | 2010-12-27 | 2014-07-16 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Program analysis method, system and program |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB602591A (en) * | 1945-02-12 | 1948-05-31 | Du Pont | Improvements in or relating to the electro-deposition of metals |
| GB895156A (en) * | 1959-03-19 | 1962-05-02 | Metal & Thermit Corp | Electrodeposition of copper |
| JPS4840543B1 (en) * | 1970-04-24 | 1973-12-01 | ||
| DE2160081A1 (en) * | 1970-12-03 | 1972-08-03 | Popescu geb. Micsunescu, Francine, Paris | Process for the production of brighteners for baths for electroplating, the brighteners thus obtained and baths for the use of these brighteners |
| JPS5249297B2 (en) * | 1973-05-24 | 1977-12-16 |
-
1980
- 1980-11-14 GB GB8036594A patent/GB2064585B/en not_active Expired
- 1980-11-17 CH CH850380A patent/CH647009A5/en not_active IP Right Cessation
- 1980-11-18 ES ES496940A patent/ES496940A0/en active Granted
- 1980-11-18 IT IT50187/80A patent/IT1142191B/en active
- 1980-11-18 BE BE2/58861A patent/BE886216A/en not_active IP Right Cessation
- 1980-11-18 SE SE8008081A patent/SE8008081L/en not_active Application Discontinuation
- 1980-11-18 AU AU64493/80A patent/AU536353B2/en not_active Ceased
- 1980-11-19 JP JP55162102A patent/JPS5841357B2/en not_active Expired
- 1980-11-19 FR FR8024575A patent/FR2470169B1/en not_active Expired
- 1980-11-19 BR BR8007548A patent/BR8007548A/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2557892A1 (en) * | 1984-01-09 | 1985-07-12 | Omi Int Corp | ACID SOLUTION FOR ELECTROLYTIC COATING OF ZINC AND ZINC ALLOY, AND METHOD FOR USING THE SAME |
| GB2152535A (en) * | 1984-01-09 | 1985-08-07 | Omi Int Corp | Zinc and zinc alloy electroplating |
| FR2595102A1 (en) * | 1986-03-03 | 1987-09-04 | Omi Int Corp | POLYOXYALKYL POLYHYDROXYL COMPOUNDS AS ADDITIVES IN ZINC ALLOY ELECTROLYTES |
| GB2188334A (en) * | 1986-03-03 | 1987-09-30 | Omi Int Corp | Electrolyte for zinc alloy deposition |
| GB2188334B (en) * | 1986-03-03 | 1990-08-22 | Omi Int Corp | Zinc alloy electrolytes |
| GB2266894A (en) * | 1992-05-15 | 1993-11-17 | Zinex Corp | Modified tin brightener for tin-zinc alloy electroplating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2470169B1 (en) | 1985-09-27 |
| AU536353B2 (en) | 1984-05-03 |
| JPS5693889A (en) | 1981-07-29 |
| ES8204769A1 (en) | 1982-05-01 |
| IT8050187A0 (en) | 1980-11-18 |
| AU6449380A (en) | 1981-05-28 |
| GB2064585B (en) | 1983-11-09 |
| BE886216A (en) | 1981-05-18 |
| SE8008081L (en) | 1981-05-20 |
| BR8007548A (en) | 1981-06-02 |
| JPS5841357B2 (en) | 1983-09-12 |
| CH647009A5 (en) | 1984-12-28 |
| IT1142191B (en) | 1986-10-08 |
| FR2470169A1 (en) | 1981-05-29 |
| ES496940A0 (en) | 1982-05-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19971114 |