US3453186A - Additives for tin electroplating bath - Google Patents
Additives for tin electroplating bath Download PDFInfo
- Publication number
- US3453186A US3453186A US597847A US3453186DA US3453186A US 3453186 A US3453186 A US 3453186A US 597847 A US597847 A US 597847A US 3453186D A US3453186D A US 3453186DA US 3453186 A US3453186 A US 3453186A
- Authority
- US
- United States
- Prior art keywords
- thiourea
- weight
- additive
- additives
- tin
- 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
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- 239000000654 additive Substances 0.000 title description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 19
- 238000009713 electroplating Methods 0.000 title description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 50
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 21
- 230000000996 additive effect Effects 0.000 description 19
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000004615 ingredient Substances 0.000 description 16
- 238000007747 plating Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- -1 glycol alkyl ether Chemical class 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000002659 electrodeposit Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000264 sodium ferrocyanide Substances 0.000 description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000010257 thawing Methods 0.000 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 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005028 tinplate Substances 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
Definitions
- the tinplating bath additive contains a mixture of thiourea, a glycol alkyl ether, a polyethylene oxide or mixtures of polyalkylene oxides having a molecular weight in the range from about 600 to 20,000 and water.
- thiourea is only slighly soluble in an aqueous medium
- the start-up of a halogen tin electroplating bath can be efiected by separately adding thiourea and the polyalkylene oxide to a new plating bath. It is necessary, however, to replenish these materials from time to time after the bath is in operation.
- the thiourea and polyalkylene oxide are depleted at approximately the same rate. Therefore, for control purpose, it would be desirable to be able to make a single addition of these materials to the plating bath. It is essential, however, that the thiourea be solubilized in order to perform its sludge inhibition function in the bath.
- halogen tin electroplating bath additives of this invention consist of the following essential ingredients: (A) from about 5 to 20% by weight of thiourea; (B) from about 5 to 45% by weight of a polyalkylene oxide or mixture of polyalkylene oxides having molecular weights in the range from about 600 to 20,000; and (C) from about 50 to 90% of a mixture consisting of 10 to 75 parts by weight of a glycol alkyl ether and from about to parts by weight of water.
- Various combinations of the ingredients can be made within the limits just specified to provide clear, freeze-thaw stable additives for halogen tin plating baths.
- the ingredients are combined to provide an additive consisting of: (A) from about 15 to 20% by weight of thiourea; (B) from about 15 to 40% by weight of polyalkylene oxide; and (C) from about 20 to 40% by weight of the glycol alkyl ether and from about 20 to 30% by weight of water.
- Sufiicient additive should be included in the electroplating bath to maintain a concentration of polyalkylene oxide of from 0.001 to 25, preferably 1 to 5 grams per liter and a concentration of thiourea of about 0.1 to 5, preferably 2 to 3 grams per liter.
- concentration of polyalkylene oxide of from 0.001 to 25, preferably 1 to 5 grams per liter and a concentration of thiourea of about 0.1 to 5, preferably 2 to 3 grams per liter.
- the additives of this invention may be prepared by adding the ingredients in the proportions previously specified to a container and heating the mixture of ingredients to a slightly elevated temperature, e.g., 40 to 80 C. By gentle stirring, a clear solution is obtained.
- the solution is storage stable and retains its clarity at elevated temperatures. If subjected to freezing temperatures, the solution will solidify; however, the clear appearance is restored upon thawing with no deleterious effects.
- the ingredients for the additives of this invention may be obtained from commercial sources.
- the glycol alkyl ether may be selected from a variety of available materials such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether and glycol monomethyl ether.
- the polyalkylene oxides are of the type described in U.S. Patent 2,457,152 and the U.S. patents identified therein. In general, these polyalkylene oxides having a molecular weight, calculated as specified in U.S. Patent 2,457,152, in the range from about 600 to 20,000 are used, with the polyalkylene oxides having a molecular weight from about 4,000 to 20,000 being preferred. Polyethylene oxide or a mixture of polyethylene oxides having molecular weights within the just-mentioned range are preferred.
- diethylene glycol monoethyl ether diethylene glycol monomethyl ether and glycol monoeth, yl ether, respectively, were used.
- the mixtures were each gently stirred at a temperature between 50 and 60 C. to provide a clear solution. Each solution was then cooled overnight in a deep freeze compartment at a temperature below 0 C. When the containers were removed from the deep freeze, the solutions were found to have solidified. The separate preparations were allowed to thaw at room temperature after which they are examined and found to be clear.
- a standard halogen-tin electroplating bath having a pH of 3.3 was prepared by combining the following ingredients:
- Hull cells were filled with the plating bath solution just described and 0.4 ml. of each of the preparations of plating bath additive was added, thereby providing a concentration of 0.25 gram per liter of thiourea and 0.33 gram per liter of polyethylene oxides.
- Steel Hull cell panels were pickled in an aqueous hydrochloric acid solution (1:1), rinsed in water and plated in the Hull cell using a current of 3 amperes for 30 seconds with the bath temperature being maintained in the range from 130 to 140 F.
- a normal appearing, semibright tin electrodeposit was obtained throughout the current density range of 2.5 to 150 amperes per square foot.
- tin plating bath solution A portion of the tin plating bath solution was added to a Hull cell and suificient additive was added to provide a concentration of 1.7 gm./l. of thiourea and 2.2 gm./l. of
- the additives of this invention provide semibright tin electrodeposits when added to standard halogen tin electroplating baths.
- the additives are stable and remain clear after they are subjected to a freeze-thaw cycle.
- An additive for a halogen tin electroplating bath consisting of the following essential ingredients: (A) from about 5 to 20% by weight of thiourea; (B) from about 5 to 45% by weight of a polyalkylene oxide having a molecular weight in the range from about 600 to 20,000; and (C) from about 50 to by weight of a mixture consisting of 10 to 75 parts by weight of a glycol alkyl ether and from about 15 to 80 parts by weight of water.
- glycol alkyl ether is ethylene glycol monomethyl ether.
- polyalkylene oxide is a polyethylene oxide or mixture of polyethylene oxides having molecular weights in the range from about 4,000 to 20,000.
- ingredients are present in the following amounts: (A) from about 15 to 20% by weight of thiourea; (B) from about 15 to 40% by weight of said polyalkylene oxide; and (C) from about 20 to 40% by weight of said glycol alkyl ether and from about 20 to 30% by weight of water.
- glycol alkyl 2,736,692 2/1956 Eckert 20454 ether is ethylene glycol monomethyl ether. 2,930,740 3/1960 Francisco et al 20454 6.
- polyalkylene oxide is a polyethylene oxide or mixture of polyethylene FOREIGN PATENTS having molecular weights from about 4,000 to 5 592,442 9 /1947 Great Britain. References Cited JOHN H. MACK, Primary Examiner.
Description
United States Patent 3,453,186 ADDITIVES FOR TIN ELECTROPLATING BATH Norman L. Hause, Wilmington, and Donald Arthur Swalheim, Hockessin, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Nov. 30, 1966, Ser. No. 597,847
Int. Cl. C23b 5/14 U.S. Cl. 20454 6 Claims ABSTRACT OF THE DISCLOSURE The tinplating bath additive contains a mixture of thiourea, a glycol alkyl ether, a polyethylene oxide or mixtures of polyalkylene oxides having a molecular weight in the range from about 600 to 20,000 and water.
Summary of the invention Solutions of stannous chloride containing relatively large amounts of alkali metal fluoride have been utilized to produce excellent deposits of electroplated tin. These solutions are referred to in the trade as halogen tin electroplating baths and are described in detail in U.S. Patent 2,407,579. In using tinplating baths of this type, considerable difficulty has been experienced by the formation of insoluble material, chiefly, fluo-stannate, which settles to the bottom of the plating bath forming a sludge which must be periodically removed. Various means have been proposed for inhibiting the sludge formation. The most satisfactory method heretofore known has been the addition of a small amount of an alkali metal ferrocyanide or ferricyanide. The addition of thiourea has been found to be helpful in inhibiting the sludge formation. Also, addition of a polyalkylene oxide has been found to improve the quality of the electrodeposit.
Although thiourea is only slighly soluble in an aqueous medium, the start-up of a halogen tin electroplating bath can be efiected by separately adding thiourea and the polyalkylene oxide to a new plating bath. It is necessary, however, to replenish these materials from time to time after the bath is in operation. The thiourea and polyalkylene oxide are depleted at approximately the same rate. Therefore, for control purpose, it would be desirable to be able to make a single addition of these materials to the plating bath. It is essential, however, that the thiourea be solubilized in order to perform its sludge inhibition function in the bath.
A problem has been encountered in attempting to combine the aforementioned materials due to the relative insolubility of thiourea in an aqueous thiourea-polyalkylene oxide system. Due to its solubility characteristic, the thiourea tends to crystallize from the system as the temperature drops. In fact, with certain materials, the combination. of ingredients congeals upon freezing and after thawing either remains in a solid gel or turbid state.
It has been found that by combining thiourea, a glycol alkyl ether, a polyalkylene oxide and water in proportions specified in detail later herein, the solubility of thiourea in the system is markedly improved and a freeze-thaw stable additive is provided.
Detailed description of the invention The halogen tin electroplating bath additives of this invention consist of the following essential ingredients: (A) from about 5 to 20% by weight of thiourea; (B) from about 5 to 45% by weight of a polyalkylene oxide or mixture of polyalkylene oxides having molecular weights in the range from about 600 to 20,000; and (C) from about 50 to 90% of a mixture consisting of 10 to 75 parts by weight of a glycol alkyl ether and from about to parts by weight of water. Various combinations of the ingredients can be made within the limits just specified to provide clear, freeze-thaw stable additives for halogen tin plating baths. In a preferred embodiment of this invention, the ingredients are combined to provide an additive consisting of: (A) from about 15 to 20% by weight of thiourea; (B) from about 15 to 40% by weight of polyalkylene oxide; and (C) from about 20 to 40% by weight of the glycol alkyl ether and from about 20 to 30% by weight of water.
Sufiicient additive should be included in the electroplating bath to maintain a concentration of polyalkylene oxide of from 0.001 to 25, preferably 1 to 5 grams per liter and a concentration of thiourea of about 0.1 to 5, preferably 2 to 3 grams per liter. When added to a halogen tin electroplating bath of the type described in U.S. Patent 2,407,579 there is a significant reduction in the amount of sludge formed without affecting the quality of the tin plate.
The additives of this invention may be prepared by adding the ingredients in the proportions previously specified to a container and heating the mixture of ingredients to a slightly elevated temperature, e.g., 40 to 80 C. By gentle stirring, a clear solution is obtained. The solution is storage stable and retains its clarity at elevated temperatures. If subjected to freezing temperatures, the solution will solidify; however, the clear appearance is restored upon thawing with no deleterious effects.
The ingredients for the additives of this invention may be obtained from commercial sources. The glycol alkyl ether may be selected from a variety of available materials such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether and glycol monomethyl ether. The polyalkylene oxides are of the type described in U.S. Patent 2,457,152 and the U.S. patents identified therein. In general, these polyalkylene oxides having a molecular weight, calculated as specified in U.S. Patent 2,457,152, in the range from about 600 to 20,000 are used, with the polyalkylene oxides having a molecular weight from about 4,000 to 20,000 being preferred. Polyethylene oxide or a mixture of polyethylene oxides having molecular weights within the just-mentioned range are preferred.
The following examples in which parts and percentages are by weight unless otherwise specified further illustrate the present invention. I
EXAMPLE I Three separate preparations of halogen tin plating bath additives were made by combining the following ingredients in a glass container equipped with a magnetic stirrer.
Table 1 Grams Thiourea 18.0 Glycol ethyl ether 34.5 Water 25.0 Polyethylene oxide (M.W. 6,000) 7.5 Polyethylene oxide (M.W. 4,000) 7.5 Polyethylene oxide (M.W. 20,000) 7.5
1 In the three preparations diethylene glycol monoethyl ether. diethylene glycol monomethyl ether and glycol monoeth, yl ether, respectively, were used.
The mixtures were each gently stirred at a temperature between 50 and 60 C. to provide a clear solution. Each solution was then cooled overnight in a deep freeze compartment at a temperature below 0 C. When the containers were removed from the deep freeze, the solutions were found to have solidified. The separate preparations were allowed to thaw at room temperature after which they are examined and found to be clear.
A standard halogen-tin electroplating bath having a pH of 3.3 was prepared by combining the following ingredients:
3 Table 2 Grams Stannous chloride 42.8 Sodium fluoride 38.3 Sodium difiuoride 21.7 Sodium chloride I 36.9 Sodium ferrocyanide 1.2
Water, to make 1 liter.
In separate experiments Hull cells were filled with the plating bath solution just described and 0.4 ml. of each of the preparations of plating bath additive was added, thereby providing a concentration of 0.25 gram per liter of thiourea and 0.33 gram per liter of polyethylene oxides. Steel Hull cell panels were pickled in an aqueous hydrochloric acid solution (1:1), rinsed in water and plated in the Hull cell using a current of 3 amperes for 30 seconds with the bath temperature being maintained in the range from 130 to 140 F. A normal appearing, semibright tin electrodeposit was obtained throughout the current density range of 2.5 to 150 amperes per square foot.
In a control experiment in which no additive was included in the plating bath the plate was dull throughout most of the range and no plate was obtained at very low current densities.
EXAMPLE II The experiment of Example I was repeated except that the three preparations consisted of the following ingredients:
Table 3 Preparation No. 1: Percent by weight Thiourea 18.0 Ethylene glycol monoethyl ether 34.5 Water 25.0 Polyethylene oxide (M.W. 6,000) 22.5
Preparation No. 2:
Thiourea 18.0 Ethylene glycol monoethyl ether 34.5 Water 25.0 Polyethylene oxide (M.W. 20,000) 5.62 Polyethylene oxide (M.W. 6,000) 11.25 Polyethylene oxide (M.W. 4,000) 5.63
Preparation No. 3:
Thiourea 18.0 Ethylene glycol monoethyl ether 34.5 Water 25.0 Polyethylene oxide (M.W. 20,000) 11.25 Polyethylene oxide (M.W. 6,000) 5.62 Polyethylene oxide (M.W. 4,000) 5.63
All three solutions were clear after exposure to the freeze-thaw cycle. When added to a standard tin plating solution as described in Example I, a semibright tin electrodeposit is obtained.
EXAMPLE III Example I is repeated except the tin plating bath and additive are comprised of the following ingredients:
Table 4 Grams Stannous chloride 16.2 Sodium fluoride 14.5 Sodium difluoride 58.0 Sodium chloride 14.0 Sodium ferrocyanide 4.55 Water, to make 1 gal. Additive:
Thiourea 18.0 Diethylene glycol monomethyl ether 24.5 Water 35.0 Polyethylene oxide (M.W. 6,000) 22.5
A portion of the tin plating bath solution was added to a Hull cell and suificient additive was added to provide a concentration of 1.7 gm./l. of thiourea and 2.2 gm./l. of
EXAMPLE IV Example I is repeated except that the additive consists of the following ingredients:
Table 5 Percent by weight Thiourea 5 Ethylene glycol monomethyl ether 75 Water 15 Polyethylene oxide (M.W. 6, 00) 5 A clear solution is provided. The solution remains clear after exposure to the freeze-thaw cycle. In a Hull cell plating experiment the tin electrodeposit has a normal appearance when the additive is included in the Hull cell as described in Example I.
EXAMPLE V Example I is repeated with similar results except that the additive consists of the following ingredients:
Table 6 Percent by weight Thiourea 20 Ethylene glycol monomethyl ether 10 Water 25 Polyethylene oxide (M.W. 6,000) 45 EXAMPLE VI Example I is repeated except that the additive consists of the following ingredients:
Table 7 Percent by weight Thiourea 5 Ethylene glycol monomethyl ether 10 Water Polyethylene oxide (M.W. 6,000) 5 The solution obtained is clear and freeze-thaw stable. When added to the halogen tin plating bath of Example III, a semibright electrodeposit is obtained.
As shown in the foregoing examples the additives of this invention provide semibright tin electrodeposits when added to standard halogen tin electroplating baths. The additives are stable and remain clear after they are subjected to a freeze-thaw cycle.
We claim:
1. An additive for a halogen tin electroplating bath consisting of the following essential ingredients: (A) from about 5 to 20% by weight of thiourea; (B) from about 5 to 45% by weight of a polyalkylene oxide having a molecular weight in the range from about 600 to 20,000; and (C) from about 50 to by weight of a mixture consisting of 10 to 75 parts by weight of a glycol alkyl ether and from about 15 to 80 parts by weight of water.
2. The additive of claim 1 wherein said glycol alkyl ether is ethylene glycol monomethyl ether.
3. The additive of claim 2 wherein said polyalkylene oxide is a polyethylene oxide or mixture of polyethylene oxides having molecular weights in the range from about 4,000 to 20,000.
4. The additive of claim 1 wherein said ingredients are present in the following amounts: (A) from about 15 to 20% by weight of thiourea; (B) from about 15 to 40% by weight of said polyalkylene oxide; and (C) from about 20 to 40% by weight of said glycol alkyl ether and from about 20 to 30% by weight of water.
5 6 5. The additive of claim 4 wherein said glycol alkyl 2,736,692 2/1956 Eckert 20454 ether is ethylene glycol monomethyl ether. 2,930,740 3/1960 Francisco et al 20454 6. The additive of claim 5 wherein said polyalkylene oxide is a polyethylene oxide or mixture of polyethylene FOREIGN PATENTS having molecular weights from about 4,000 to 5 592,442 9 /1947 Great Britain. References Cited JOHN H. MACK, Primary Examiner.
UNITED STATES PATENTS 2,407,579 9/1946 Schweikher 20 1-54 2,585,902 2/1952 Graiy 204.- 54 U.S.C1.X.R.
G. L. KAPLAN, Assistant Examiner.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US59784766A | 1966-11-30 | 1966-11-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3453186A true US3453186A (en) | 1969-07-01 |
Family
ID=24393162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US597847A Expired - Lifetime US3453186A (en) | 1966-11-30 | 1966-11-30 | Additives for tin electroplating bath |
Country Status (7)
Country | Link |
---|---|
US (1) | US3453186A (en) |
BE (1) | BE706582A (en) |
FR (1) | FR1546176A (en) |
GB (1) | GB1215696A (en) |
GR (1) | GR36171B (en) |
NL (1) | NL6715785A (en) |
SU (1) | SU415891A3 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3642590A (en) * | 1969-07-16 | 1972-02-15 | Philips Corp | Acid electroplating bath for depositing tin |
US4073701A (en) * | 1976-10-15 | 1978-02-14 | Bethlehem Steel Corporation | Acid electrotinning bath |
US4502926A (en) * | 1983-08-22 | 1985-03-05 | Macdermid, Incorporated | Method for electroplating metals using microemulsion additive compositions |
US4601847A (en) * | 1983-08-22 | 1986-07-22 | Macdermid, Incorporated | Composition for use in electroplating of metals |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2013241B (en) * | 1977-11-16 | 1982-03-24 | Dipsol Chem | Electroplating bath for depositing tin or tin alloy with brightness |
JPS5818996B2 (en) * | 1980-02-21 | 1983-04-15 | キザイ株式会社 | Neutral tin electroplating bath to obtain a dense plating film |
US6322686B1 (en) | 2000-03-31 | 2001-11-27 | Shipley Company, L.L.C. | Tin electrolyte |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2407579A (en) * | 1942-07-04 | 1946-09-10 | Du Pont | Electrodeposition of tin |
GB592442A (en) * | 1944-08-23 | 1947-09-18 | E I Du Pont De Nemours An Co | Improvements in or relating to the electrodeposition of tin |
US2585902A (en) * | 1949-02-02 | 1952-02-19 | Du Pont | Inhibition of oxidation in tin solutions |
US2736692A (en) * | 1952-05-14 | 1956-02-28 | Du Pont | Electrodeposition of tin |
US2930740A (en) * | 1958-05-14 | 1960-03-29 | Bethlehem Steel Corp | Electrodeposition of tin |
-
1966
- 1966-11-30 US US597847A patent/US3453186A/en not_active Expired - Lifetime
-
1967
- 1967-10-31 GR GR670136171A patent/GR36171B/en unknown
- 1967-11-16 BE BE706582D patent/BE706582A/xx unknown
- 1967-11-21 NL NL6715785A patent/NL6715785A/xx unknown
- 1967-11-25 SU SU1199708A patent/SU415891A3/en active
- 1967-11-30 FR FR130489A patent/FR1546176A/en not_active Expired
- 1967-11-30 GB GB54548/67A patent/GB1215696A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2407579A (en) * | 1942-07-04 | 1946-09-10 | Du Pont | Electrodeposition of tin |
GB592442A (en) * | 1944-08-23 | 1947-09-18 | E I Du Pont De Nemours An Co | Improvements in or relating to the electrodeposition of tin |
US2585902A (en) * | 1949-02-02 | 1952-02-19 | Du Pont | Inhibition of oxidation in tin solutions |
US2736692A (en) * | 1952-05-14 | 1956-02-28 | Du Pont | Electrodeposition of tin |
US2930740A (en) * | 1958-05-14 | 1960-03-29 | Bethlehem Steel Corp | Electrodeposition of tin |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3642590A (en) * | 1969-07-16 | 1972-02-15 | Philips Corp | Acid electroplating bath for depositing tin |
US4073701A (en) * | 1976-10-15 | 1978-02-14 | Bethlehem Steel Corporation | Acid electrotinning bath |
US4502926A (en) * | 1983-08-22 | 1985-03-05 | Macdermid, Incorporated | Method for electroplating metals using microemulsion additive compositions |
US4601847A (en) * | 1983-08-22 | 1986-07-22 | Macdermid, Incorporated | Composition for use in electroplating of metals |
Also Published As
Publication number | Publication date |
---|---|
GR36171B (en) | 1968-12-30 |
FR1546176A (en) | 1968-11-15 |
SU415891A3 (en) | 1974-02-15 |
NL6715785A (en) | 1968-05-31 |
BE706582A (en) | 1968-05-16 |
GB1215696A (en) | 1970-12-16 |
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