US2846381A - Method of electrolytically depositing smooth layers of tin - Google Patents
Method of electrolytically depositing smooth layers of tin Download PDFInfo
- Publication number
- US2846381A US2846381A US633393A US63339357A US2846381A US 2846381 A US2846381 A US 2846381A US 633393 A US633393 A US 633393A US 63339357 A US63339357 A US 63339357A US 2846381 A US2846381 A US 2846381A
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- United States
- Prior art keywords
- tin
- smooth
- acid
- layer
- electrolyte
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 123
- 238000000151 deposition Methods 0.000 title claims description 57
- 238000000034 method Methods 0.000 title 1
- 230000008021 deposition Effects 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 30
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 claims description 28
- 235000011957 flavonols Nutrition 0.000 claims description 28
- -1 FLAVONOL COMPOUND Chemical class 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 26
- 239000012266 salt solution Substances 0.000 description 21
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 18
- 150000002216 flavonol derivatives Chemical class 0.000 description 15
- 238000007792 addition Methods 0.000 description 12
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 9
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 9
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 9
- 235000005875 quercetin Nutrition 0.000 description 9
- 229960001285 quercetin Drugs 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- YXOLAZRVSSWPPT-UHFFFAOYSA-N Morin Chemical compound OC1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 YXOLAZRVSSWPPT-UHFFFAOYSA-N 0.000 description 7
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 7
- 235000007708 morin Nutrition 0.000 description 7
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 description 5
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 description 5
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 5
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 5
- 235000005493 rutin Nutrition 0.000 description 5
- 229960004555 rutoside Drugs 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- LUJAXSNNYBCFEE-UHFFFAOYSA-N Quercetin 3,7-dimethyl ether Natural products C=1C(OC)=CC(O)=C(C(C=2OC)=O)C=1OC=2C1=CC=C(O)C(O)=C1 LUJAXSNNYBCFEE-UHFFFAOYSA-N 0.000 description 4
- PUTDIROJWHRSJW-UHFFFAOYSA-N Quercitrin Natural products CC1OC(Oc2cc(cc(O)c2O)C3=CC(=O)c4c(O)cc(O)cc4O3)C(O)C(O)C1O PUTDIROJWHRSJW-UHFFFAOYSA-N 0.000 description 4
- OXGUCUVFOIWWQJ-XIMSSLRFSA-N acanthophorin B Natural products O[C@H]1[C@H](O)[C@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OXGUCUVFOIWWQJ-XIMSSLRFSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- XHEFDIBZLJXQHF-UHFFFAOYSA-N fisetin Chemical compound C=1C(O)=CC=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 XHEFDIBZLJXQHF-UHFFFAOYSA-N 0.000 description 4
- 229930182470 glycoside Natural products 0.000 description 4
- OEKUVLQNKPXSOY-UHFFFAOYSA-N quercetin 3-O-beta-D-glucopyranosyl(1->3)-alpha-L-rhamnopyranosyl(1->6)-beta-d-galactopyranoside Natural products OC1C(O)C(C(O)C)OC1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OEKUVLQNKPXSOY-UHFFFAOYSA-N 0.000 description 4
- QPHXPNUXTNHJOF-UHFFFAOYSA-N quercetin-7-O-beta-L-rhamnopyranoside Natural products OC1C(O)C(O)C(C)OC1OC1=CC(O)=C2C(=O)C(O)=C(C=3C=C(O)C(O)=CC=3)OC2=C1 QPHXPNUXTNHJOF-UHFFFAOYSA-N 0.000 description 4
- OXGUCUVFOIWWQJ-HQBVPOQASA-N quercitrin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OXGUCUVFOIWWQJ-HQBVPOQASA-N 0.000 description 4
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- CYGSXDXRHXMAOV-UHFFFAOYSA-N o-cresol hydrogen sulfate Chemical compound CC1=CC=CC=C1OS(O)(=O)=O CYGSXDXRHXMAOV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- IKMDFBPHZNJCSN-UHFFFAOYSA-N Myricetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC(O)=C(O)C(O)=C1 IKMDFBPHZNJCSN-UHFFFAOYSA-N 0.000 description 2
- 241001300834 Pictetia aculeata Species 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000011990 fisetin Nutrition 0.000 description 2
- 150000002338 glycosides Chemical group 0.000 description 2
- PCOBUQBNVYZTBU-UHFFFAOYSA-N myricetin Natural products OC1=C(O)C(O)=CC(C=2OC3=CC(O)=C(O)C(O)=C3C(=O)C=2)=C1 PCOBUQBNVYZTBU-UHFFFAOYSA-N 0.000 description 2
- 235000007743 myricetin Nutrition 0.000 description 2
- 229940116852 myricetin Drugs 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 1
- XUDNWQSXPROHLK-OACYRQNASA-N 2-phenyl-3-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxychromen-4-one Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=CC=CC=2)OC2=CC=CC=C2C1=O XUDNWQSXPROHLK-OACYRQNASA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000306760 Thinora Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000007946 flavonol Chemical class 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- GPGMRSSBVJNWRA-UHFFFAOYSA-N hydrochloride hydrofluoride Chemical compound F.Cl GPGMRSSBVJNWRA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000001993 wax 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
- This invention relates to the electrolytic deposition of tin.
- Electrolytes for the deposition of layers of tin on wire or broad band steel in modern tin plating plants should yield smooth, properly adhering deposits, as bright and free of pores as possible, with the highest possible cur:
- Alkaline electrolytes having qnadri-valent tin reach only a modest speed of deposition and are therefore hardly practicable for high output plants.
- Baths of acid electrolytes were used to a fairly large extent based on cresolsulphonic acid with addition of organic sulphones or sulphoxides. These baths permit the very high speeds for the separation oftin, but, owing to the comparatively low'conductivity and high polarisation of the electrodes, they require rather high terminal voltages for electrolytic deposition. Current densities of 20-60 amps.
- An object of the invention is to produce electrolytes for the deposition of tin which work at low voltages with high current densities and yield smooth deposits of either a thin ora thick metal covering and which can be melted on very well.
- the electrolytes used in accordance with the invention are easy to maintain and involve no special risks to the health of the operators.
- acid tin electrolytes with additions of flavonols are used.
- the tin may be present in the electrolytes as fluoborate, sulphate or cresolsulphonate, for example.
- Tin electrolytes based on fluoboric acid are known. It is usual for acid tin baths, other than fluoboric acid tin baths, to contain free acid of the same kind as the acid radical in suitable quantity. For depositing a dense,
- flavonols particularly those containing several hydroxyl groups
- very eflicient tin baths may be obtained even with a low tin concentration in the electrolyte.
- quercetin, fisetin, morin and myricetin are concerned, for example.
- These substances are preferably first dissolved in alcohol and stirred in this form into the electrolytes.
- concentration of these additions may be varied within wide limits according to the desired working conditions.
- quercetin per litre of-bath will prevent the separation of tin bars and tin needles in an electrolyte having 30 g. per litre of tin as fluoborate and 60 g. per litre of free fluoboric acid, and render possible a deposition of tin which, even though still crystalline has excellent .covering power.
- a further increase of the addition of quercetin to -100 mg. yields a very smooth fine grain and bright tin deposit.
- a favourable feature in the use of flavonols is the fact that even a large increase of the I added quantities beyond the concentration ascertained to be necessary is not harmful for the deposition elfect.
- a supply of additives may be addedto the baths sufficient for a longer operating period. Therefore, the limit of solubility of the said additions in the electrolyte may be regarded as the upper limit for making additions.
- the protectiveness of the flavonols may be further intensified.
- polycondensation compounds of ethylene oxide with aliphatic alcohols having an average chain length of about 8-16 carbon atoms are particularly suitable. Such compounds have been used as working agents.
- polycondensation compounds of ethylene oxide which are known for example as carbowaxes or poly-waxes, are practically without effect.
- the combination of flavonols with the said substances in many cases makes possible a uniform, smooth deposit of tin over a wide range of current density. Therefore, the property of the tin baths known as throwing power is assisted.
- flavonols are theirparticularly eflective with tin baths based on fluoboric acid.
- flavonols exert a considerable smoothing efi'ect.
- the flavonols are preferably added in pure form, bu natural products in which these products are present in appreciable quantity, if necessary, in the form of glycosides and other compound forms, are also efiective in the majority of cases.
- extracts of fustic may in part replace the action of pure flavonols, even if only to a slight extent.
- the accompanying substances present in this case adversely affect the action I of flavonols.
- Pure glycosides of flavonols such as querci trin or rutin may be used in higher concentration similarly to pure flavonols.
- Example 1 30 per litre of tin as tin fluoborate g. per litre of free fluoboric acid 0.04-02 g. per litre quercetin
- Example 2 50 g. per litre of tin as tin fluoborate g. per litre of free fluoboric acid 0.04-0.3 g. per litre quercetin I 1.5 g. per litre of a condensation product from ethylene oxide and Cur-C14 316011015
- Example 3 50 g. per litre of tin as tin sulphate 60 g. per litre of free sulphuric acid O.l-LO.25 g. per litre morin oxide and lauryl alcohol 0.05-0.25 g.
- Example 5 40 g. per litre of tin as fluoborate 140 g. per litre of free fluoboric acid 2-3 g. per litre of quercitrin
- Example 6 35 g. per litre of tin as fluoborate 100 g.,per litre of free fluoboric acid 2 g. per litre of a condensation product from ethylene oxideand lauryl alcohol 1.02.5 g. per litre of rutin From the said baths, according to the tin concentration and the other conditions, deposits may be separated with current densities from l-SO amps. per square decimetre. At the same time high current densities require higher bath temperatures up to 70 C.
- The'highest current densities may be used for producing thin tin coatings such as are used in the tin plate industry. Such deposits may be melted on with a highly lustrous efiect under the usual conditions. For producing thicker tin coatings up to 5 in thickness, low current densities should be selected. Then, under suitable working conditions smooth deposits may be produced up to a thickness of 0.05 mm. and above.
- the step comprising depositing said tin from an acid tin electrolyte which contains a flavonol compound in an amount sufilcient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
- the step comprising depositing said tin from an acid tin electrolyte which contains a fiavonol selected from the group consisting of quercetin, fisetin, myricetin and morin in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
- a fiavonol selected from the group consisting of quercetin, fisetin, myricetin and morin in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
- the step comprising depositing said tin-from an acid tin electrolyte which contains a naturally occurring flavonol glycoside selected from the group consisting of quercitrin, rutin and fustic extract in an amount sufticient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
- an acid tin electrolyte which contains a naturally occurring flavonol glycoside selected from the group consisting of quercitrin, rutin and fustic extract in an amount sufticient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
- the step comprising depositing said tin from an acid tin electrolyte which contains a flavonol compound in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities and a polymerisation product of ethylene oxide with an aliphatic alcohol containing at least 6 carbon atoms per molecule.
- the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid and a flavonol compound in an amount sutficient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid and a flavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin cresolsulphonate, cresolsulphonic acid and a flavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid and quercetin in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fiuoboric acid, quercetin and a condensation product of ethylene oxide with an aliphatic alcohol containing 10 to 14 carbon atoms per molecule, said quercetin being present in said tin salt solution in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high current densities.
- a tin salt solution which contains tin fluoborate, fiuoboric acid, quercetin and a condensation product of ethylene oxide with an aliphatic alcohol containing 10 to 14 carbon atoms per molecule
- the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid and morin in an amount suflicient to cause deposition of a smooth vtin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid, morin and a condensation product from ethylene oxide and lauryl' alcohol, said morin being present in said tin salt solution in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fiuoboric acid and quercitrin in an amount suflicient tocause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation a low voltages with high current densities.
- the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid, rutin and a condensation product from ethylene oxide and lauryl alcohol, said rutin being present in said tin salt solution in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high densities.
- the step comprising depositing tin from an acid tin electrolyte containing at least about 0.02 g./l. of a flavonol compound selected from the group consisting of fiavonols and flavonol glyeosides.
- An acid tin electrolyte for the electrolytic deposition of a tin layer said electrolyte containing a tin salt and a fiavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of said electrolyte on operation at low voltages with high current densities.
- An acid tin electrolyte for the electrolytic deposition of a tin layer said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound.
- An acid tin electrolyte for the electrolytic deposit-ion of a tin layer said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound 0 selected from the group consisting of flavonols and flavonol glycosides.
- An acid tin electrolyte for the electrolytic deposition of a tin layer said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound selected from the group consisting of fiavonols and flavonol glycosides, and a polymerization product of ethylene oxide with an aliphatic alcohol containing at least 6 carbon atoms per molecule.
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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)
- Electrolytic Production Of Metals (AREA)
- Cosmetics (AREA)
Description
United States Patent Germany, assignors to Dr. lng. Max Schliitter, Geislingen, Steige, Germany No Drawing. Application January 10, 1957 Serial No. 633,393
Claims priority, application Germany January 16, 1956 18 Claims. (Cl. 204-54) This invention relates to the electrolytic deposition of tin.
Electrolytes for the deposition of layers of tin on wire or broad band steel in modern tin plating plants should yield smooth, properly adhering deposits, as bright and free of pores as possible, with the highest possible cur:
rent densities. Byhigh current densities, at least amps. per square decimetre are understood. -Fast running tin plating plants for band steel require even higher current densities. The said properties must be well defined already in the case of layer thicknesses of 0.3-0.4 In addition it is required that these tin layers should melt onto the wire or band steel with a highly lustring elfect.
To achieve this object, both alkaline and acid tin electrolytes have been used. Alkaline electrolytes having qnadri-valent tin reach only a modest speed of deposition and are therefore hardly practicable for high output plants. Baths of acid electrolytes were used to a fairly large extent based on cresolsulphonic acid with addition of organic sulphones or sulphoxides. These baths permit the very high speeds for the separation oftin, but, owing to the comparatively low'conductivity and high polarisation of the electrodes, they require rather high terminal voltages for electrolytic deposition. Current densities of 20-60 amps. per square decimetre may be achieved with electrolytes which, apart from stannous chloride, contain certain ratherlarge quantities of alkali metal fluorides together with free hydrofluoric acid. These baths also have an advantageously low terminal voltage, but require special care in service, since, owing to the content of acid fluoride, they can lead to serious damage to the skin of the persons working in the plants and, if the baths are insufficiently ventilated, may also lead to damage tothe breathing organs of said persons.
An object of the invention is to produce electrolytes for the deposition of tin which work at low voltages with high current densities and yield smooth deposits of either a thin ora thick metal covering and which can be melted on very well. The electrolytes used in accordance with the invention are easy to maintain and involve no special risks to the health of the operators.
These advantages ,are substantially achieved in that, in accordance with the invention, acid tin electrolytes with additions of flavonols are used. The tin may be present in the electrolytes as fluoborate, sulphate or cresolsulphonate, for example.
Tin electrolytes based on fluoboric acid are known. It is usual for acid tin baths, other than fluoboric acid tin baths, to contain free acid of the same kind as the acid radical in suitable quantity. For depositing a dense,
fine granular deposit, organic additions such as size, gelatine, ,B-naphthol, dihydroxydiphenylsulphone, and dihydroxy-diphenylmethane have already been proposed. With these additions, however, no baths are obtained which yield tin layers which may readily be melted on in only very thin coatings with current densities of 10- 50 amps. per square decimetre, and with them no thick tin layers of 10p thickness and above can be obtained with low current densities without tin bars or tin needles growing out of the deposit.
If, in accordance with the invention, flavonols, particularly those containing several hydroxyl groups, are used as additions to the fluoborate electrolytes, then very eflicient tin baths may be obtained even with a low tin concentration in the electrolyte. As flavonols, quercetin, fisetin, morin and myricetin are concerned, for example. These substances are preferably first dissolved in alcohol and stirred in this form into the electrolytes. The concentration of these additions may be varied within wide limits according to the desired working conditions.
20 mg. quercetin per litre of-bath will prevent the separation of tin bars and tin needles in an electrolyte having 30 g. per litre of tin as fluoborate and 60 g. per litre of free fluoboric acid, and render possible a deposition of tin which, even though still crystalline has excellent .covering power. A further increase of the addition of quercetin to -100 mg. yields a very smooth fine grain and bright tin deposit. A favourable feature in the use of flavonols is the fact that even a large increase of the I added quantities beyond the concentration ascertained to be necessary is not harmful for the deposition elfect. A supply of additives may be addedto the baths sufficient for a longer operating period. Therefore, the limit of solubility of the said additions in the electrolyte may be regarded as the upper limit for making additions.
By combination with other additions the protectiveness of the flavonols may be further intensified. As combined additions polycondensation compounds of ethylene oxide with aliphatic alcohols having an average chain length of about 8-16 carbon atoms are particularly suitable. Such compounds have been used as working agents. On the other hand, polycondensation compounds of ethylene oxide which are known for example as carbowaxes or poly-waxes, are practically without effect. The combination of flavonols with the said substances in many cases makes possible a uniform, smooth deposit of tin over a wide range of current density. Therefore, the property of the tin baths known as throwing power is assisted.
The addition of flavonols is'particularly eflective with tin baths based on fluoboric acid. However, also in the case of-tin baths based on sulphuric acid,*cresolsulphonic acid and stannous chloride-fluoride, flavonols exert a considerable smoothing efi'ect.
The flavonols are preferably added in pure form, bu natural products in which these products are present in appreciable quantity, if necessary, in the form of glycosides and other compound forms, are also efiective in the majority of cases. Thus extracts of fustic may in part replace the action of pure flavonols, even if only to a slight extent. Obviously, the accompanying substances present in this case adversely affect the action I of flavonols. Pure glycosides of flavonols such as querci trin or rutin may be used in higher concentration similarly to pure flavonols.
- The following examples illustrate the possible uses of flavonols in accordance with the present invention:
Example 1 30 per litre of tin as tin fluoborate g. per litre of free fluoboric acid 0.04-02 g. per litre quercetin Example 2 50 g. per litre of tin as tin fluoborate g. per litre of free fluoboric acid 0.04-0.3 g. per litre quercetin I 1.5 g. per litre of a condensation product from ethylene oxide and Cur-C14 316011015 Example 3 50 g. per litre of tin as tin sulphate 60 g. per litre of free sulphuric acid O.l-LO.25 g. per litre morin oxide and lauryl alcohol 0.05-0.25 g. per litre of morin Example 5 40 g. per litre of tin as fluoborate 140 g. per litre of free fluoboric acid 2-3 g. per litre of quercitrin Example 6 35 g. per litre of tin as fluoborate 100 g.,per litre of free fluoboric acid 2 g. per litre of a condensation product from ethylene oxideand lauryl alcohol 1.02.5 g. per litre of rutin From the said baths, according to the tin concentration and the other conditions, deposits may be separated with current densities from l-SO amps. per square decimetre. At the same time high current densities require higher bath temperatures up to 70 C. and movement of the goods to be tin-plated or of the bath. The'highest current densities may be used for producing thin tin coatings such as are used in the tin plate industry. Such deposits may be melted on with a highly lustrous efiect under the usual conditions. For producing thicker tin coatings up to 5 in thickness, low current densities should be selected. Then, under suitable working conditions smooth deposits may be produced up to a thickness of 0.05 mm. and above. I
' We claim:
1. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from an acid tin electrolyte which contains a flavonol compound in an amount sufilcient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
2. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from an acid tin electrolyte which contains a fiavonol selected from the group consisting of quercetin, fisetin, myricetin and morin in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
3. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin-from an acid tin electrolyte which contains a naturally occurring flavonol glycoside selected from the group consisting of quercitrin, rutin and fustic extract in an amount sufticient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities.
4. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from an acid tin electrolyte which contains a flavonol compound in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of the electrolyte on operation at low voltages with high current densities and a polymerisation product of ethylene oxide with an aliphatic alcohol containing at least 6 carbon atoms per molecule.
5. In the electrolytic depositionof tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid and a flavonol compound in an amount sutficient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
6. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid and a flavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
7. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin cresolsulphonate, cresolsulphonic acid and a flavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
8. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid and quercetin in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
9. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fiuoboric acid, quercetin and a condensation product of ethylene oxide with an aliphatic alcohol containing 10 to 14 carbon atoms per molecule, said quercetin being present in said tin salt solution in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high current densities.
10. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid and morin in an amount suflicient to cause deposition of a smooth vtin layer and improvement of the throwing power of the tin salt solution on operation at low voltages with high current densities.
11. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin sulphate, sulphuric acid, morin and a condensation product from ethylene oxide and lauryl' alcohol, said morin being present in said tin salt solution in an amount suflicient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high current densities.
12. In the electrolytic deposition of tin 'as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fiuoboric acid and quercitrin in an amount suflicient tocause deposition of a smooth tin layer and improvement of the throwing power of the tin salt solution on operation a low voltages with high current densities.
13. In the electrolytic deposition oftin as a smooth layer, the step comprising depositing said tin from a tin salt solution which contains tin fluoborate, fluoboric acid, rutin and a condensation product from ethylene oxide and lauryl alcohol, said rutin being present in said tin salt solution in an amount sufficient to cause deposition of a smooth tin layer and improvement of the throwing power of said tin salt solution on operation at low voltages with high densities.
14. In the electrolytic deposition of tin as a smooth layer, the step comprising depositing tin from an acid tin electrolyte containing at least about 0.02 g./l. of a flavonol compound selected from the group consisting of fiavonols and flavonol glyeosides.
15. An acid tin electrolyte for the electrolytic deposition of a tin layer, said electrolyte containing a tin salt and a fiavonol compound in an amount sufiicient to cause deposition of a smooth tin layer and improvement of the throwing power of said electrolyte on operation at low voltages with high current densities.
16. An acid tin electrolyte for the electrolytic deposition of a tin layer, said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound.
17. An acid tin electrolyte for the electrolytic deposit-ion of a tin layer, said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound 0 selected from the group consisting of flavonols and flavonol glycosides.
18. An acid tin electrolyte for the electrolytic deposition of a tin layer, said electrolyte containing a tin salt and at least about 0.02 g./l. of a flavonol compound selected from the group consisting of fiavonols and flavonol glycosides, and a polymerization product of ethylene oxide with an aliphatic alcohol containing at least 6 carbon atoms per molecule.
No references cited.
Claims (1)
1. IN THE ELECTROLYTIC DEPOSITION OF TIN AS A SMOOTH LAYER, THE STEP COMPRISING DEPOSITING SAID TIN FROM AN ACID TIN ELECTROLYTE WHICH CONTAINS A FLAVONOL COMPOUND IN AN AMOUNT SUFFICIENT TO CAUSE DEPOSITION OF A SMOOTH TIN LAYER AND IMPROVEMENT OF THE THROWING POWER OF THE ELECTROLYTE ON OPERATION AT LOW VOLTAGES WITH HIGH CURRENT DENSITIES.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DESCH19418A DE1009880B (en) | 1956-01-16 | 1956-01-16 | Acid bath for galvanic deposition of smooth tin layers |
Publications (1)
Publication Number | Publication Date |
---|---|
US2846381A true US2846381A (en) | 1958-08-05 |
Family
ID=7428483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US633393A Expired - Lifetime US2846381A (en) | 1956-01-16 | 1957-01-10 | Method of electrolytically depositing smooth layers of tin |
Country Status (5)
Country | Link |
---|---|
US (1) | US2846381A (en) |
BE (1) | BE553400A (en) |
DE (1) | DE1009880B (en) |
FR (1) | FR1189894A (en) |
GB (1) | GB842898A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2973308A (en) * | 1958-08-25 | 1961-02-28 | Acme Steel Co | Complexed plating electrolyte and method of plating therewith |
US3082157A (en) * | 1958-06-23 | 1963-03-19 | Bethlehem Steel Corp | Electrodeposition of tin |
US3251715A (en) * | 1961-06-13 | 1966-05-17 | Little Inc A | Method of forming a laminar superconductor |
US3926749A (en) * | 1971-12-20 | 1975-12-16 | M & T Chemicals Inc | Tin-lead alloy plating |
US20100000873A1 (en) * | 2008-06-12 | 2010-01-07 | Rohm And Haas Electronic Materials Llc | Electrolytic tin plating solution and electrolytic tin plating method |
CN103122465A (en) * | 2012-10-25 | 2013-05-29 | 扬州双盛锌业有限公司 | Preparation method of flaky metal powder |
JP2016000844A (en) * | 2014-06-11 | 2016-01-07 | 上村工業株式会社 | Electrotinning bath and tin plating film |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL128321C (en) * | 1965-02-13 |
-
0
- BE BE553400D patent/BE553400A/xx unknown
-
1956
- 1956-01-16 DE DESCH19418A patent/DE1009880B/en active Pending
- 1956-12-13 FR FR1189894D patent/FR1189894A/en not_active Expired
-
1957
- 1957-01-01 GB GB57/57A patent/GB842898A/en not_active Expired
- 1957-01-10 US US633393A patent/US2846381A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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None * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3082157A (en) * | 1958-06-23 | 1963-03-19 | Bethlehem Steel Corp | Electrodeposition of tin |
US2973308A (en) * | 1958-08-25 | 1961-02-28 | Acme Steel Co | Complexed plating electrolyte and method of plating therewith |
US3251715A (en) * | 1961-06-13 | 1966-05-17 | Little Inc A | Method of forming a laminar superconductor |
US3926749A (en) * | 1971-12-20 | 1975-12-16 | M & T Chemicals Inc | Tin-lead alloy plating |
TWI468554B (en) * | 2008-06-12 | 2015-01-11 | 羅門哈斯電子材料有限公司 | Electrolytic tin plating solution and electrolytic tin plating method |
US20100000873A1 (en) * | 2008-06-12 | 2010-01-07 | Rohm And Haas Electronic Materials Llc | Electrolytic tin plating solution and electrolytic tin plating method |
CN103122465A (en) * | 2012-10-25 | 2013-05-29 | 扬州双盛锌业有限公司 | Preparation method of flaky metal powder |
CN103122465B (en) * | 2012-10-25 | 2015-06-17 | 扬州双盛锌业有限公司 | Preparation method of flaky metal powder |
JP2016000844A (en) * | 2014-06-11 | 2016-01-07 | 上村工業株式会社 | Electrotinning bath and tin plating film |
CN106414808A (en) * | 2014-06-11 | 2017-02-15 | 上村工业株式会社 | Tin electroplating bath and tin plating film |
EP3156522A4 (en) * | 2014-06-11 | 2017-11-08 | C. Uyemura & Co., Ltd. | Tin electroplating bath and tin plating film |
CN106414808B (en) * | 2014-06-11 | 2019-02-15 | 上村工业株式会社 | Tin electroplating bath and tin electroplating film |
TWI688679B (en) * | 2014-06-11 | 2020-03-21 | 日商上村工業股份有限公司 | Tin plating bath and tin coating |
Also Published As
Publication number | Publication date |
---|---|
FR1189894A (en) | 1959-10-07 |
DE1009880B (en) | 1957-06-06 |
GB842898A (en) | 1960-07-27 |
BE553400A (en) |
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