US2846381A - Method of electrolytically depositing smooth layers of tin - Google Patents

Method of electrolytically depositing smooth layers of tin Download PDF

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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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Expired - Lifetime
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US633393A
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English (en)
Inventor
Frick Wolfgang
Geldbach Alfred
Korpiun Joachim
Sedlacek Friedrich
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—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)
  • Cosmetics (AREA)
  • Electrolytic Production Of Metals (AREA)
US633393A 1956-01-16 1957-01-10 Method of electrolytically depositing smooth layers of tin Expired - Lifetime US2846381A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DESCH19418A DE1009880B (de) 1956-01-16 1956-01-16 Saures Bad zur galvanischen Abscheidung glatter Zinnschichten

Publications (1)

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US2846381A true US2846381A (en) 1958-08-05

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US (1) US2846381A (enrdf_load_stackoverflow)
BE (1) BE553400A (enrdf_load_stackoverflow)
DE (1) DE1009880B (enrdf_load_stackoverflow)
FR (1) FR1189894A (enrdf_load_stackoverflow)
GB (1) GB842898A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
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 (zh) * 2012-10-25 2013-05-29 扬州双盛锌业有限公司 一种片状金属粉末的制备方法
JP2016000844A (ja) * 2014-06-11 2016-01-07 上村工業株式会社 錫電気めっき浴および錫めっき皮膜

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL128321C (enrdf_load_stackoverflow) * 1965-02-13

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (13)

* Cited by examiner, † Cited by third party
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 (zh) * 2008-06-12 2015-01-11 羅門哈斯電子材料有限公司 電解錫電鍍溶液及電解錫電鍍方法
US20100000873A1 (en) * 2008-06-12 2010-01-07 Rohm And Haas Electronic Materials Llc Electrolytic tin plating solution and electrolytic tin plating method
CN103122465A (zh) * 2012-10-25 2013-05-29 扬州双盛锌业有限公司 一种片状金属粉末的制备方法
CN103122465B (zh) * 2012-10-25 2015-06-17 扬州双盛锌业有限公司 一种片状金属粉末的制备方法
JP2016000844A (ja) * 2014-06-11 2016-01-07 上村工業株式会社 錫電気めっき浴および錫めっき皮膜
CN106414808A (zh) * 2014-06-11 2017-02-15 上村工业株式会社 锡电镀浴和锡电镀膜
EP3156522A4 (en) * 2014-06-11 2017-11-08 C. Uyemura & Co., Ltd. Tin electroplating bath and tin plating film
CN106414808B (zh) * 2014-06-11 2019-02-15 上村工业株式会社 锡电镀浴和锡电镀膜
TWI688679B (zh) * 2014-06-11 2020-03-21 日商上村工業股份有限公司 錫電鍍浴及鍍錫被膜

Also Published As

Publication number Publication date
BE553400A (enrdf_load_stackoverflow)
DE1009880B (de) 1957-06-06
FR1189894A (fr) 1959-10-07
GB842898A (en) 1960-07-27

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