US3404075A - Electrodeposition of tin - Google Patents
Electrodeposition of tin Download PDFInfo
- Publication number
- US3404075A US3404075A US642305A US64230567A US3404075A US 3404075 A US3404075 A US 3404075A US 642305 A US642305 A US 642305A US 64230567 A US64230567 A US 64230567A US 3404075 A US3404075 A US 3404075A
- Authority
- US
- United States
- Prior art keywords
- tin
- plating
- product
- phenol
- cresol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 14
- 238000004070 electrodeposition Methods 0.000 title description 3
- 238000007747 plating Methods 0.000 description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 25
- 239000000654 additive Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 125000001174 sulfone group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CYGSXDXRHXMAOV-UHFFFAOYSA-N o-cresol hydrogen sulfate Chemical compound CC1=CC=CC=C1OS(O)(=O)=O CYGSXDXRHXMAOV-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- 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 present invention concerns improvements in or relating to tin-plating and in particular toelectroplating compositions for use in the electrodeposition of tin or tin-alloys on metal, and particularly on iron and steel substrates, especially the electrolytic production of tinned sheet, and to electroplating by using such compositions.
- the present invention provides a process of producing an additive for a tin-plating bath which comprises sulphonating phenol and/or cresol and thereafter heating the resulting snlphonated product for at least one hour without adding further phenol or cresol, at a subatmospheric pressure and at a temperature within the range of from 120 to 190 C.
- the tin-plating additive obtained according to the process of the present invention has been found to be greatly superior to previously-known additives especially in re spect of the current density range over which acceptable plating can be achieved.
- the present invention also provides an additive for a tin-plating bath, which additive is produced by the process of the present invention.
- the present invention further provides a tin-plating bath comprising a source of tin available for electroplating, and an additive produced by the process of the present invention.
- the present invention still further provides an electroplating process which comprises electrodepositing tin using the tin-plating bath of the present invention.
- the present invention provides a process of producing an additive for a tin-plating bath comprising two consecutive stages, namely:
- the initial sulphonation step may be conveniently effected by first melting the phenol and/or cresol and adding thereto, at an elevated temperature for instance a temperature within the range of from 60 to C., the sulphonating agent preferably, whilst stirring the mixture.
- the sulphonation reaction is preferably taken to completion by heating the reaction mixture at a further elevated temperature for instance a temperature within the range of from to C.
- the phenolic starting-materials for use in the process of this invention are advantageously of technical grades. If a mixture of phenol and cresol is used as starting-material, such a mixture preferably contains predominately the cresol component. More preferably however, the phenolic starting-material consists entirely of o-cresol.
- chlorosulphonic acid or a commercially available grade of stabilized sulphur trioxide may be used, if desired, but it is particularly advantageous to employ oleum, preferably containing at least 60 percent by weight of sulphur trioxide, as the sulphonating agent.
- the subsequent heating of the sulphonated product may be conveniently elfected by slowly raising the temperature of the reaction mixture to a temperature within the preferred range of from 120 to 165 C., and heating the mixture within this temperature range under subatrnospheric pressure for at least one hour. It is particularly preferred When carrying out this post-sulphonation heating procedure to effect the heating at a temperature of about to C., a pressure of about 5 to 24 millimetres of mercury pressure and for a period of about 4 hours or even longer, for instance up to 20 hours.
- a pressure of about 5 to 24 millimetres of mercury pressure and for a period of about 4 hours or even longer, for instance up to 20 hours.
- the crude reaction product after cooling may then be advantageously added directly to a tinplating bath in solid form or as an aqueous solution prepared therefrom.
- EXAMPLE 1 150 g. of phenol were melted and gradually reacted with 132 g. of oleum (60%) at 70 C. sulphonation was continued for 1 hour at 100 C. while stirring, and the resultant phenol sulphonic acid was then slowly heated in vacuo to 155160 C. at 11 millimetres of mercury pressure, to keep the distillation of phenol to a minimum. Condensation under vacuum was continued for hours. The yield was 237 g.
- acceptable tin-plating is meant the deposition of an integral semibright tin coating which, on flow-melting, gives a bright tin-plate free from pin holes or orange-peeling and of good adhesion.
- the product was heated under reflux for two hours. It was then cooled and diluted to 65% with water.
- a plating solution for a continuous plating machine was then made up by dissolving the following ingredients in water:
- the sulphonated product was then heated for six hours at 135 C. in the following consecutive stages:
- sulphonated product is heated at a temperature of [from about to 7.
- An aqueous acidic tin-plating bath comprising a source of tin for electroplating and an additive, in an amount sufl'icient to give a bright tin electrodeposit, produced by the steps of (1) sulphonating a phenolic starting material selected from the group consisting of phenol, cresols and mixtures thereof and (2) heating the resulting sulphonated product for at least one hour, without adding further phenol or cresol, at a pressure of from 5 to 25 mm. Hg and at a temperature within the range of 120 to C.
- a tin-plating bath according to claim 8 in which the oleum is present in an excess of about 10 to 30 percent by weight above the amount stoichiometrically required in the sulphonating to the respective sulphonic acid, calculated on the weight of the phenolic starting material.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1307562 | 1962-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3404075A true US3404075A (en) | 1968-10-01 |
Family
ID=10016345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US642305A Expired - Lifetime US3404075A (en) | 1962-04-05 | 1967-05-31 | Electrodeposition of tin |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3404075A (en, 2012) |
| BE (1) | BE630620A (en, 2012) |
| CH (1) | CH439908A (en, 2012) |
| DE (1) | DE1251613C2 (en, 2012) |
| GB (1) | GB1033662A (en, 2012) |
| SE (1) | SE305102B (en, 2012) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2313371A (en) * | 1940-06-28 | 1943-03-09 | Carnegie Illinois Steel Corp | Electrodeposition of tin and its alloys |
| GB683084A (en) * | 1949-06-20 | 1952-11-19 | Geigy Ag J R | Manufacture of new condensation products, being more especially improved tanning agents and their application |
| US2716098A (en) * | 1951-02-13 | 1955-08-23 | Geigy Ag J R | Water soluble condensation products with a tanning action |
| CA580454A (en) * | 1959-07-28 | Lomas Harold | Tin-plating |
-
0
- DE DENDAT1251613D patent/DE1251613C2/de not_active Expired
- GB GB1033662D patent/GB1033662A/en active Active
- BE BE630620D patent/BE630620A/xx unknown
-
1963
- 1963-03-27 CH CH385863A patent/CH439908A/de unknown
- 1963-04-04 SE SE3757/63A patent/SE305102B/xx unknown
-
1967
- 1967-05-31 US US642305A patent/US3404075A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA580454A (en) * | 1959-07-28 | Lomas Harold | Tin-plating | |
| US2313371A (en) * | 1940-06-28 | 1943-03-09 | Carnegie Illinois Steel Corp | Electrodeposition of tin and its alloys |
| GB683084A (en) * | 1949-06-20 | 1952-11-19 | Geigy Ag J R | Manufacture of new condensation products, being more especially improved tanning agents and their application |
| US2716098A (en) * | 1951-02-13 | 1955-08-23 | Geigy Ag J R | Water soluble condensation products with a tanning action |
Also Published As
| Publication number | Publication date |
|---|---|
| SE305102B (en, 2012) | 1968-10-14 |
| CH439908A (de) | 1967-07-15 |
| BE630620A (en, 2012) | |
| DE1251613C2 (de) | 1973-03-01 |
| GB1033662A (en, 2012) | |
| DE1251613B (de) | 1967-10-05 |
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