US2303035A - Brightening electrodeposited tincontaining coatings - Google Patents
Brightening electrodeposited tincontaining coatings Download PDFInfo
- Publication number
- US2303035A US2303035A US458320A US45832042A US2303035A US 2303035 A US2303035 A US 2303035A US 458320 A US458320 A US 458320A US 45832042 A US45832042 A US 45832042A US 2303035 A US2303035 A US 2303035A
- Authority
- US
- United States
- Prior art keywords
- coating
- bath
- brightening
- coatings
- oil
- 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
- 238000000576 coating method Methods 0.000 title description 61
- 238000005282 brightening Methods 0.000 title description 15
- 239000011248 coating agent Substances 0.000 description 44
- ORTFAQDWJHRMNX-UHFFFAOYSA-M oxidooxomethyl Chemical compound [O-][C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-M 0.000 description 25
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 23
- 239000002480 mineral oil Substances 0.000 description 15
- 235000010446 mineral oil Nutrition 0.000 description 15
- 150000001735 carboxylic acids Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 230000004927 fusion Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 150000007524 organic acids Chemical class 0.000 description 9
- 239000010953 base metal Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 235000019482 Palm oil Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000273930 Brevoortia tyrannus Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241001125048 Sardina Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000010514 hydrogenated cottonseed oil Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Description
Patented Nov. 24, 1942 BRIGHTENIN G ELECTRODEPOSITED TINL CONTAINING COATINGS Colin G. Fink, New York, N. Y., assignor to Crucible Steel Company of America, New York, p N. Y., a corporation of New Jersey No Drawing. Application September 14, 1942,
-- Serial No. 458,320
Claims. (Cl. 204-36) This invention relates generally to a process of brightening electrodeposited tin-containing coatings and to a brightening bath for such coatings. It is known that electrodeposited tin-containing coatings have many advantages over those produced by the hot dip process. Electrodeposited coatings may be-made more uniformly than those obtained by hot dipping and with, a thinner coat and freer from porosity. However, one objection to electrodeposited tin coatings is that they have a dull or matte finish which preeludes their use in certain industries.
In accordance with the present invention, I have provided a process whereby the dull finish characteristic of electrodeposited tin-containing coatings can be converted efliciently and simply into a bright mirror-like finish. I have found that this may be accomplished by heating the tin coated body, for example a steel strip coated with tin, to a temperature above its fusion point in an oil bath containing sufflcient uncombined organic carboxylic acid to provide the carboxyl radical (COOH) within certain proportions by weight of the oil bath. I may start with a mineral oil bath which of itself is ineffec tive for brightening the coating and add to this oil bath a certain proportion of one or more organic acids. I have found that if the amount of carboxyl radical is below or above a certain percentage by weight of the oil, bath, it is not effective in brightening the coating. Where the amount of carboxyl group is too low, it does not brighten the coating, and where it is too high, it attacks the coating, giving etching or breaking of the crystalline film, which precludes the production of a mirror finish. I have found that a bright mirror finish may be obtained on a tin coating by heating the coating to a temperature above its fusion point in an oil bath containing preferably from 0.10-2.6% by weight of carboxyl radical, although the upper limit may be increased up to about 4% without pronounced roughening effect rendering the product unmerchantable, when the preliminary steps of plating, cleaning and pickling have been very eiliciently performed. The coating is then rapidly cooled. If the coating after fusion in the oil bath is cooled slowly, it results in spangling. The preferred oil bath, is one consisting principally of mineral oil but adjusted by the addition thereto of an organic acid so as to give the content of carboxyl radical above specified.
Tests have been made starting with either a Russian mineral oil or a mineral oil known as "Quaker State lubricating oil S. A. E. 50, and
adding to these oils various amounts of organic acids. The electrodeposited tin coated bodies were immersed in the oil bath heated to a temperature of about 250 C. for various periods of time, usually about ten seconds, and were then rapidly cooled by immersing in a cooling bath of oil or water. It was found that the straight mineral oil baths without the addition of organic acid did notproduce a bright finish, irrespective of how short or how long the coatings were heated. However, the addition of organic acids to produce the carboxyl content of the bath within the range referred to resulted in bright mirror finishes irrespective of the particular organic acid which was employed. It was found that twice as much capric acid as sebacic acid, figured on a molar basis, was needed to give a mirror plate. It will be noted that capric and sebacic acids are similar instructure except that the sebacic acid has two carboxyl groups, whereas capric acid has only one.
The following table illustrates the results of tests carried out by adding various amountsof different organic acids to mineral oil and testing them for their brightening effect on electrodeposited tin coatings. The coil bath was heated to 250 C. and the samples were immersed in the bath for a period of about ten seconds. After immersing, the samples were withdrawn from the oil bath and rapidly cooled. The table shows the lower and upper limits of carboxyl radical for each of the acids within which bright surfaces are produced.
It will be seen that bright surfaces are produced when the carboxyl radical constitutes between 0.10 and 2.6% by weight of the mineral oil bath, which may be regarded as the preferred general range, although it should be noted that the appropriate lower and upper limits vary somewhat depending on the particular constituents used. Also, as already mentioned, it is possible by the use of particular care in the preliminary plating, cleaning and pickling steps, to add carboxyl radical up to about 4% by weight,
before the roughening effect becomes so serious as to render the product unmerchantable. However as the upper limit is approached, the brightening efiect is'to some extent impaired by the increased roughness of the surface.
In carrying out the invention on a commercial scale, an organic acid or a mixture of organic acids may be added to a mineral oil until the carboxyl radical content is within the limits given above. These oil baths in use are likely to change in composition, due to oxidation, polymerization and contamination and it is necessary in order to retain the effectiveness of the bath in its brightening action to maintain thecarboxyl radical content within the limits referred to. In the event that the carboxyl content falls below 0.10% by weight, the bath may be adjusted by adding a carboxylic acid to raise the carboxyl radical content. If, on the other hand, the carboxyl radical content rises above 2.6%, due to oxidation or other causes, it is preferred to lower the carboxyl content, and as above stated this becomes absolutely necessary at about 4% of carboxyl content. This may be done by adding an alkali to the bath, for example, sodium hydroxide, or by adding a further quantity of mineral oil which by dilution reduces the concentration of carboxyl radical. Instead of adding mineral oil, I might add any other oil which has a lower carboxyl content than the carboxyl content of the oil bath, in order to reduce the carboxyl content to within the limits referred to. The brightening bath of the present invention preferably consists principally of mineral oil but it may comprise certain non-drying vegetable, fish, animal oils or fats, for example, hydrogenated cottonseed oil, hydrogenated pilchard oil, palm oil, lard, menhaden oil and the like, provided that in any case the carboxyl content of the oil bath is within the range specified.
I may employ a flash coat of nickel, copper, cobalt, tungsten, iron or other metal as an underccat for the electrodeposited tin coating and then treat the coated body in the manner described.
Although it is preferred to add carboxylic acid to a mineral oil bath and then heat the tin coated body in the adjusted bath, good results have been obtained by putting a film of predetermined thickness of a carboxylic acid on the electrodeposited tin coating by wiping it with a cloth moistened with a carboxylic acid or by a dipping operation and then heating the coated body with the acid film on it in a hot oil bath of plain mineral oil. If the film of acid on the coating is too thick, etching of thecoating occurs. It is intended in the claims where reference is made to heating the coating in an oil bath containing a certain amount of carboxyl radical to cover not only the process wherein the carboxyl radical is added directly to the oil bath but also the case where the carboxyl radical is supplied in a film on the article and the article then heated to a temperature above the fusion point of the coating.
This application is a continuation in part of my prior application Serial Number 280,102, filed June 30, 1939. Reference is also made to my application Serial Number 134,798, filed August 3, 1937, and to my application Serial Number 51,800, filed November 27, 1935. In my application, Serial No. 149,885, filed June 23, 1937, a method is described in which a steel strip is given a flash coating of tin, the coated strip is then heated in a non-oxidizing gaseous atmosphere, in order to form a tin-iron alloy at the surface of the strip, a second tin-containing coating is then deposited on the first coating and the coated body is immersed in a heated .pil bath for a time sufficient to fuse the second coating. The heated oil bath has a willciently high acid number to produce a bright within the scope of the following claims.
I claim:
1. The process of brightening electrodeposited tin-containing coatings,'which comprises heating the coating to a temperature above its fusion point in an oil bath containing sufllcient uncombined organic carboxylic acid to provide 0.10-2.6% of the carboxyl radical by weight of the bath, and rapidly cooling the coating.
2. The process of brightening electrodeposited tin-containing coatings, which comprises heating the coating to a temperature above its fusion point in a mineral oil bath containing sufilcient uncombined organic carboxylic acid to provide 0.10-2.6% of the carboxyl radical by weight of the bath, and rapidly cooling the coating.
3. In the process of coating a metal body wherein a tin-containing dull finish coating is electrodeposited on the body and the body is heated in a brightening bath of oil containing sufficient uncombined organic carboxylic acid initially to provide 0.1 to 2.6% by weight of the carboxyl radical, but which after a period of use becomes inefiective in .brightening the coating due to changes in acidity of the bath, the step which comprises adjusting and maintaining the acidity of the bath at said carboxyl radical content of 0.10-2.6% by weight.
4. The process of coating a metal body, which comprises electrodepositing a tin-containing.
coating on the body, heating the coated body to a temperature above the fusion point of the coating in a brightening bath of oil containing uncombined organic carboxylic acid, and regulating and maintaining the carboxyl radical content of the bath at 0.10-2.6% by weight in maintaining the emciency thereof to produce a bright finish on the coating, andrapidly cooling the coating.
5. A bath for brightening electrodeposited tincontaining coatings, said bath consisting principally of mineral oil but containing sufilcient uncombined organic carboxylic acid to provide 0.10-2.6% by weight of the carboxyl radical.
6. A process for brightenin electrodeposited, tin-containing coatings, which comprises fusing the coating in a hot oleaginous bath containing sufflcient uncombined organic carboxylic acid to brighten said coating and such as to provide upwards of about 0.1% of the carboxyl radical by weight of the bath, but in amount insufficient to cause substantial etching of said coating and insufficient to preclude the production of a mirror finish and thereafter solidifying the coating by rapid cooling.
7. A process for producing bright, tin-containing coatings on a higher melting base metal, which comprises: electrodepositing the coating material on the base metal, heating the coating to a temperature above its fusion point in a hot oleaginous bath containing sufilcient uncombined organic carboxylic acid to provide about 0.1 to
2.6% of the carboxyl radical by weight of the bath, and thereafter solidifying the coating by rapid cooling.
8. A process for producing bright, tin-containing coatings on a higher melting base metal, which comprises: electrodepositing the coating material on the base metal, heating the coating to a temperature above its fusion point in a hot bath of palm oil containing sumcient uncombined organic carboigvlic acid to provide about 0.1 to 2.6% of the carboxyl radical by weight of the bath, and thereafter solidifying the coating by rapid cooling.
0. A process for producing bright, tin-containing coatings on a higher melting base metal, which comprises: electrodepositing the coating material on the base metal, heating the coating to a temperature above its fusion point in a hot bath of palm oil containing sufllcient uncombined organic carboxylic acid to provide about 0.1 to 4.0% of the carboxyl radical by weight of the bath, and thereafter solidifying the coating by rapid cooling.
10. A process for producing bright, tin-containing coatings on a higher melting base metal, which comprises: electrodepositing the coating material on the base metal, heating the coating to a temperature above its fusion point while surrounded by hot oleaginous liquid containing sufficient uncombined organic carboxylic acid to provide about 0.1 to 4.0% of the carboxyl radical by weight of the liquid, and thereafter solidifying the coating by rapid cooling. COLIN G. FINK.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US458320A US2303035A (en) | 1942-09-14 | 1942-09-14 | Brightening electrodeposited tincontaining coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US458320A US2303035A (en) | 1942-09-14 | 1942-09-14 | Brightening electrodeposited tincontaining coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2303035A true US2303035A (en) | 1942-11-24 |
Family
ID=23820318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US458320A Expired - Lifetime US2303035A (en) | 1942-09-14 | 1942-09-14 | Brightening electrodeposited tincontaining coatings |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2303035A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2458525A (en) * | 1943-05-17 | 1949-01-11 | John S Nachtman | Method and apparatus for brightening tin plate |
| US2710272A (en) * | 1950-01-13 | 1955-06-07 | United States Steel Corp | Tin pot oil composition |
| US2839437A (en) * | 1955-04-21 | 1958-06-17 | Jones & Laughlin Steel Corp | Method of producing a dull finished fused tin coating |
| US2907701A (en) * | 1956-02-29 | 1959-10-06 | Rheem Mfg Co | Method of producing electroplated containers |
| US3074154A (en) * | 1959-11-02 | 1963-01-22 | Inland Steel Co | Tin plate and method of producing |
| US3075897A (en) * | 1960-05-27 | 1963-01-29 | United States Steel Corp | Method of making tin plate |
| US3445351A (en) * | 1964-10-21 | 1969-05-20 | Du Pont | Process for plating metals |
| US3528892A (en) * | 1968-04-08 | 1970-09-15 | Joseph J Mazur | Plating method |
| US4413039A (en) * | 1980-03-22 | 1983-11-01 | Nippon Steel Corporation | Steel sheet plated with layers of NiSn and Pb-Sn alloy for automotive fuel tank |
| US4461679A (en) * | 1979-10-02 | 1984-07-24 | Nippon Steel Corporation | Method of making steel sheet plated with Pb-Sn alloy for automotive fuel tank |
-
1942
- 1942-09-14 US US458320A patent/US2303035A/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2458525A (en) * | 1943-05-17 | 1949-01-11 | John S Nachtman | Method and apparatus for brightening tin plate |
| US2710272A (en) * | 1950-01-13 | 1955-06-07 | United States Steel Corp | Tin pot oil composition |
| US2839437A (en) * | 1955-04-21 | 1958-06-17 | Jones & Laughlin Steel Corp | Method of producing a dull finished fused tin coating |
| US2907701A (en) * | 1956-02-29 | 1959-10-06 | Rheem Mfg Co | Method of producing electroplated containers |
| US3074154A (en) * | 1959-11-02 | 1963-01-22 | Inland Steel Co | Tin plate and method of producing |
| US3075897A (en) * | 1960-05-27 | 1963-01-29 | United States Steel Corp | Method of making tin plate |
| US3445351A (en) * | 1964-10-21 | 1969-05-20 | Du Pont | Process for plating metals |
| US3528892A (en) * | 1968-04-08 | 1970-09-15 | Joseph J Mazur | Plating method |
| US4461679A (en) * | 1979-10-02 | 1984-07-24 | Nippon Steel Corporation | Method of making steel sheet plated with Pb-Sn alloy for automotive fuel tank |
| US4413039A (en) * | 1980-03-22 | 1983-11-01 | Nippon Steel Corporation | Steel sheet plated with layers of NiSn and Pb-Sn alloy for automotive fuel tank |
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