US2624684A - Method and composition for coating aluminum with tin - Google Patents
Method and composition for coating aluminum with tin Download PDFInfo
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- US2624684A US2624684A US259725A US25972551A US2624684A US 2624684 A US2624684 A US 2624684A US 259725 A US259725 A US 259725A US 25972551 A US25972551 A US 25972551A US 2624684 A US2624684 A US 2624684A
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- aluminum
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- fluoride
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 69
- 229910052782 aluminium Inorganic materials 0.000 title claims description 67
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 47
- 238000000576 coating method Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 18
- 239000011248 coating agent Substances 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- -1 HYDROXY AROMATIC COMPOUND Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000001464 adherent effect Effects 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 23
- 238000007654 immersion Methods 0.000 description 21
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 21
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000003292 glue Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229940071182 stannate Drugs 0.000 description 3
- 125000005402 stannate group Chemical group 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Chemical class 0.000 description 2
- 239000011591 potassium Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 2
- 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 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005031 sulfite paper Substances 0.000 description 1
- DGCPSAFMAXHHDM-UHFFFAOYSA-N sulfuric acid;hydrofluoride Chemical compound F.OS(O)(=O)=O DGCPSAFMAXHHDM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000002699 waste material 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
Definitions
- This invention relates to a method of coating metals on articles of aluminum or alloys thereof by immersion of the articles in aqueous solutions of suitable composition. More specifically the invention relates to a method of producing smooth and adherent deposits of tin on aluminum surfaces by immersion in aqueous baths without the use of electric current.
- the immersion deposits have a sound structure and such an unusually high degree of adhesion to the aluminum that they may be used as a base for the subsequent electrodeposition of other metals.
- Tin may be deposited on aluminum by immersion from stannate solutions. This process is used commercially for tin coating aluminum automotive and airplane engine pistons. The lubricating qualities imparted by the tin serve to reduce seizing and scufling and decrease engine break-in time.
- the process using stannate solutions however is critical.
- the temperature must be maintained at 1'75 to 180 F. Allowing the temperature to rise above 180 F. causes blisters in the tin coating. Powdery tin coatings are encountered in present-day practice and this is objectionable because it scores the aluminum during the initial breaking-in period of engine pistons.
- the stannate process is applicable only to some aluminum alloys such as castings; other alloys and pure aluminum (2S) yield powdery deposits. Even on the preferred alloys the adhesion of the tinis poor as may be readily shown by depositing copper on the tin coatings. The copper readily peels oil the separation is between the aluminum and the tin.
- the essential features of my invention are illustrated by the following specific examples for pro-- ducing smooth, uniform adherent coatings of tin on aluminum articles.
- My process is suitable for producing metallic tin deposits on aluminum articles or alloys thereof containing aluminum as the essential component.
- the expression alumi- 2 num in the claims is intended to include articles made of commercially pure aluminum (2S) or aluminum alloys having aluminum as the essential component.
- the aluminum article is first thoroughly degreased and cleaned so as to remove any grease, dirt or other undesirable foreign materials on the surface of the aluminum article.
- the aluminum article is first immersed in an organic solvent, such as trichlorethylene. The article is then treated to activate the surface.
- the aluminum article may be immersed for about one to three minutes at room temperature in a bath containing 0.5 to 5.0 Nhydrofiuoric acid.
- a film may remain on the surface of the article which consists of the metals alloyed with the aluminum. It may be readily removed by dipping the article in 50% or more by volume of nitric acid at room temperature from ten to twenty seconds. This treatment is then followed by a cold water rinse. Warm or hot water should not be used to rinse the aluminum article because of the tendency to form a heavier oxide film on .the aluminum surface which may interfere with the subsequent immersion process.
- Aluminum articles may also be satisfactorily cleaned preparatory to my immersion process by usingsuitable alkaline cleaners such as caustic soda or trisodium phosphate.
- suitable alkaline cleaners such as caustic soda or trisodium phosphate.
- a solution of 50 g. l. of sodium hydroxide at a temperature of C. is satisfactory.
- the aluminum article after preliminary cleaning treatment previously described is then immersed in an aqueous bath containing a tin cation and a fluoride anion.
- a suitable bath for such purpose consists of:
- the hydrolyzed glue is prepared by adding one cc. of 10% sodium hydroxide solution to cc. of 10% bone glue solution and boiling under a reflux condenser for two hours. The excess alkali is neutralized with sulfuric acid and the solution then filtered to remove suspended matter.
- Goulac is a concentrated sulfite paper pulp process waste and contains lignin sulfonates.
- phenolic type compounds and hydrophilic colloids in these solutions leads to smoother, brighter and harder deposits of smaller grain size and less ductility.
- phenolic type of compounds are generally designated as hydroxy aromatic compounds.
- the optimum time of immersion of the aluminum in the tin solution is important for good results and is relatively critical.
- the preferred time of immersion varies with the concentrations of stannous sulfate and hydrofluoric acid. The lower the S11E04 and the higher the HF concentrations, the shorter the time for good tin deposits. In general, the immersion time should not be longer than about ten seconds.
- the amount of stannous sulfate in the bath may range from 0.5 to 2.5 N and the hydrofluoric acid from 0.25 to 5 N.
- the present invention it is possible to produce on aluminum articles deposits thereon of tin by immersion of the aluminum articles in an aqueous bath containing the cation of tin and a fluoride anion.
- the scientific basis of my invention is not fully known to me but it appears that the fluoride anion has a very high solvent action on the surface oxide which may be present on the aluminum, the presence of which normally prevents adherent immersion coatings on aluminum.
- My immersion bath acts to remove the oxide film present and permits the tin to be deposited on the aluminum surface in metal to metal contact before any substantial formation of an intervening oxide film.
- the present invention thus makes it possible to deposit tin on aluminum for any desired purpose, either for protecting the aluminum, for electrodeposition of other metals thereon, or for receiving other coatings such as paint, lacquer, plastic films and the like.
- baths containing compositions of the following components and under conditions given are also suitable for depositing tin Agitation Mild.
- compositions of stannous sulfate and ammonium fluoride within which good tin deposits may be obtained is very striking.
- copper was plated upon the tin immersion deposit to a thickness of 0.0005" and the adhesion determined qualitatively by bending.
- the solubility of stannous sulfate in water at room temperature is 1.8 N.
- the increased solubility of stannous sulfate in the presence of ammonium fluoride is caused by the formation of a tin fluoride complex.
- the fluoride in my bath appears to have two functions: (1) to dissolve the oxide film on the aluminum as previously discussed and (2) to form a tin fluoride complex and thereby greatly extend the range of concentrations of tin and fluoride constituents.
- the SnSO4NH4F' bath is preferred over the solution.
- the time of immersion in the HF bath is very critical and ranges from 5 to 10 seconds. If the time is greater than about ten seconds, the HF attacks the aluminum through the pores in the tin and resulting gassin causes deterioration of the tin deposit. In the NH4F bath there is no gassing, consequently the aluminum may be left in solution up to 1 or 2 minutes without deleterious effect.
- the above differences between the HF and the NH4F baths appear to result from the difference in pH of the two types of solution.
- the pH of the HF baths ranges from 0.2 to 1.0 whereas the pH of the NH4F solutions ranges from 5.0 to 6.5.
- the pH was measured by Accutint pH papers, which are manufactured by Anahemia Co., New York.
- fluoride ion which is the solvent for the oxide film on aluminum and the fluoride salts of ammonium, sodium and potassium are just as effective for this purpose as hydrofiuoric acid.
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to re- .move substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of Water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, a water-soluble tin salt and a watersoluble fluoride, the concentration of tin salt in said bath being in the range of 0.05 N to 7.25 N and the concentration of fluoride being in the range of 0.1 N to 14 N.
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consistin essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride bein in the range of 0.1 N to i l N.
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and hydrofluoric acid, the concentration of stannous sulfate in said bath being in the range of 0.5 N to 2.5 N and the concentration of hydrofluoric acid being in the range of 0.25 N to 5 N.
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.25 N to 3 N and the concentration of ammonium fluoride being in the range of 0.5 N to 0 N.
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article from 2 to 60 seconds in an aqueous bath at a temperature from 20 to 60 0. consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N
- the method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath having a pH from 5.0 to 6.5 and consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride being in the range of 0.1 to 14 N.
- An immersion aqueous bath for depositing metallic tin on.a clean aluminum surface substantially free of surface oxide film which con sists essentially of water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride being in the range of 0.1 N to 14 N.
- An immersion aqueous bath for depositing metallic tin on a clean aluminum surface substantially free of surface oxide film which consists essentially of Water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.25 N to 3 N and the concentration of ammonium fluoride being in the range of 0.5 N to 9 N.
- An immersion aqueous bath for depositing metallic tin on a clean aluminum surface substantially free of surface oxide film which consists essentially of Water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride beingin the range of 0.1 N to 14 N, said bath having a pH from 5.0 to 6.5.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Treatment Of Metals (AREA)
Description
Patented Jan. 6, 1 953 METHOD AND COMPOSITION FOR COATING ALUMINUM WITH TIN Samuel Heiman, Philadelphia, Pa., assignor to Philadelphia Rust-Proof 00., Philadelphia, Pa., a firm of Pennsylvania No Drawing. Application December 3, 1951,
Serial No. 259,725
9 Claims.
This invention relates to a method of coating metals on articles of aluminum or alloys thereof by immersion of the articles in aqueous solutions of suitable composition. More specifically the invention relates to a method of producing smooth and adherent deposits of tin on aluminum surfaces by immersion in aqueous baths without the use of electric current. The immersion deposits have a sound structure and such an unusually high degree of adhesion to the aluminum that they may be used as a base for the subsequent electrodeposition of other metals.
This application is a continuation-in-part of my copending application Serial No. 41,891 filed July 31, 1948, now Patent No. 2,580,773.
Tin may be deposited on aluminum by immersion from stannate solutions. This process is used commercially for tin coating aluminum automotive and airplane engine pistons. The lubricating qualities imparted by the tin serve to reduce seizing and scufling and decrease engine break-in time.
The process using stannate solutions however is critical. The temperature must be maintained at 1'75 to 180 F. Allowing the temperature to rise above 180 F. causes blisters in the tin coating. Powdery tin coatings are encountered in present-day practice and this is objectionable because it scores the aluminum during the initial breaking-in period of engine pistons.
The stannate process is applicable only to some aluminum alloys such as castings; other alloys and pure aluminum (2S) yield powdery deposits. Even on the preferred alloys the adhesion of the tinis poor as may be readily shown by depositing copper on the tin coatings. The copper readily peels oil the separation is between the aluminum and the tin.
I have discovered that it is possible to produce smooth, extremely adherentand uniform coatings on aluminum surfaces of tin by immersion of the cleaned aluminum in aqueous baths containing water-soluble fluorides or fluoride complexes of tin. I may also use suitable water-soluble salts of tin with the addition of suitable amounts of hydrofluoric acid, sodium fluoride, ammonium .fiuoride, ammonium bifiuoride, potassium fluoride, or potassium bifluoride to generate a fluoride anion in the bath.
The essential features of my invention are illustrated by the following specific examples for pro-- ducing smooth, uniform adherent coatings of tin on aluminum articles. My process is suitable for producing metallic tin deposits on aluminum articles or alloys thereof containing aluminum as the essential component. The expression alumi- 2 num in the claims is intended to include articles made of commercially pure aluminum (2S) or aluminum alloys having aluminum as the essential component. The aluminum article is first thoroughly degreased and cleaned so as to remove any grease, dirt or other undesirable foreign materials on the surface of the aluminum article. For example, the aluminum article is first immersed in an organic solvent, such as trichlorethylene. The article is then treated to activate the surface. For this purpose the aluminum article may be immersed for about one to three minutes at room temperature in a bath containing 0.5 to 5.0 Nhydrofiuoric acid. In case the article treated is made of an aluminum alloy, a film may remain on the surface of the article which consists of the metals alloyed with the aluminum. It may be readily removed by dipping the article in 50% or more by volume of nitric acid at room temperature from ten to twenty seconds. This treatment is then followed by a cold water rinse. Warm or hot water should not be used to rinse the aluminum article because of the tendency to form a heavier oxide film on .the aluminum surface which may interfere with the subsequent immersion process.
Aluminum articles may also be satisfactorily cleaned preparatory to my immersion process by usingsuitable alkaline cleaners such as caustic soda or trisodium phosphate. For example, a solution of 50 g. l. of sodium hydroxide at a temperature of C. is satisfactory. The aluminum article after preliminary cleaning treatment previously described is then immersed in an aqueous bath containing a tin cation and a fluoride anion.
Satisfactory deposits of tin on aluminum surfaces can be produced in accordance with the present invention. For example, a suitable bath for such purpose consists of:
SnS04 1.5 N (161.1 g./l.). HF 2.0 N (70.0 ml./l. of 48% acid). Hydrolyzed glue 1.0 g./l. Goulac 0.2 g./l. Purified residue acid .4 1.3 ml./l.
The hydrolyzed glue is prepared by adding one cc. of 10% sodium hydroxide solution to cc. of 10% bone glue solution and boiling under a reflux condenser for two hours. The excess alkali is neutralized with sulfuric acid and the solution then filtered to remove suspended matter. Goulac is a concentrated sulfite paper pulp process waste and contains lignin sulfonates. Purified residue acid is a mixture of high boiling coal tar phenols and had the following distillation range: I. B. P.102; 5%:212"; %=222; %:232"; 50%- 235; '70%=238; E. P.=276.
Without the presence of addition agents, a heavy, black, pulverulent deposit of tin is precipitated on the aluminum which could be easily wiped off. The addition of glue and cresylic acid, to the stannous sulfate-hydrofluoric acid system results in sound, homogeneous tin deposits. Furthe;- improvement is effected by using a mixture of hydrolyzed glue, goulac and purified residue acid. These addition agents are added to the SnSOr-HF solution in the order given above and with vigorous stirring. The solution is then filtered through coarse filter paper to remove suspended matter and excess purified residue acid.
. The presence of small amounts of phenolic type compounds and hydrophilic colloids in these solutions leads to smoother, brighter and harder deposits of smaller grain size and less ductility. These phenolic type of compounds are generally designated as hydroxy aromatic compounds.
Good agitation of the aluminum in the tin solution is essential for sound tin immersion deposits. Lack of agitation may result in dark streaks in the tin and subsequently poor adhesion of the copper plate.
The optimum time of immersion of the aluminum in the tin solution is important for good results and is relatively critical. The preferred time of immersion varies with the concentrations of stannous sulfate and hydrofluoric acid. The lower the S11E04 and the higher the HF concentrations, the shorter the time for good tin deposits. In general, the immersion time should not be longer than about ten seconds. The amount of stannous sulfate in the bath may range from 0.5 to 2.5 N and the hydrofluoric acid from 0.25 to 5 N.
According to the present invention it is possible to produce on aluminum articles deposits thereon of tin by immersion of the aluminum articles in an aqueous bath containing the cation of tin and a fluoride anion. The scientific basis of my invention is not fully known to me but it appears that the fluoride anion has a very high solvent action on the surface oxide which may be present on the aluminum, the presence of which normally prevents adherent immersion coatings on aluminum. My immersion bath acts to remove the oxide film present and permits the tin to be deposited on the aluminum surface in metal to metal contact before any substantial formation of an intervening oxide film. The present invention thus makes it possible to deposit tin on aluminum for any desired purpose, either for protecting the aluminum, for electrodeposition of other metals thereon, or for receiving other coatings such as paint, lacquer, plastic films and the like.
I have found that baths containing compositions of the following components and under conditions given are also suitable for depositing tin Agitation Mild.
The wide range of compositions of stannous sulfate and ammonium fluoride within which good tin deposits may be obtained is very striking. In testing the deposits, copper was plated upon the tin immersion deposit to a thickness of 0.0005" and the adhesion determined qualitatively by bending. The solubility of stannous sulfate in water at room temperature is 1.8 N. The increased solubility of stannous sulfate in the presence of ammonium fluoride is caused by the formation of a tin fluoride complex. I prefer to use baths containing 0.5 N to 9 N NHiF and 0.25 N to 3 N SnSO4 at a temperature of 25 C.
The fluoride in my bath appears to have two functions: (1) to dissolve the oxide film on the aluminum as previously discussed and (2) to form a tin fluoride complex and thereby greatly extend the range of concentrations of tin and fluoride constituents.
In regard to the operating conditions, the SnSO4NH4F' bath is preferred over the solution. The time of immersion in the HF bath is very critical and ranges from 5 to 10 seconds. If the time is greater than about ten seconds, the HF attacks the aluminum through the pores in the tin and resulting gassin causes deterioration of the tin deposit. In the NH4F bath there is no gassing, consequently the aluminum may be left in solution up to 1 or 2 minutes without deleterious effect.
In the HE bath, vigorous agitation of the aluminum is essential. Lack of agitation results in dark streaks in the tin and subsequently poor adhesion of the copper plate. In the NH4F bath, the agitation need be only mild in accordance with good plating practice for deposition by immersion.
The above differences between the HF and the NH4F baths appear to result from the difference in pH of the two types of solution. The pH of the HF baths ranges from 0.2 to 1.0 whereas the pH of the NH4F solutions ranges from 5.0 to 6.5. The pH was measured by Accutint pH papers, which are manufactured by Anahemia Co., New York.
As previously explained, it is the fluoride ion which is the solvent for the oxide film on aluminum and the fluoride salts of ammonium, sodium and potassium are just as effective for this purpose as hydrofiuoric acid.
The results obtained with NH4F were also obtained with either sodium fluoride or potassium fiouride. The pH of all three types of solutions were from 5.0 to 6.5. This further appears to establish that the important conditions for the deposition of adherent tin deposits are (1) presence of fluoride ion and (2) relatively high pH in the range of 5.0 to 6.5.
It will be apparent that the novel and essential features of my invention may be utilized to prepare a large number of immersion baths depending upon the metal desired to be coated, the aluminum article to be coated and the operating conditions under which the coating is to be carried out. The specific examples given herein are intended to be illustrative embodiments of the basic essential features of my invention as defined in the appended claims.
I claim:
1. The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to re- .move substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of Water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, a water-soluble tin salt and a watersoluble fluoride, the concentration of tin salt in said bath being in the range of 0.05 N to 7.25 N and the concentration of fluoride being in the range of 0.1 N to 14 N.
2. The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consistin essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride bein in the range of 0.1 N to i l N.
3. The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and hydrofluoric acid, the concentration of stannous sulfate in said bath being in the range of 0.5 N to 2.5 N and the concentration of hydrofluoric acid being in the range of 0.25 N to 5 N.
a. The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.25 N to 3 N and the concentration of ammonium fluoride being in the range of 0.5 N to 0 N.
The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article from 2 to 60 seconds in an aqueous bath at a temperature from 20 to 60 0. consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N
to 7.25 N and the concentration of ammonium fluoride being in the range of 0.1 N to 14 N.
6. The method of coating aluminum articles with an adherent, smooth deposit of tin which comprises cleaning the aluminum article to remove substantially all of the surface oxide film and immersing the cleaned aluminum article in an aqueous bath having a pH from 5.0 to 6.5 and consisting essentially of water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride being in the range of 0.1 to 14 N.
7. An immersion aqueous bath for depositing metallic tin on.a clean aluminum surface substantially free of surface oxide film which con sists essentially of water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride being in the range of 0.1 N to 14 N.
8. An immersion aqueous bath for depositing metallic tin on a clean aluminum surface substantially free of surface oxide film which consists essentially of Water, an organic addition agent consisting essentially of a Water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.25 N to 3 N and the concentration of ammonium fluoride being in the range of 0.5 N to 9 N.
9. An immersion aqueous bath for depositing metallic tin on a clean aluminum surface substantially free of surface oxide film which consists essentially of Water, an organic addition agent consisting essentially of a water-soluble glue and a hydroxy aromatic compound, stannous sulfate and ammonium fluoride, the concentration of stannous sulfate in said bath being in the range of 0.05 N to 7.25 N and the concentration of ammonium fluoride beingin the range of 0.1 N to 14 N, said bath having a pH from 5.0 to 6.5.
SAMUEL I-IEIMAN.
REFERENCES CITED UNITED STATES PATENTS Name Date Heiman Jan. 1, 1952 Number
Claims (1)
1. THE METHOD OF COATING ALUMINUM ARTICLES WITH AN ADHERENT, SMOOTH DEPOSIT OF TIN WHICH COMPRISES CLEANING THE ALUMINUM ARTICLE TO REMOVE SUBSTANTIALLY ALL OF THE SURFACE OXIDE FILM AND IMMERSING THE CLEANED ALUMINUM ARTICLE IN AN AQUEOUS BATH CONSISTING ESSENTIALLY OF WATER AN ORGANIC ADDITION AGENT CONSISTING ESSENTIALLY OF A WATER-SOLUBLE GLUE AND A HYDROXY AROMATIC COMPOUND, A WATER-SOLUBLE TIN SALT AND A WATERSOLUBLE FLUORIDE, THE CONCENTRATION OF TIN SALT IN SAID BATH IN THE RASNGE OF 0.05 N TO 7.25 N AND THE CONCENTRATION OF FLUORIDE BEING IN THE RANGE OF 0.01 N TO 14 N.
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US259725A US2624684A (en) | 1951-12-03 | 1951-12-03 | Method and composition for coating aluminum with tin |
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US259725A US2624684A (en) | 1951-12-03 | 1951-12-03 | Method and composition for coating aluminum with tin |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2830881A (en) * | 1954-01-25 | 1958-04-15 | Kaiser Aluminium Chem Corp | Treatment of material |
US2836510A (en) * | 1953-05-21 | 1958-05-27 | Gen Motors Corp | Nickel plating by chemical reduction |
US2938841A (en) * | 1956-04-13 | 1960-05-31 | Olin Mathieson | Preparation of zirconium for cold working |
US2940867A (en) * | 1958-12-24 | 1960-06-14 | Du Pont | Immersion tin plating and composition therefore |
US3262764A (en) * | 1963-08-19 | 1966-07-26 | United Aircraft Corp | Coatings for columbium base alloys |
USB399766I5 (en) * | 1973-09-20 | 1975-01-28 | ||
US3881999A (en) * | 1973-05-25 | 1975-05-06 | Westinghouse Electric Corp | Method of making abrasion resistant coating for aluminum base alloy |
US4170525A (en) * | 1978-04-28 | 1979-10-09 | Gould Inc. | Process for plating a composite structure |
US5456323A (en) * | 1993-12-15 | 1995-10-10 | Piper Farm Products, Inc. | Agricultural sweep and method of manufacture |
EP0779941A1 (en) * | 1995-06-07 | 1997-06-25 | Atotech Usa, Inc. | Etchant for aluminium alloys |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2580773A (en) * | 1948-07-31 | 1952-01-01 | Philadelphia Rust Proof Co | Method and composition for coating aluminum with zinc |
-
1951
- 1951-12-03 US US259725A patent/US2624684A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2580773A (en) * | 1948-07-31 | 1952-01-01 | Philadelphia Rust Proof Co | Method and composition for coating aluminum with zinc |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2836510A (en) * | 1953-05-21 | 1958-05-27 | Gen Motors Corp | Nickel plating by chemical reduction |
US2830881A (en) * | 1954-01-25 | 1958-04-15 | Kaiser Aluminium Chem Corp | Treatment of material |
US2938841A (en) * | 1956-04-13 | 1960-05-31 | Olin Mathieson | Preparation of zirconium for cold working |
US2940867A (en) * | 1958-12-24 | 1960-06-14 | Du Pont | Immersion tin plating and composition therefore |
US3262764A (en) * | 1963-08-19 | 1966-07-26 | United Aircraft Corp | Coatings for columbium base alloys |
US3881999A (en) * | 1973-05-25 | 1975-05-06 | Westinghouse Electric Corp | Method of making abrasion resistant coating for aluminum base alloy |
USB399766I5 (en) * | 1973-09-20 | 1975-01-28 | ||
US3915667A (en) * | 1973-09-20 | 1975-10-28 | Westinghouse Electric Corp | Abrasion resistant coating for aluminum base alloy and method |
US4170525A (en) * | 1978-04-28 | 1979-10-09 | Gould Inc. | Process for plating a composite structure |
FR2424330A1 (en) * | 1978-04-28 | 1979-11-23 | Gould Inc | METHOD FOR METALLIZING A COMPOSITE STRUCTURE |
US5456323A (en) * | 1993-12-15 | 1995-10-10 | Piper Farm Products, Inc. | Agricultural sweep and method of manufacture |
EP0779941A1 (en) * | 1995-06-07 | 1997-06-25 | Atotech Usa, Inc. | Etchant for aluminium alloys |
EP0779941A4 (en) * | 1995-06-07 | 1998-11-25 | Atotech Usa Inc | Etchant for aluminium alloys |
KR100476497B1 (en) * | 1995-06-07 | 2005-09-07 | 아토테크 도이칠란드 게엠베하 | Processing method of aluminum alloy and the product manufactured by this method |
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