US2828193A - Method for rejuvenation of aluminum treating solutions - Google Patents
Method for rejuvenation of aluminum treating solutions Download PDFInfo
- Publication number
- US2828193A US2828193A US448775A US44877554A US2828193A US 2828193 A US2828193 A US 2828193A US 448775 A US448775 A US 448775A US 44877554 A US44877554 A US 44877554A US 2828193 A US2828193 A US 2828193A
- Authority
- US
- United States
- Prior art keywords
- solution
- acid
- aluminum
- fluoride
- smut
- 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
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 15
- 230000003716 rejuvenation Effects 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 70
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 31
- 239000003929 acidic solution Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 FLUORIDE IONS Chemical class 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000002222 fluorine compounds Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000080 wetting agent Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 7
- 238000005530 etching Methods 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000011775 sodium fluoride Substances 0.000 description 7
- 235000013024 sodium fluoride Nutrition 0.000 description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 6
- 150000001455 metallic ions Chemical class 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 230000001464 adherent effect Effects 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZRGXFRPXHJVPCM-UHFFFAOYSA-N 3-butyl-2-phenylphenol;sodium Chemical compound [Na].CCCCC1=CC=CC(O)=C1C1=CC=CC=C1 ZRGXFRPXHJVPCM-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004897 Triton X-45 Polymers 0.000 description 1
- 241000221561 Ustilaginales Species 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229940074323 antara Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- URXDZIFZXGLYIT-UHFFFAOYSA-N decylbenzene;sodium Chemical compound [Na].CCCCCCCCCCC1=CC=CC=C1 URXDZIFZXGLYIT-UHFFFAOYSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- YMTINGFKWWXKFG-UHFFFAOYSA-N fenofibrate Chemical compound C1=CC(OC(C)(C)C(=O)OC(C)C)=CC=C1C(=O)C1=CC=C(Cl)C=C1 YMTINGFKWWXKFG-UHFFFAOYSA-N 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Definitions
- the acidic solutions employed above for these various purposes have all in common the property of dissolving aluminum oxide, or where the acidic salt solutions contain fluorides or acid fluorides they will dissolve smut readily but have an unsubstantial rate of attack on the elemental aluminum. They are all acid or acid salt solutions of pH of 4 or less and they are used at temperatures at which the attack rate on the elemental aluminum is substantially less than its attack on smut or aluminum oxide film and may be substantially entirely inactive to dissolve the aluminum metal for exposure times sufficient to remove the oxide or smut.
- These acidic solutions may be those made by a solution of HNO H 50 phosphoric acid, and mixtures of these acids, or acid salts, such as sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate, sodium acid sulfate, or sodium nitrate acidified with sulfuric acid, or the equivalent potassium and ammonium salts, all having a pH less than about 4 to which I may, and preferably do, add sodium, potassium or ammonium chromate or dichrornate or chromic acid, adding the agents, when alkaline or neutral, in amount insuflicient to raise the pH above 4.
- HNO H 50 phosphoric acid and mixtures of these acids, or acid salts, such as sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate, sodium acid sulfate, or sodium nitrate acidified with sulfuric acid, or the equivalent potassium and ammonium salts, all having a pH less than about 4 to which I may, and preferably do, add sodium, potassium or ammonium
- I When I use the acid salts for smut removal, I preferably add a small amount of hydrofluoric acid or an alkali metal StQIS r fluoride or alkali metal acid fluoride or ammonium acid fluoride. All of these solutions will remove smut or aluminum oxide film or film of other compounds produced in the etching process without any substantial attack on the elemental aluminum surface and may be classified as acidic solutions safe on aluminum.
- a convenient reagent for the purpose is ammonium acid fluoride NHQFl-IF, or I may use sodium acid fluoride NaF.HF, or potassium acid fluoride KFl-IF.
- NHQFl-IF ammonium acid fluoride
- I may use sodium acid fluoride NaF.HF, or potassium acid fluoride KFl-IF.
- the addition of the NH FfiF to the spent acidic solution results in the precipitation of a white silky flock, which rapidly settles to the bottom of the vessel, and which contains Al, F, Na, as well as Fe and Cu, if these be present in solution in the spent acidic solution.
- Aluminum may be etched with solutions of sodium or potassium hydroxide, tri sodium or tri potassium phosphate, sodium or potassium carbonate, or a similar reagent having an alkalinity equivalent to that of .l to 10 normal NaOH solution.
- the result is a solution of the elemental aluminum from the surface exposed to the alkali. The surface will be contaminated by the smut if the aluminum is one which is alloyed as described above.
- such smut contaminated aluminum may be cleaned of the contaminating smut by washing the aluminum surface with an acidic solution containing nitric acid or nitric sulfuric acid or sulfuric acid mixed with chromic acid. Such mixtures are hazardous to handle.
- dry mixture may be used in place of the above acids.
- dry mixtures may be mixtures of the acid salts of sulfuric acid and chromic acid to which may be added suitable non-ionic or anionic acid stable wetting agents.
- an anionic or non-ionic acid stable wetting agent 150% sodium or potassium or ammonium chromate or dichromate or chromic acid using them in amount to add up to 100%.
- NaHSO sodium acid sulfate
- NH F.HF ammonium bi fluoride
- an anionic or non-ionic wetting agent for example, Nacconol Z, which is an alkyl aryl sulfonate sold by National Aniline, Div. Allied Chemical & Dye Corp., N. Y. C.
- anionic wetting agents are a Well recognized class of wetting agents.
- anionic wetting agents in addition to Nacconol Z, are: Nornol MB or C (sodium lauryl sulfate) or Aresltap (monobutylphenylphenol sodium sulfonate) sold by Monsanto Chemical Co., or Santomerse D (decyl benzene sodium sulfonate) sold by Monsanto Chemical Co. of St. Louis, Missouri.
- non-ionic wetting agents examples include alkyl aryl polyoxyethylene alcohols (Triton X-45 and Triton X-100, sold by Rohm and Haas Co. of Philadelphia), alkyl phenoxy polyoxyethylene ethanols (Igepol CO-630, Igepol CO-730 and Igepal CO850, sold by Antara Chemicals, Div. General Dyestutf Corp. of N. Y.), polyoxyethylene thioether (Sterox SK, sold by Monsanto Chemical Co. of St. Louis, Mo.).
- the mixtures may be used in concentration of from 4 oz. of the mixture per gallon of water to 32 oz. per gallon of water.
- a preferred acid concentration is about 16 oz. per gallon water.
- the smut contaminated aluminum alloy such as 245, when immersed or sprayed with this solution at a temperature of 60-180 degrees F. for about 2 to 10 minutes, depending on the degree of contamination by smut and the temperature employed, becomes smut free, the surface appearing clean and bright and without any substantial corrosive attack on the aluminum surface.
- the aluminum after removal of the smut, begins to oxidize in the solution and an oxide film is developed.
- the time of immersion or other contact with the solution should be such that the smut is removed and the process discontinued before any substantial buildup of oxide film on the metal surface occurs.
- alkali 4 or ammonium acid fluoride that is, NH F.HF, or KF.I-IF, or NaF.I-IF, or NaF, or KF, or HF, or other soluble fluorides.
- alkali 4 or ammonium acid fluoride that is, NH F.HF, or KF.I-IF, or NaF.I-IF, or NaF, or KF, or HF, or other soluble fluorides.
- the addition of these materials causes the precipitation of the dissolved aluminum and other metallic ions higher in the electromotive series than aluminum, which have been dissolved, may be precipitated substantially quantitatively.
- a white silky flocculent precipitate is
- the acid fluoride or fluoride is added in an amount stoichiometrically equivalent to the Al ions in solution, 3 mols of acid fluoride or fluoride, for example 3 mols NH F.HF, being employed per mol of Al. it is believed that the fluoride precipitates the Al+++ as insoluble aluminum fluoride complex. If the acid fluoride is added in amount, so that after precipitating the metallic ions some of the acid fluoride or fluoride is present in excess then, on reuse, some solution of the aluminum from the aluminum object occurs. If a substantial excess of the acid fluoride or fluoride is employed this results in a corrosion of the surface of the aluminum which is undesirable. Some small excess of free fluoride or acid fluoride in the order of about 0.25% by weight of the solution may be tolerated, if care is taken in the treatment not to permit too great a length of time in the exposure of the aluminum to the solution.
- the solution after having been treated with the fluoride, may be reused since its smut and oxide removal capacity is substantially completely restored.
- Example 1 Parts which have been etched with caustic soda solutions, such as described above, and which are covered with dark adherent surface layers of smut are rinsed free of the etchant caustic.
- the rinsed part is introduced into a tank and sprayed with a solution or dipped into a solution, made up by dissolving 16 oz. per gallon of the mixture identified above, that is, 77.1% NaHSO 1% NHEHF; 21.8% K Cr O and 0.1% of Nacconol Z (all percentages are by weight).
- the part is wetted for a period of 3 minutes, the solution having a temperature of 80 degrees F.
- the parts are then removed, rinsed and dried. They are cleaned of the adherent smut.
- the solution When the solution is active, it will desmut such parts and may be repeatedly used on new parts to be desmutted. A time will be reached, depending on how many parts are desmutted and the volume of the solution employed, when the solution no longer will desmut parts at the above temperature and exposure time.
- the solution is thus termed exhausted under the condition as imposed by the time and temperature specified. It is to be noted that the prolongation of time of exposure or elevation of temperature would cause additional activity in smut removal until the chemical capacity of the solution to remove smut is chemically exhausted. However, I have found it more convenient to continue the treatment for the chosen times and temperature and to revivify the solution instead of increasing the time or temperature of reatment and to revivify the solution when it is substantially completely chemically exhausted.
- I may, and usually prefer to, add an inhibitor, such as NO ion.
- an inhibitor such as NO ion.
- I have found that the addition of concentrated HNO above about 0.1% to 1% by volume of the solution to be revivified, for example: one-half gallon of concentrated HNO (67% HNO by volume) per 1,000 gallons of solution (that is, .03% HNO by volume) is sufiicient to prevent corrosive attack by excess acid fluoride when the acid fluoride is added in the proportions given above, that is, 0.2 oz. per gallon Where NH.,F.HF is used or 0.3 oz. per gallon where NaF.HF is used.
- I may also use a soluble nitrate such as sodium, potassium or ammonium nitrate in amounts chemicaly equivalent to the HNO as specified above in solutions sufliciently acid to give the above HN0 equivalent.
- the added fluoride ion yielding compound being chosen from the group consisting of hydrofluoric acid, sodium acid fluoride, potassium acid fluoride, ammonium acid fluoride, sodium fluoride, potassium fluoride, and ammonium fluoride.
- the aqueous acidic solution containing fluoride ions containing about 4 oz. to 32 oz. per gallon of water of a mixture consisting essentially of about to 99 percent of an acid salt chosen from the group consisting of sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate and sodium acid sulfate, about 0.1 to 2 percent of a fluoride chosen from the group consisting of sodium, potassium, and ammonium fluorides, and equivalent acid fluorides, about 0 to 1.0 percent of a wetting agent, and about 1 to 50 percent of a compound chosen from the group consisting of potassium chromate, potassium dichromate, the equivalent sodium and ammonium salts thereof, and chromic acid, all percentages being on the basis of weight.
- an acid salt chosen from the group consisting of sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate and sodium acid sulfate
- a fluoride chosen from the group consisting of sodium, potassium, and ammonium fluorides, and
Description
METHOD FOR REJUVENATION OF ALUMINUM TREATING SOLUTIONS No Drawing. Application August 9, 1954 Serial No. 448,775
3 Claims. (Cl. 41-42) In a copending application for patent, Ser. No. 445,196, filed July 22, 1954, now Patent No. 2,762,694, I have disclosed the conditioning of aluminum surfaces preparatory both to masking with surface coating compositions and also as a preconditioning operation to improve the uniformity of etching of the aluminum surfaces with alkali etching agents.
I have found that the use of water solutions of acids other than hydrochloric acid, and acid salts of acid having a pH of 4 or less, may be used to remove the aluminum oxide film, which covers surfaces of aluminum and alloys of aluminum, to improve the adherence of masking coatings, and also to improve the uniformity of etching attack by alkaline etching reagents on the exposed elemental metal surface.
I have also found such acidic solutions are useful for the removal of the so-called smut which appears on surfaces of aluminum alloys, particularly when aluminum is alloyed with elements, such as for example, copper, iron, silicon and carbon, etc. Such aluminum alloys, when etched with caustic soda, produce a film which is black and highly adherent to the surface. It is conventionally referred to as smut in this art. These smuts are insoluble in water and in most acids. They are soluble in HNO mixtures of I-INO and H 80 and in mixtures of chromic acid and sulfuric acid. Such acids are extremely hazardous to use industrially.
It has been found that the addition of a fluoride ion yielding compound, that is, hydrofluoric acid, alkali metal or ammonium fluoride or equivalent acid fluoride salts, to the acid salts when dissolved in water produces a relatively mild acidic solution which, however, has the property of dissolving smut.
The acidic solutions employed above for these various purposes have all in common the property of dissolving aluminum oxide, or where the acidic salt solutions contain fluorides or acid fluorides they will dissolve smut readily but have an unsubstantial rate of attack on the elemental aluminum. They are all acid or acid salt solutions of pH of 4 or less and they are used at temperatures at which the attack rate on the elemental aluminum is substantially less than its attack on smut or aluminum oxide film and may be substantially entirely inactive to dissolve the aluminum metal for exposure times sufficient to remove the oxide or smut. These acidic solutions may be those made by a solution of HNO H 50 phosphoric acid, and mixtures of these acids, or acid salts, such as sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate, sodium acid sulfate, or sodium nitrate acidified with sulfuric acid, or the equivalent potassium and ammonium salts, all having a pH less than about 4 to which I may, and preferably do, add sodium, potassium or ammonium chromate or dichrornate or chromic acid, adding the agents, when alkaline or neutral, in amount insuflicient to raise the pH above 4. When I use the acid salts for smut removal, I preferably add a small amount of hydrofluoric acid or an alkali metal StQIS r fluoride or alkali metal acid fluoride or ammonium acid fluoride. All of these solutions will remove smut or aluminum oxide film or film of other compounds produced in the etching process without any substantial attack on the elemental aluminum surface and may be classified as acidic solutions safe on aluminum.
It has been found that their usefulness, in conditioning the surfaces of the aluminum prior to etching or in clearing up the etched surfaces to clean them of films or layers of compounds of aluminum such as smut or aluminum oxide film or film of other compounds which may be formed in the etching process, gradually diminishes during continued use so that longer and longer exposure times are required for the acidic solution to do its work. The solutions are said to be exhausted. A time comes when it is no longer economical to continue the use of such solutions and they are discarded and fresh solutions are made up.
I have found that such solutions may be revivified and their activity restored by adding hydrofluoric acid or a water soluble fluoride and preferably an alkali metal fluoride or an alkali metal acid fluoride or the equivalent ammonium salts which for this purpose are equivalent in action to the alkali metal fluorides or acid fluorides.
While I do not wish to be bound by any theory of the process, I believe that the hydrofluoric acid or the fluoride salts cause the precipitation from solution in the spent acidic reagent of dissolved metallic ions which have gone into solution as a result of the treatment of the aluminum body with the acidic material. I have found that by adding an amount of fluoride ions stoichiometrically equivalent to the Al+++ ion and other metallic ions, for example Cu and Fe, in solution in the spent acid solution, that I can substantially quantitatively precipitate the aluminum and other metallic ions dissolved from the aluminum surface in the removal of smut (that is, those metallic ions lower than Al in the electromotive series which are present in the acidic solution) and substantially completely revivify, the acidic solution to reestablish in substantial effect its original activity as when freshly prepared.
A convenient reagent for the purpose is ammonium acid fluoride NHQFl-IF, or I may use sodium acid fluoride NaF.HF, or potassium acid fluoride KFl-IF. Thus, for example, the addition of the NH FfiF to the spent acidic solution results in the precipitation of a white silky flock, which rapidly settles to the bottom of the vessel, and which contains Al, F, Na, as well as Fe and Cu, if these be present in solution in the spent acidic solution.
illustrating the usefulness of my process is the application of the acid fluorides for the revivification of acid solutions employed in removal of smut which have become exhausted because of their use in the removal of smut.
Aluminum may be etched with solutions of sodium or potassium hydroxide, tri sodium or tri potassium phosphate, sodium or potassium carbonate, or a similar reagent having an alkalinity equivalent to that of .l to 10 normal NaOH solution. The result is a solution of the elemental aluminum from the surface exposed to the alkali. The surface will be contaminated by the smut if the aluminum is one which is alloyed as described above.
Asstated above, such smut contaminated aluminum may be cleaned of the contaminating smut by washing the aluminum surface with an acidic solution containing nitric acid or nitric sulfuric acid or sulfuric acid mixed with chromic acid. Such mixtures are hazardous to handle.
I have found that the dry mixture may be used in place of the above acids. Such dry mixtures may be mixtures of the acid salts of sulfuric acid and chromic acid to which may be added suitable non-ionic or anionic acid stable wetting agents.
I may employ solid mixtures of the following composition:
50-99% of the acid salts referred to above 0.12% fluoride, or acid fluoride described above 04.0% of an anionic or non-ionic acid stable wetting agent 150% sodium or potassium or ammonium chromate or dichromate or chromic acid using them in amount to add up to 100%.
An example of such mixture is as follows:
77.1% NaHSO (sodium acid sulfate) 1% NH F.HF (ammonium bi fluoride) 0.1% of an anionic or non-ionic wetting agent, for example, Nacconol Z, which is an alkyl aryl sulfonate sold by National Aniline, Div. Allied Chemical & Dye Corp., N. Y. C.
21.8% K Cr O potassium dichromate The acid stable anionic and non-ionic wetting agents referred to are a Well recognized class of wetting agents. Examples of anionic wetting agents, in addition to Nacconol Z, are: Dupanol MB or C (sodium lauryl sulfate) or Aresltap (monobutylphenylphenol sodium sulfonate) sold by Monsanto Chemical Co., or Santomerse D (decyl benzene sodium sulfonate) sold by Monsanto Chemical Co. of St. Louis, Missouri. Examples of non-ionic wetting agents are alkyl aryl polyoxyethylene alcohols (Triton X-45 and Triton X-100, sold by Rohm and Haas Co. of Philadelphia), alkyl phenoxy polyoxyethylene ethanols (Igepol CO-630, Igepol CO-730 and Igepal CO850, sold by Antara Chemicals, Div. General Dyestutf Corp. of N. Y.), polyoxyethylene thioether (Sterox SK, sold by Monsanto Chemical Co. of St. Louis, Mo.).
The mixtures may be used in concentration of from 4 oz. of the mixture per gallon of water to 32 oz. per gallon of water. A preferred acid concentration is about 16 oz. per gallon water.
The smut contaminated aluminum alloy, such as 245, when immersed or sprayed with this solution at a temperature of 60-180 degrees F. for about 2 to 10 minutes, depending on the degree of contamination by smut and the temperature employed, becomes smut free, the surface appearing clean and bright and without any substantial corrosive attack on the aluminum surface.
The higher the concentration of the mixture employed in the solution, the more critical becomes the time of immersion. Thus, the aluminum, after removal of the smut, begins to oxidize in the solution and an oxide film is developed. The time of immersion or other contact with the solution should be such that the smut is removed and the process discontinued before any substantial buildup of oxide film on the metal surface occurs.
The same precaution should be employed when the above solution is employed to remove an aluminum oxide film in addition to or in place of smut. The time of contact and preferred concentration may or may not be the same as in the above case depending on the nature of the oxide surface.
In both cases whatever time rate is established for desmutting or deoxidizing the metal at the temperature employed, it will be found that as more and more pieces of metal are treated with the solution, a point is reached when the solution will no longer desmut or deoxidize the aluminum at the temperature and the times chosen as above. They are spent solutions within the criteria set forth above.
In order to continue to use this solution, either the time must be prolonged or the temperature increased or the solution revivified.
I have found that I can revivify such solutions which have become spent by adding small amounts of alkali 4 or ammonium acid fluoride, that is, NH F.HF, or KF.I-IF, or NaF.I-IF, or NaF, or KF, or HF, or other soluble fluorides. The addition of these materials causes the precipitation of the dissolved aluminum and other metallic ions higher in the electromotive series than aluminum, which have been dissolved, may be precipitated substantially quantitatively. A white silky flocculent precipitate is formed. This precipitate settles to the bottom of the container and when the container is cleaned the precipitate, which is not adherent, may be readily flushed out.
it is preferred that the acid fluoride or fluoride is added in an amount stoichiometrically equivalent to the Al ions in solution, 3 mols of acid fluoride or fluoride, for example 3 mols NH F.HF, being employed per mol of Al. it is believed that the fluoride precipitates the Al+++ as insoluble aluminum fluoride complex. If the acid fluoride is added in amount, so that after precipitating the metallic ions some of the acid fluoride or fluoride is present in excess then, on reuse, some solution of the aluminum from the aluminum object occurs. If a substantial excess of the acid fluoride or fluoride is employed this results in a corrosion of the surface of the aluminum which is undesirable. Some small excess of free fluoride or acid fluoride in the order of about 0.25% by weight of the solution may be tolerated, if care is taken in the treatment not to permit too great a length of time in the exposure of the aluminum to the solution.
Small amount of nitrate ions (in the order of about 0.04% or greater weight percentage of the solution) when added to the solution inhibits the corrosive attack of the free acid fluoride. Y
The solution, after having been treated with the fluoride, may be reused since its smut and oxide removal capacity is substantially completely restored.
The following is an example of the application of my process which is given as illustrating a preferred embodiment of my invention but not as a limitation of my invention:
Example 1 Parts which have been etched with caustic soda solutions, such as described above, and which are covered with dark adherent surface layers of smut are rinsed free of the etchant caustic. The rinsed part is introduced into a tank and sprayed with a solution or dipped into a solution, made up by dissolving 16 oz. per gallon of the mixture identified above, that is, 77.1% NaHSO 1% NHEHF; 21.8% K Cr O and 0.1% of Nacconol Z (all percentages are by weight). The part is wetted for a period of 3 minutes, the solution having a temperature of 80 degrees F. The parts are then removed, rinsed and dried. They are cleaned of the adherent smut. When the solution is active, it will desmut such parts and may be repeatedly used on new parts to be desmutted. A time will be reached, depending on how many parts are desmutted and the volume of the solution employed, when the solution no longer will desmut parts at the above temperature and exposure time. The solution is thus termed exhausted under the condition as imposed by the time and temperature specified. It is to be noted that the prolongation of time of exposure or elevation of temperature would cause additional activity in smut removal until the chemical capacity of the solution to remove smut is chemically exhausted. However, I have found it more convenient to continue the treatment for the chosen times and temperature and to revivify the solution instead of increasing the time or temperature of reatment and to revivify the solution when it is substantially completely chemically exhausted.
To revivify the solutions, I add NHEHF, or NaEHF, or KEHF, or NaF, or KP, or HP, or other fluorides. For the procedure set forth above, that is, where treatment is for 3 minutes and at 80 degrees F. with the above acid salt solution, I have found that the addition of NELRHF in an amount equal to 0.2 oz. per gallon of solution or 0.3 oz. of NaF.HF per gallon of solution, will revivify the solution to restore its original activity.
Since because of variations in operating conditions, where repeated revivification of the solution is desired, it may be found that the concentrations of acid fluorides or fluorides stated above may exceed the stoichiometric requirements of the spent solution and result in an excess of free acid fluoride in solution. At other times the above treatment will not completely revivify the solution since it may not be sufiicient to completely precipitate the Al ions in solution. In the latter case, no serious difliculty occurs and the solution merely becomes spent sooner on repeated use. However, in the former case, the solution may be corrosive to aluminum to give a white adherent coat to the desmutted aluminum.
In order to avoid this latter contingency, I may, and usually prefer to, add an inhibitor, such as NO ion. I have found that the addition of concentrated HNO above about 0.1% to 1% by volume of the solution to be revivified, for example: one-half gallon of concentrated HNO (67% HNO by volume) per 1,000 gallons of solution (that is, .03% HNO by volume) is sufiicient to prevent corrosive attack by excess acid fluoride when the acid fluoride is added in the proportions given above, that is, 0.2 oz. per gallon Where NH.,F.HF is used or 0.3 oz. per gallon where NaF.HF is used. I may also use a soluble nitrate such as sodium, potassium or ammonium nitrate in amounts chemicaly equivalent to the HNO as specified above in solutions sufliciently acid to give the above HN0 equivalent.
While I have described a particular embodiment of my invention for the purpose of illustration, it should be understood that various modifications and adaptations thereof may be made within the spirit of the invention as set forth in the appended claims.
I claim:
1. In a method of treating aluminum objects having a surface layer of metal compounds thereon to remove said compounds, wherein said compounds are removed by contacting said surface layer with an aqueous acidic solution containing fluoride ions, said solution being adapted to react with and dissolve said layer without appreciably corroding the aluminum objects; the improvement of revivifying said solution, after treatment and removal of said aluminum objects from the bath, by increasing the free fluoride concentration thereof above that existing during the metal compound dissolving procedure to a concentration corrosive to aluminum objects by adding to said solution a free fluoride ion yielding compound in an amount substantially equal to the amount of said compound stoichiomet-rically equivalent to the dissolved metal ions present in the solution, to precipitate substantially all the dissolved metal ions from said solution in combination with the additional fluoride ions.
2. In a method as set forth in claim 1, the added fluoride ion yielding compound being chosen from the group consisting of hydrofluoric acid, sodium acid fluoride, potassium acid fluoride, ammonium acid fluoride, sodium fluoride, potassium fluoride, and ammonium fluoride.
3. In a method as set forth in claim 2, the aqueous acidic solution containing fluoride ions containing about 4 oz. to 32 oz. per gallon of water of a mixture consisting essentially of about to 99 percent of an acid salt chosen from the group consisting of sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate and sodium acid sulfate, about 0.1 to 2 percent of a fluoride chosen from the group consisting of sodium, potassium, and ammonium fluorides, and equivalent acid fluorides, about 0 to 1.0 percent of a wetting agent, and about 1 to 50 percent of a compound chosen from the group consisting of potassium chromate, potassium dichromate, the equivalent sodium and ammonium salts thereof, and chromic acid, all percentages being on the basis of weight.
References Cited in the file of this patent UNITED STATES PATENTS 2,593,447 Hesch Apr. 22, 1952 2,614,913 Reindl et al. Oct. 21, 1952 2,625,468 France et al. Jan. 13, 1953 2 19,079 Murphy Sept. 27, 1955
Claims (1)
1. IN A METHOD FOR TREATING ALUMINUM OBJECTS HAVING A SURFACE LAYER OF METAL COMPOUNDS THEREON TO REMOVE SAID COMPOUNDS, WHEREIN SAID COMPOUNDS ARE REMOVED BY CONTACTING SAID SURFACE LAYER WITH AN AQUEOUS ACIDIC SOLUTION CONTAINING FLUORIDE IONS, SAID SOLUTION BEING ADAPTED TO REACT WITH AND DISSOLVE SAID LAYER WITHOUT APPRECIABLY CORRODING THE ALUMINUM OBJECTS; THE IMPROVEMENT OF REVIVIFYING SAID SOLUTION, AFTER TREATMENT AND REMOVAL OF SAID ALUMINUM OBJECTS FROM THE BATH, BY INCREASING THE FREE FLUORIDE CONCENTRATION THEREOF ABOVE THAT EXISTING DURING THE METAL COMPOUND DISSOLVING PROCEDURE TO A CONCENTRATION CORROSIVE TO ALUMINUM OBJECTS BY ADDING SAID SOLUTION A FREE FLUORIDE ION YIELDING COMPOUND IN AN AMOUNT SUBSTANTIALLY EQUAL TO THE AMOUNT OF SAID COMPOUND STOICHIMETRICALLY EQUIVALENT TO THE DISSOLVED METAL IONS PRESENT IN THE SOLUTION, TO PRECIPITATE SUBSTANTIALLY ALL THE DISSOLVED METAL IONS FROM SAID SOLUTION IN COMBINATION WITH THE ADDITIONAL FLORIDE IONS.
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Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3108919A (en) * | 1959-06-17 | 1963-10-29 | North American Aviation Inc | Etching process |
US3140203A (en) * | 1961-04-24 | 1964-07-07 | Macdermid Inc | Method of and composition for treating aluminum and aluminum alloys |
US3155556A (en) * | 1960-01-13 | 1964-11-03 | Vaw Ver Aluminium Werke Ag | Method for glossing articles made of aluminum and particularly pure aluminum and itsalloys |
US3197340A (en) * | 1960-10-05 | 1965-07-27 | Conversion Chem Corp | Composition and method for cleaning aluminum castings |
US3230172A (en) * | 1961-04-10 | 1966-01-18 | Montedison Spa | Pickling bath for stainless steel and process for the preparation thereof |
US3275562A (en) * | 1963-11-12 | 1966-09-27 | Pennsalt Chemicals Corp | Non-chromated aluminum desmutting compositions |
US3296141A (en) * | 1965-03-25 | 1967-01-03 | R O Hull & Company Inc | Bright dip compositions for the treatment of steel |
US3314890A (en) * | 1965-04-09 | 1967-04-18 | Pennsalt Chemicals Corp | Alkali etching solution for aluminum |
US3373114A (en) * | 1967-01-03 | 1968-03-12 | Macdermid Inc | Dry compositions for deoxidizing and desmutting aluminum and aluminum alloys |
US3549540A (en) * | 1966-10-31 | 1970-12-22 | Amchem Prod | Method and compositions for treating aluminum surfaces |
DE2506066A1 (en) * | 1974-02-14 | 1975-08-21 | Amchem Prod | METHOD OF CLEANING ALUMINUM |
US3951681A (en) * | 1973-11-01 | 1976-04-20 | Kolene Corporation | Method for descaling ferrous metals |
DE2546316A1 (en) * | 1974-10-18 | 1976-04-22 | Philips Nv | PROCESS FOR TREATMENT OF BODIES WITH A CORROSIVE AGENT FOR ALUMINUM OXIDE, IN PARTICULAR IN THE PRODUCTION OF SEMI-CONDUCTOR ARRANGEMENTS |
US4126483A (en) * | 1977-06-03 | 1978-11-21 | Ford Motor Company | Method of adherency of electrodeposits on light weight metals |
US4136026A (en) * | 1977-11-23 | 1979-01-23 | Aluminum Company Of America | Caustic solution having controlled dissolved aluminum content |
DE3048083A1 (en) * | 1980-12-19 | 1982-07-01 | Ludwig 8900 Augsburg Fahrmbacher-Lutz | METHOD FOR CHEMICAL REMOVAL OF OXIDE LAYERS FROM OBJECTS FROM METALS |
USRE31198E (en) * | 1974-02-14 | 1983-04-05 | Amchem Products, Inc. | Method for cleaning aluminum at low temperatures |
US4673521A (en) * | 1986-01-21 | 1987-06-16 | Enthone, Incorporated | Process for regenerating solder stripping solutions |
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US2593447A (en) * | 1949-06-27 | 1952-04-22 | Permanente Metals Corp | Method and composition for treating aluminum and aluminum alloys |
US2614913A (en) * | 1950-10-20 | 1952-10-21 | Gen Motors Corp | Brightening bath |
US2625468A (en) * | 1951-05-03 | 1953-01-13 | Gen Motors Corp | Method of conditioning brightening baths |
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Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3108919A (en) * | 1959-06-17 | 1963-10-29 | North American Aviation Inc | Etching process |
US3155556A (en) * | 1960-01-13 | 1964-11-03 | Vaw Ver Aluminium Werke Ag | Method for glossing articles made of aluminum and particularly pure aluminum and itsalloys |
US3197340A (en) * | 1960-10-05 | 1965-07-27 | Conversion Chem Corp | Composition and method for cleaning aluminum castings |
US3230172A (en) * | 1961-04-10 | 1966-01-18 | Montedison Spa | Pickling bath for stainless steel and process for the preparation thereof |
US3140203A (en) * | 1961-04-24 | 1964-07-07 | Macdermid Inc | Method of and composition for treating aluminum and aluminum alloys |
US3275562A (en) * | 1963-11-12 | 1966-09-27 | Pennsalt Chemicals Corp | Non-chromated aluminum desmutting compositions |
US3296141A (en) * | 1965-03-25 | 1967-01-03 | R O Hull & Company Inc | Bright dip compositions for the treatment of steel |
US3314890A (en) * | 1965-04-09 | 1967-04-18 | Pennsalt Chemicals Corp | Alkali etching solution for aluminum |
US3549540A (en) * | 1966-10-31 | 1970-12-22 | Amchem Prod | Method and compositions for treating aluminum surfaces |
US3373114A (en) * | 1967-01-03 | 1968-03-12 | Macdermid Inc | Dry compositions for deoxidizing and desmutting aluminum and aluminum alloys |
US3951681A (en) * | 1973-11-01 | 1976-04-20 | Kolene Corporation | Method for descaling ferrous metals |
DE2506066A1 (en) * | 1974-02-14 | 1975-08-21 | Amchem Prod | METHOD OF CLEANING ALUMINUM |
USRE31198E (en) * | 1974-02-14 | 1983-04-05 | Amchem Products, Inc. | Method for cleaning aluminum at low temperatures |
USRE32661E (en) * | 1974-02-14 | 1988-05-03 | Amchem Products, Inc. | Cleaning aluminum at low temperatures |
DE2546316A1 (en) * | 1974-10-18 | 1976-04-22 | Philips Nv | PROCESS FOR TREATMENT OF BODIES WITH A CORROSIVE AGENT FOR ALUMINUM OXIDE, IN PARTICULAR IN THE PRODUCTION OF SEMI-CONDUCTOR ARRANGEMENTS |
US4126483A (en) * | 1977-06-03 | 1978-11-21 | Ford Motor Company | Method of adherency of electrodeposits on light weight metals |
US4136026A (en) * | 1977-11-23 | 1979-01-23 | Aluminum Company Of America | Caustic solution having controlled dissolved aluminum content |
DE3048083A1 (en) * | 1980-12-19 | 1982-07-01 | Ludwig 8900 Augsburg Fahrmbacher-Lutz | METHOD FOR CHEMICAL REMOVAL OF OXIDE LAYERS FROM OBJECTS FROM METALS |
US4673521A (en) * | 1986-01-21 | 1987-06-16 | Enthone, Incorporated | Process for regenerating solder stripping solutions |
WO1987004451A1 (en) * | 1986-01-21 | 1987-07-30 | Enthone, Incorporated | Process for regenerating solder stripping solutions |
AU591761B2 (en) * | 1986-01-21 | 1989-12-14 | Enthone, Incorporated | Process for regenerating solder stripping solutions |
US5700383A (en) * | 1995-12-21 | 1997-12-23 | Intel Corporation | Slurries and methods for chemical mechanical polish of aluminum and titanium aluminide |
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