US3166444A - Method for cleaning metal articles - Google Patents
Method for cleaning metal articles Download PDFInfo
- Publication number
- US3166444A US3166444A US190259A US19025962A US3166444A US 3166444 A US3166444 A US 3166444A US 190259 A US190259 A US 190259A US 19025962 A US19025962 A US 19025962A US 3166444 A US3166444 A US 3166444A
- Authority
- US
- United States
- Prior art keywords
- solution
- metal
- cleaning
- sodium
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 50
- 239000002184 metal Substances 0.000 title claims description 50
- 238000004140 cleaning Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 15
- 239000000243 solution Substances 0.000 claims description 69
- 230000002378 acidificating effect Effects 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 24
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 23
- 238000000576 coating method Methods 0.000 description 21
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 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 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000002689 soil Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229940085991 phosphate ion Drugs 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000001455 metallic ions Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 3
- ZNQOETZUGRUONW-UHFFFAOYSA-N 1-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOC(C)O ZNQOETZUGRUONW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- XZZDWCJZCAQFDF-UHFFFAOYSA-N sodium;tridecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 XZZDWCJZCAQFDF-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- PJLNKDOTLJCXSN-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[Li] Chemical compound C(CCCCCCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.[Li] PJLNKDOTLJCXSN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 241000775881 Haematopota pluvialis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NUDPHCYTFOZJRA-UHFFFAOYSA-M potassium 2,3-dihexylbenzenesulfonate Chemical compound C(CCCCC)C=1C(=C(C=CC1)S(=O)(=O)[O-])CCCCCC.[K+] NUDPHCYTFOZJRA-UHFFFAOYSA-M 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical class [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- TYHSWAWOZSVJLP-UHFFFAOYSA-M potassium;tridecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCCS([O-])(=O)=O TYHSWAWOZSVJLP-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical class [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- QTUIJRIDZOSXHJ-UHFFFAOYSA-M tridecyl sulfate Chemical compound CCCCCCCCCCCCCOS([O-])(=O)=O QTUIJRIDZOSXHJ-UHFFFAOYSA-M 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 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
Definitions
- the present invention relates, as indicated, to a method for cleaning metal articles, especially ferrous metal articles. In a more particular sense, it relates to a novel, acidic aqueous solution adapted for the cleaning of metal articles prior to a surface-treatment thereof.
- a further object isto provide an improved method for cleaning and phosphating a soiled metal article.
- the anion-cation balance of the solution will be controlled by the addition of a sufiicient amount of a base containing ammonium, substituted ammonium, or metal cations so that the pH of the solution lies within the range from about 3.0 to about 6.5, preferably from about 5.0 to about 6.0.
- these cations are most conveniently introduced into the solution by the addition thereto of nitrogen bases such as ammonia, ammonium hydroxide, and substituted ammonias such as dirnethyl amine, trimethyl amine, ethyl amine, diethyl amine, aniline, etc., or of basic metal compounds such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, barium hydroxide, strontium hydroxide, and other basic alkali or alkaline earth metal compounds.
- nitrogen bases such as ammonia, ammonium hydroxide, and substituted ammonias such as dirnethyl amine, trimethyl amine, ethyl amine, diethyl amine, aniline, etc.
- basic metal compounds such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, barium hydroxide, strontium hydroxide, and other basic alkali or alkaline earth metal compounds.
- the solution exhibits
- an alkali metal salt ordinarily a sodium or potassium salt, of an aromatic carboxylic acid, which component appears to inhibit further any corrosive action of the solution on ferrous metals.
- Alkali metal salts useful for the purpose include the alkali metal salts, principally the sodium or potassium salts, of aromatic car- .boxylic acids such as benzoic,.
- alkali metal salt will be a sodium salt of an aryl monocarboxylic is a minor proportion, generally from about 0.5 to about,
- a water-soluble alcohol such as ethanol, isopropanol, beta-butoxyethoxy-ethanol, betabutoxy-ethanol, etc.
- the alcohol appears to aid the surface-active agent in reducing the surface tensionbetween the solution and the soil on the metal article being cleaned.
- the tartaric acid,.citric acid, and oxalic acid anions which'characterize the solution of this invention are ordinarily supplied by dissolvingminor proportions, generally I from about 0.05 to about 3 and more often from about 0.5 to about 1.5 weight percent, of each of the corresponding acids in water.
- the resulting solution will then contain the corresponding weightpercentages of the several acid anions.
- it may be desirable to use a mixture of acids and salts such as, for
- either acid mixtures or acid-salt mixtures may be used just so long as the solution thereof in water is acidic, i.e., exhibits a pH less than 7.
- the pH of the solution is adjusted, if necessary, to come within the preferred pH range by the introduction of a base containing ammonium, substituted ammonium, or metal cations. It is generally preferred to control the anion-cation balance and pH of the solution by the introduction of a base containing ammonium or sodium cations. If the pH of the solution has risen above 6.5, it can be restored conveniently to the desired pH range by the addition of one or more of the above characterizing acids. In some instances, it is also desirable to buffer the pH of the solution by means of boric acid.
- the surface-active agent employed in the solution of this invention must be one which is stable at a pH less than 7, i.e., does not lose its surface-active properties by reason of chemical transformation or decomposition at the indicated pH.
- Conventional soaps such as sodium or potassium stearates and oleates are not suitable for the purposes of this invention since they tend to precipitate the parent fatty acid in acidic solutions.
- Surface-active agents which are stable at a pH less than 7 include principally the commercially available wetting agents and detergents such as alkali metal aliphatic sulfonates, alkali metal alkaryl sulfonates, alkali metal aliphatic sulfates, alkylcarboxypolyalkoxyalkanols, polyalkoxyalkanols, and alkaryloxypolyalkoxyalkanols.
- This list is, of course, not complete. Continuing research in the field of detergents and wetting agents will undoubtedly result in new materials which are stable in solution at a pH less than 7 and which, therefore, will serve the purposes of this invention.
- the surface-active agent is present in a minor proportion, generally from about 0.02 to about 0.5 wt. percent, in the solution of this invention. Although a single surface-active agent is serviceable, best results are obtained when two or more chemically different surface agents, e.g., a sodium alkaryl sulfonate and an alkylp henoxypolyalkoxyalkanol, are employed.
- the alkaryloxypolyalkoxyalkanols of which the just-cited alkylpheuoxypolyalkoxyalkanol is a sub-genus, form an important class of commercial wetting agents. They possess the following structure:
- Q monoor poly'aryl nucleus
- sium tridecyl sulfate sodium mono-dodecylbenzene sulfonate, sodium monotridecylbenzene sulfonate, lithium cetylbenzene sulfonate, potassium dihexylbenzene sulfonate, octylphenoxyheptaethoxyethanol, isononylphenoxyoctadecaethoxyethanol, etc.
- the metal article to be cleaned is contacted with the hereindescribed acidic aqueous solution, usually at an elevated temperature in the range from about F. to about 212 F. and preferably in the range from about F. to about F. If desired, temperatures above 212 R, such as 250 F., 300 F, or higher can be employed by contacting the metal article with the solution at super-atmospheric pressures.
- the contacting of the metal article with the solution may be accomplished by any of the ordinary techniques employed in the metal finishing industry such as dipping, spraying, tumbling, brushing, etc. Spraying appears to be the most effective and, therefore, preferred method.
- the time of cleaning will vary from as little as one or two seconds to ten minutes or more. In most cases, one or two minutes is suflicient to clean the article thoroughly.
- the article After the article has been cleaned, it is optionally rinsed with water and/or a water-soluble alcohol. Subsequent surface treatments such as phosphating, anodizing, bluing, etc., are preferably carried out on the cleaned metal article without delay, since the cleaned article, particularly if it is made from a ferrous metal, is very susceptible to oxidation or rusting.
- Such coatings which are widely used in the metal finishing industry to inhibit oxidation or rusting and to form an adherent substrate for the subsequent application of organic coating compositions such as paint, varnish, enamel, lacquer, synthetic resins, etc., are generally formed on a metal surface by means of aqueous solutions which contain the phosphate ion and, optionally, certain auxiliary ions including metallic ions such as sodium, manganese, zinc, cadmium, iron, copper, lead, nickel, cobalt, and antimony ions, and non-metallic ions such as ammonium, chloride, bromide, nitrate, and chlorate ions.
- metallic ions such as sodium, manganese, zinc, cadmium, iron, copper, lead, nickel, cobalt, and antimony ions
- non-metallic ions such as ammonium, chloride, bromide, nitrate, and chlorate ions.
- Aqueous phosphating solutions are generally prepared by dissolving in water minor amounts of phosphoric acid and, optionally, a metal salt such as a nitrate, phosphate, nitrite, sulfate, chloride, or bromide of manganese, sodium, zinc, cadmium, iron, nickel, copper, lead, or antimony.
- a metal salt such as a nitrate, phosphate, nitrite, sulfate, chloride, or bromide of manganese, sodium, zinc, cadmium, iron, nickel, copper, lead, or antimony.
- an oxidizing agent such as sodium chlorate, potassium perborate, sodium nitrate, ammonium nitrate, sodium chlorite, potassium perchlorate, or hydrogen peroxide is included in the phosphating solution to depolarize the metal surface being treated and thereby increase the rate at which the phosphate coating is formed on the metal surface.
- auxiliary agents such as antisludging agents, coloring agents, and metal cleaning agents may also be incorporated in the phosphating solution.
- phosphating bath which contains zinc ion, phosphate ion, and a depolarizing agent is made by dissolving small amounts of zinc dihydrogen phosphate, sodium nitrate, and phosphoric acid in water.
- an aqueous phosphating solution should generally have a total acidity within the range from about 5 to about 100 points, preferably from about 5 to about 50points. It is possible, however, by certain special techniques to employ phosphatingsolutions having a total acidity substantially higher than 100 points, e.g., 1-25, 200, 250, or 300 points or more.
- points total acidity as employed in the phosphating art reprehydroxide solution required to neutralize a milliliter sample of a phosphating solution in the presence of phenolphthalein as an indicator.
- aqueous phosphating solutions or baths A particularly desirable and effective class of aqueous phosphating solutions or baths is set forth in co-pending application Ser. No. 373,449, 'filed August 10, 1953. It is intended that the disclosure of' the said application be considered as forming a part of the present specification.
- the phosphating solutions described therein have a total acidity within the range from about 5 to about 100 points and contain as essential ingredients zinc ion, phosphate ion, nitrate ion, and an ion selected from the group consisting of lithium, beryllium, magnesium, calcium, strontium, cadmium, and barium ions. Of the several metallic ions enumerated, the calcium ion is preferred.
- Such phosphating solutions provide a dense, adherent, microcrystalline or amorphous phosphate coating which shows substantially no visible crystal structure at a magnification of 100 diameters and which is preferred for the purposes of the present invention.
- a particularly useful sub-group of aqueous phosphating solutions for the purposes of this invention have a total acidity within the range from about 5 to about 100 points and contain as essential ingredients from about 0.1 to about 1.0 percent of zinc ion, from about 0.25 to about 2.0 percent of phosphate ion, from about 0.25 to about 8.0 percent of nitrate ion, and from about 0.1 to about 4.0 percent of calcium ion.
- any of the commonly used phosphating techniques such as spraying, brushing, dipping, roller-coating, or flow-coating may be employed, and that the temperature of the aqueous phosphating solutions may vary within wide limits, e.g'., from room temperature to about 212 F. In general, best results are obtained when the phosphating solution is used at a temperature' within the range from about 150 F. to about 210 F. If desired, however, the aqueous phosphating bath may be used at higher temperatures, e.g., 225 F., 250 F., or even 300 F., by employing superatmosphericv pressures. V
- the phosphating operation is usually carried out until the weight of the phosphate coating formed on the cleaned metallic surfaceis at least about 25 mg. per square foot of surface area and is preferably within the range from about 50 to about 1000 mg. per square foot of surface area.
- the time required to form the phosphate coating will vary according to the temperature, the type'of phosphating solution employed, the particular technique of applying the phosphating solution, and the coating weight desired. In most instances, however, the time required to produce a phosphate coating of the weight preferred for the purposes of the present invention will be within the range from about 5 seconds to about or minutes.
- phosphated metal article is rinsed, optionally, withwater and/or a hot, dilute aqueous solution of chromic acid containing from about 0.01 to about 0.2 percent of CrO Q specific modes of practicing the present invention.
- EXAMPLE 1 An acidic aqueous solution is prepared by dissolving 26.7 grams (0.66 percent) of tartaric acid, 26.7 grams (0.66 percent) of oxalic acid, 26.7 grams (0.66 percent) of citric acid, 1.5 grams (0.038 percent) of a sodium alkaryl sulfonate available commercially under the trade designation Santomerse S, and 0.5 gram (0.0125 percent) of an isooctylphenoxypolyethoxyethanol available commer cially under the trade designation Triton X-100 in sufficient water to yield 4 liters of solution. The resulting solution shows a pH of 1.6.
- EXAMPLE 2 0.3 grams of 75% aqueous ammonium hydroxide is added to the solution of Example 1, whereupon the pH rises to 5.5.
- EXAMPLE 3 An acidic aqueous solution is prepared by dissolving 50 grams (1.25 percent) of sodium potassium tartrate, 40 grams (1.0 percent) of oxalic acid, 30 grams (0.75 percent) of citric acid, and 4 grams (0.1 percent) of sodium lauryl sulfate in sufficient Water to yield 4 liters of solution. While the solution is stirred, 25% aqueous sodium carbonate is added slowly until the pH rises to 6.0.
- EXAMPLE 4 An acidic aqueous solution isprepared by dissolving 40 grams (1.0 percent) of tartaric acid, grams of oxalic acid (2.0 percent), 20 grams (0.5 percent) of sodium citrate, and 10 grams (0.25 percent) of sodium dodecy1- benezene sulfonate in suflicient water to yield 4 liters of solution. While the solution is stirred, trimethyl amine is added slowly until the pH rises to 3.5.
- EXAMPLE 7 An acidic aqueous solution is prepared in the manner 7 set forth in Example 5 with the following exceptions: 86.2
- Table II SEQUENCE OF CLEANING AND PHOSPHAIING OPERATIONS Operation Description Spray the panel with the selected cleaning solution for one minute at 140l00 F.
- the aqueous phosphating solution employed contains 0.17% zinc ion, 0.58% phosphate ion, 1.34% nitrate ion, 0.37% calcium ion, and 0.07% sodium ion. It is prepared by dissolving 2.1 grams of Z110, 8.0 grams of 75% HsPOi, 3.0 grams of 42 Bennie HNOa, 1.2 grams of NaOI-I, and 20 grams oi Ca (N Oa)z-3H O in 200 ml. of water and then diluting the whole to make one liter of solution.
- aqueous acid cleaner (contains orthophosphoric acid, bctabutoxyethanol and surfaceactive agents).
- Borderline acceptable phosphate coating yellow stain near edges due to incomplete removal of soil.
- a laboratory corrosion test was employed to determine the relative corrosiveness toward steel of a widely-used commercial aqueous acid cleaner and the acidic aqueous solutions of this invention.
- a 1-inch X 3-inch strip of ZO-gauge SAE 1020 cold-rolled steel is immersed to a depth of 1.5 inches in the solution being tested and the whole is maintained at :5" F. for 9 days. Every third day, the pH of the solution is measured and, if it has changed, it is restored to the original pH by the addition of more of the fresh acidic aqueous solution (in the case of a higher measured pH) or of ammonium hydroxide (in the case of a lower measured pH).
- the steel strip is removed at the end of the ninth day, dried by heating on a hot plate for a few minutes under a current of dry air, and weighed.
- Table IV The results obtained in this corrosion test are set forth in Table IV.
- the acidic aqueous solutions of the present invention find their principal utility in the cleaning of ferrous metals, they are also useful for the cleaning of non-ferrous metals and alloys thereof such as aluminum, magnesium, copper, brass, bronze, white metal, etc. They are also useful for the cleaning of galvanized ferrous surfaces or plated ferrous surfaces such as, e.g., copperplated, nickel-plated, and cadmium-plated ferrous surfaces.
- An acidic aqueous solution adapted for the cleaning of metal articles which consists essentially of water; from about 0.05 to about 3 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; a cation selected from the group consisting of ammonium, substituted ammonium, and metal cations in an amount sufiicient to adjust the pH of said acidic aqueous solution to a value within the range from about 3.0 to about 6.5; and at least one surface-active agent which is stable at a pH less than 7 and which is selected from the group consisting of alkali metal aliphatic sulfonates, alkali metal alkaryl sulfonates, alkali metal aliphatic sulfates, and alkaryloxypolyalkoxyalkanols.
- An acidic aqueous solution in accordance wtih claim 1 further characterized in that it additionally contains a minor proportion of an alkali metal salt of an aromatic carboxylic acid.
- An acidic aqueous solution adapted for the cleaning of metal articles which has a pH within the range from about 3.0 to about 6.5 and which contains as essential ingredients from about 0.05 to about 3 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; an amount of sodium ion efiective to produce an anion-cation balance within the aforesaid pH range; from about 0.01 to about 0.5 percent of a sodium alkaryl sulfonate; and from about 0.02 to about 0.5 percent of a sodium salt of an aryl monocarboxylic acid.
- An acidic aqueous solution adapted for the cleaning of metal articles which has a pH.
- a pH Within the range from about 5.0 to about 6.0 and which contains as essential ingredients from about 0.5 to about '1.5 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; an amount of sodium ion efiective to produce an anion-cation balance within the aforesaid range; from about 0.01 to about 0.25 percent each of a sodium alkylphenyl sulfonate and an octylphenoxypolyethoxyethanol; and from about 0.05 to about 0.2 percent of sodium benzoate.
- a method for cleaning a metal article which comprises contacting said article with the acidic aqueous solution of claim 1, said solution being maintained at a temperature within the range from about 100 F. to about 212 F.
- a method for cleaning a metal article which comprises spraying said article with the acidic aqueous solution of claim 3 at a temperature within the range from about 120 F. to about 190 F.
Description
United States Patent 3 166,444 METHOD FOR CLEG METAL ARTHCLES Irwin R. Ehren, Cleveland Heights, and David G. Eliis,
Par-ma Heights, Ghio, assignors to The Luhrizol Corporation, Wicklifi'e, Ohio, a corporation of Ohio No Drawing. Filed Apr. 26, 1962, Ser. No. 190,259 6 Claims. (Cl. 134-3) The present invention relates, as indicated, to a method for cleaning metal articles, especially ferrous metal articles. In a more particular sense, it relates to a novel, acidic aqueous solution adapted for the cleaning of metal articles prior to a surface-treatment thereof.
In the metal finishing industry, it is known that a metal article must be thoroughly cleaned prior to subjecting said article to surface-treatment operations such as phosphating, anodizing, bluing, staining, etc. If the metal article has not been cleaned adequately, satisfactory results are not secured in subsequent surface-treatment operations. Thus, it becomes important to provide a method for cleaning a metal article in a manner so as to insure the success of later surface-treatment operations.
Nearly all unfinished. metal articles such as plate steel, steel strip stock, rough core castings, etc., bear surface contaminants or soils such as drawing compounds, slushing oils, cutting oils, core compounds, and the like. It is common practice in the industry to clean such unfinished metal articles by subjecting them to the action of hot aqueous solutions containing one or more alkaline materials such as sodium hydroxide, potassium hydroxide, trisodium phosphate, sodium carbonate, sodium silicates, sodium polyphosphates, etc. In many instances, however, the contaminants on the surface of the metal article'are not satisfactorily removed by these known alkaline solutions. Then additional costly and time consuming cleaning operations such as vapor-degreasing, pickling, sandblasting, or polishing must be employed to prepare the article for surface-treatment.
Commercially available acidic cleaning solutions (principally dilute aqueous solutions of orthophosphoric acid containing minor amounts of water-soluble monoor poly-hydric alcohols) have been shown to be useful in some instances where alkaline cleaning solutions have been unsatisfactory. They have not, however, proved effective for removing many frequently-encountered soils. Moreover, such available acidic cleaning solutions are highly corrosive to iron and steel and, consequently, all associated apparatus such as tanks, piping, and spraynozzles must be made corrosion-proof by the use of special alloys, rubber or plastic linings, etc. As a result, dilute acidic cleaning solutions (to be distinguished from the concentrated pickling acids employed to remove mill scale) have not gained wide acceptance in the metal finishing industry. j
in accordance with the present invention, certain novel, acidic aqueous solutions characterized principally by the presence therein of the anions of a plurality of certain lower aliphatic dicarboxylic acids and of certain cations have been found to be eifective against a'wide variety of soils and to be substantially non-corrosive to ferrou metals.
It is, therefore, an object of this invention to provide a novel, substantially non-corrosive, acidic aqueous solution adapted for the cleaning of metal articles.
able soil.
A further object isto provide an improved method for cleaning and phosphating a soiled metal article.
3,166,444 Patented Jan. 19, 1965 These and other objects of the invention are realized by means of an acidic aqueous solution adapted for the cleaning of metal articles which contains as essential ingredients a majorproportion of water and minor proportions each of tartaric acid anion; oxalic acid anion; citric acid anion; a cation selected from the group consisting of ammonium, substituted ammonium, and metal cations; and at least one surface-active agent which is stable at a pH less than 7.
In most instances, the anion-cation balance of the solution will be controlled by the addition of a sufiicient amount of a base containing ammonium, substituted ammonium, or metal cations so that the pH of the solution lies within the range from about 3.0 to about 6.5, preferably from about 5.0 to about 6.0. These cations are most conveniently introduced into the solution by the addition thereto of nitrogen bases such as ammonia, ammonium hydroxide, and substituted ammonias such as dirnethyl amine, trimethyl amine, ethyl amine, diethyl amine, aniline, etc., or of basic metal compounds such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, barium hydroxide, strontium hydroxide, and other basic alkali or alkaline earth metal compounds. In the above-indicated pH ranges, the solution exhibits the maximum cleansing power consistent-with a desirably low corrosive action on the ferrous metal apparatus normally used to contain and convey the solution.
Optionally present in the solution of this-invention is a minor proportion, generally from about 0.02 to about 0.5 and more often from about 0.05 to about 0.2 weight percent, of an alkali metal salt, ordinarily a sodium or potassium salt, of an aromatic carboxylic acid, which component appears to inhibit further any corrosive action of the solution on ferrous metals. Alkali metal salts useful for the purpose include the alkali metal salts, principally the sodium or potassium salts, of aromatic car- .boxylic acids such as benzoic,. anthranilic, para-tertiary butylbenzoic, para-phenylbenzoic, para-methoxybenzoic, salicylic, isopropyl salicylic, phthalic, terephthalic, naphthoic, para-amino benzoic, ortho-chlorobenzoic, orthonithrobenzoic, etc., acids. In most instances the alkali metal salt will be a sodium salt of an aryl monocarboxylic is a minor proportion, generally from about 0.5 to about,
5 weight percent, of a water-soluble alcohol such as ethanol, isopropanol, beta-butoxyethoxy-ethanol, betabutoxy-ethanol, etc. The alcohol appears to aid the surface-active agent in reducing the surface tensionbetween the solution and the soil on the metal article being cleaned.
Either or both of the above-described optional components may be omitted from the solution of this invention; .Best results are obtained, however, when at least one and preferably both of these components are present.
The tartaric acid,.citric acid, and oxalic acid anions which'characterize the solution of this invention are ordinarily supplied by dissolvingminor proportions, generally I from about 0.05 to about 3 and more often from about 0.5 to about 1.5 weight percent, of each of the corresponding acids in water. The resulting solution will then contain the corresponding weightpercentages of the several acid anions. In some instances, however, it may be desirable to use a mixture of acids and salts such as, for
example, a mixture o-f oxalic acid, citric acid, and sodium a potassium tartrate (Rochelle salt) or a mixture of sodium citrate, tartaric acid, and oxalic acid. In any event, either acid mixtures or acid-salt mixtures may be used just so long as the solution thereof in water is acidic, i.e., exhibits a pH less than 7. As indicated eariler, the pH of the solution is adjusted, if necessary, to come within the preferred pH range by the introduction of a base containing ammonium, substituted ammonium, or metal cations. It is generally preferred to control the anion-cation balance and pH of the solution by the introduction of a base containing ammonium or sodium cations. If the pH of the solution has risen above 6.5, it can be restored conveniently to the desired pH range by the addition of one or more of the above characterizing acids. In some instances, it is also desirable to buffer the pH of the solution by means of boric acid.
The surface-active agent employed in the solution of this invention must be one which is stable at a pH less than 7, i.e., does not lose its surface-active properties by reason of chemical transformation or decomposition at the indicated pH. Conventional soaps such as sodium or potassium stearates and oleates are not suitable for the purposes of this invention since they tend to precipitate the parent fatty acid in acidic solutions. Surface-active agents which are stable at a pH less than 7 include principally the commercially available wetting agents and detergents such as alkali metal aliphatic sulfonates, alkali metal alkaryl sulfonates, alkali metal aliphatic sulfates, alkylcarboxypolyalkoxyalkanols, polyalkoxyalkanols, and alkaryloxypolyalkoxyalkanols. This list is, of course, not complete. Continuing research in the field of detergents and wetting agents will undoubtedly result in new materials which are stable in solution at a pH less than 7 and which, therefore, will serve the purposes of this invention. The surface-active agent is present in a minor proportion, generally from about 0.02 to about 0.5 wt. percent, in the solution of this invention. Although a single surface-active agent is serviceable, best results are obtained when two or more chemically different surface agents, e.g., a sodium alkaryl sulfonate and an alkylp henoxypolyalkoxyalkanol, are employed. The alkaryloxypolyalkoxyalkanols, of which the just-cited alkylpheuoxypolyalkoxyalkanol is a sub-genus, form an important class of commercial wetting agents. They possess the following structure:
Q=monoor poly-aryl nucleus R=alky1 or alkenyl radical containing from to 40 carbon atoms R'=lower alkylene radical containing 2-5 carbon atoms x=1-5 inclusive y=1-50, inclusive The sodium alkaryl sulfonates, likewise an important and well-known class of commercial wetting agents and detergents, possess the following structure:
Q=monoor poly'aryl nucleus R==alkyl or alkenyl radical containing from 5 to 20 carbon atoms a: 1-3, inclusive b=12, inclusive potassium tridecylsulfonate, sodium lauryl sulfate, potas-.
sium tridecyl sulfate, sodium mono-dodecylbenzene sulfonate, sodium monotridecylbenzene sulfonate, lithium cetylbenzene sulfonate, potassium dihexylbenzene sulfonate, octylphenoxyheptaethoxyethanol, isononylphenoxyoctadecaethoxyethanol, etc.
The metal article to be cleaned is contacted with the hereindescribed acidic aqueous solution, usually at an elevated temperature in the range from about F. to about 212 F. and preferably in the range from about F. to about F. If desired, temperatures above 212 R, such as 250 F., 300 F, or higher can be employed by contacting the metal article with the solution at super-atmospheric pressures. The contacting of the metal article with the solution may be accomplished by any of the ordinary techniques employed in the metal finishing industry such as dipping, spraying, tumbling, brushing, etc. Spraying appears to be the most effective and, therefore, preferred method. Depending on the character and quantity of the soil present on the metal article and'the technique of applying the solution, the time of cleaning will vary from as little as one or two seconds to ten minutes or more. In most cases, one or two minutes is suflicient to clean the article thoroughly.
After the article has been cleaned, it is optionally rinsed with water and/or a water-soluble alcohol. Subsequent surface treatments such as phosphating, anodizing, bluing, etc., are preferably carried out on the cleaned metal article without delay, since the cleaned article, particularly if it is made from a ferrous metal, is very susceptible to oxidation or rusting. I
Metal articles cleaned by the hereindescribed method have been found to be very receptive to phosphate coatings. Such coatings, which are widely used in the metal finishing industry to inhibit oxidation or rusting and to form an adherent substrate for the subsequent application of organic coating compositions such as paint, varnish, enamel, lacquer, synthetic resins, etc., are generally formed on a metal surface by means of aqueous solutions which contain the phosphate ion and, optionally, certain auxiliary ions including metallic ions such as sodium, manganese, zinc, cadmium, iron, copper, lead, nickel, cobalt, and antimony ions, and non-metallic ions such as ammonium, chloride, bromide, nitrate, and chlorate ions. These auxiliary ions modify the character of the phosphate coating and adapt it for a wide variety of applications. The preparation and use of aqueous phosphating solutions is well-known in the metal finishing industry as shown by U.S. Patents 1,206,075; 1,247,668; 1,305,331; 1,485,025; 1,610,362; 1,980,518; 2,001,754; and 2,859,145.
Aqueous phosphating solutions are generally prepared by dissolving in water minor amounts of phosphoric acid and, optionally, a metal salt such as a nitrate, phosphate, nitrite, sulfate, chloride, or bromide of manganese, sodium, zinc, cadmium, iron, nickel, copper, lead, or antimony. Ordinarily an oxidizing agent such as sodium chlorate, potassium perborate, sodium nitrate, ammonium nitrate, sodium chlorite, potassium perchlorate, or hydrogen peroxide is included in the phosphating solution to depolarize the metal surface being treated and thereby increase the rate at which the phosphate coating is formed on the metal surface. Other auxiliary agents such as antisludging agents, coloring agents, and metal cleaning agents may also be incorporated in the phosphating solution. One common type of commercial phosphating bath which contains zinc ion, phosphate ion, and a depolarizing agent is made by dissolving small amounts of zinc dihydrogen phosphate, sodium nitrate, and phosphoric acid in water.
In order to provide commercially satisfactory coating weights and coating speeds, an aqueous phosphating solution should generally have a total acidity within the range from about 5 to about 100 points, preferably from about 5 to about 50points. It is possible, however, by certain special techniques to employ phosphatingsolutions having a total acidity substantially higher than 100 points, e.g., 1-25, 200, 250, or 300 points or more. The term points total acidity as employed in the phosphating art reprehydroxide solution required to neutralize a milliliter sample of a phosphating solution in the presence of phenolphthalein as an indicator.
A particularly desirable and effective class of aqueous phosphating solutions or baths is set forth in co-pending application Ser. No. 373,449, 'filed August 10, 1953. It is intended that the disclosure of' the said application be considered as forming a part of the present specification. The phosphating solutions described therein have a total acidity within the range from about 5 to about 100 points and contain as essential ingredients zinc ion, phosphate ion, nitrate ion, and an ion selected from the group consisting of lithium, beryllium, magnesium, calcium, strontium, cadmium, and barium ions. Of the several metallic ions enumerated, the calcium ion is preferred. Such phosphating solutions provide a dense, adherent, microcrystalline or amorphous phosphate coating which shows substantially no visible crystal structure at a magnification of 100 diameters and which is preferred for the purposes of the present invention. A particularly useful sub-group of aqueous phosphating solutions for the purposes of this invention have a total acidity within the range from about 5 to about 100 points and contain as essential ingredients from about 0.1 to about 1.0 percent of zinc ion, from about 0.25 to about 2.0 percent of phosphate ion, from about 0.25 to about 8.0 percent of nitrate ion, and from about 0.1 to about 4.0 percent of calcium ion In View of the extensive commercial development of the phosphating art and the many journal publications and patents describing the application of phosphating solutions, it is believed unnecessary to lengthen this specification unduly by a detailed recitation of the many ways in which the phosphating step may be accomplished. Sufiice it to say that any of the commonly used phosphating techniques such as spraying, brushing, dipping, roller-coating, or flow-coating may be employed, and that the temperature of the aqueous phosphating solutions may vary within wide limits, e.g'., from room temperature to about 212 F. In general, best results are obtained when the phosphating solution is used at a temperature' within the range from about 150 F. to about 210 F. If desired, however, the aqueous phosphating bath may be used at higher temperatures, e.g., 225 F., 250 F., or even 300 F., by employing superatmosphericv pressures. V
The phosphating operation is usually carried out until the weight of the phosphate coating formed on the cleaned metallic surfaceis at least about 25 mg. per square foot of surface area and is preferably within the range from about 50 to about 1000 mg. per square foot of surface area. The time required to form the phosphate coating will vary according to the temperature, the type'of phosphating solution employed, the particular technique of applying the phosphating solution, and the coating weight desired. In most instances, however, the time required to produce a phosphate coating of the weight preferred for the purposes of the present invention will be within the range from about 5 seconds to about or minutes. Upon completion of the phosphating operation, the
phosphated metal article is rinsed, optionally, withwater and/or a hot, dilute aqueous solution of chromic acid containing from about 0.01 to about 0.2 percent of CrO Q specific modes of practicing the present invention. They are submitted for purposes of illustration onlyand are not to, be construed as :limitingthe scope of the present invention, except as the latter is defined by the appended 7 6 claims. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1 An acidic aqueous solution is prepared by dissolving 26.7 grams (0.66 percent) of tartaric acid, 26.7 grams (0.66 percent) of oxalic acid, 26.7 grams (0.66 percent) of citric acid, 1.5 grams (0.038 percent) of a sodium alkaryl sulfonate available commercially under the trade designation Santomerse S, and 0.5 gram (0.0125 percent) of an isooctylphenoxypolyethoxyethanol available commer cially under the trade designation Triton X-100 in sufficient water to yield 4 liters of solution. The resulting solution shows a pH of 1.6.
EXAMPLE 2 0.3 grams of 75% aqueous ammonium hydroxide is added to the solution of Example 1, whereupon the pH rises to 5.5.
EXAMPLE 3 An acidic aqueous solution is prepared by dissolving 50 grams (1.25 percent) of sodium potassium tartrate, 40 grams (1.0 percent) of oxalic acid, 30 grams (0.75 percent) of citric acid, and 4 grams (0.1 percent) of sodium lauryl sulfate in sufficient Water to yield 4 liters of solution. While the solution is stirred, 25% aqueous sodium carbonate is added slowly until the pH rises to 6.0.
EXAMPLE 4 An acidic aqueous solution isprepared by dissolving 40 grams (1.0 percent) of tartaric acid, grams of oxalic acid (2.0 percent), 20 grams (0.5 percent) of sodium citrate, and 10 grams (0.25 percent) of sodium dodecy1- benezene sulfonate in suflicient water to yield 4 liters of solution. While the solution is stirred, trimethyl amine is added slowly until the pH rises to 3.5.
EXAMPLE 5 7 EXAMPLE 6 An acidic aqueous solution is prepared in the manner set forth in Example 5, except that in lieu of the indicated quantities of Triton X- and Santomerse S there is employed 38.3 grams (0.135 percent) each of Triton QS-15 (an oxyethylated sodium phenolate) and Triton CF-lO (an alkaryl polyether).
EXAMPLE 7 An acidic aqueous solution is prepared in the manner 7 set forth in Example 5 with the following exceptions: 86.2
grams (0.3 percent) of sodium mono-tridecylbenzene sulfonate is used in lieu of the indicated quantities of Santomerse S and Triton X-100, and 1,136 grams (4 percent) of beta-butoxyethoxyethanol is used in lieu of the indicated quantity of beta-butoxyethanol.
A number of solutions of the invention were compared with known solutions in tests designed to evaluate their corrosive action upon ferrous metals and their effectiveness as cleaners in sequential'cleaning and phosphating operations.
A large number of 4-inch x 8-inch panels of 20-gauge SAE 1012 cold-rolled steel were brush-coated with several diiferent commercially available drawing compounds and then placed in an oven for 3 minutes at 400 F. to fix the drawing compounds on the panels. For convenient iden- Table I..
Table l Panels,
Type of Drawing Compound on Surface Thereof Group Thereafter, the panels were cleaned and phosphated in a continuous conveyor-line apparatus according to the schedule set forth in Table II.
Table II SEQUENCE OF CLEANING AND PHOSPHAIING OPERATIONS Operation Description Spray the panel with the selected cleaning solution for one minute at 140l00 F.
Spray-rinse the panel with water for one to two minutes at 140-l50 F.
Spray the panel with an aqueous phosphating solution for two minutes at 160 F The aqueous phosphating solution employed contains 0.17% zinc ion, 0.58% phosphate ion, 1.34% nitrate ion, 0.37% calcium ion, and 0.07% sodium ion. It is prepared by dissolving 2.1 grams of Z110, 8.0 grams of 75% HsPOi, 3.0 grams of 42 Bennie HNOa, 1.2 grams of NaOI-I, and 20 grams oi Ca (N Oa)z-3H O in 200 ml. of water and then diluting the whole to make one liter of solution.
Spray-rinse the panel with water for one minute at 120 F.
Spray-rinse the panel with dilute aqueous ohromic acid (0.125 gram CIOs per liter) for one minute at room temperature.
prior to phosphating.
Table III CLEANING AND PHOSPHATING OF STEEL PANELS Panels, Group Cleaning Solution Used in Operation No. 1
Appearance of Phosphate Coating, Inspector's Remarks Commercial alkali-base cleaner (used at recommended concentration of 1 oz./gal.).
Cleaning solution of this invention, Example 5.
Cleaning solution of this invention. Example 6.
Commercial alkali-base cleaner (used at recommended concentration of 1 oz./gal.).
Cleaning solution of this invention, Example 5.
Cleaning solution of this invention, Example 6.
Commercial alkali-base cleaner (used at recommended eoncentration oi 1 oz./gal.).
Cleaning solution of thi invention, Example 5.
Cleaning solution of this invention, Example 0.
Commercial alkali-base cleaner (used at recommended concentration of 1 oz./gal.).
Commercial aqueous acid cleaner (contains orthophosphoric acid, bctabutoxyethanol and surfaceactive agents).
Cleaning solution of this invention, Example 5.
Cleaning solution of this invention, Example 0.
Borderline acceptable phosphate coating; yellow stain near edges due to incomplete removal of soil.
Good phosphate coating; a {6% light streaks are visible.
Very poor, spotty phosphate coating-unacceptable.
Fair, acceptable phosphate coating.
Very similar to the above result, but panel has somewhat darker appearance.
Poor, heavily stained, unaccepta le phosphate coatmg.
Fair, acceptable phosphate coating; a slight stain is visible.
Very similar to the above result, but panel is slightly darker.
Very poor and largely incomplete phosphate coating due to incomplete removal oi yellowish-appearing soil.
Poor, incomplete phosphate coating; areas of unrcmovcd soil are clearly visible.
Fair, acceptable phosphate coating; a few dark spots and stains are evident.
Good phosphate coating; a few dark spots are evident.
A laboratory corrosion test was employed to determine the relative corrosiveness toward steel of a widely-used commercial aqueous acid cleaner and the acidic aqueous solutions of this invention. In this test a 1-inch X 3-inch strip of ZO-gauge SAE 1020 cold-rolled steel is immersed to a depth of 1.5 inches in the solution being tested and the whole is maintained at :5" F. for 9 days. Every third day, the pH of the solution is measured and, if it has changed, it is restored to the original pH by the addition of more of the fresh acidic aqueous solution (in the case of a higher measured pH) or of ammonium hydroxide (in the case of a lower measured pH). The steel strip is removed at the end of the ninth day, dried by heating on a hot plate for a few minutes under a current of dry air, and weighed. The results obtained in this corrosion test are set forth in Table IV.
Table IV CORROSION OF SAE 1020 STEEL, NINE-DAY TEST Weight Change of Steel Strip, Milligrams Acidic Solution under Test Commercial aqueous acid cleaner (contains orthophpsphoric acid, beta-butoxy-ethanol, surface-active 1 Light yellow film on the steel strip; no corrosion evident beneath this film.
It will be noted that whereas the commercial aqueous acid cleaner severely corroded the steel, the solutions of this invention actually prevented corrosion (believed to be due at least in part to the thin protective film formed on the metal surface).
Although the acidic aqueous solutions of the present invention find their principal utility in the cleaning of ferrous metals, they are also useful for the cleaning of non-ferrous metals and alloys thereof such as aluminum, magnesium, copper, brass, bronze, white metal, etc. They are also useful for the cleaning of galvanized ferrous surfaces or plated ferrous surfaces such as, e.g., copperplated, nickel-plated, and cadmium-plated ferrous surfaces.
What is claimed is:
1. An acidic aqueous solution adapted for the cleaning of metal articles which consists essentially of water; from about 0.05 to about 3 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; a cation selected from the group consisting of ammonium, substituted ammonium, and metal cations in an amount sufiicient to adjust the pH of said acidic aqueous solution to a value within the range from about 3.0 to about 6.5; and at least one surface-active agent which is stable at a pH less than 7 and which is selected from the group consisting of alkali metal aliphatic sulfonates, alkali metal alkaryl sulfonates, alkali metal aliphatic sulfates, and alkaryloxypolyalkoxyalkanols.
2. An acidic aqueous solution in accordance wtih claim 1 further characterized in that it additionally contains a minor proportion of an alkali metal salt of an aromatic carboxylic acid.
3. An acidic aqueous solution adapted for the cleaning of metal articles which has a pH within the range from about 3.0 to about 6.5 and which contains as essential ingredients from about 0.05 to about 3 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; an amount of sodium ion efiective to produce an anion-cation balance within the aforesaid pH range; from about 0.01 to about 0.5 percent of a sodium alkaryl sulfonate; and from about 0.02 to about 0.5 percent of a sodium salt of an aryl monocarboxylic acid.
4. An acidic aqueous solution adapted for the cleaning of metal articles which has a pH. Within the range from about 5.0 to about 6.0 and which contains as essential ingredients from about 0.5 to about '1.5 percent each of tartaric acid anion, oxalic acid anion, and citric acid anion; an amount of sodium ion efiective to produce an anion-cation balance within the aforesaid range; from about 0.01 to about 0.25 percent each of a sodium alkylphenyl sulfonate and an octylphenoxypolyethoxyethanol; and from about 0.05 to about 0.2 percent of sodium benzoate.
5. A method for cleaning a metal article which comprises contacting said article with the acidic aqueous solution of claim 1, said solution being maintained at a temperature within the range from about 100 F. to about 212 F.
6. A method for cleaning a metal article which comprises spraying said article with the acidic aqueous solution of claim 3 at a temperature within the range from about 120 F. to about 190 F.
References Cited in the file of this patent UNIT ED STATES PATENTS 1,334,092 Harneling Mar. 16, 1920 1,911,537 Tanner May 30, 1933 2,067,215 Tanner et a1. Jan. 12, 1937 2,164,042 Romig June 27, 1939 2,178,831 Bruson Nov. 7, 1939 2,250,508 Thompson et al July 29, 1949 2,469,493 Barker May 10, 1949 2,493,327 Vance Ian. 3, 1950 2,552,874 Snyder et a1 May 15, 1951 2,860,106 Little et a1 Nov. 11, 1958 3,011,907 Davis et a1. Dec. 5, *1961 3,070,464 Levy Dec. 25, 1962
Claims (2)
1. AN ACIDIC AQUEOUS SOLUTION ADAPTED FOR THE CLEANING OF METAL ARTICLES WHICH CONSISTS ESSENTIALLY OF WATER; FROM ABOUT 0.05 TO ABOUT 3 PERCENT EACH OF TARTARIC ACID ANION, OXALIC ACID ANION, AND CITRIC ACID ANION; A CATION SELECTED FROM THE GROUP CONSISTING OF AMMONIUM, SUBSTITUTED AMMONIUM, AND METAL CATIONS IN AN AMOUNT SUFFICIENT TO ADJUST THE PH OF SAID ACIDIC AQUEOUS SOLUTION TO A VALUE WITHIN THE RANGE FROM ABOUT 3.0 TO ABOUT 6.5; AND AT LEAST ONE SURFACE-ACTIVE AGENT WHICH IS STABLE AT A PH LESS THAN 7 AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL ALIPHATIC SULFONATES, ALKALI METAL ALKARYL SULFONATES, ALKALI METAL ALIPHATIC SULFATES, AND ALKARYLOXYPOLYALKOXYALKANOLS.
5. A METHOD FOR CLEANING A METAL ARTICLE WHICH COMPRISES CONTACTING SAID ARTICLE WITH THE ACIDIC AQUEOUS SOLUTION OF CLAIM 1, SAID SOLUTION BEING MAINTAINED AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 100*F. TO ABOUT 212*F.
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US3491027A (en) * | 1966-02-28 | 1970-01-20 | Us Navy | Composition and method for cleaning salt residues from metal surfaces |
US3502511A (en) * | 1965-01-15 | 1970-03-24 | Lubrizol Corp | Electrophoretic coating process |
US3510351A (en) * | 1964-11-27 | 1970-05-05 | Paul Van Dillen | Method for etching and cleaning of objects and plants,particularly tube systems and boiler plants,consisting of iron or steel |
US3510432A (en) * | 1966-02-03 | 1970-05-05 | Albert T Squire | Noncorrosive rust remover |
US3516875A (en) * | 1966-06-11 | 1970-06-23 | Hooker Chemical Corp | Process for coating ferrous surfaces |
US3519783A (en) * | 1965-01-15 | 1970-07-07 | Lubrizol Corp | Welding process |
US3522093A (en) * | 1967-02-27 | 1970-07-28 | Chem Cleaning & Equipment Serv | Processes of cleaning and passivating reactor equipment |
US3645806A (en) * | 1968-08-16 | 1972-02-29 | Ici Ltd | Coating solutions derived from peroxy disulfuric acid or peroxy diphosphoric acid |
US3754967A (en) * | 1971-06-18 | 1973-08-28 | Dow Corning | Method of adhering silicone rubber to metal surfaces using salts |
US3754969A (en) * | 1971-06-18 | 1973-08-28 | Dow Corning | Method of adhering room temperature vulcanizable silicone rubber to metal surfaces |
JPS4982537A (en) * | 1972-11-24 | 1974-08-08 | ||
US3868311A (en) * | 1971-11-09 | 1975-02-25 | Citroen Sa | Methods for the formation on a wall exposed to frictional forces and belonging to a light alloy element, of a wear-resistant composite coating metallic |
US3915633A (en) * | 1972-09-21 | 1975-10-28 | Colgate Palmolive Co | Complexing acid pre-wash composition and method |
US3993575A (en) * | 1975-05-27 | 1976-11-23 | Fine Organics Inc. | Hard surface acid cleaner and brightener |
US3996148A (en) * | 1974-07-25 | 1976-12-07 | Pierre Fusey | Basic detergent for liquid lyes |
US4003761A (en) * | 1974-04-13 | 1977-01-18 | Gerhard Collardin Gmbh | Process for the production of sprayed phosphate coats on iron and steel |
US4116755A (en) * | 1977-09-06 | 1978-09-26 | Mcdonnell Douglas Corporation | Chem-milling of titanium and refractory metals |
US4181622A (en) * | 1976-11-01 | 1980-01-01 | Gavin David C | Cleaning composition and method for removing marine accumulations from surfaces |
US4252842A (en) * | 1977-02-17 | 1981-02-24 | Basf Aktiengesellschaft | Electrical insulation of metallic conductors |
US4264418A (en) * | 1978-09-19 | 1981-04-28 | Kilene Corp. | Method for detersifying and oxide coating removal |
US4367092A (en) * | 1981-07-16 | 1983-01-04 | Roto-Finish Company, Inc. | Corrosion-inhibiting acid burnishing compound |
US4379834A (en) * | 1978-11-17 | 1983-04-12 | Hoechst Aktiengesellschaft | Process for cleaning copper-containing metal surfaces |
US4713119A (en) * | 1986-03-20 | 1987-12-15 | Stauffer Chemical Company | Process for removing alkali metal aluminum silicate scale deposits from surfaces of chemical process equipment |
US4824490A (en) * | 1986-10-25 | 1989-04-25 | Metallgesellschaft Aktiengesellschaft | Process of producing phosphate coatings on metals |
US4988401A (en) * | 1988-06-15 | 1991-01-29 | Cegedur Pechiney Rhenalu | Process for sticking rubber to aluminum |
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US5110710A (en) * | 1988-12-13 | 1992-05-05 | Konica Corporation | Light-sensitive lithographic printing plate wherein the support is treated with an aqueous solution containing nitrites |
US5160551A (en) * | 1990-04-21 | 1992-11-03 | Metallgesellschaft Aktiengesellschaft | Activator for use in phosphating processes |
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US3510351A (en) * | 1964-11-27 | 1970-05-05 | Paul Van Dillen | Method for etching and cleaning of objects and plants,particularly tube systems and boiler plants,consisting of iron or steel |
US3519783A (en) * | 1965-01-15 | 1970-07-07 | Lubrizol Corp | Welding process |
US3502511A (en) * | 1965-01-15 | 1970-03-24 | Lubrizol Corp | Electrophoretic coating process |
US3364081A (en) * | 1965-01-15 | 1968-01-16 | Lubrizol Corp | Aqueous phosphating solutions |
US3460966A (en) * | 1965-04-06 | 1969-08-12 | Aluminum Co Of America | Method of improving the receptivity for adhesively applied coatings of aluminum surfaces having residual rolling oils thereon |
US3510432A (en) * | 1966-02-03 | 1970-05-05 | Albert T Squire | Noncorrosive rust remover |
US3491027A (en) * | 1966-02-28 | 1970-01-20 | Us Navy | Composition and method for cleaning salt residues from metal surfaces |
US3516875A (en) * | 1966-06-11 | 1970-06-23 | Hooker Chemical Corp | Process for coating ferrous surfaces |
US3522093A (en) * | 1967-02-27 | 1970-07-28 | Chem Cleaning & Equipment Serv | Processes of cleaning and passivating reactor equipment |
US3645806A (en) * | 1968-08-16 | 1972-02-29 | Ici Ltd | Coating solutions derived from peroxy disulfuric acid or peroxy diphosphoric acid |
US3754967A (en) * | 1971-06-18 | 1973-08-28 | Dow Corning | Method of adhering silicone rubber to metal surfaces using salts |
US3754969A (en) * | 1971-06-18 | 1973-08-28 | Dow Corning | Method of adhering room temperature vulcanizable silicone rubber to metal surfaces |
US3868311A (en) * | 1971-11-09 | 1975-02-25 | Citroen Sa | Methods for the formation on a wall exposed to frictional forces and belonging to a light alloy element, of a wear-resistant composite coating metallic |
US3915633A (en) * | 1972-09-21 | 1975-10-28 | Colgate Palmolive Co | Complexing acid pre-wash composition and method |
JPS4982537A (en) * | 1972-11-24 | 1974-08-08 | ||
US4003761A (en) * | 1974-04-13 | 1977-01-18 | Gerhard Collardin Gmbh | Process for the production of sprayed phosphate coats on iron and steel |
US3996148A (en) * | 1974-07-25 | 1976-12-07 | Pierre Fusey | Basic detergent for liquid lyes |
US3993575A (en) * | 1975-05-27 | 1976-11-23 | Fine Organics Inc. | Hard surface acid cleaner and brightener |
US4181622A (en) * | 1976-11-01 | 1980-01-01 | Gavin David C | Cleaning composition and method for removing marine accumulations from surfaces |
US4252842A (en) * | 1977-02-17 | 1981-02-24 | Basf Aktiengesellschaft | Electrical insulation of metallic conductors |
US4116755A (en) * | 1977-09-06 | 1978-09-26 | Mcdonnell Douglas Corporation | Chem-milling of titanium and refractory metals |
US4264418A (en) * | 1978-09-19 | 1981-04-28 | Kilene Corp. | Method for detersifying and oxide coating removal |
US4379834A (en) * | 1978-11-17 | 1983-04-12 | Hoechst Aktiengesellschaft | Process for cleaning copper-containing metal surfaces |
US4367092A (en) * | 1981-07-16 | 1983-01-04 | Roto-Finish Company, Inc. | Corrosion-inhibiting acid burnishing compound |
US4713119A (en) * | 1986-03-20 | 1987-12-15 | Stauffer Chemical Company | Process for removing alkali metal aluminum silicate scale deposits from surfaces of chemical process equipment |
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Owner name: MAN-GILL CHEMICAL COMPANY, 23000 ST. CLAIR AVE., C Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE JUNE 30, 1981.;ASSIGNOR:ROHCO, INC., AN OH CORP.;REEL/FRAME:003928/0049 Effective date: 19810630 |