US3630790A - Method of protection of metal surfaces from corrosion - Google Patents
Method of protection of metal surfaces from corrosion Download PDFInfo
- Publication number
- US3630790A US3630790A US824246A US3630790DA US3630790A US 3630790 A US3630790 A US 3630790A US 824246 A US824246 A US 824246A US 3630790D A US3630790D A US 3630790DA US 3630790 A US3630790 A US 3630790A
- Authority
- US
- United States
- Prior art keywords
- acid
- metal
- corrosion
- phosphonous
- phosphonic acid
- 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 abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title abstract description 12
- 230000007797 corrosion Effects 0.000 title abstract description 12
- 239000002253 acid Substances 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- -1 organo phosphonic Chemical compound 0.000 abstract description 16
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 5
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVFWBONDEHMDEU-UHFFFAOYSA-N CCCCCCCCCCCOP(=O)OCCCCCCCCCCC Chemical compound CCCCCCCCCCCOP(=O)OCCCCCCCCCCC BVFWBONDEHMDEU-UHFFFAOYSA-N 0.000 description 1
- MKQQKQMGWJAILG-UHFFFAOYSA-N CCCCP(O)(=O)Cc1ccccc1 Chemical compound CCCCP(O)(=O)Cc1ccccc1 MKQQKQMGWJAILG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KZIUWSQALWALJH-UHFFFAOYSA-N bis(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)CP(O)(=O)CC(CC)CCCC KZIUWSQALWALJH-UHFFFAOYSA-N 0.000 description 1
- DRDKFCAHTAHYER-UHFFFAOYSA-N bis(2-methylpropyl)phosphinic acid Chemical compound CC(C)CP(O)(=O)CC(C)C DRDKFCAHTAHYER-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- OBQIMLAGVUXZMH-UHFFFAOYSA-N butyl(phenyl)phosphinic acid Chemical compound CCCCP(O)(=O)C1=CC=CC=C1 OBQIMLAGVUXZMH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- NNPWWKQUTCVLAD-UHFFFAOYSA-N di(nonyl)phosphinic acid Chemical compound CCCCCCCCCP(O)(=O)CCCCCCCCC NNPWWKQUTCVLAD-UHFFFAOYSA-N 0.000 description 1
- UHHOEOSKGDFVPB-UHFFFAOYSA-N di(propan-2-yl)phosphinic acid Chemical compound CC(C)P(O)(=O)C(C)C UHHOEOSKGDFVPB-UHFFFAOYSA-N 0.000 description 1
- KSHDLNQYVGBYHZ-UHFFFAOYSA-N dibutylphosphinic acid Chemical compound CCCCP(O)(=O)CCCC KSHDLNQYVGBYHZ-UHFFFAOYSA-N 0.000 description 1
- HPGNDWLQFVMVSL-UHFFFAOYSA-N didecylphosphinic acid Chemical compound CCCCCCCCCCP(O)(=O)CCCCCCCCCC HPGNDWLQFVMVSL-UHFFFAOYSA-N 0.000 description 1
- NGKCHGKFHQDOPZ-UHFFFAOYSA-N dihexylphosphinic acid Chemical compound CCCCCCP(O)(=O)CCCCCC NGKCHGKFHQDOPZ-UHFFFAOYSA-N 0.000 description 1
- YTMRJBAHYSIRMZ-UHFFFAOYSA-N dioctylphosphinic acid Chemical compound CCCCCCCCP(O)(=O)CCCCCCCC YTMRJBAHYSIRMZ-UHFFFAOYSA-N 0.000 description 1
- KUFDFOXPFQCUST-UHFFFAOYSA-N dipentylphosphinic acid Chemical compound CCCCCP(O)(=O)CCCCC KUFDFOXPFQCUST-UHFFFAOYSA-N 0.000 description 1
- WMDPJKZHARKRQI-UHFFFAOYSA-N dipropylphosphinic acid Chemical compound CCCP(O)(=O)CCC WMDPJKZHARKRQI-UHFFFAOYSA-N 0.000 description 1
- GZWFFPNAVPOUBD-UHFFFAOYSA-N ditert-butylphosphinic acid Chemical compound CC(C)(C)P(O)(=O)C(C)(C)C GZWFFPNAVPOUBD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WAAOFXJSLMXEIQ-UHFFFAOYSA-N ethyl(propan-2-yl)phosphinic acid Chemical compound CCP(O)(=O)C(C)C WAAOFXJSLMXEIQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AHXZGOMBHYIOMA-UHFFFAOYSA-N heptan-3-ylphosphonic acid Chemical compound CCC(CCCC)P(O)(O)=O AHXZGOMBHYIOMA-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RWYACTMFBZKJIX-UHFFFAOYSA-N nonadecylphosphonic acid Chemical compound C(CCCCCCCCCCCCCCCCCC)P(O)(O)=O RWYACTMFBZKJIX-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ULIMUQCIZMJOHK-UHFFFAOYSA-N pentadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCP(O)(O)=O ULIMUQCIZMJOHK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 0.000 description 1
- LOGVGIKCMBMJEE-UHFFFAOYSA-N pentylphosphonous acid Chemical compound CCCCCP(O)O LOGVGIKCMBMJEE-UHFFFAOYSA-N 0.000 description 1
- WDAZGGOERNQOIY-UHFFFAOYSA-N phenyl(propan-2-yl)phosphinic acid Chemical compound CC(C)P(O)(=O)C1=CC=CC=C1 WDAZGGOERNQOIY-UHFFFAOYSA-N 0.000 description 1
- MIBXHGZAARWAGI-UHFFFAOYSA-N phenylmethoxyphosphonoyloxymethylbenzene Chemical compound C=1C=CC=CC=1COP(=O)OCC1=CC=CC=C1 MIBXHGZAARWAGI-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- UBOWNAQTTSJZFQ-UHFFFAOYSA-N tetracosylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCP(O)(O)=O UBOWNAQTTSJZFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GKIQHTGBORJXKZ-UHFFFAOYSA-N undecylphosphonic acid Chemical compound CCCCCCCCCCCP(O)(O)=O GKIQHTGBORJXKZ-UHFFFAOYSA-N 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
- C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
Definitions
- the present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.
- METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION BACKGROUND OF THE INVENTION inhibition of the process is provided by formation of a hydroly sis resistant MO-P bond between the metal and the acid, thus setting up a layer of organic moieties of the acid on the metal surface.
- the layer effectively keeps water and water- Thi metal Surfaces are reactive and require protection 5 borne corrosives out of contact with the metal surface. The' from water corrosion and waterborne corrosive agents.
- the pihtehhoh ihoiehjses as the length of the carbon chain of h surface of plastic which has been coated with a thin metal is organic moiety .ihcrehses' h i f h as the chrhhh Chhlh especially susceptible to corrosion. Aluminum has been found becomes hxceedihgiy iohg ihhihihoh h chiiosioh hecoihes to be an effective coating for polyester plastic films.
- phosphoric acid may be used to form a cor- Phosphohie acids have been tieuhd to Provide Protection rosion resistant coating on metal surfaces.
- the process is normally used to prosubstitutehts which ay form a P of theorgahie moiety are tect massive forms of metal and coatings having a thickness of Preferably those Whleh do not slghlfieahtly decrease from 0.000l5 to 0.0003 inch are normally applied to effecy p y- Fluorihei chlorine, bromine 'y are tively protect the metal substrate.
- PrefeTredother Substituehts include y i mereapto and readily applicable to thin metal films due to the excessive y y p thiekhess of e coating
- the PmeeSS also p y reagents
- the invention is normally practices by practiced a dilute which would smp the Polyester film of its aluminum ssolution of the acid to be applied and dipping the metal into it.
- a 3135 i 7558 teaches the use of a PhOSPhQhate ih Polar organic liquids such as acetone, tetrahydrofuran and the comhihahoh with a deieigehcy buiidei'
- This composition is lower ethers, i.e., those ethers containing from two to 10 cartaught to have the effect of reducing the cori'osivehess of the hon atoms, are convenient solvents for the acids used in the detergency builder by the in situ formation of a protective present method water and nonpolar organic Solvents may coming the metai surface and is mended for use in aqhe' also be used although the acids are somewhat less soluble in ous solutlon wherein the acid salt acts as the corrosion inhibithese Solvents.
- the PH of the solution should be less than 7.
- a dipping period of from It would be deslrable and it is an ob ect of the present lnvenabout 10 to 15 Seconds is Sufficiem to impart a protective tion to provide a method for inhibiting corrosion of metal surcoating to the memL Repeated dipping may be employed to provide a more substantial protective coating.
- the coated h h hmhhi: ohiect provide Such a meihhd ,which h metal may then be washed with the solvent and allowed to dry.
- :sggh be carried out whhoht the use of Specihhzed equip
- the metal may be contacted with the acid solution by other means such as spraying, brushing or roll coating.
- the protecbeast films by lntroduclng the acld to a fluld contained in a metal vessel.
- the method can be used to coat an of the metals which The present lhvehhoh h methhd for phhechhg metal form insoluble phosphates.
- the comm n construction metals faces h applying pmthchve Cohhhgs metal shrfhces'
- the such as iron. nickel, copper, zinc, lead, tin, magnesium, and method involves contacting the metal with a solutlon of an aIuminum may be coated by the present method.
- the method it o o is especially effective for coating thin sheets of aluminum.
- Aluminum coated polyethylene terephthalate film was Unexpectedly the aeid is h e p the acid Salts of dipped into the solution for a period of from about 10 to 15 i 8 in providing coiiosioh proiechoh to seconds. In each case the film was cut in half before treatment meiiii surfaces especiahy meiai surfaces which i'eadiiy form with the acid solution and one-half left untreated as a control. oxide surface coatings.
- a piece of aluminum coated polyethylene terephthalate film was cut into four pieces. The pieces were designated A, B, C and D and treated as follows:
- A was dipped in a solution of 0.1 gram dodecyl phosphonic acid in 100 milliliters of acetone for 30 seconds.
- I l. B was dipped in a solution of 0. 1 gram of the sodium salt of dodecyl phosphonic acid in 100 milliliters of boiling water for 30 seconds.
- C was dipped in a solution of 0.l gram of dodecyl phosphonic acid in 100 milliliters of water for 30 seconds. The water was heated to its boiling point in order to get the acid into solution.
- protective coatings can be applied to the surfaces of metals other than aluminum, such as for example. iron, nickel, copper, zinc, lead, tin or magnesium.
- the invention is practiced in a manner similar to that of the above examples wherein the acid employed is characterized of the formula and R is straight or branched chain, substituted or unsubstituted, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, nonadecyl, docosyl and tetracosyl.
- R is selected so that the total number of carbon atoms in the molecule does not exceed about 24.
- n-pentyl phosphonic acid (p-t-butylstyryl) phosphonic acid, hexyl phosphonic acid, n-heptyl phosphonic acid, 3-heptyl phosphonic acid, octyl phosphonic acid, n-nonyl phosphonic acid 4-nonyl phosphonic acid, n-undecyl phosphonic acid, n-pentadecyl phosphonic acid, n-nonadecyl phosphonic acid, n-tetracosyl phosphonic acid, dipentyl phosphinic acid, heptyl butyl phosphinic acid, dinonyl phosphinic acid, benzyl butyl phosphinic acid, benzyl heptyl phosphinic acid, benzyl hexyl phosphinic acid, dibenzyl phosphonic acid, di-n-butyl
- a method for protecting thin metal films not adaptable to treatment with phosphoric acid from corrosion which comprises contacting the metal film with a polar organic liquid solution of an acid characterized by the formula wherein R is a straight or branched chain, hydrophobic, substttuted or unsubstituted alkyl, aryl, alkaryl or arylalkyl group containing from to l4 carbon atoms; thereby setting up a layer of organic moieties of the acid on the metal surface.
- R is an alkyl containing from 10 to 14 carbon atoms.
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Abstract
The present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.
Description
United States Patent Donald L. Schmidt;
William J. Leahy, both of Midland, Mich. 824,246
May 13, 1969 Dec. 28, 1971 The Dow Chemical Company Midland, Mich.
inventors Appl. No. Filed Patented Assignee METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION 8 Claims, No Drawings U.S. Cl l48/6.15 R, 106/14, 252/389 Int. Cl C23! 7/00 Field 01 Search 148/615;
Faulkner, .1. Oil Col. Chem. Assn., 1967 Vol. 50 pp. 524, 525, 526, 541, 542, 544
Primary Examiner-Ralph S. Kendall Attorneys-Griswold and Burdick, William R. Norris and Lloyd S. Jowanovitz ABSTRACT: The present invention is a method of protecting metal surfaces from corrosion which comprises contacting the metal with an organo phosphonic, phosphonous or phosphinic acid.
METHOD OF PROTECTION OF METAL SURFACES FROM CORROSION BACKGROUND OF THE INVENTION inhibition of the process is provided by formation of a hydroly sis resistant MO-P bond between the metal and the acid, thus setting up a layer of organic moieties of the acid on the metal surface. The layer effectively keeps water and water- Thi metal Surfaces are reactive and require protection 5 borne corrosives out of contact with the metal surface. The' from water corrosion and waterborne corrosive agents. The pihtehhoh ihoiehjses as the length of the carbon chain of h surface of plastic which has been coated with a thin metal is organic moiety .ihcrehses' h i f h as the chrhhh Chhlh especially susceptible to corrosion. Aluminum has been found becomes hxceedihgiy iohg ihhihihoh h chiiosioh hecoihes to be an effective coating for polyester plastic films. However, i effective and aiess Protective homing is provided Acids the aforementioned difficulties are quite apparent when aluin which the organic moiety chhthihs h one to about 24 minum is applied to the polyester film in very thin layers. caihoh atoms are P h Acihs having 10 to i4 carhoh Present methods of protecting such films include anodization htohis in h organic moieiiy provide especially effective and overlacquering or laminating the aluminum Surface with a tectlon, with the aclds havlng 12 carbon atoms being the most tough corrosion resistant plastic. 15 preferred It is known that phosphoric acid may be used to form a cor- Phosphohie acids have been tieuhd to Provide Protection rosion resistant coating on metal surfaces. This method of Perior to that of the Phosphihie and Phosphohous acid and are coating metal Surfaces commonly known as parka-hing, the preferred acids for the practice of the present invention. volves coating the metal by dipping or spraying it with a solu- The Orgahie moiety y be Substituted Substitutedtion of phosphoric acid. The process is normally used to prosubstitutehts which ay form a P of theorgahie moiety are tect massive forms of metal and coatings having a thickness of Preferably those Whleh do not slghlfieahtly decrease from 0.000l5 to 0.0003 inch are normally applied to effecy p y- Fluorihei chlorine, bromine 'y are tively protect the metal substrate. Such a method would not be PrefeTredother Substituehts include y i mereapto and readily applicable to thin metal films due to the excessive y y p thiekhess of e coating The PmeeSS also p y reagents The invention is normally practices by practiced a dilute which would smp the Polyester film of its aluminum ssolution of the acid to be applied and dipping the metal into it.
a 3135 i 7558 teaches the use ofa PhOSPhQhate ih Polar organic liquids such as acetone, tetrahydrofuran and the comhihahoh with a deieigehcy buiidei' This composition is lower ethers, i.e., those ethers containing from two to 10 cartaught to have the effect of reducing the cori'osivehess of the hon atoms, are convenient solvents for the acids used in the detergency builder by the in situ formation of a protective present method water and nonpolar organic Solvents may coming the metai surface and is mended for use in aqhe' also be used although the acids are somewhat less soluble in ous solutlon wherein the acid salt acts as the corrosion inhibithese Solvents. w water is emp|oyed as the Solvent, the PH of the solution should be less than 7. A dipping period of from It would be deslrable and it is an ob ect of the present lnvenabout 10 to 15 Seconds is Sufficiem to impart a protective tion to provide a method for inhibiting corrosion of metal surcoating to the memL Repeated dipping may be employed to provide a more substantial protective coating. The coated h h hmhhi: ohiect provide Such a meihhd ,which h metal may then be washed with the solvent and allowed to dry. :sggh be carried out whhoht the use of Specihhzed equip The metal may be contacted with the acid solution by other means such as spraying, brushing or roll coating. The protecbeast films by lntroduclng the acld to a fluld contained in a metal vessel.
' By such addition, the sides of the vessel will be protected from SUMMARY OF THE INVENTION corrosion- The method can be used to coat an of the metals which The present lhvehhoh h methhd for phhechhg metal form insoluble phosphates. The comm n construction metals faces h applying pmthchve Cohhhgs metal shrfhces' The such as iron. nickel, copper, zinc, lead, tin, magnesium, and method involves contacting the metal with a solutlon of an aIuminum may be coated by the present method. The method it o o is especially effective for coating thin sheets of aluminum. (R3 on) phosphonic (R son r phosphonous (Rt 0) acid The following examples will serve to more fully illustrate the l present lnventlon. OH H The R group attached to the acid radical is a hydrophobic or- EXAMPLES i 9 gahie moiety having one to about 24 Carbon atoms- Solutions of acids were prepared by dissolving 0.1 gram of ampleS of R g p are a Straight branched chain the acid in 100 milliliters of solvent, Examples 1-5 used i h or unsubstituted y i 'y aikaryi or arylaikyi tetrahydrofuran and examples 6-9 used acetone as the soltalhlhg from one to abl1t24 vent. Aluminum coated polyethylene terephthalate film was Unexpectedly the aeid is h e p the acid Salts of dipped into the solution for a period of from about 10 to 15 i 8 in providing coiiosioh proiechoh to seconds. In each case the film was cut in half before treatment meiiii surfaces especiahy meiai surfaces which i'eadiiy form with the acid solution and one-half left untreated as a control. oxide surface coatings. Particularly useful results are achieved After the m which had been treated was allowed to dry and in the instance of thin meiai himswashed with acetone to remove unreacted acid, it and the con- DESCRIPTION OF PREFERRED EMBODIMENTS trol sample were immersed in boiling deionized water and the time requlred for removal of the metal coating was vlsually ob- While the present invention is not premised on an explanaserved. Table i represents the results of these tests for a tion of its underlying theory, it is believed that the corrosion number of acids.
TABLE I Time required to Ex. Demetalizo Demvtalizo No. Acid Formula treated him untreated film 0 1. Methyl phospllonic acid CH3? e011 1 mill. 4?. sue. 1 mill. 3 sec.
Me -ll.-
Ex. \o \t'ill l mmul l 2 lhi-nyl phosphonic acid. sllsl ()lI ,2 3 n-Octyl phosphonic acid (tllni (HI 4 ll-l)(lll\l' \l I phosphonic acid (nligs l (i ll 5 li-(irtadvcvl phosphonic acid ('nlla: l (HI l) ll U ti ()ctyl phosphinic acid ltslliml Ull 0 T 3.3.3-1rillum'opropyl phosphinic acid F11 Hit-l: l U l[ ll a lhvni'l phosphonous arid. y I 1) ll U 7 .I ||-l )orll'ryl l phosphonic acid (r ll '5 l 0 ll 'limo required to lhmv-tzilizt lhmctulizt' trvatvil lilm untreated lilni l min. 12 si'v l min. 3 sec.
min. 7 sec 1 min. 15sec.
16 111111.!) svc 1min. 3 t(.
15 min. 0 S 1 min. 3 svc.
l min. Stt 54 sec,
1 min. 30 sec. 54 sec.
1 min. 5N SI(' 54 sec.
16 min. l S l. 36 set.
I Whvn dodecyl phosphonic acid was usml, no (li'nwliilization had occurred in 16 minutes, at which Linn this-xpl-rinulit was stopped.
EXAMPLES lO-l 3 In order to compare the elTectiveness of the present method, wherein the solvent was either aqueous or nonaqueous, and the method of providing protection by using the aqueous solution of the acid salt, the following experiment was conducted:
A piece of aluminum coated polyethylene terephthalate film was cut into four pieces. The pieces were designated A, B, C and D and treated as follows:
10. A was dipped in a solution of 0.1 gram dodecyl phosphonic acid in 100 milliliters of acetone for 30 seconds.
I l. B was dipped in a solution of 0. 1 gram of the sodium salt of dodecyl phosphonic acid in 100 milliliters of boiling water for 30 seconds.
12. C was dipped in a solution of 0.l gram of dodecyl phosphonic acid in 100 milliliters of water for 30 seconds. The water was heated to its boiling point in order to get the acid into solution.
13. D was left untreated and used as a control.
Each of the treated samples was washed with the acid solvent and allowed to dry after treatment. Each sample was dipped into boiling deionized water and the time required for the metal coating to be removed was visually observed. Table ll represents the results of these tests.
The above data indicate that the sample treated with a 75 nonaqucous solution of the acid took more than twice as long to demetalize than did that treated with a water solution of the acid. The acid salt imparted some protection to the metal surface but considerably less than did the unaltered acid.
In a manner similar to that of examples l and ll protective coatings can be applied to the surfaces of metals other than aluminum, such as for example. iron, nickel, copper, zinc, lead, tin or magnesium.
The invention is practiced in a manner similar to that of the above examples wherein the acid employed is characterized of the formula and R is straight or branched chain, substituted or unsubstituted, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, nonadecyl, docosyl and tetracosyl. However, R is selected so that the total number of carbon atoms in the molecule does not exceed about 24.
Specific examples of such acids are n-pentyl phosphonic acid, (p-t-butylstyryl) phosphonic acid, hexyl phosphonic acid, n-heptyl phosphonic acid, 3-heptyl phosphonic acid, octyl phosphonic acid, n-nonyl phosphonic acid 4-nonyl phosphonic acid, n-undecyl phosphonic acid, n-pentadecyl phosphonic acid, n-nonadecyl phosphonic acid, n-tetracosyl phosphonic acid, dipentyl phosphinic acid, heptyl butyl phosphinic acid, dinonyl phosphinic acid, benzyl butyl phosphinic acid, benzyl heptyl phosphinic acid, benzyl hexyl phosphinic acid, dibenzyl phosphonic acid, di-n-butyl phosphinic acid, diundecyl phosphonic acid, didocyl phosphinic acid, dihexyl phosphinic acid, di-n-octyl phosphinic acid, bis(2-ethyl hexyl) phosphinic acid, butyl phenyl phosphinic acid, decyl ethyl phosphinic acid, di-t-butyl phosphinic acid, didecyl phosphinic acid, diisobutyl phosphinic acid, diisopropyl phosphinic acid, di-n-propyl phosphinic acid, ethyl isopropyl phosphinic acid, isopropyl phenyl phosphinic acid, n-pentyl phosphonous acid, 6-undecyl phosphonous acid, n-tridecyl phosphonous l. A method for protecting thin metal films not adaptable to treatment with phosphoric acid from corrosion which comprises contacting the metal film with a polar organic liquid solution of an acid characterized by the formula wherein R is a straight or branched chain, hydrophobic, substttuted or unsubstituted alkyl, aryl, alkaryl or arylalkyl group containing from to l4 carbon atoms; thereby setting up a layer of organic moieties of the acid on the metal surface.
2. The method of claim 1 wherein R is an alkyl containing from 10 to 14 carbon atoms.
3. The method of claim 2 wherein the acid is characterized by the formula CERTIFICATE OF CORRECTION Patent No. 3,630,790 Dated 28 December 1971 In fl Donald L. Schmidt and William J. Leahy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line &7, insert organo phosphinic at the end of the line following "an"; line 57 insert -ca.rbonbetween "2h" and "atoms."-
Column 2, line 25, delete practices by" and insert -by preparing-- between "practiced" and "a dilute".
Column l, line +6, delete "of" and insert -by-; in the blank space between lines k8 and 53 insert the following formulae:
Column l, line 76, insert the following after the last word in the column, "phosphonous" acid, lO-nonadecyl phosphonous acid, n-docosyl phosphonous I acid, and n-tetracosyl phosphonous acid.
Signed and sea-led this 27th day of June 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents P0405) Q UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3,630,790 Dated 28 December 1971 Inventorv(s) Donald L. Schmidt and William Leahy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line &7, insert organo phosphinicat the end ofthe line following "an"; line 5? insert --carbonbetween "2 and "atoms."
Column 2, line 25 delete "practices by" and insert by preparing-- between "practiced" and "a dilute".
Column l, line L6, delete "of" and insert -;by--; in the blank space between lines &8 and 53 insert the following formulae:
Column line 76, insert the'following after the last word in the column, "phosphonous":
- acid, lO-nonadecyl phosphonous acid, n-docosyl phosphonous acid, and n-tetracosyl phosphonous acid.
Signed and sealed this 27th day of June 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOT'ISCHALK Attesting Officer Commissioner of Patents
Claims (7)
- 2. THe method of claim 1 wherein R is an alkyl containing from 10 to 14 carbon atoms.
- 3. The method of claim 2 wherein the acid is characterized by the formula
- 4. The method of claim 3 wherein R is an alkyl containing 12 carbon atoms.
- 5. The method of claim 1 wherein the solvent is acetone, tetrahydrofuran or a lower ether.
- 6. The method of claim 1 wherein the metal is selected from the group consisting of iron, nickel, copper, zinc, lead, tin, magnesium or aluminum.
- 7. The method of claim 1 wherein the metal is dipped into the acid solution, rinsed with the acid solvent and allowed to dry.
- 8. The method of claim 1 wherein the metal film is aluminum.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82424669A | 1969-05-13 | 1969-05-13 |
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| Publication Number | Publication Date |
|---|---|
| US3630790A true US3630790A (en) | 1971-12-28 |
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| US824246A Expired - Lifetime US3630790A (en) | 1969-05-13 | 1969-05-13 | Method of protection of metal surfaces from corrosion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3900370A (en) * | 1972-03-10 | 1975-08-19 | Henkel & Cie Gmbh | Process for treating aluminum surfaces |
| US3960576A (en) * | 1973-06-25 | 1976-06-01 | Betz Laboratories, Inc. | Silicate-based corrosion inhibitor |
| US4048374A (en) * | 1973-09-01 | 1977-09-13 | Dynamit Nobel Aktiengesellschaft | Functional organophosphonic acid esters as preservative adhesion promoting agents and coating for metals |
| US4042324A (en) * | 1975-02-08 | 1977-08-16 | Hoechst Aktiengesellschaft | Process for inhibiting the corrosions and deposition of boiler scale in water-conveying systems |
| EP0009247A1 (en) * | 1978-09-25 | 1980-04-02 | Henkel Kommanditgesellschaft auf Aktien | Corrosion inhibitors for acidic solutions |
| DE2841641A1 (en) * | 1978-09-25 | 1980-04-03 | Henkel Kgaa | CORROSION INHIBITOR FOR ACID SOLUTIONS |
| US4293441A (en) * | 1979-03-12 | 1981-10-06 | Minnesota Mining And Manufacturing Company | Corrosion inhibiting heat transfer liquid |
| US4202706A (en) * | 1979-03-12 | 1980-05-13 | Minnesota Mining And Manufacturing Company | Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof |
| US4264379A (en) * | 1980-01-11 | 1981-04-28 | Olin Corporation | Process for coating copper and copper alloy |
| US4452650A (en) * | 1980-01-11 | 1984-06-05 | Olin Corporation | Copper and copper alloy coating |
| US4427459A (en) | 1982-01-25 | 1984-01-24 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced coating weights and crystal sizes |
| US4505748A (en) * | 1982-11-10 | 1985-03-19 | International Paint | Anti-corrosive paint |
| WO1987002714A1 (en) * | 1985-10-28 | 1987-05-07 | Giovanni Bozzetto S.P.A. | Process for the preservation of organic products |
| US5318838A (en) * | 1988-01-22 | 1994-06-07 | Fuji Photo Film Co., Ltd. | Magnetic recording medium comprising ferromagnetic particles, binder resins and phenyl phosphonic acid |
| EP0520649A3 (en) * | 1991-06-21 | 1995-03-29 | American Telephone & Telegraph | Process for making corrosion-resistant coatings |
| EP0544345A1 (en) * | 1991-11-23 | 1993-06-02 | Fmc Corporation (Uk) Limited | Corrosion and/or scale inhibition |
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