WO1999018044A1 - Hybrid pigment grade corrosion inhibitor compositions and procedures - Google Patents
Hybrid pigment grade corrosion inhibitor compositions and procedures Download PDFInfo
- Publication number
- WO1999018044A1 WO1999018044A1 PCT/US1998/020801 US9820801W WO9918044A1 WO 1999018044 A1 WO1999018044 A1 WO 1999018044A1 US 9820801 W US9820801 W US 9820801W WO 9918044 A1 WO9918044 A1 WO 9918044A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- corrosion
- organic
- dimercapto
- mbt
- Prior art date
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 128
- 238000005260 corrosion Methods 0.000 title claims abstract description 117
- 230000007797 corrosion Effects 0.000 title claims abstract description 117
- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 91
- 239000003112 inhibitor Substances 0.000 title description 50
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 240
- 239000011701 zinc Substances 0.000 claims abstract description 101
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- -1 molybdates Chemical class 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 235000021317 phosphate Nutrition 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 10
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 150000004760 silicates Chemical class 0.000 claims abstract description 8
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims abstract description 7
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 7
- 150000001912 cyanamides Chemical class 0.000 claims abstract description 7
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims abstract description 6
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims abstract description 6
- KXZSVYHFYHTNBI-UHFFFAOYSA-N 1h-quinoline-2-thione Chemical compound C1=CC=CC2=NC(S)=CC=C21 KXZSVYHFYHTNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 229920000620 organic polymer Polymers 0.000 claims abstract description 4
- 239000001205 polyphosphate Substances 0.000 claims abstract description 4
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- JLAMDELLBBZOOX-UHFFFAOYSA-N 3h-1,3,4-thiadiazole-2-thione Chemical compound SC1=NN=CS1 JLAMDELLBBZOOX-UHFFFAOYSA-N 0.000 claims abstract 6
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims abstract 5
- 229920000388 Polyphosphate Polymers 0.000 claims abstract 2
- 229910001868 water Inorganic materials 0.000 claims description 102
- 229910052882 wollastonite Inorganic materials 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000725 suspension Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000007900 aqueous suspension Substances 0.000 claims description 11
- 239000011859 microparticle Substances 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims description 8
- IDYUFXLSXUPQOY-UHFFFAOYSA-N 4,6-bis(sulfanylidene)-1,3,5-triazinan-2-one Chemical compound O=C1NC(=S)NC(=S)N1 IDYUFXLSXUPQOY-UHFFFAOYSA-N 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 8
- OHOJRYNNXNLLOK-UHFFFAOYSA-N imidazolidine-2,4-dithione Chemical compound S=C1CNC(=S)N1 OHOJRYNNXNLLOK-UHFFFAOYSA-N 0.000 claims description 8
- CYWHLOXWVAWMFO-UHFFFAOYSA-N 3-sulfanyl-1h-pyridine-2-thione Chemical compound SC1=CC=CN=C1S CYWHLOXWVAWMFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical group [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 150000003573 thiols Chemical class 0.000 claims description 4
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 92
- 239000000470 constituent Substances 0.000 abstract description 23
- 239000007790 solid phase Substances 0.000 abstract description 13
- 239000010949 copper Substances 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 abstract description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-O cyclohexylammonium Chemical compound [NH3+]C1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-O 0.000 abstract description 2
- 229910003480 inorganic solid Inorganic materials 0.000 abstract description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical class CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 65
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 49
- 239000000243 solution Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000003973 paint Substances 0.000 description 26
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 25
- 230000005764 inhibitory process Effects 0.000 description 24
- 230000005484 gravity Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000005204 segregation Methods 0.000 description 16
- 238000013019 agitation Methods 0.000 description 15
- 229920000180 alkyd Polymers 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000005538 encapsulation Methods 0.000 description 12
- 230000002195 synergetic effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000003556 assay Methods 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000002987 primer (paints) Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 229910000165 zinc phosphate Inorganic materials 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 239000011686 zinc sulphate Substances 0.000 description 3
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 2
- IILRWDAJGJROQW-UHFFFAOYSA-N 2-sulfanyl-3h-1,3-benzothiazole-2-carboxylic acid Chemical compound C1=CC=C2SC(C(=O)O)(S)NC2=C1 IILRWDAJGJROQW-UHFFFAOYSA-N 0.000 description 1
- NWICXXZEVNQOGF-UHFFFAOYSA-N 5,6-dicyclohexyl-4-sulfanyl-1,3-benzothiazole-2-carboxylic acid Chemical compound C1CCCCC1C=1C=C2SC(C(=O)O)=NC2=C(S)C=1C1CCCCC1 NWICXXZEVNQOGF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- HNCMAIWIHYESBQ-UHFFFAOYSA-M C(CC)O[SH-]C([O-])=S.[Zn+2] Chemical compound C(CC)O[SH-]C([O-])=S.[Zn+2] HNCMAIWIHYESBQ-UHFFFAOYSA-M 0.000 description 1
- RJDBFTRNYPFFBT-UHFFFAOYSA-N CCCO[SH2]C(O)=S Chemical compound CCCO[SH2]C(O)=S RJDBFTRNYPFFBT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- QBAUCMJDMDLVLE-UHFFFAOYSA-L SC1(SCC=N1)C(=O)[O-].[Zn+2].SC1(SCC=N1)C(=O)[O-] Chemical compound SC1(SCC=N1)C(=O)[O-].[Zn+2].SC1(SCC=N1)C(=O)[O-] QBAUCMJDMDLVLE-UHFFFAOYSA-L 0.000 description 1
- JMKXRFGJWPNWOR-UHFFFAOYSA-N SC=1[N-]C2=C(N1)C=CC=C2.[Zn+2].SC=2[N-]C1=C(N2)C=CC=C1 Chemical compound SC=1[N-]C2=C(N1)C=CC=C2.[Zn+2].SC=2[N-]C1=C(N2)C=CC=C1 JMKXRFGJWPNWOR-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical class SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MPJBNIGEWQWBFE-UHFFFAOYSA-N dicyclohexylazanium;2-sulfanyl-3h-1,3-benzothiazole-2-carboxylate Chemical compound C1CCCCC1[NH2+]C1CCCCC1.C1=CC=C2SC(C(=O)[O-])(S)NC2=C1 MPJBNIGEWQWBFE-UHFFFAOYSA-N 0.000 description 1
- OYBNYAHZVHYOIJ-UHFFFAOYSA-N dicyclohexylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.C1CCCCC1[NH2+]C1CCCCC1.C1CCCCC1[NH2+]C1CCCCC1 OYBNYAHZVHYOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- HJZYBDPHAHGHAZ-UHFFFAOYSA-N thiadiazole-4-carboxylic acid Chemical compound OC(=O)C1=CSN=N1 HJZYBDPHAHGHAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XNEOWYGUBMTFKT-UHFFFAOYSA-H trizinc;diphosphate;dihydrate Chemical compound O.O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XNEOWYGUBMTFKT-UHFFFAOYSA-H 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
Definitions
- Organic protective coatings represent the most versatile and economical technology available for protection of metals against atmospheric corrosion.
- Corrosion inhibitive primer coatings are solid composites, comprising finely divided, usually multi-component, inorganic pigment phases dispersed in continuous organic polymer phases, which provide strong adherence to the protected metal substrates. Although the physical characteristics of primers are reinforced by the dispersed inorganic pigment phases, they nevertheless remain permeable to 0 2 , H 2 0 and air-borne pollutants. As a consequence, thin organic coatings do not prevent atmospheric corrosion of metals, unless they are specifically formulated with active corrosion inhibitor constituents, included in the pigment phase.
- a metal substrate protective primer in equilibrium with its environment is a dynamic medium which accommodates several concurrently occurring physical and chemical processes, in which water, always present due to the resin phase's permeability, plays a critical role.
- Water content affects the physical integrity of organic coatings in several ways. Most importantly, in this specific sense, it dissolves all soluble components (inclusive of pigments) to saturation concentrations and supports in situ diffusional transport processes of dissolved constituents. Water accumulates preferentially at metal-coating interfaces, causing loss of interfacial adhesion and more specifically supporting the electrochemical processes of metal corrosion. Paradoxically, in actively pigmented organic coatings water supports the inhibition of metal substrates' atmospheric corrosion, as well, by in situ solubilization of active pigments. Corrosion inhibitor pigment constituents of protective primers can be regarded as built in reservoirs of corrosion inhibitive species.
- Chemically active corrosion inhibitor pigments used for Fe, Al, or Cu protection belong exclusively to only a few classes of inorganic compounds, such as chromates, phosphates or polyphophates, molybdates, borates, silicates and phosphites of Zn, Ca, Sr, Ba, Al, Mg, Pb, Cr, Fe, or various combinations of these anionic and cationic species. Chromates and some of the latter cationic species, particularly Ba, Pb and Cr are known to be toxic. Transition metal derivatives of hydrogen cyanamide, particularly ZnNCN are also known for pigment grade application, limited, however, to special mirror backing coatings intended for Ag protection.
- the active inhibitor species are the anionic constituents. Cations present, however, determine important physical properties of pigments such as solubility. Chromates, and specifically SrCr0 4 , are the standard of the industry, being the most versatile, applicable on all metal substrates such as Fe and specifically Al alloys and being highly effective, although toxic, pigment grade corrosion inhibitors. It is the redox activity of chro ate species, accountable for their inhibitive efficiency which provides interference with corrosion processes in both, anodic and cathodic environments.
- pigment grade quality is defined by an additional, quite limiting set of parameters. Most important of these are non-volatility, solid consistency, specific gravity of 2.5-5.0, effective but limited solubility in water, virtual insolubility in organic solvents, absence of deleterious effects on coating's mechanical properties and, notably, no interference with curing processes. It will be apparent in this sense, that coatings related applications are not compatible with physical properties such as volatility, excessive solubility in water or organic mediums, which are however, critical requirements of gas phase or liquid medium related applications of organic corrosion inhibitors, respectively.
- organic compounds with -SH functionality such as thiols, derivatives of dithiocarbonic, dithiocarbamic and dithiophosphoric acids
- thiols such as N- containing heterocyclic mercapto derivatives, i.e, 2-mercaptobenzothiazole (MBT)
- MBT 2-mercaptobenzothiazole
- Typical applications of organic corrosion inhibitors in water, polar organic solvents or hydrocarbons include heat exchangers, anti-freeze systems, steam condensers or hydraulic oils, metal cutting liquids, and lubricants.
- Water soluble related Na or K salts for example Na-MBT
- “thio" compounds in their more hydrocarbon soluble acidic form such as MBT
- U.S. Patent 4,329,381 shows the use of toxic Pb and Zn salts of selected five or six membered nitrogen-containing heterocyclic mercapto derivatives, notably Zn(MBT) 2 , as corrosion inhibitor components of organic coatings, more specifically by incorporating such compounds as finely divided, distinct solid component phases into paint or coating systems, more specifically for protection of Fe.
- Quantitative determination of unreacted MBT content of Zn(MBT) 2 can be conveniently carried out gravimetrically, by repeated extraction in acetone, or it can be estimated by IR spectroscopy. Intense absorption bands situated at 1496 and 1425 cm(-l) of the related spectrum, are characteristic for MBT (See Comparative Example 1)
- An additional limitation of the concept of the '381 patent relates to the fact that the specific gravity of Zn(MBT) 2 (1.5-1.7), and generally that of other mercapto derivatives, is quite low in comparison with such values typical for other components of a paint system's dispersed inorganic phase, which range from 2.5 to 5.0, or with density values of cured coatings of about 2.0.
- the zinc and lead salts of mercapto derivatives form ordinary mixtures with other components of the dispersed pigment phase.
- shelf-stable paint systems' dispersed solid phases tend to segregate by "flooding", if they contain components with appreciably different specific gravities.
- Solid solutions although formed spontaneously, are not commonly found in multi- phased solid systems.
- distinct combinations of three or more anionic and cationic constituents which ordinarily form two or more solid phases of distinct chemical composition, in special conditions form unified solid phases of complex chemical composition.
- Such unified phases are characterized by uniform distribution at molecular level of all constituent ionic species.
- Ordinary mixtures of finely divided (and normally polydispersed) solid phases of different chemical composition are constituted of distinct and separable microparticles of the distinct component phases, mixed and uniformly distributed in the system.
- Ordinary mixtures can be prepared by simple mechanical procedures. However, they are often formed spontaneously in chemical processes as well, such as during concurrent or subsequent formation by precipitation of two or more solid phases in aqueous systems.
- micro-composite multi-phase and finely divided solid systems are constituted of microparticles, containing distinctly identifiable, but physically inseparable component phases of different chemical composition which form common interfaces and are held together by chemical forces.
- composite microparticles possess a structural configuration of a coating-core type, often formed in some heterogenous chemical processes, such as described in my U.S. Patent 5,176,894, wherein a finely divided suspension of an essentially insoluble solid reactant is reacted with a dissolved component reactant of a liquid phase and consequently is converted into a finely divided suspension of a solid reaction product, which is insoluble in the reaction medium.
- the suspended solid phase consists of composite micro-particles of a coating-core configuration, in which both solid component phases, i.e., the reaction product coating and the reactant core are simultaneously present, separated and bound together by an interface which in many cases is of a generally spherical shape, but also may consist of other configurations such as lamina, etc.
- This mechanism obviously, implies the reagent species' continuous diffusion through the coating phase toward the reactant core and generally, the reaction is diffusionally impeded.
- the solid product's micro-composite structure is preserved.
- micro- composite multi-phase solid systems by, in comparison, a quite different process and mechanism.
- particle encapsulation procedures widely used in the pigment manufacturing industry, are the formation by precipitation of chemically inert coatings of diverse chemical composition on the surfaces of finely divided solids in aqueous suspension.
- the microcomposite structures of multiphase solids prepared in aqueous processes commonly are preserved throughout typical pigment manufacturing operations, which include filtration, dehydration and grinding. Pertinent experimental data are presented in Comparative Examples 2.1 and 2.2.
- thio- organic salts such as Zn(MBT) 2
- inorganic constituents such as ZnNCN are incorporated into pigment grade organic-inorganic hybrids.
- the hybrids are found to possess heretofore undiscovered corrosion inhibiting properties on a wide variety of metals.
- novel procedures are disclosed for synthesis of inorganic/organic hybrids which are in the characteristic micro-composite structural state.
- pigment grade hybrids of the present invention do not segregate into phase components by physical processes such as flotation or flooding. Importantly, such segregation does not occur when these hybrids are dispersed in liquid phases such as paint vehicles. Furthermore, as a direct consequence of pigment grade hybrid's uniphase behavior, pertinent specific gravity, pH and solubility values are approximately weighed averages of the component phase ' s characteristic values. It is particularly important to note, that pigment grade hybrid products according to the present invention, and particularly those containing Zn(MBT) 2 , do not display cure inhibitive activity in alkyd resin based paint systems. Consequently, they are actual pigment grade products, compatible with all paint vehicle systems, as documented hereinafter.
- the hybrid corrosion inhibitors of this invention have applicability to other polymer-based systems where inhibition of metal corrosion is important.
- adhesive systems intended for use in bonding together of metals, especially aluminum in aircraft applications can be provided with corrosion resisting properties by addition thereto of the pigment grade hybrids of this invention.
- pigment grade hybrids produced according to the present invention display synergistic behavior with respect to metal corrosion inhibition.
- novel pigment grade hybrids ' synergistic behavior are their ability to effectively retard all of the important metals' corrosion, particularly of Fe, Al, Cu and Ag, as well as their compatibility with all paint vehicle systems, inclusive of water reducible and solvent based alkyds.
- synergistic behavior with respect to corrosion inhibition is understood as the capacity of pigment grade hybrid products to display, in identical coating formulations, similar or generally enhanced corrosion inhibitive performance in comparison to state of the art corrosion inhibitor pigments typically applied on all of the above-noted metal substrates. The comparison in this sense refers to all individual phase components of related hybrid compositions, as well.
- synergistic behavior with respect to corrosion inhibition is not an ordinary characteristic provided just any randomly selected mixtures of chemically different, finely divided solid constituents containing inhibitor species.
- a high degree of synergy rather, is an unpredictable property of very few multi-phase pigment systems of distinct chemical and phase compositions, having two, or typically more, solid component phases, preferably all insoluble in organic media, which are, however, water soluble to an effective, but limited extent.
- microparticles are defined as particles having diameters of approximately 0.5 to 20 microns. The preferred particles are in an approximate diameter range of 1 to 10 microns.
- the invention provides corrosion inhibiting compositions for application to metal substrates, in which a film-forming continuous organic polymer phase contains a dispersed finely divided, corrosion inhibiting micro-composite pigment phase, consisting of corrosion inhibitor inorganic and organic component phases which are distinctively identifiable, however inseparable by physical means, such as flooding, flotation or sedimentation.
- the corrosion inhibitor inorganic component phase typically includes selected phosphates, phosphites, molybdates, borates, silicates and cyanamides, specifically ZnNCN or mixtures or solid solutions thereof.
- the corrosion inhibitor organic component phase is a zinc-, or an alkyl- or cyclo- alkyl ammonium salt of selected thio-organic compounds, such as mercaptans, hetero-cyclic mercapto derivatives, derivatives of dithio- carbonic, dithio-carbamic and dithio-phosphoric acids.
- the invention offers a method of providing corrosion resistance to a metal substrate, which includes applying to the substrate's surface a film-forming organic coating composition containing a dispersed pigment phase, which pigment phase contains a hybrid organic- inorganic product in a corrosion protecting amount.
- coating composition is intended to refer generally to film-forming compositions such as paints, lacquers, adhesives, etc. suitable for application to metal substrates.
- the invention also provides methods for synthesis of organic-inorganic hybrid corrosion inhibitor micro-composite products, such as by reacting selected mercaptans with aqueous suspension of ZnNCN, or by the distinctively different way, by co-precipitation (double decomposition) of dissolved mixtures of organic and inorganic corrosion inhibitor anionic species with dissolved mixtures of selected cationic species.
- the present invention discloses a procedure to convert ordinary mixtures of distinctively different solids into micro- composites, by particle encapsulation or adsorption of freshly precipitated hydrous Zr0 2 , or alternatively of Al, Zn silicates or phosphates onto the surface of finely divided and dispersed solid particles.
- novel corrosion inhibiting hybrid pigments and corrosion preventing compositions and processes based on poly-thiols, especially di-, tri-, and tetra- mercapto derivatives are provided with particular applicability to prevention of corrosion of silver and aluminum.
- Figures 1-8 are graphical prints representing IR spectra of products produced pursuant to the invention.
- DETAILED DESCRIPTION OF THE INVENTION The synthesis of pigment grade organic- inorganic hybrid products, pursuant to the present invention is preferably accomplished by combining selected organic and inorganic constituents, in preferred stoichiometric ratios according to procedures which promote formation of organic- inorganic interfaces.
- Inorganic constituents preferred according to the present invention are as follows: Cations: Zn(II) , Al(III), Mg(II) , Ca(II), Sr(II), Ti(IV), Zr(IV), Ce(III or IV), Fe(II or
- Selected organic constituents of hybrid pigments synthesized according to the present invention are the zinc salts, cyclo-alkyl-ammonium or alkyl-ammonium (For example: cyclohexyl- ammonium, di-cyclohexyl-ammonium, octyl-ammonium) salts of organic mercapto- and thio- compounds or their alkyl-substituted derivatives, as follows: mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, ercaptoimidazoles, 2,5- dimercapto-1, 3,4-thiodiazole, 5, 5-dithio- bis(l,3 ,4-thiadiazole-2 (3H) -thione, mercaptobenzoxazoles , mercaptothiazole, mercaptotriazole, mercaptopyrimidine, mercaptopyridine, mercaptoquinoline, alkyl- and cyclo
- di-, tri-, and tetra- mercapto derivatives have also been found applicable to the practice of the invention, for example, dithiocyanuric acid, trithiocyanuric acid, dimercapto pyridine, 2, 4- dithiohydantoin, and 2,4-dimercapto-6-amino-5- triazine. Also applicable are dimers or oligomers of di- or tri- mercapto derivatives, containing -S-S- functional groups obtained by oxidation of the former.
- Reaction 4 is the process generally preferred for the formation of organic-inorganic interfaces, characteristic to pigment grade hybrid products according to the present invention. As hereinafter further disclosed, this procedure offers significant advantages, the absence of soluble by-products being one of the most important.
- reaction 4 implies that H 2 NCN diffusion to the ZnO core is not obstructed.
- the component phases are inseparable by physical processes such as flooding, flotation, or sedimentation in liquid media and thus are believed to be in a micro- composite structural state of a coating-core type.
- Reaction 4 is performed with less than stoichiometrically required amounts of H 2 NCN, it yields three-phase hybrid products containing variable amounts of ZnO, presumably in core- coating structural configuration, symbolized by the formula:
- Reaction 3 applies also to DMTD and MBI
- Reaction 4 is substantially obstructed. This observation is interpreted as a manifestation of the reaction products' micro-composite structure. in which freshly formed Zn(DMTD) 2 or Zn(MBI) 2 coexist with unreacted ZnO presumably in a coating- core structural configuration. In contrast with MBT, MTH and MBO, where this apparently is not the case, Zn(DMTD) 2 and Zn(MBI) 2 form dense coatings on ZnO cores, thus preventing H 2 NCN diffusion.
- Reaction 7 can be performed also with other mercaptans such as MBI, MBT (See Example 2), MBO and MTH. Reaction 7 is favored to a variable extent, as a function of the acidity of various mercaptans, generally stronger in comparison to H 2 NCN and the low solubility of the resultant zinc salts.
- MBI mercaptans
- MBT See Example 2
- MBO metal-oxide-semiconitrile
- Reaction 7 is favored to a variable extent, as a function of the acidity of various mercaptans, generally stronger in comparison to H 2 NCN and the low solubility of the resultant zinc salts.
- a distinct objective of the present invention is to synthesize organic-inorganic microcomposite hybrid corrosion inhibitor pigments comprising, in addition to the preferred organic constituents and cyanamides, other corrosion inhibitive anionic species or inorganic component phases such as phosphates, phosphites, silicates, molybdates and borates.
- Reactions similar to Reaction 9 also can be performed with MBO and MTH.
- Reaction 9 is important with respect to the practice of the present invention to synthesize multi-phase organic-inorganic hybrid pigments having synergistic corrosion inhibitive properties. It is based on the unexpected capability of H 2 NCN to react selectively with a ZnO core in the presence of previously formed component phases such as Zn(MBT) 2 (or alternatives) and zinc phosphate, resulting in multi-phase products with negligible contents of ZnO. It was noted, however, that DMTD and MBI require alternative synthesis processes exemplified by:
- ZnNCN+ (0.3-0.4) CaSi0 3 ] do not display tendency for segregation into component phases, in dispersed form.
- Molybdates are conveniently incorporated into multi-phase hybrid pigments as Zn-, Ca- or Sr-molybdate, without by-products, according to
- Reactions 14 to 16 are preferably performed in situ , as variations of Reactions 8 and 9, where Mo203 addition follows MBT (or alternatives') introduction and it precedes or is concurrent with H3P04 introduction. Note the similarity of Reactions 13 and 16.
- Reaction 14 can be also performed "ex situ” followed by surface modification (particle encapsulation) which reduces the solubility of the resultant, relatively soluble product.
- the latter procedure is conveniently performed by precipitation of aluminum or zinc silicate or phosphate, as subsequently described, in situ in the ZnMo04 aqueous suspension, which then is post- added into the product suspension of Reaction 9, or alternatives thereof.
- Ca(B0 2 ) 2 or Sr(B0 2 ) 2 are the preferred component phases, which can be produced in aqueous media according to:
- Reaction 17 is preferably realized ex situ followed by particle encapsulation and subsequent post-addition, performed identically to the above procedure regarding ZnMo0 4 .
- phase composition of multi- component hybrid pigments comprising, among others, molybdates and borates, can be represented by :
- alkyl-ammonium salts of mercapto derivatives for example dicyclohexylammonium-2- mercaptobenzothiazolate, are also preferably incorporated into hybrid compositions as separately prepared aqueous suspensions. (See Example 10)
- the preferred procedure consists of gradual introduction, prior or subsequent to any performed synthesis reaction, of an aqueous zirconyl salt solution into an intensively stirred aqueous suspension of ordinary mixtures, and, if required, moderate heating and pH neutralization of the system.
- Any water soluble zirconyl salt is suitable, at a specific consumption equivalent to 1-3% Zr0 2 per total solids treated.
- Zirconyl acetate is available commercially at a typical assay of 20-22% Zr02. As for the mechanism, it is plausible that hydrated Zr hydroxide species nonselectively deposit and uniformly coat the surfaces of dispersed crystallites of the treated component phases. Subsequently dehydrated by drying, a typical operation in pigment manufacture, component phases develop common interfaces of Zr0 2 , which results in characteristic "non-segregation" behavior displayed by organic-inorganic microcomposites. This "particle encapsulation" process can be presented as follows:
- An alternative particle encapsulation procedure employed, pursuant to the present invention, is based on precipitation of hydrated aluminum or zinc silicate, phosphate or pyro- phosphate in situ of aqueous dispersions of solids. The procedure is also applied preferentially to reduce the solubility of separately prepared, relatively soluble component phases of multiphase pigments such as ZnMo0 4 or Ca(B0 2 ) 2 , as above indicated.
- the process is completed by extensive stirring, and, if applicable, by adjusting the pH of the dispersion to neutral.
- crystallite encapsulation i.e., a microcomposite state
- surface treat Al-silicate encapsulated pigment dispersions by post-addition of polymeric dispersants, such as Solsperse 24000 (from Zeneca Resins) .
- the organic treatment is applied at about 0.1-0.5% by weight total solids.
- the alternative synthesis procedure for multi- component, organic-inorganic hybrid pigments is based on coprecipitation by double decomposition of mixtures of soluble salts containing the above- specified selected anionic and cationic species. See Examples 7-11. Accordingly, soluble salts of selected organic thio-compounds are co- precipitated as Zn-derivatives, with phosphates, molybdates, phosphites, poly-phosphates and cyanamides of Zn, Al, Ca, Sr, Mg, Ti, Zr and Ce.
- DT symbolizes thio-organic compounds, such as O,0-di-alkyl-dithiophosphates, O-alkyl- dithiocarbonates, N-alkyl- (or N-aryl-) dithiocarbamates or mercaptans.
- a multi-phase inorganic system which consists of ZnNCN, Zn 3 (P0 4 ) 2H 2 0, ZnO, CaSi0 3 and Notably, SrC0 3 component phases in specific molar ratios, displays a high degree of synergy as to corrosion inhibition.
- a detailed description of the multi-phase inorganic pigment's synthesis is disclosed in Example 18, infra. It will be observed that SrC0 3 and CaSi0 3 (see also Reaction 13) under the specified reaction conditions, are subject to surface modification according to:
- the multi-phase pigment grade product can be described as an ordinary mixture of finely divided three component phases: surface modified SrCr0 3 (Reaction 21) , surface modified CaSi0 3 (Reaction 22) and the product of Reaction 11, the latter being a micro-composite, presumably consisting of 3 component phases.
- Comparative Example 1 Examples Experimental data presented under Comparative Example 1 are intended to demonstrate the above specified limitations of the concept and practice promoted by U.S. Patent No. 4,329,381. In comparative Example 2 experimental data are presented regarding the phase segregation tendency of finely divided multi-phase ordinary solid mixtures comparatively to "non-segregation" behavior of micro-composite organic-inorganic hybrids according to the present invention. Comparative Example 1
- Technical grade Zn(MBT) 2 was precipitated by introducing the above solutions, simultaneously at identical delivery rate (in about 30 min.), into well agitated 300 ml of water, at ambient temperature. After 1 hour of stirring at that temperature, the obtained slurry was filtered, washed intensively to salt-free conditions and further processed in identical fashion, as disclosed above.
- Related analytical data are presented below. Notably, the final product contained about 13% unreacted MBT.
- Comparative Example 2 The purpose of this Example is to produce an ordinary mixture of Zn(MBT) 2 and an inert inorganic product, (both finely divided) essentially according to the concept promoted by U.S. Patent 4,329,381 and to demonstrate the tendency for component phase segregation of such system, by sedimentation in aqueous dispersion. Comparative Example 2.1.
- an aqueous dispersion of AlbaShield 50, a high purity wet ground muscovite mica (aluminum silicate & inert mineral filler pigment, commercially available from Aspect Minerals, Inc. with the following quality specifications: specific gravity 2.8; + 200 mesh > 98%; +325 mesh > 90%; in the form of fine flakes) was prepared by stirring 100.0 g of the former into 1000 ml water. Subsequently, an aqueous dispersion of the ordinary mixture, formed by the two finely divided solids, was prepared by mixing together the above described dispersions, under intense agitation and by completing the volume of the dispersion to 2000 ml. The phase composition of this ordinary mixture can be symbolized by the formula :
- the solid samples' Zn(MBT) 2 contents were determined by selective solubilization of the latter in aqueous NaOH solution; it was experimentally confirmed, that AlbaShield 50 is not soluble in the same solution.
- Each solid sample was re-dispersed in approximately 300 ml NaOH 10% solution, stirred for 30 minutes, filtered, well washed and dried to constant weight, which represented the pertinent AlbaShield content, whereas the observed weight loss represented the solid samples' Zn(MBT) 2 content.
- the Segregation Index (% Iseg.), was determined according to the following formula:
- the ordinary mixture's %ZnMBT 20%, and, consequently, positive or negative values of %Isg. indicate segregation (relative accumulation or depletion of Zn(MBT) 2 in the fractions of the respective dispersion samples.
- %Isg. 0 indicates no segregation.
- Experimental data and results are presented in Comparative Table 2. COMPARATIVE EXAMPLE 2.2.
- the objective of this experimental work was to demonstrate that a prior art ordinary mixture of Zn(MBT) 2 and an inert inorganic product, both finely divided, if converted into micro-composite (organic-inorganic hybrid) by particle encapsulation, (one of the applicable techniques of the present invention) does not display a tendency for phase segregation.
- organic-inorganic hybrid micro-composite of identical phase composition to that of Comparative Example 2.1 was produced by precipitating Zn(MBT) 2 , the organic component phase, "in situ" in an aqueous dispersion of finely ground inorganic AlbaShield 50 and by particle encapsulation.
- 25g. (0.065 moles) of Zn(MBT) 2 were synthesized by double decomposition, according to Comparative Example 1.2 in situ of 100 g. intensely stirred, previously prepared, AlbaShield 50 in 500 ml water which also contained 13 g. Of zirconyl acetate solution for particle encapsulation. (See Example 1.2)
- the dispersion was filtered, washed, dried, and pulverized in a mechanical lab pulverizer to 100% +270 mesh in accord with conventional pigment manufacturing procedures.
- Example 1 Pigment grade, organic-inorganic hybrids, characterized by synergistic corrosion inhibition with respect to Ag, Cu, Al, Fe and symbolized by phase-composition formulas: 1.1: [0.05Zn(MBT) 2 /ZnNCN] , and 1.2: [0.05Zn (MBT) 2 / ZnNCN + 0.5CaSi0 3 ] /0.03ZrO 2 were produced according to Reactions 3 and 4 and the following procedure:
- ZnO ZnO 66 grade, characterized by 0.25 micron average particle size, assay: >99.9%, from American Smelting and Refining Co.
- ZnO ZnO 66 grade, characterized by 0.25 micron average particle size, assay: >99.9%, from American Smelting and Refining Co.
- the dispersion and hydration process was completed by maintaining the same conditions (85-90°C)for one additional hour.
- aqueous suspension of MBT (technical grade 98% 2-Mercaptobenzothiazole, available from Aldrich Chemical Co.) was obtained in similar fashion, containing 0.1 moles (17.0 g. of 98%) of the same in 200 ml of water at ambient temperature, using, however, a small but effective amount of non-ionic surfactant (Igepal-CA 630, distributed by Hydrite Chemical Co., WI . ) as a wetting aid.
- non-ionic surfactant Igepal-CA 630, distributed by Hydrite Chemical Co., WI .
- a mixed suspension was formed and converted, at 85-90OC and intense agitation for 2.5 hours, into a Zn(MBT) 2 /ZnO suspension.
- a pigment grade hybrid according to the above noted phase-composition, was produced by introducing in about 30 min. into the reaction mixture, 1.05 moles of H 2 NCN (as aqueous solution of 50 weight %, available from S.K.W., Germany) and keeping the same conditions (80-85OC, intense agitation) for one hour.
- the resultant product suspension's solid phase was separated by filtration.
- the presscake, without washing, was dried at 105-110oc for 12 hours and pulverized to a fineness of 100% +270 mesh.
- Organic-inorganic hybrid pigment 1.2 was synthesized, in identical fashion as disclosed for Example 1.1, except that a mixed suspension of 1.0 moles (81.38 g) ZnO and 0.5 moles (58.0 g) Wollastonite grade CaSi0 3 (NYAD 1250 grade Wollastonite from NYCO Minerals) in 1000 ml of water was processed. Notably however, for particle encapsulation purposes 20g of aqueous zirconyl acetate solution (assay: 20% Zr0 2 , from Magnesium Electron, Inc.) was gradually post-added into the intensively stirred suspension of the final product and the same conditions were extended for 30 minutes.
- aqueous zirconyl acetate solution assay: 20% Zr0 2 , from Magnesium Electron, Inc.
- a pigment grade hybrid of [0.25Zn(MBT) 2 / ZnNCN] composition was synthesized according to Reaction 7 and the following procedure: Aqueous ZnO slurry, containing 1.0 moles in 500 ml H 2 0, was prepared as describe in Example 1.1. Keeping the reaction conditions the same for an additional hour, ZnO suspension was converted into ZnNCN suspension (procedure according to my U.S. Patent 5,176,894), by introducing into it in about 15 min, 1.1 moles (46.5 g) of H 2 NCN as aqueous solution of 50% by weight.
- a pigment grade, multi-phase organic- inorganic hybrid corrosion inhibitor symbolized by:
- Pigment grade, organic-inorganic hybrid corrosion inhibitor symbolized by [ 0.88 Zn(DMTD) 2 /ZnNCN/0.22 Zn 3 (P0 4 ) 2 (H 2 0) 2 /0.15 ZnO/ 1.11 CaSi0 3 + 0.28 ZnMoO 4 /0.026 Al-Si0 3 + 0.5 Sr(BO 2 ) 2 /0.026 Al-Si0 3 ] /0.17 Zr0 2 theoretical formula, was synthesized following a combined procedure based on Reactions 10-12, 14, 17 and encapsulated according to 18. Notably, ZnMo0 4 and Sr(B0 2 ) 2 prepared in accordance with reactions 14 and 17, were selectively subsequently encapsulated with Al-silicate, Al-Si0 3 . The following precursors were initially prepared:
- Dispersion (F) containing 0.22 moles of [ZnMo0 4 / 0.09 Al 2 0 3 (Si0 2 ) 3 ] in 150 ml H 2 0, was prepared at 80-85°C, by intense agitation of an aqueous mixed dispersion of finely divided 0.22 moles ZnO + 0.22 moles Mo0 3 , for about 60 minutes.
- Dispersion (G) containing 0.39 moles of [Sr (BO 2 ) 2 /0.05 Al 2 0 3 (Si0 2 ) 3 ] in 150 ml H 2 0, was prepared by double decomposition of 0.39 moles Sr(N0 3 ) 2 and 0.19 moles of Na 2 B 4 O 7 »10H 2 O, technical grades. The resultant product was particle encapsulated in identical fashion as above described.
- Emulsion (H) containing 1.2 g Solsperse 24000/10 ml H 2 0 (polymeric dispersant from Zeneca Resins) was prepared according to ordinary procedures known to the art.
- a pigment grade organic-inorganic hybrid corrosion inhibitor symbolized by: [ 0 . 06 Zn (MBT) 2 / 0 . 06 Zn (MTH) 2 /
- Solution (B) 1.8 moles H 2 NCN/500 ml.H 2 0;
- Solution (D) 0.3 moles of MBT (36.5 g. of 98%), 0.3 moles of MTH (51.2 g. of 98%), and 1.0 moles of H 3 P0 4 were dissolved in 1000 ml. aqueous solution of 4.8 moles NaOH. After cooling it to ambient temperature, 0.6 moles of H 2 NCN were added and the volume completed to 1500 ml.
- Pigment grade hybrid was produced by introducing first, in about 30 min. , Solution (B) and then, simultaneously, in about 30 min. , Solutions ⁇ and (D) into intensively stirred Dispersion (A) .
- Pertinent analytical data are presented in Table 5. Table 5
- Solution (C) 0.15 moles ZnSO 4 /200 ml. H 2 0 at pH ⁇ 4.0;
- Solution (D) 0.15 moles of Na 2 DMTD/200 ml. H 2 0, by solubilization of DMTD (technical grade, from
- the synthesis was carried out by simultaneous introduction, in about 30 min. , of
- Hybrid pigment varieties 7.1., 7.2. and 7.3 were produced in essentially identical fashion.
- First (B) was introduced, in about 15 min. with intense agitation, into (A) at 65-85 °C.
- C) and (Dl) or, alternatively, for 7.2, (C) and (D2) , or, in the case of 7.3 , (C) and (D3) were introduced simultaneously, in about 15 min. , into the reaction medium.
- C) and (D3) were introduced simultaneously, in about 15 min. , into the reaction medium.
- E was introduced in about 30 min. and the same conditions were extended for one additional hour.
- Na-n-propyl-dithiocarbonate was synthesized pursuant to known procedure, as follows: into a mixture of 0.61 moles n-propanol and 0.6 moles NaOH / 100 ml H 2 0, 0.61 moles of CS 2 were gradually introduced under moderate agitation and at 40-50°C, after which the same conditions were kept for one hour. The obtained solution was subsequently incorporated into solution (D) . Results are shown in Table 9.
- a multi-phase pigment grade hybrid corrosion inhibitor for Ag, Cu, Al, Fe represented by:
- Pigment grade hybrid was synthesized by simultaneous introduction, in about 30 minutes, of (B) and (C) into (A) , intensively stirred at 65- 75 °C. After subsequent addition of (D) and keeping the same conditions for one hour, the pigment slurry was cooled to normal temperature and processed as described in Example 5.
- Example 11 Organic-inorganic hybrid corrosion inhibitor, corresponding to:
- Solution (B) 1.8 moles H 2 NCN /500 ml.H 2 0;
- Pigment grade hybrid composites synthesized according to Examples 1.2 and 6 were tested comparatively to a strontium chromate control, as pigment components of protective primer formulations, specifically for their inhibitive activity to metal corrosion.
- Test formulation 12.1 (see Example 12) was employed to evaluate corrosion inhibitive activity on aluminum of a pigment grade hybrid symbolized by [0.05Zn(MBT) 2 / ZnNCN + 0.5CaSiO 3 ] /0.02ZrO 2 synthesized per Example 1.2
- the 12.1 test and related control formulations were applied by wire-wound rod on Type A 3003 H14 aluminum panels (from The Q-Panel Co.), at 0.6-0.8 mils thickness, aged for 7 days at room temperature, vertically scribed and subsequently subjected to salt spray exposure (according to ASTM B-117) . It will be noted, that the coatings' observed corrosion inhibitive performance is considered being directly proportional to the tested pigment components' corrosion inhibitive activity. Test results are summarized in Table 13. Table 13 .
- Example 14 Based on these experimental results, it can be concluded that hybrid pigment of Example 1.2 possesses excellent corrosion inhibitive activity on aluminum, comparable to SrCr0 4 , the industrial standard for such applications.
- Example 14
- Test formulations 12.1 and 12.2 were used to assess the corrosion inhibitive activity on copper of pigment grade hybrids symbolized by [0.05Zn(MBT) 2 / ZnNCN + 0.5CaSi0 3 ] /0.03ZrO 2 and [0.075. Zn-DMTD/ZnNCN] synthesized according to Example 1.2 and Example 6, respectively.
- Anodically polarized test and control panels were simultaneously immersed in an aqueous electrolyte solution containing -Cl, and -S0 4 species and surfactant at ambient temperature and moderately alkaline pH. After low DC voltage was applied, the physical integrity of the coatings were visually evaluated and performance graded on a 1 (worst) to 5 (best) scale.
- Pigment grade hybrids synthesized according to Examples 1.1, 1.2, 7.1 and 7.2 were tested for their corrosion inhibitive activity on silver, as pigment components of "mirror backing" coating formulations.
- the test and control formulations employed, known by the industry, are presented below: Table 15 . 1
- Pigment grade organic-inorganic hybrid according to Example 1.2 symbolized by [0.05Zn(MBT) 2 /ZnNCN + 0.5CaSi0 3 ] /0.03ZrO 2 , was evaluated in a solvent based medium oil alkyd test formulation for synergistic behavior for inhibition of steel corrosion.
- Distinct versions of the test formulation containing the pigment grade hybrid composition, its phase constituents (pigment grade ZnNCN, CaSi0 3 -Wollstonite grade, technical grade Zn(MBT) 2 produced according to Example 1.3), pigment grade SrCr0 4 and zinc phosphate dihydrate (for pigments see Table 16.2), respectively, were sprayed on cold rolled steel panels (from The Q- Panel Co.), at 1.5 mil film thickness.
- the exhibits were air dried, aged overnight at 130°F, scribed, and subsequently exposed to salt spray conditions for 670 hours, following ASTM B-117 and evaluated by ASTM D-714; the test coatings' overall corrosion inhibitive performances, considered directly proportional with pertinent pigments' corrosion inhibitive activity, were comparatively evaluated and graded on 0 (worst) to 10 (best) scale.
- the test formulations and results are presented below in Tables 16.1 and 16.2, respectively. Tablel ⁇ .l C omponents of Trade Names & test formulation Suppliers Parts by Weight
- Raw material suppliers (1) McWhorther Technologies; (2) SCM; (3) Pfizer Inc ., Chemical Div.; (4) Harcros; (5) Rheox, Inc.; (6) Interstab Chemicals, Inc.;
- Pigment grade hybrid according to Example 1.2 thus, displays synergistically enhanced corrosion inhibitive activity on cold rolled steel, performing substantially better in that sense, than pigment grade Zn 3 (P0 4 ) 2 (H 2 0) 2 and at comparative level to SrCr0 4 . It is a manifestation of synergy when the pigment composition outperforms each of the individual components of which it is constituted.
- Example 17
- a multi-component, microcomposite inorganic/ inorganic pigment of this invention characterized by synergistic behavior in respect of inhibition of steel corrosion, symbolized by the theoretical phase composition formula of [0.77.Zn 3 (PO 4 ) 2 . (H 2 0) 4 /ZnNCN/
- Solution (B) containing 0.38 moles H 3 PO 4 /200ml water.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU11859/99A AU1185999A (en) | 1997-10-02 | 1998-10-02 | Hybrid pigment grade corrosion inhibitor compositions and procedures |
CA002305593A CA2305593A1 (en) | 1997-10-02 | 1998-10-02 | Hybrid pigment grade corrosion inhibitor compositions and procedures |
US09/319,231 US6139610A (en) | 1996-01-05 | 1998-10-02 | Hybrid pigment grade corrosion inhibitor compositions and procedures |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US94293297A | 1997-10-02 | 1997-10-02 | |
US08/942,932 | 1997-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999018044A1 true WO1999018044A1 (en) | 1999-04-15 |
Family
ID=25478838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/020801 WO1999018044A1 (en) | 1996-01-05 | 1998-10-02 | Hybrid pigment grade corrosion inhibitor compositions and procedures |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU1185999A (en) |
CA (1) | CA2305593A1 (en) |
WO (1) | WO1999018044A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7578878B2 (en) | 2001-05-04 | 2009-08-25 | Wayne Pigment Corp. | Pigment grade corrosion inhibitor host-guest compositions and procedure |
US7662241B2 (en) | 2001-05-04 | 2010-02-16 | Wayne Pigment Corp. | Corrosion inhibitor composition applicable for aluminum and steel protection and procedure |
WO2016049118A1 (en) * | 2014-09-26 | 2016-03-31 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
WO2016154680A1 (en) * | 2015-03-31 | 2016-10-06 | Commonwealth Scientific And Industrial Research Organisation | Compositions for inhibiting corrosion |
US20180087162A1 (en) * | 2016-09-23 | 2018-03-29 | The Boeing Company | Corrosion resistant surface treatment and primer system for aluminum aircraft using chromium-free inhibitors |
WO2018064721A1 (en) | 2016-10-04 | 2018-04-12 | Commonwealth Scientific And Industrial Research Organisation | Methods for inhibiting corrosion |
CN108892686A (en) * | 2018-06-13 | 2018-11-27 | 烟台恒邦化工助剂有限公司 | A kind of production technology of butyl ammonium aerofloat |
WO2023135327A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Coating composition for reinforced protective layer |
WO2023135326A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Use of a zinc salt of dmtd in a coating composition |
WO2023135328A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Coating composition for reinforced protective layer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4329381A (en) * | 1978-02-23 | 1982-05-11 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for providing corrosion resistance to metal objects |
US5176894A (en) * | 1991-12-06 | 1993-01-05 | Wayne Pigment Corp. | Process for making improved corrosion preventive zinc cyanamide |
US5487779A (en) * | 1993-11-19 | 1996-01-30 | Wayne Pigment Corp. | Corrosion inhibiting pigment composition and method |
US5558706A (en) * | 1993-11-19 | 1996-09-24 | Wayne Pigment Corp. | Corrosion inhibiting pigment composition |
-
1998
- 1998-10-02 WO PCT/US1998/020801 patent/WO1999018044A1/en active Application Filing
- 1998-10-02 AU AU11859/99A patent/AU1185999A/en not_active Abandoned
- 1998-10-02 CA CA002305593A patent/CA2305593A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4329381A (en) * | 1978-02-23 | 1982-05-11 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for providing corrosion resistance to metal objects |
US5176894A (en) * | 1991-12-06 | 1993-01-05 | Wayne Pigment Corp. | Process for making improved corrosion preventive zinc cyanamide |
US5487779A (en) * | 1993-11-19 | 1996-01-30 | Wayne Pigment Corp. | Corrosion inhibiting pigment composition and method |
US5558706A (en) * | 1993-11-19 | 1996-09-24 | Wayne Pigment Corp. | Corrosion inhibiting pigment composition |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7578878B2 (en) | 2001-05-04 | 2009-08-25 | Wayne Pigment Corp. | Pigment grade corrosion inhibitor host-guest compositions and procedure |
US7662241B2 (en) | 2001-05-04 | 2010-02-16 | Wayne Pigment Corp. | Corrosion inhibitor composition applicable for aluminum and steel protection and procedure |
US7662312B2 (en) | 2001-05-04 | 2010-02-16 | Wayne Pigment Corp. | Pigment grade corrosion inhibitor host-guest compositions and procedure |
USRE45612E1 (en) | 2001-05-04 | 2015-07-14 | Md Fifth Ward Properties, Inc. | Corrosion inhibitor composition applicable for aluminum and steel protection and procedure |
US10508203B2 (en) | 2014-09-26 | 2019-12-17 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
US11459466B2 (en) | 2014-09-26 | 2022-10-04 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
CN106715758A (en) * | 2014-09-26 | 2017-05-24 | 波音公司 | Compositions and coatings with non-chrome corrosion inhibitor particles |
WO2016049118A1 (en) * | 2014-09-26 | 2016-03-31 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
EP4086316A1 (en) * | 2014-09-26 | 2022-11-09 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
EP3696240A1 (en) * | 2014-09-26 | 2020-08-19 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
CN107709475A (en) * | 2015-03-31 | 2018-02-16 | 联邦科学和工业研究组织 | For suppressing the composition of corrosion |
WO2016154680A1 (en) * | 2015-03-31 | 2016-10-06 | Commonwealth Scientific And Industrial Research Organisation | Compositions for inhibiting corrosion |
US11987726B2 (en) | 2015-03-31 | 2024-05-21 | The Boeing Company | Compositions for inhibiting corrosion |
US11560483B2 (en) | 2015-03-31 | 2023-01-24 | The Boeing Company | Compositions for inhibiting corrosion |
US10800929B2 (en) | 2015-03-31 | 2020-10-13 | The Boeing Company | Composition for inhibiting corrosion |
AU2016240407B2 (en) * | 2015-03-31 | 2021-03-11 | Commonwealth Scientific And Industrial Research Organisation | Compositions for inhibiting corrosion |
US20180087162A1 (en) * | 2016-09-23 | 2018-03-29 | The Boeing Company | Corrosion resistant surface treatment and primer system for aluminum aircraft using chromium-free inhibitors |
WO2018064721A1 (en) | 2016-10-04 | 2018-04-12 | Commonwealth Scientific And Industrial Research Organisation | Methods for inhibiting corrosion |
JP2020503429A (en) * | 2016-10-04 | 2020-01-30 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション | Methods for controlling corrosion |
CN110036140A (en) * | 2016-10-04 | 2019-07-19 | 联邦科学和工业研究组织 | Inhibit the method for corrosion |
CN108892686A (en) * | 2018-06-13 | 2018-11-27 | 烟台恒邦化工助剂有限公司 | A kind of production technology of butyl ammonium aerofloat |
WO2023135327A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Coating composition for reinforced protective layer |
WO2023135326A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Use of a zinc salt of dmtd in a coating composition |
WO2023135328A1 (en) * | 2022-01-17 | 2023-07-20 | Akzo Nobel Coatings International B.V. | Coating composition for reinforced protective layer |
Also Published As
Publication number | Publication date |
---|---|
CA2305593A1 (en) | 1999-04-15 |
AU1185999A (en) | 1999-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6139610A (en) | Hybrid pigment grade corrosion inhibitor compositions and procedures | |
AU2013251173B2 (en) | Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide | |
US8722147B2 (en) | Corrosion resistant primer coating | |
CA2587714C (en) | Anticorrosive coating compositions | |
CA2330093C (en) | Flowable and pumpable metallic-pigment semifinished product for the production of paints and lacquers | |
EP0331600A2 (en) | A corrosion inhibiting pigment and a process for the manufacturing thereof | |
EP0869914B1 (en) | Pigment grade corrosion inhibitor hybrid compositions and procedures | |
US4808231A (en) | Inhibitive treatment for aluminum pigments | |
WO1999018044A1 (en) | Hybrid pigment grade corrosion inhibitor compositions and procedures | |
KR20200049727A (en) | Anti-corrosive pigment and usage thereof | |
JP5175472B2 (en) | Production method of hydrocalumite | |
CN113462199A (en) | Preparation method of inorganic oxide pigment filler loaded with composite corrosion inhibitor | |
CA1112433A (en) | Anti-corrosive pigment and anti-corrosive aqueous paint | |
CA1085153A (en) | Calcium-silico-zirconate primer pigment | |
CN111440469B (en) | Antirust pigment and preparation method thereof | |
Thu Thuy et al. | Effect of Zn/Al Cation Ratio on Corrosion Inhibition Capabilities of Hydrotalcites Containing Benzoate Against Carbon Steel | |
JPH0158224B2 (en) | ||
CN117264474A (en) | Anti-flash rust water-based acrylic acid anticorrosive paint and preparation method thereof | |
Thorn et al. | Il Cill liitit Ci | |
MXPA96001660A (en) | Preparation of pigme | |
AU5420490A (en) | Inhibitive treatment for metal pigments | |
JPH0444608B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09319231 Country of ref document: US |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2305593 Country of ref document: CA Ref country code: CA Ref document number: 2305593 Kind code of ref document: A Format of ref document f/p: F |
|
122 | Ep: pct application non-entry in european phase |