US3118048A - Liquid coating composition - Google Patents
Liquid coating composition Download PDFInfo
- Publication number
- US3118048A US3118048A US124796A US12479661A US3118048A US 3118048 A US3118048 A US 3118048A US 124796 A US124796 A US 124796A US 12479661 A US12479661 A US 12479661A US 3118048 A US3118048 A US 3118048A
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- United States
- Prior art keywords
- pigment
- metal
- coating
- oxidation potential
- substrate
- Prior art date
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- Expired - Lifetime
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- 239000007788 liquid Substances 0.000 title claims description 50
- 239000008199 coating composition Substances 0.000 title claims description 40
- 239000000049 pigment Substances 0.000 claims description 128
- 229910052751 metal Inorganic materials 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 60
- 239000011248 coating agent Substances 0.000 claims description 58
- 238000007254 oxidation reaction Methods 0.000 claims description 50
- 230000003647 oxidation Effects 0.000 claims description 49
- 230000007797 corrosion Effects 0.000 claims description 42
- 238000005260 corrosion Methods 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000013270 controlled release Methods 0.000 claims description 8
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- 229920005989 resin Polymers 0.000 description 50
- 239000011347 resin Substances 0.000 description 50
- 239000000203 mixture Substances 0.000 description 47
- 239000000956 alloy Substances 0.000 description 28
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000463 material Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- 239000003981 vehicle Substances 0.000 description 16
- 238000003466 welding Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 239000013008 thixotropic agent Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229920000180 alkyd Polymers 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 238000004210 cathodic protection Methods 0.000 description 10
- 239000011253 protective coating Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000002274 desiccant Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000013032 Hydrocarbon resin Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920006270 hydrocarbon resin Polymers 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910000979 O alloy Inorganic materials 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- IRFCNWQWXDPBID-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;propane-1,2,3-triol Chemical group OCC(O)CO.OC(=O)C1=CC=CC(C(O)=O)=C1 IRFCNWQWXDPBID-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 241000212977 Andira Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- 239000004860 Dammar gum Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000043158 Lens esculenta Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 108010038629 Molybdoferredoxin Proteins 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-UHFFFAOYSA-N Triricinolein Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCC(O)CCCCCC)COC(=O)CCCCCCCC=CCC(O)CCCCCC ZEMPKEQAKRGZGQ-UHFFFAOYSA-N 0.000 description 1
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- GBROPGWFBFCKAG-UHFFFAOYSA-N benzochrysene Natural products C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000001039 zinc pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09D5/24—Electrically-conducting paints
Definitions
- Corrosion of a metallic substrate is primarily an electrochemical phenomena wherein the metallic component of the substrate undergoes an oxidation reaction involving the loss of electrons and a chan e in a valence.
- the ease with which a particular metal or alloy corrodes is a function of an electrochemical activity which is conveniently expressed as an oxidation potential relative to the hydrogen-hydrogen ion couple. Protection against corrosion may be achieved by placing in intimate contact with the base a metal having an oxidation potential greater than the base so as to provide a source which is oxidized more readily than the base.
- a well known example of a protective coating of this type is a liquid coating composition including a finely divided metallic pigment, such as zinc, dispersed in a vehicle of a film forming binder which is employed to cause the pigment to adhere to a suitable substrate, for example ferrous alloys, such as steel.
- Iron has an oxidation potential of about +0.44 volt while zinc, for example, has an oxidation potential of about +0163 volt, and thus it can be seen that the zinc which is in intimate contact with the iron will operate galvanically to protect the iron from corrosion by giving off electrons, i.e., become oxidized before oxidation of the iron substrate.
- metals hi h in the electromotive series are too active to be employed per se in corrosion resistant coatings of the type above described, and these metals include, for example, cesium, sodium and the like. It has been discovered in accordance with the present invention that alloys of the metals high in the electromotive series may be employed in relatively small amounts to improve the overall corrosion protection of a liquid coating composition.
- Another object of the present invention is the provision or" a liquid coating composition of the type described providing superior corrosion resistant properties for an extended period of time and which when dried on a suitable substrate provide for Weldability thereof.
- Still another object of the present invention is the provision of a liquid coating composition including a component capable of acting as a thixotropic agent and which does not materially interfere with the weldability or corrosion protection of the dried coating.
- a further object of the present invention is the provision of a liquid coating composition for application to a metal substrate for providing, when dried thereon, a Weld- 2 able and corrosion resistant coating, and wherein the liquid composition includes a finely divided metallic dust having an oxidation potential greater than the substrate and a finely divided alloy containing at least one metal having an oxidation potential greater than that of the metallic dust.
- one of the prime considerations involves the relationship between the metallic pigment and the metal constitutents of the substrate.
- the alkali metals appear to be most advantageous, however, the action of such metals, because of their high reactivity, is far too fast to provide a protective coating capable of imparting galvanic or cathodic protection for any extended period of time.
- materials such as magnesium, alumium, titanium, zinc, iron, cadmium, cobalt, nickel, molybdenum, and copper represent materials which may be employed, provided the oxidation potential of the substrate is less than that of the particular material.
- the metal in the coating be in a finely divided state for ease of distribution in the film forming resin and for uniformity of application to the substrate. It has been found in accordance with the present invention that particle sizes in excess of about microns may be too large to provide an adherent coating capable of providing corrosion and galvanic protection for extended periods of time. With particle sizes in excess of about 150 microns, oxidation of the pigment particle during the course of its sacrificial action results in the creation of sizable voids in the coating, and ultimately the coating may peel and crack from the surface. It has been found in accordance with the present invention that advantageous results have been produced with particle sizes whose average ranges from about two microns up to about sixty microns. In instances where it is desired to provide corrosion and galvanic protection as well as Weld-ability, it is preferred to employ the larger sized particles for reasons which will be discussed more fully hereinbelow.
- the finely divided metallic component of the protective coating is dispersed in a resin capable of adhering to the metallic base or substrate for maintaining the finely divided metal on the base, and generally operates as a carrier for the metallic component.
- the resin also operates, to some extent, to provide mechanical and physical protection of the base by virtue of the film which is formed as the resin solidifies.
- Resins which have been employed and produced satisfactory results in accordance with the present invention include phenolic modified and maleic modified alkyd resins, the glycerol isophthalate group of resins, phenolic or maleic modifications thereof, the epoxy resins, glyptal resins, ester gums and damrnar gums, polyester resins, polybutene resins, polyurethanes, and hydrocarbon resins such as methylated paraffinic hydrocarbons, polydiene, polyturpene, polyethylene and polypropylene resins, or mixtures of the above resins.
- alkyds it is preferred that the alkyd have an acid number below about ten and preferably about five.
- alkyds may be included linseed modified alkyds, soya modified alkyds, mixtures of bodied linseed oil and alkyds, or any of the well known oil or acid modified alkyds having an acid number as previously mentioned.
- each of the resins previously mentioned in the dried state exhibit a characteristic resistance, that is, the resistance of the film formed by each of the resins varies from one resin to the next.
- the protective coating in accordance with the present invention may be salaries welded and is employed to provide galvanic protection, it is desirable to control the amount of conductive material in the dried coating in order to provide a protective coating having the desired electrical characteristics insofar as weldability and galvanic protection are concerne Satisfactory results have been achieved in accordance with the present invention by employing a composition wherein the metallic pigment constitutes approximately 76% to 97% of the total solids of the composition in order to provide adequate galvanic action or cathodic protection of the coated part.
- the welding properties of the dried coating appear to be greatly influenced by the ratio of resin or hinder solids to the amount of conductive pigments present, and satisfactory results have been obtained with compositions wherein the ratio of resin to pigment in the composition falls within the range from a low of 12 parts resin to or parts pigment to a high of about 4 parts resin to parts pigment, that is, with the pigment present in the amount of 5 to 20 times the amount of resin.
- the resin to pigment ratio may be as low as 1:1.
- the coating possesses an electrical resistance which is too high for efficient welding and may be too high to provide efiicient galvanic and cathodic protection.
- the coating contains insufficient resin to provide a mechanically stable coating.
- the gradual consummation of pigment during the course of protection creates voids, and the coating becomes dimensionally unstable exhibiting cracks and blisters after continued ex posure to the elements and particularly salt sprays, for example.
- the particle size of the pigment is of importance because of the dimensional stability of the coating as Well as the durability of the coating. From the standpoint of durability, and for a given resin to pigment ratio, a finer particle size is the desired condition since the particles of pigment are small and as they are consumed during the course of their action the mechanical strength of the coating is not materially reduced. In contrast to this, it has been found, for a given resin to pigment ratio, that larger particles operate more satisfactorily from the standpoint of weldability since the larger particles provide electrically conductive paths through the coating in which the paths have less electrical resistance than is the case with relatively small particles. This situation is analogous to a comparison between a relatively fine conductive wire and a relatively thick conductive wire wherein both wires are of the same material. As was mentioned previously, it is preferred that the particle size be in the range of about two microns to about seventy-five, or that the pigment have an average size falling within the above range.
- One feature of the present invention relates to the use of a controlled amount of finely divided alloy vhich operates to increase significantly the duration of the corrosion protection of a metallically pigmented coating composition over that achieved with coating compositions wherein the alloy is not present. It has been found in accordance with the present invention that the addition to the composition of about 0.5% to about 6%, and preferably about 1% to 3% of a finely divided alloy operates to increase the duration of protection by a factor of about l0.
- the metallic pigment portion of the coating composition selected from materials having an oxidation potential higher than that of the base metal material, for example, in the case of ferrous bases, cadmium, zinc, manganese, aluminum and magnesium may be employed. As a practical matter many compositions include Zinc as the metallic pigment since zinc operates satisfactorily with most of the base materials, especially the ferrous base materials.
- alloys containing at least one metal higher in the electromotive series than the metallic pigment operate to prolong the effective corrosion resistance of the protective coating. While the exact mechanics of such improved results are not. completely understood at the present time, it may be postulated that the alloys, for example, a magnesium-aluminum alloy, operate to effect a controlled release of electrons during the corrosion process thus providing enhanced protection of the base metal. Since the alloy includes at least one metal capable of releasing electrons at a rate faster than that of the sacrifical metallic pigment, the combined action of the alloy and the sacrificial pigment, in fact, operates to extend the life of the coating.
- the presence of the alloy mate rials with the metallic pigment does not appreciably alter the weldability of the coating.
- the weldability since about 0.5% to 6% by weight of an alloy material in finely divided form, as previously noted, operates to de crease the electrical resistance of tie coating thereby effecting a reduction in the current required for weldmg.
- liquid vehicles including a solvent in a synthetic resin component of the type previously mentioned
- certain components which react with the finely divided pigment, which reaction may use up or waste a substantial portion of the pigment or nullify the utility thereof for the desired corrosion resistance, cathodic protection, and electrical conductivity particularly in the event that the coated parts are thereafter to be welded or spot: welded.
- the several dis es resulting from a reaction between the metallic pigment and the reactive components of the liquid vehicle are disclosed in copendlng application Serial No. 779,541, filed December 11, 8 and assigned to the same assignee.
- a moisture absorption component or desiccant is added to the vehicle along with a basic material capable of reacting with the acids in the vehicle prior to addition of the pigment. Satisfactory results in rendering any reactive components of the vehicle inactive have been produced by the addition of plaster of Paris, calcium oxide in the form of quick lime, anhydrous silicate gel, potassium hydroxide powder, or other suitable materials.
- thixotropic agents may be added for adjusting and improving the final rheology of the composition.
- Components such as castor oil, soap, Thixcin are well known thixotropic agents or thickeners employed alone or in combination with such materials as lead, cobalt, manganese and zirconium naphthenates, the latter materials being employed as driers.
- Ciroxin which is believed to be a hydrogenated castor oil.
- castor oil is 70 to 95% triricinolein, that is, the glyceride of ricinoleic acid.
- a hydrogenated product operates quite satisfactorily to maintain the metallic portion of the composition uniformly and evenly distributed therethrough in order to effect a substantial increase in the shelf life of the premixed or ready mixed liquid coating composition.
- the advantage of using Ciroxin stems from the fact that the Ciroxin is easily added to the mixture during formulation thereof by employing heat.
- compositions embodying and for practicing this invention the following may be noted:
- Hydrocarbon resin available under the trademark Piccopal
- Phenolic modified resin (50% solution) 360.0 Solvent 120.0 Thixotropic agent (Ciroxin) 7.0 Anti-gassing agent (CaO) 3.0 Desiccant (silica gel) 3.0 Aluminum 5.0
- Glycerol Isophthalate resin (50% solution) 308.0 Al Paste 36.0
- finely divided iron may be used as the pigment portion of the composition and an alloy of copper and magnesium or molybdenum iron may be emphasized to enhance or increase the duration of the corrosion protection.
- finely divided chromium may be employed as the pigment portion with about 0.5% to about 6% of magnesium-nickel alloy. It is preferred however to employ the combination of zinc with a magnesiumaluminum alloy since these materials are readily available commercially and operate to provide satisfactory results with most base materials.
- Ciroxin The above specific formulations employing Ciroxin were prepared by adding the Ciroxin to the solvent and heating the resultant mixture to about to 280 F. at which point the Ciroxin goes into solution with the solvent. Thereafter the desiccant, the anti-gassing agents, and the resinous film forming components are added, while mixing and maintaining the solution at a temperature of 120 F. As the solution cools down, it takes on a cloudy appearance. Thereafter the metallic pigment and finely divided alloys are added and the mixture is again stirred to provide a uniform dispersion.
- the reactive components of the vehicle are neutralized or otherwise rendered inactive prior to the addition of the metallic pigment. For this reason, there is very little, if any, pigment present in the form of nonconductive pigment, and essentially all of the pigment present in the composition is unreacted and available as an active component of the final coating. Stated another way, the entire amount of pigment present in the composition is present in the form of electroconductivc pigment as opposed to salts thereof.
- One feature of the present invention which is of interest is the healing action that takes place on the exposed area of the base metal attributable to the deposition of salts on the exposed area.
- This feature is of considerable interest with respect to corrosion protection extending over long periods of time. It has been found that with proper resin to pigment ratios, the consumption of the active components of the protective coating operate to deposit or otherwise form a metal salt or an insoluble zinc hydroxide on those portions of the base member which have been exposed.
- the metal salts are relatively inert to further reaction under ordinary conditions and operate to form an inert coating on those portions of the base material which may have been exposed in order to provide protection against corrosion even though the film may have been chipped away or otherwise removed from that particular portion of the surface.
- the healing action above described is a characteristic of a properly formulated paint composition, and each of the compositions specifically set forth above operates to provide the above healing action.
- each article are coated with one of the compositions previously described, and the coating is allowed to dry. Thereafter, the articles are placed in contact such that the areas to be spot welded are overlapping and a welding current is passed through the articles to fuse the articles together in the area of each spot weld. Passage of a welding current through the articles and the coating therebetween operates to effect a fusion of the metallic pigment of the coating in the area of the weld.
- compositions above described for providing cathodic or galvanic protection as well as providing a weldable surface operate quite satisfactorily due to the proper relationship of resin to pigment ratio and percentage of metallic solids to total solids as previously described. Additionally, selecting the size of the pigment as above described operates to provide a coating which may be welded satisfactorily.
- Enhanced or improved corrosion protection has been achieved by the addition of an alloy which operates to effect a controlled release of electrons during the course of sacrificial action of the components of the composition. It is also possible in accordance with this invention to provide ready mixed or premixed compositions which may be stored without rupture of the container, and wherein the shelf life thereof has been extended by provision of suitable thixotropic agents which operate to disperse the metallic components of the composition evenly and uniformly therethrough.
- a liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon comprising a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming resinous component for ad.- hering said pigment to said substrate, a finely divided metallic alloy dispersed in said coating composition including a first metal having oxidation potential greater than that of said pigment and a.
- said second metal having an oxidation potential less than that of said pigment, said sec ond metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, and the ratio of resin to pigment in said liquid coating composition falling approximately within the range of 1:1 to 1:20.
- a liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon, comprising a finely divided solid inorganic water insoluble metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming resinous component for adhering said pigment to said substrate, said film forming component being selected from the class consisting of phenolic, maleic and linse d oil modified alkyd resins, glycerol isophthalate resins and phenolic and maleic modifications thereof, epoxy resins, glyptal resins, ester and dammar gum resins, polybutene resins, polyurethane resins, methylated parafinic hydrocarbon resins, polydiene, polyturpene, polyethylene and polypropylene resins, and compatible mixtures thereof, a finely divided metallic alloy
- a ready mixed liquid coating composition for plication to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon comprising a finely divided solid inorganic water insoluble metallic electroconductive pigment having an oxi ation potential greater than the oxidation potential of said substrate, said pigment being un 'ornily dispersed in a liquid vehicle system therefor including a solvent and a synthetic film formin resinous component and driers therefor for adhering said pigment to said substrate, said vehicle having reactive components susceptible to chemical reaction and combination with said pigment, a finely divided metallic alloy dispersed in said coating composition including a first metal having oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than it of said pigment, said second metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, the ratio of resin tol
- a liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion rcsistant and electroconductive weldable coating thereon comprising a finely divided solid inorganic water insolule metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming a resinous component for adhering said pigment to said substrate, a finely divided metallic alloy present in said coating composition in an amount of 0.5% to 6% by weight and including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said second metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, the ratio of resin to pigment in said liquid coating composition falling approximately
- the method of spot welding metallic articles which comprises applying to a surface of at least one of the articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic waterinsoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic water-insoluble film forming resin component for providing said continuous film for corrosion resistance, a finely divided alloy material dispersed in said composition including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy operating to increase the electrical conductivity of said protective coating during welding and increasing the corrosion protection provided by said electroconductive pigment, the ratio of said resin to said pigment in the liquid coating composition falling
- the method of spot welding metallic articles which comprises applying to at least one surface of said articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic water insoluble film forming resin component for providing said continuous film for corrosion resistance, a finely divided alloy material dispersed in said compositions including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy being present in an amount of about 0.5% to 6% by weight of said liquid composition, said pigment being present in an amount of about to 97% of the total solids in the dried coating,
- the method of spot welding metallic articles which comprises applying to opposite surfaces of the articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid vehicle system therefor including a solvent and a synthetic water-insoluble film forming resin component for providing said film for corrosion resistance, said vehicle having reactive components susceptible to chemical reaction and combination with said pigment, a finely divided alloy material dispersed in said compositions including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy being present in an amount of about 0.5% to 6% by weight of said liquid composition, said alloy operating to increase the electrical conductivity of said
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Description
United States Patent 3,118,048 LllQUiD @GAllllNG CUMPOSETION .l'ohn lit. Fisher, .ha, and Ira W. Dance, Dayton, Ohio, assignors to Industrial Metal Frotectives, llnc., Dayton, @hio, acorporation of Delaware No Drawing. Filed July is, H61, Ser. No. 124,796 9 Claims. {CL M l-92) This invention relates to liquid coating compositions for providing corrosion resistant coatings on metal parts and the like, and more particularly to an improved metallically pigmented, electrically conductive liquid coating composition for providing an improved anticorrosive coat ing on metal parts so that such parts, when coated, may be welded together.
Corrosion of a metallic substrate is primarily an electrochemical phenomena wherein the metallic component of the substrate undergoes an oxidation reaction involving the loss of electrons and a chan e in a valence. The ease with which a particular metal or alloy corrodes is a function of an electrochemical activity which is conveniently expressed as an oxidation potential relative to the hydrogen-hydrogen ion couple. Protection against corrosion may be achieved by placing in intimate contact with the base a metal having an oxidation potential greater than the base so as to provide a source which is oxidized more readily than the base. The usual arrangement involves positioning such a metal of higher oxidation potential in close contact with the base, as by coating and the like, so as to provide a metal on that surface of the base which is capable of providing a readily oxidizable metal operating to protect the base. A Well known example of a protective coating of this type is a liquid coating composition including a finely divided metallic pigment, such as zinc, dispersed in a vehicle of a film forming binder which is employed to cause the pigment to adhere to a suitable substrate, for example ferrous alloys, such as steel. Iron has an oxidation potential of about +0.44 volt while zinc, for example, has an oxidation potential of about +0163 volt, and thus it can be seen that the zinc which is in intimate contact with the iron will operate galvanically to protect the iron from corrosion by giving off electrons, i.e., become oxidized before oxidation of the iron substrate.
Many of the metals hi h in the electromotive series are too active to be employed per se in corrosion resistant coatings of the type above described, and these metals include, for example, cesium, sodium and the like. It has been discovered in accordance with the present invention that alloys of the metals high in the electromotive series may be employed in relatively small amounts to improve the overall corrosion protection of a liquid coating composition.
Accordingly, it is a primary object of the present invention to provide a novel liquid coating composition which is capable of providing increased corrosion protection when applied to a substrate and dried thereon, and wherein the protection afforded by the dried coating ex tends for relatively long periods of time.
Another object of the present invention is the provision or" a liquid coating composition of the type described providing superior corrosion resistant properties for an extended period of time and which when dried on a suitable substrate provide for Weldability thereof.
Still another object of the present invention is the provision of a liquid coating composition including a component capable of acting as a thixotropic agent and which does not materially interfere with the weldability or corrosion protection of the dried coating.
A further object of the present invention is the provision of a liquid coating composition for application to a metal substrate for providing, when dried thereon, a Weld- 2 able and corrosion resistant coating, and wherein the liquid composition includes a finely divided metallic dust having an oxidation potential greater than the substrate and a finely divided alloy containing at least one metal having an oxidation potential greater than that of the metallic dust.
Other objects and advantages of the invention will be apparent from the following description and the appended claims.
Insofar as corrosion and galvanic protection are concerned, one of the prime considerations involves the relationship between the metallic pigment and the metal constitutents of the substrate. Considered from the viewpoint of released electrons, the alkali metals appear to be most advantageous, however, the action of such metals, because of their high reactivity, is far too fast to provide a protective coating capable of imparting galvanic or cathodic protection for any extended period of time. As a practical matter, materials such as magnesium, alumium, titanium, zinc, iron, cadmium, cobalt, nickel, molybdenum, and copper represent materials which may be employed, provided the oxidation potential of the substrate is less than that of the particular material.
It is preferred that the metal in the coating be in a finely divided state for ease of distribution in the film forming resin and for uniformity of application to the substrate. It has been found in accordance with the present invention that particle sizes in excess of about microns may be too large to provide an adherent coating capable of providing corrosion and galvanic protection for extended periods of time. With particle sizes in excess of about 150 microns, oxidation of the pigment particle during the course of its sacrificial action results in the creation of sizable voids in the coating, and ultimately the coating may peel and crack from the surface. It has been found in accordance with the present invention that advantageous results have been produced with particle sizes whose average ranges from about two microns up to about sixty microns. In instances where it is desired to provide corrosion and galvanic protection as well as Weld-ability, it is preferred to employ the larger sized particles for reasons which will be discussed more fully hereinbelow.
The finely divided metallic component of the protective coating is dispersed in a resin capable of adhering to the metallic base or substrate for maintaining the finely divided metal on the base, and generally operates as a carrier for the metallic component. The resin also operates, to some extent, to provide mechanical and physical protection of the base by virtue of the film which is formed as the resin solidifies.
Resins which have been employed and produced satisfactory results in accordance with the present invention include phenolic modified and maleic modified alkyd resins, the glycerol isophthalate group of resins, phenolic or maleic modifications thereof, the epoxy resins, glyptal resins, ester gums and damrnar gums, polyester resins, polybutene resins, polyurethanes, and hydrocarbon resins such as methylated paraffinic hydrocarbons, polydiene, polyturpene, polyethylene and polypropylene resins, or mixtures of the above resins. In the case of alkyds, it is preferred that the alkyd have an acid number below about ten and preferably about five. Within this group of alkyds may be included linseed modified alkyds, soya modified alkyds, mixtures of bodied linseed oil and alkyds, or any of the well known oil or acid modified alkyds having an acid number as previously mentioned.
it is noted that each of the resins previously mentioned in the dried state exhibit a characteristic resistance, that is, the resistance of the film formed by each of the resins varies from one resin to the next. Because the protective coating in accordance with the present invention may be salaries welded and is employed to provide galvanic protection, it is desirable to control the amount of conductive material in the dried coating in order to provide a protective coating having the desired electrical characteristics insofar as weldability and galvanic protection are concerne Satisfactory results have been achieved in accordance with the present invention by employing a composition wherein the metallic pigment constitutes approximately 76% to 97% of the total solids of the composition in order to provide adequate galvanic action or cathodic protection of the coated part. in the case of resins having a high dielectric constant, i.e., those having a high resistance, such as polyurethane and polyester resins, it is preferred to employ about 90% to 97% conductive solids in the composition, while in the case of epoxy type resins the use of between 80% to 90% conductive solids operates in a satisfactory manner. With resins of the alkyd type, previously mentioned, approximately 75% to 85% conductive solids in the composition produce acceptable results.
A convenient method of determining the overall efiiciency of the film constants in testing the electrical resistance of the coating as described in detail in the military specification MlL-P26915A (USAF). All of the above percentages operate satisfactorily to provide a coating having an electrical resistance which is less than the ohms per square inch thickness as set forth in the above identified military specification.
Additionally, the welding properties of the dried coating appear to be greatly influenced by the ratio of resin or hinder solids to the amount of conductive pigments present, and satisfactory results have been obtained with compositions wherein the ratio of resin to pigment in the composition falls within the range from a low of 12 parts resin to or parts pigment to a high of about 4 parts resin to parts pigment, that is, with the pigment present in the amount of 5 to 20 times the amount of resin. With a composition including polybutane type resins, the resin to pigment ratio may be as low as 1:1.
At ratios above those previously mentioned, that is, with the resin present in excess of 1:5, the coating possesses an electrical resistance which is too high for efficient welding and may be too high to provide efiicient galvanic and cathodic protection. On the other hand, with too high a ratio of pigment, for example in excess of 1:20, the coating contains insufficient resin to provide a mechanically stable coating. Additionally, with such relatively large proportions of pigment, the gradual consummation of pigment during the course of protection creates voids, and the coating becomes dimensionally unstable exhibiting cracks and blisters after continued ex posure to the elements and particularly salt sprays, for example.
As was mentioned previously, the particle size of the pigment is of importance because of the dimensional stability of the coating as Well as the durability of the coating. From the standpoint of durability, and for a given resin to pigment ratio, a finer particle size is the desired condition since the particles of pigment are small and as they are consumed during the course of their action the mechanical strength of the coating is not materially reduced. In contrast to this, it has been found, for a given resin to pigment ratio, that larger particles operate more satisfactorily from the standpoint of weldability since the larger particles provide electrically conductive paths through the coating in which the paths have less electrical resistance than is the case with relatively small particles. This situation is analogous to a comparison between a relatively fine conductive wire and a relatively thick conductive wire wherein both wires are of the same material. As was mentioned previously, it is preferred that the particle size be in the range of about two microns to about seventy-five, or that the pigment have an average size falling within the above range.
One feature of the present invention relates to the use of a controlled amount of finely divided alloy vhich operates to increase significantly the duration of the corrosion protection of a metallically pigmented coating composition over that achieved with coating compositions wherein the alloy is not present. It has been found in accordance with the present invention that the addition to the composition of about 0.5% to about 6%, and preferably about 1% to 3% of a finely divided alloy operates to increase the duration of protection by a factor of about l0. The metallic pigment portion of the coating composition selected from materials having an oxidation potential higher than that of the base metal material, for example, in the case of ferrous bases, cadmium, zinc, manganese, aluminum and magnesium may be employed. As a practical matter many compositions include Zinc as the metallic pigment since zinc operates satisfactorily with most of the base materials, especially the ferrous base materials.
It has been discovered in accordance with the present invention that alloys containing at least one metal higher in the electromotive series than the metallic pigment operate to prolong the effective corrosion resistance of the protective coating. While the exact mechanics of such improved results are not. completely understood at the present time, it may be postulated that the alloys, for example, a magnesium-aluminum alloy, operate to effect a controlled release of electrons during the corrosion process thus providing enhanced protection of the base metal. Since the alloy includes at least one metal capable of releasing electrons at a rate faster than that of the sacrifical metallic pigment, the combined action of the alloy and the sacrificial pigment, in fact, operates to extend the life of the coating.
As will be understood, the presence of the alloy mate rials with the metallic pigment does not appreciably alter the weldability of the coating. As a matter of fact there appears to be a slight improvement in the weldability since about 0.5% to 6% by weight of an alloy material in finely divided form, as previously noted, operates to de crease the electrical resistance of tie coating thereby effecting a reduction in the current required for weldmg.
In the case of liquid vehicles including a solvent in a synthetic resin component of the type previously mentioned, there may be present in the solvent and/ or film forming resin certain components which react with the finely divided pigment, which reaction may use up or waste a substantial portion of the pigment or nullify the utility thereof for the desired corrosion resistance, cathodic protection, and electrical conductivity particularly in the event that the coated parts are thereafter to be welded or spot: welded. The several dis es resulting from a reaction between the metallic pigment and the reactive components of the liquid vehicle are disclosed in copendlng application Serial No. 779,541, filed December 11, 8 and assigned to the same assignee.
In order to provide a ready mixed composition which may be stored without rupture of the container because of hydrogen evolution during the reaction between the components of the liquid vehicle and the metallic pigment, it is preferred to employ materials capable of effectively neutralizing the reactive components of the vehicle prior to adding the pigment thereto. To this end, a moisture absorption component or desiccant is added to the vehicle along with a basic material capable of reacting with the acids in the vehicle prior to addition of the pigment. Satisfactory results in rendering any reactive components of the vehicle inactive have been produced by the addition of plaster of Paris, calcium oxide in the form of quick lime, anhydrous silicate gel, potassium hydroxide powder, or other suitable materials. in addition to the above desiccant and acid neutralizing agents, thixotropic agents may be added for adjusting and improving the final rheology of the composition. Components such as castor oil, soap, Thixcin are well known thixotropic agents or thickeners employed alone or in combination with such materials as lead, cobalt, manganese and zirconium naphthenates, the latter materials being employed as driers.
In addition to the preceding thixotropic agents, extremely satisfactory results have been produced by employing agents available commercially under the trademark Ciroxin, which is believed to be a hydrogenated castor oil. As is well known, castor oil is 70 to 95% triricinolein, that is, the glyceride of ricinoleic acid. A hydrogenated product operates quite satisfactorily to maintain the metallic portion of the composition uniformly and evenly distributed therethrough in order to effect a substantial increase in the shelf life of the premixed or ready mixed liquid coating composition. The advantage of using Ciroxin stems from the fact that the Ciroxin is easily added to the mixture during formulation thereof by employing heat. In contrast to this, many of the other thixotropic agents heretofore employed require a ball millin operation which consumes considerable time in formulation techniques. Additionally, the Ciroxin does not interfere materially with the charcteristics of the final coating, and in fact, improves the welda'bility by providing a more uniform dispersion of pigment throughout the dried coating.
Merely as illustrative of compositions embodying and for practicing this invention, the following may be noted:
Hydrocarbon resin (available under the trademark Piccopal) 18.6 Solvent 124.6 Thixotropic agent (Ciroxin) 7.9 Epoxy ester resin (50% solution in xylene) 309.5 Anti-gassing agent (CaO) 3.0 Desiccant (silica gel) 3.0 Aluminum 6.0 M /Al Alloy 5050 alloy .s 24.5 Solvent 92.9 Powdered Metallic Pigment (Zinc) 13940 Hydrocarbon resin (available under trademark Piccopal) 14.2 Solvent 94.9 Thixotropic agent (Ciroxin) 6.0 Epoxy ester resin (50% solution in xylene) 235.6 Anti-gassing agent (CaO) 2.2 Desiccant (silica gel) 2.2 Aluminum 4.5 Mg/Al alloy 60-40 alloy 18.7 Solvent 230.7 Powdered metallic pigment (zinc) 106 1.0
III.
Phenolic modified resin (50% solution) 360.0 Solvent 120.0 Thixotropic agent (Ciroxin) 7.0 Anti-gassing agent (CaO) 3.0 Desiccant (silica gel) 3.0 Aluminum 5.0
Alloy 20.0 Pigment 1400.0
Maleic modified alkyd (50% solution in xylene) 400.0 Solvent 194.0 Lead Napthenate (drier) 2.0 Cobalt Napthenate (drier) 2.0 Thixotropic agent (Thixcin) 3.0 A1 pigment 300.0 Zinc pigment 700.0 Alloy Mg-Al alloy (65-35) 45.0
Glycerol Isophthalate resin (50% solution) 308.0 Al Paste 36.0
Solvent 149.0 Lead Napthenate 3.0 Cobalt Napthenate 1.0 Desiccant 1.0 Anti-gassing agent 1.0 Alloy 14.0 Thixotropic agent 15.0 Pigment 1000.0
Polyurethane 40.0 Solvent 40.0 Thixotropic agent 3.0 Alloy 44.0 Pigment 800.0
In the case of a base member formed of a nickel, finely divided iron may be used as the pigment portion of the composition and an alloy of copper and magnesium or molybdenum iron may be emphasized to enhance or increase the duration of the corrosion protection. For ferrous base materials, finely divided chromium may be employed as the pigment portion with about 0.5% to about 6% of magnesium-nickel alloy. It is preferred however to employ the combination of zinc with a magnesiumaluminum alloy since these materials are readily available commercially and operate to provide satisfactory results with most base materials.
The above specific formulations employing Ciroxin were prepared by adding the Ciroxin to the solvent and heating the resultant mixture to about to 280 F. at which point the Ciroxin goes into solution with the solvent. Thereafter the desiccant, the anti-gassing agents, and the resinous film forming components are added, while mixing and maintaining the solution at a temperature of 120 F. As the solution cools down, it takes on a cloudy appearance. Thereafter the metallic pigment and finely divided alloys are added and the mixture is again stirred to provide a uniform dispersion.
It is to be noted that by adding the desiccant and the anti-gasing agent to the vehicle prior to addition of the metallic pigment, the reactive components of the vehicle are neutralized or otherwise rendered inactive prior to the addition of the metallic pigment. For this reason, there is very little, if any, pigment present in the form of nonconductive pigment, and essentially all of the pigment present in the composition is unreacted and available as an active component of the final coating. Stated another way, the entire amount of pigment present in the composition is present in the form of electroconductivc pigment as opposed to salts thereof.
One feature of the present invention which is of interest is the healing action that takes place on the exposed area of the base metal attributable to the deposition of salts on the exposed area. This feature is of considerable interest with respect to corrosion protection extending over long periods of time. It has been found that with proper resin to pigment ratios, the consumption of the active components of the protective coating operate to deposit or otherwise form a metal salt or an insoluble zinc hydroxide on those portions of the base member which have been exposed. The metal salts are relatively inert to further reaction under ordinary conditions and operate to form an inert coating on those portions of the base material which may have been exposed in order to provide protection against corrosion even though the film may have been chipped away or otherwise removed from that particular portion of the surface. The healing action above described, is a characteristic of a properly formulated paint composition, and each of the compositions specifically set forth above operates to provide the above healing action.
If the coated parts are to be welded, at least one surface and preferably both surfaces of each article are coated with one of the compositions previously described, and the coating is allowed to dry. Thereafter, the articles are placed in contact such that the areas to be spot welded are overlapping and a welding current is passed through the articles to fuse the articles together in the area of each spot weld. Passage of a welding current through the articles and the coating therebetween operates to effect a fusion of the metallic pigment of the coating in the area of the weld.
The improved compositions above described for providing cathodic or galvanic protection as well as providing a weldable surface operate quite satisfactorily due to the proper relationship of resin to pigment ratio and percentage of metallic solids to total solids as previously described. Additionally, selecting the size of the pigment as above described operates to provide a coating which may be welded satisfactorily.
Enhanced or improved corrosion protection has been achieved by the addition of an alloy which operates to effect a controlled release of electrons during the course of sacrificial action of the components of the composition. It is also possible in accordance with this invention to provide ready mixed or premixed compositions which may be stored without rupture of the container, and wherein the shelf life thereof has been extended by provision of suitable thixotropic agents which operate to disperse the metallic components of the composition evenly and uniformly therethrough.
While the processes and products herein described constitute a preferred embodiment of the invention, it is to be understood that the invention is not limited to these precise processes and products, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims.
What is claimed is:
1. A liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon, comprising a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming resinous component for ad.- hering said pigment to said substrate, a finely divided metallic alloy dispersed in said coating composition including a first metal having oxidation potential greater than that of said pigment and a. second metal having an oxidation potential less than that of said pigment, said sec ond metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, and the ratio of resin to pigment in said liquid coating composition falling approximately within the range of 1:1 to 1:20.
2. The composition as set forth in claim 1 wherein the metallic alloy is present in an amount of approximately 0.5% to 6% by weight of the liquid composition.
3. A liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon, comprising a finely divided solid inorganic water insoluble metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming resinous component for adhering said pigment to said substrate, said film forming component being selected from the class consisting of phenolic, maleic and linse d oil modified alkyd resins, glycerol isophthalate resins and phenolic and maleic modifications thereof, epoxy resins, glyptal resins, ester and dammar gum resins, polybutene resins, polyurethane resins, methylated parafinic hydrocarbon resins, polydiene, polyturpene, polyethylene and polypropylene resins, and compatible mixtures thereof, a finely divided metallic alloy dispersed in said coating composition including a first ietal having oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said second metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, and the ratio of resin to pignent in said liquid coating composition falling approximately within the range of 1:1 to 1:20.
4. A ready mixed liquid coating composition for plication to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon, comprising a finely divided solid inorganic water insoluble metallic electroconductive pigment having an oxi ation potential greater than the oxidation potential of said substrate, said pigment being un 'ornily dispersed in a liquid vehicle system therefor including a solvent and a synthetic film formin resinous component and driers therefor for adhering said pigment to said substrate, said vehicle having reactive components susceptible to chemical reaction and combination with said pigment, a finely divided metallic alloy dispersed in said coating composition including a first metal having oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than it of said pigment, said second metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, the ratio of resin to pigment in said liquid coating composition falling approximately within the range of 1:1 to 1:20, and said pigment being present in the liquid composition as the elemental metal and uncombined and unreacted with other components of said composition.
5. A liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion rcsistant and electroconductive weldable coating thereon, comprising a finely divided solid inorganic water insolule metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic film forming a resinous component for adhering said pigment to said substrate, a finely divided metallic alloy present in said coating composition in an amount of 0.5% to 6% by weight and including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said second metal acting as an agent efecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, the ratio of resin to pigment in said liquid coating composition falling approximately within the range of 1:1 to 1:26, and said pigment having an average particle size falling in the range of two to sixty microns.
6. A ready mixed liquid coating composition for application to a metal substrate having a given oxidation potential for providing, when dried on said substrate, a corrosion resistant and electroconductive weldable coating thereon, comp ing a finely divided solid inorganic water insoluble metallic electroconductive pigment having an oxidation potential greater than the oxidation potential of said substrate, said pigment being uniformly dispersed in a liquid vehicle system therefor including a solvent and a synthetic film forming a resinous component for adhering said pigment to said substrate, said vehicle having reactive components susceptible to chemi cal reaction and combination with said pigment, a finely divided metallic alloy present in said coating composition in an amount between 0.5% and 6% by weight and including a first metal having oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said second metal acting as an agent effecting controlled release of electrons from said first metal for increasing the corrosion protection provided by said pigment, said electroconductive pigment being present in an amount of 75% to 97% of the total solids in the dried coating, the ratio of resin to pigment in said liquid coating composition falling approximately within the range of 1:1 to 1:20, said pigment being present in the liquid composition as the elemental metal and uncombined and unreacted with the other components of said composition, and said pigment having an average particle size falling in the range of two to sixty microns.
7. The method of spot welding metallic articles which comprises applying to a surface of at least one of the articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic waterinsoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic water-insoluble film forming resin component for providing said continuous film for corrosion resistance, a finely divided alloy material dispersed in said composition including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy operating to increase the electrical conductivity of said protective coating during welding and increasing the corrosion protection provided by said electroconductive pigment, the ratio of said resin to said pigment in the liquid coating composition falling approximately within the range of 1:1 to 1:20, said pigment being present in an amount of 75% to 97% of the total solids in the dried coating, contacting at least a portion of said one article with another article of metal to be welded, passing a welding current through said articles of metal and said coating thereon at the spots selected for welding, and fusing said articles together in the area of each said spot weld.
8. The method of spot welding metallic articles which comprises applying to at least one surface of said articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid binder and carrier therefor including a solvent and a synthetic water insoluble film forming resin component for providing said continuous film for corrosion resistance, a finely divided alloy material dispersed in said compositions including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy being present in an amount of about 0.5% to 6% by weight of said liquid composition, said pigment being present in an amount of about to 97% of the total solids in the dried coating, said alloy operating to increase the electrical conductivity of said protective coating during welding and increasing the corrosion protection provided by said electroconductive pigment, the ratio of said resin to said pigment in the liquid coating composition falling approximately within the range of 1:1 to 1:20, placing at least a portion of the coated surface of one article in contact with at least a portion of the surface of a second article, passing a welding current through the two articles of metal and the coating between them at the spots selected for welding, and fusing said articles and the coating between them together in the area of each spot weld.
9. The method of spot welding metallic articles which comprises applying to opposite surfaces of the articles to be welded together at least one coating of a liquid coating composition for providing, when dried upon the articles, a continuous surface coating thereover effecting corrosion resistance, weldable electroconductivity and cathodic protection, said liquid coating composition including a finely divided solid inorganic water-insoluble metallic electroconductive pigment having an oxidation potential higher than that of the metal of said metallic article for providing said conductivity and cathodic protection, said pigment being uniformly dispersed in a liquid vehicle system therefor including a solvent and a synthetic water-insoluble film forming resin component for providing said film for corrosion resistance, said vehicle having reactive components susceptible to chemical reaction and combination with said pigment, a finely divided alloy material dispersed in said compositions including a first metal having an oxidation potential greater than that of said pigment and a second metal having an oxidation potential less than that of said pigment, said alloy being present in an amount of about 0.5% to 6% by weight of said liquid composition, said alloy operating to increase the electrical conductivity of said protective coating during welding and increasing the corrosion protection provided by said electroconductive pigment, the ratio of said resin to said pigment in the liquid coating composition falling approximately within the range of 1:1 to 1:20, said pigment being present in an amount of about 75 to 97% of the total solids in the dried coating and being present in the liquid composition as the elemental metal and uncombined and unreacted with the other components of said composition, a thixotropic agent present in said composition maintaining said pigment and said alloy evenly and uniformly distributed throughout said composition in a substantially uniform manner, contacting at least a portion of one article with another article of metal to be selected, passing a welding current through the two articles to be Welded at the coating thereon at the spots selected for welding, and fusing said article to the coating thereon together in the area of each spot weld.
References Cited in the file of this patent UNITED STATES PATENTS 1,770,540 Lunn July 15, 1930 2,243,832 Bohn June 3, 1941 2,452,805 Sussembach Nov. 2, 1948 2,726,308 Cinamon Dec. 6, 1955 2,970,204 Picen et al. Jan. 31, 1961 FOREIGN PATENTS 825,910 France Dec. 16, 1937
Claims (1)
1. A LIQUID COATING COMPOSITION FOR APPLICATION TO A METAL SUBSTRATE HAVING A GIVEN OXIDATION POTENTIAL FOR PROVIDING, WHEN DRIED ON SAID SUBSTRATE, A CORROSION RESISTANT AND ELECTROCONDUCTIVE WELDABLE COATING THEREON, COMPRISING A FINELY DIVIDED SOLID INORGANIC WATER-INSOLUBLE METALLIC ELECTROCONDUCTIVE PIGMENT HAVING AN OXIDATION POTENTIAL GREATER THAN THE OXIDATION POTENTIAL OF SAID SUBSTRATE, SAID PIGMENT BEING UNIFORMLY DISPERSED IN A LIQUID BINDER AND CARRIER THEREFOR INCLUDING A SOLVENT AND A SYNTHETIC FILM FORMING RESINOUS COMPONENT FOR ADHERING SAID PIGMENT TO SAID SUBSTRATE, A FINELY DIVIDED METALLIC ALLOY DISPERSED IN SAID COATING COMPOSITION INCLUDING A FIRST METAL HAVING OXIDATION POTENTIAL GREATER THAN THAT OF SAID PIGMENT AND A SECOND METAL HAVING AN OXIDATION POTENTIAL LESS THAN THAT OF SAID PIGMENT, SAID SECOND METAL ACTING AS AN AGENT EFFECTING CONTROLLED RELEASE OF ELECTRONS FROM SAID FIRST METAL FOR INCREASING THE CORROSION PROTECTION PROVIDED BY SAID PIGMENT, SAID ELECTROCONDUCTIVE PIGMENT BEING PRESENT IN AN AMOUNT OF 75% TO 97% OF THE TOTAL SOLIDS IN THE DRIED COATING, AND THE RATIO OF RESIN TO PIGMENT IN SAID LIQUID COATING COMPOSITION FALLING APPROXIMATELY WITHIN THE RANGE OF 1:1 TO 1:20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US124796A US3118048A (en) | 1961-07-18 | 1961-07-18 | Liquid coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US124796A US3118048A (en) | 1961-07-18 | 1961-07-18 | Liquid coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3118048A true US3118048A (en) | 1964-01-14 |
Family
ID=22416820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US124796A Expired - Lifetime US3118048A (en) | 1961-07-18 | 1961-07-18 | Liquid coating composition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3118048A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293742A (en) * | 1964-12-03 | 1966-12-27 | Western Electric Co | Method of percussive welding |
| US3830651A (en) * | 1970-05-25 | 1974-08-20 | Owens Illinois Inc | Fine line electronic micro-circuitry printing pastes |
| US4083726A (en) * | 1976-05-28 | 1978-04-11 | Ameron, Inc. | Magnesium containing protective coating for ferrous metal |
| US4154430A (en) * | 1977-07-15 | 1979-05-15 | Anchor Post Products, Inc. | Conductive insulation electrical grounding or charging system for insulation coated chain link fabric |
| US5753316A (en) * | 1997-01-14 | 1998-05-19 | Ppg Industries, Inc. | Treatment of metal parts to provide improved sealcoat coatings |
| US10954422B2 (en) | 2014-10-13 | 2021-03-23 | Avery Dennison Corporation | Weldable and vibration damping silicone adhesives |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1770540A (en) * | 1929-03-01 | 1930-07-15 | Pullman Car & Mfg Corp | Spot welding of brass and aluminum |
| FR825910A (en) * | 1937-08-25 | 1938-03-17 | Process for obtaining by welding a tight joint between two sheets | |
| US2243832A (en) * | 1938-06-16 | 1941-06-03 | Aluminum Co Of America | Welding apparatus and method |
| US2452805A (en) * | 1944-10-14 | 1948-11-02 | Presstite Engineering Company | Composition of matter for sealing spot-welded joints |
| US2726308A (en) * | 1952-02-13 | 1955-12-06 | Cinamon Lionel | Welding method |
| US2970204A (en) * | 1958-02-27 | 1961-01-31 | Piceu | Electric welding method and composition |
-
1961
- 1961-07-18 US US124796A patent/US3118048A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1770540A (en) * | 1929-03-01 | 1930-07-15 | Pullman Car & Mfg Corp | Spot welding of brass and aluminum |
| FR825910A (en) * | 1937-08-25 | 1938-03-17 | Process for obtaining by welding a tight joint between two sheets | |
| US2243832A (en) * | 1938-06-16 | 1941-06-03 | Aluminum Co Of America | Welding apparatus and method |
| US2452805A (en) * | 1944-10-14 | 1948-11-02 | Presstite Engineering Company | Composition of matter for sealing spot-welded joints |
| US2726308A (en) * | 1952-02-13 | 1955-12-06 | Cinamon Lionel | Welding method |
| US2970204A (en) * | 1958-02-27 | 1961-01-31 | Piceu | Electric welding method and composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293742A (en) * | 1964-12-03 | 1966-12-27 | Western Electric Co | Method of percussive welding |
| US3830651A (en) * | 1970-05-25 | 1974-08-20 | Owens Illinois Inc | Fine line electronic micro-circuitry printing pastes |
| US4083726A (en) * | 1976-05-28 | 1978-04-11 | Ameron, Inc. | Magnesium containing protective coating for ferrous metal |
| US4154430A (en) * | 1977-07-15 | 1979-05-15 | Anchor Post Products, Inc. | Conductive insulation electrical grounding or charging system for insulation coated chain link fabric |
| US5753316A (en) * | 1997-01-14 | 1998-05-19 | Ppg Industries, Inc. | Treatment of metal parts to provide improved sealcoat coatings |
| US10954422B2 (en) | 2014-10-13 | 2021-03-23 | Avery Dennison Corporation | Weldable and vibration damping silicone adhesives |
| EP3910039A1 (en) | 2014-10-13 | 2021-11-17 | Avery Dennison Corporation | Weldable and vibration damping silicone adhesives |
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