Corrosion inhibitor composition applicable for aluminum and steel protection and procedure

Abstract

A corrosion-inhibiting composition for application to a metal substrate, such as aluminum or steel, and in connection with a paint, and the synthesis of the composition. The active inhibitor constituent of the composition can be selected from the group consisting of 2,5-dimercapto-1,3,4 thiadiazole (DMTD), 2,4-dimercapto-s-triazolo-[4,3-b]-1,3-4-thiadiazole, trithiocyanuric acid (TMT), and derivatives of DMTD and TMT, including various N— or S— and N, N—, S— and N—,S-substituted derivatives of DMTD, including salts of DMTD of the general formula: M(DMTD) n , where n=1,2 or 3, and M is a metal cation and preferably M=Zn(II), Bi(III), Co(II), Ni(II), Cd(II), Pb(II), Ag(I), Sb(III), Cu(II), Li(I), Ca(II), Sr(II), Mg(II), La(III), Ce(III), Pr(III), Al(III) or Zr(IV). DMTD, TMT, and their derivatives may also be combined with phosphates, molybdates, borates, silicates, tungstates, phosphotungstates, phosphomolybdates, cyanamides, carbonates, SiO 2 and mixtures thereof.

What is claimed is: 
     
       1. A process for protecting an aluminum substrate or a steel substrate against corrosion comprising:
 providing an aluminum surface to be protected, 
 applying to said surface a protective composition comprising of a pigment grade corrosion inhibitor composition, said protective composition being formed by reacting an organic compound from a group consisting of di-mercapto and poly-mercapto derivatives and their derivatives, with a cationic species selected from a group consisting of Bi(III), Co(II), Cd(II), Ag(I), Sb(III), Ni(II), Li(I), La(III), and Pr(III), said protective pigment grade corrosion inhibitor composition having a limited solubility in water of between about 0.01 and about 1000 mmoles/per liter of water, 
 whereby said pigment grade corrosion inhibitor composition is capable of preventing corrosion for at least 2000 hours in salt spray exposure conditions. 
 
     
     
       2. A process according to  claim 1  wherein said protective composition is applied as a layer of less than approximately 20 microns in thickness. 
     
     
       3. A process according to  claim 1  wherein said protective composition has a limited solubility in water of between about 0.1 and about 10 mmoles/ liter. 
     
     
       4. A process according to  claim 1  wherein said protective composition is applied as an aqueous solution and is subsequently dried whereby a conversion coating is formed on said substrate, said conversion coating being subsequently coated with a paint. 
     
     
       5. A process according to  claim 1  wherein said protective composition is incorporated into a silane-based gel coating. 
     
     
       6. A process according to  claim 1  wherein said protective corrosion inhibitor composition is selected from the group consisting of 2,5-dimercapro-1,3,4 thiadiazole or (DMTD), 2,4-dimercapto-s-triazolo-[4,3-b]-1,3-4-thiadiazole, trithiocyanuric acid or (TMT), derivatives of DMTD, and derivatives of TMT, dithiocyanuric acid, dimercaptopyridine, 2,4-dithiohydantoine, and 2,4-dimercapto-6-amino-5-triazine. 
     
     
       7. A process according to  claim 1  wherein said protective composition pigment grade corrosion inhibitor composition is selected from the group consisting of M(DMTD) n  where n=1,2 or 3, and M is a metal cation selected from the group consisting of Bi, Co, Ni, Cd, Ag, Sb, Li, La, Pr; alkyl ammonium salts of DMTD and (DMTD) n ; cyclo-alkyl ammonium salts of DMTD and (DMTD) n ; di-cyclo alkyl ammonium salts of DMTD and (DMTD) n ; aryl ammonium salts of DMTD; aryl ammonium salts of (DMTD) n ; quaternary ammonium salts of DMTD; quaternary ammonium salts of (DMTD) n ; polyaniline, polythiophen, and polypyrrol doped with DMTD; polyaniline, polythiophen, and polypyrrol doped with (DMTD) 2 ; and micro and nano composites of poly DMTD/polyaniline, DMTD/polythiophen and poly DMTD/polypyrrol. 
     
     
       8. A process according to  claim 1  wherein said protective composition is applied by incorporating the same in a curable polymeric coating composition and applying said composition over said substrate. 
     
     
       9. A process according to  claim 1  wherein said protective composition pigment grade corrosion inhibitor composition is selected from the group consisting of: N- or S- and N-, N-, S- and N-, S-substituted derivatives of DMTD such as, 5-mercapto-3-phenyl-1,3,4-thiadiazoline-2-thione (Bismuthiol II), substituted derivatives of 5,5′ dithio-bis(1,3,4 thiadiazole-2(3H)-thione (DMTD) 2 , substituted derivatives of 5,5′-Thiobis (1,3,4-thiadiazole-2(3H)-thione substituted derivatives of dimercaptopyridine, and of 2,4-dithiohydantoine, substituted derivatives of 2,4-dimercapto-6-amino-5-triazine and (DMTD) n , a polymer of DMTD; a salt of DMTD of general formula, M(DMTD) n , where n=1,2 or 3, and M is a metal cation and M=Bi, Co, Ni, Cd, Ag, Sb, Li, La, Pr; a salt of (DMTD) n  of general formula M[(DMTD) n ] m , where n=2 or n>2, m=1,2, or 3 and M=Bi, Co, Ni, Cd, Ag, Sb, Li, La, Pr; alkyl ammonium salts of DMTD and (DMTD) n ; cyclo-alkyl ammonium salts of DMTD and (DMTD) n ; di-cyclo alkyl ammonium salts of DMTD and (DMTD) n ; aryl ammonium salts of DMTD and (DMTD) n ; quaternary ammonium salts of DMTD and (DMTD) n ; polyammonium salts of DMTD and (DMTD) n  formed with a polyamine; polyaniline, polypyrrole and polythiophen doped with DMTD; polyaniline, polypyrrole and polythiophen doped with (DMTD) 2 ; micro and nano composites of poly DMTD/polyaniline, poly DMTD/polypyrrole, and poly DMTD/polythiophen; DMTD, salts of DMTD, and derivatives of DMTD, as constituents of an inorganic matrix; and a combination of said forms. 
     
     
       10. A process according to  claim 1  wherein said protective composition pigment grade corrosion inhibitor composition is selected from the group consisting of:
 S-substituted derivatives of trithiocyanuric acid (TMT); a salt of TMT of general formula, M(TMT) n , where n=1,2 or 3, and M is a metal cation and M=Bi, Go, Ni, Cd, Ag, Sb, Li, La, Pr; alkyl ammonium salts of TMT; cyclo-alkyl ammonium salts of TMT; dicyclo alkyl ammonium salts of TMT; aryl ammonium salts of TMT; quaternary ammonium salts of TMT; polyamines formed with TMT; polyaniline doped with TMT; polypyrrole and polythiophen doped with TMT; micro and nano composites of poly TMT/polyaniline, poly TMT/ polypyrrole, and poly TMT/polythiophen; TMT, salts of TMT; and derivatives of TMT, as constituents of an inorganic matrix; salts of TMT and derivatives of TMT in encapsulated form in a polymer matrix, or as a cyclodextrin-inclusion compound; and a combination of said forms. 
 
     
     
       11. The protective composition of  claim 1  wherein the protective composition is used in a paint. 
     
     
       12. A process for producing a pigment grade corrosion inhibitor composition comprising the steps of:
 providing a first aqueous slurry containing zinc oxide (ZnO);   providing an aqueous suspension containing 2,5-dimercapto-1,3,4 thiadiazole or (DMTD); and   transferring said aqueous suspension to said aqueous slurry;   wherein the ZnO and DMTD are added in a 1:2 stoichiometrical relationship of ZnO and DMTD.   
     
     
       13. The process according to claim 12 further comprising the steps of:
 separating the solid phase out of the resulting slurry; and   drying the solid phase.