Non-toxic corrosion-protection rinses and seals based on rare earth elements

• US 7,422,793 B2
• Filed: 07/23/2003
• Issued: 09/09/2008
• Est. Priority Date: 01/04/2002
• Status: Expired due to Term

• Current Assignee: University of Dayton
• Original Assignee: University of Dayton
• Inventors: Phelps, Andrew Wells, Swartzbaugh, Joseph Thomas, Sturgill, Jeffrey Allen
• Primary Examiner(s): King; Roy
• Assistant Examiner(s): Zheng; Lois L.
• Application Number:
  US10/625,886
• Publication Number:
  US 20040016910A1
• Time in Patent Office: 1,875 Days
• Field of Search: 148247-248, 148/253, 148/257, 148274-275, 148/243, 148/285, 106/14.05, 106/14.11, 106/14.12, 106/14.41, 106/480, 252/387, 252/389.2, 252/389.4, 427/385.5, 428/432, 428/469, 428/457
• US Class Current: 428/469
• CPC Class Codes: C23C 22/83 Chemical after-treatment
• CPC Class Codes: C25D 11/246 for sealing layers
• CPC Class Codes: Y10T 428/31656 With metal layer
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

Rinsing or sealing solutions comprising a rare earth element and a valence stabilizer for barrier films. The treated films contain a rare earth/valence stabilizer complex. The rare earth element is selected from cerium, praseodymium, terbium, or combinations thereof, and at least one rare earth element is in the tetravalent oxidation state. The rinsing or sealing solution may also contain an optional preparative or solubility control agent. The oxidized rare earth element is present in the coating in a “sparingly soluble” form. The valence stabilizers can be either inorganic or organic in nature. A number of rare earth/valence stabilizer combinations that match the performance of conventional hexavalent chromium systems are presented.

Claims

1. A solid corrosion-inhibiting seal formed on a coating selected from anodic coatings, phosphating coatings, or black oxide coatings, the solid corrosion-inhibiting seal comprising a rare earth element and an inorganic valence stabilizer combined to form a rare earth/valence stabilizer complex within the solid corrosion-inhibiting seal, wherein the rare earth element is selected from cerium, praseodymium, terbium, or combinations thereof and at least one rare earth element is in the tetravalent oxidation state in the rare earth/valence stabilizer complex in the solid corrosion-inhibiting seal.

2. The corrosion-inhibiting seal of claim 1 wherein the rare earth/valence stabilizer complex has a solubility in water of between about 5×

10<sup>−

1</sup> and about 1×

10<sup>−

5</sup> moles per liter of cerium, praseodymium, or terbium at about 25°

C. and about 760 Torr.

3. The corrosion-inhibiting seal of claim 2 wherein the solubility in water of the rare earth/valence stabilizer complex is between about 5×

10<sup>−

2</sup> and about 5×

10<sup>−

5</sup> moles per liter of cerium, praseodymium, or terbium at about 25°

C. and about 760 Torr.

4. The corrosion-inhibiting seal of claim 1 wherein there is an electrostatic barrier layer around the rare earth/valence stabilizer complex in aqueous solution.

5. The corrosion-inhibiting seal of claim 1 wherein the rare earth/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.

6. The corrosion-inhibiting seal of claim 1 wherein the anodic coatings, phosphating coatings, or black oxide coatings comprise a compound selected from oxides, hydroxides, phosphates, carbonates, oxalates, silicates, aluminates, borates, polymers, or combinations thereof.

7. The corrosion-inhibiting seal of claim 1 wherein the rare earth/valence stabilizer complex has a central cavity containing a cerium, praseodymium, or terbium ion and an additional ion.

8. The corrosion-inhibiting seal of claim 7 wherein the additional ion is B⁺³, Al⁺³, Si⁺⁴, P⁺⁵, Ti⁺⁴, V⁺⁵, V⁺⁴, Cr⁺⁶, Cr⁺³, Mn⁺⁴, Mn⁺³, Mn⁺², Fe⁺³, Fe⁺², Co⁺², Co⁺³, Ni⁺², Ni⁺³, Ni⁺⁴, Cu⁺², Cu⁺³, Zn⁺², Ga⁺³, Ge⁺⁴, As⁺⁵, As⁺³, or Zr⁺⁴.

9. The corrosion-inhibiting seal of claim 1 wherein the inorganic valence stabilizer is selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, carbonates, antimonates, stannates, phosphates, nitrates, bromates, sulfates, titanates, zirconates, bismuthates, germanates, arsenates, selenates, borates, aluminates, silicates, or combinations thereof.

10. The corrosion-inhibiting seal of claim 9 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, carbonates, antimonates, stannates, phosphates, nitrates, bromates, sulfates, or combinations thereof.

11. The corrosion-inhibiting seal of claim 1 further comprising a solubility control agent.

12. The corrosion-inhibiting seal of claim 11 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.

13. The corrosion-inhibiting seal of claim 12 wherein the solubility control agent is the cationic solubility control agent selected from H⁺;

Li⁺;

Na⁺;

K⁺;

Rb⁺;

Cs⁺;

NH₄⁺;

Mg⁺²;

Ca⁺²;

Sr⁺²;

Be⁺²;

Ba⁺²;

Y⁺³;

La⁺³;

Ce⁺³;

Ce⁺⁴;

Nd⁺³;

Pr⁺³;

Sc⁺³;

Sm⁺³;

Eu⁺³;

Eu₊₂;

Gd⁺³;

Tb⁺³;

Dy⁺³;

Ho⁺³;

Er⁺³;

Tm⁺³;

Yb⁺³;

Lu⁺³;

Ti⁺⁴;

Zr⁺⁴;

Ti⁺³;

Hf⁺⁴;

Nb⁺⁵;

Ta⁺⁵;

Nb⁺⁴;

Ta⁺⁴;

V⁺⁵;

V⁺⁴, V⁺³, Mo⁺⁶;

W⁺⁶;

Mo⁺⁵;

W⁺⁵;

Mo⁺⁴;

W⁺⁴, Cr⁺³;

Mn⁺²;

Mn⁺³;

Mn⁺⁴;

Fe⁺²;

Fe⁺³;

Co⁺²;

Co⁺³;

Ni⁺²;

Ni⁺³;

Ni⁺⁴;

Ru⁺²;

Ru⁺³;

R⁺⁴;

Rh⁺³;

Ir⁺³;

Rh⁺²;

Ir⁺²;

Pd⁺⁴;

Pt⁺⁴;

Pd⁺²;

Pt⁺²;

Os⁺⁴;

Cu⁺;

Cu⁺²;

Cu⁺³;

Ag⁺;

Ag⁺²;

Ag⁺³;

Au⁺;

Au⁺²;

Au⁺³;

Zn⁺²;

Cd⁺²;

Hg⁺;

Hg⁺²;

Al⁺³;

Ga⁺³;

Ga⁺;

In⁺³;

In⁺;

Tl⁺³;

Tl⁺;

Ge⁺⁴;

Ge⁺²;

Sn⁺⁴;

Sn⁺²;

Pb⁺⁴;

Pb⁺²;

Sb⁺³;

Sb⁺⁵;

As⁺³;

As⁺⁵;

Bi⁺³;

Bi⁺⁵;

organic compounds containing at least one N⁺ site;

organic compounds containing at least one phosphonium site;

organic compounds containing at least one arsonium site;

organic compounds containing at least one stibonium site;

organic compounds containing at least one oxonium site;

organic compounds containing at least one sulfonium site;

organic compounds containing at least one selenonium site;

organic compounds containing at least one iodonium site;

quaternary ammonium compounds having a formula NR₄⁺, where R is an alkyl, aromatic, or acyclic organic constituent;

or combinations thereof.

14. The corrosion-inhibiting seal of claim 13 wherein the cationic solubility control agent is selected from H⁺;

Li⁺;

Na⁺;

K⁺;

Rb⁺;

Cs⁺;

NH₄⁺;

Mg⁺²;

Ca⁺²;

Sr⁺²;

Y⁺³;

La⁺³;

Ce⁺³;

Ce⁺⁴;

Nd⁺³;

Pr⁺³;

Sc⁺³;

Sm⁺³;

Eu⁺³;

Eu₊₂;

Gd⁺³;

Tb⁺³;

Dy⁺³;

Ho⁺³;

Er⁺³;

Tm⁺³;

Yb⁺³;

Lu⁺³;

Ti⁺⁴;

Zr⁺⁴;

Ti⁺³;

Hf⁺⁴;

Nb⁺⁵;

Ta⁺⁵;

Nb⁺⁴;

Ta⁺⁴;

Mo⁺⁶;

W⁺⁶;

Mo⁺⁵;

W⁺⁵;

Mo⁺⁴;

W⁺⁴, Mn⁺²;

Mn⁺³;

Mn⁺⁴;

Fe⁺²;

Fe⁺³;

Co⁺²;

Co⁺³;

Ru⁺²;

Ru⁺³;

R⁺⁴;

Rh⁺³;

Ir⁺³;

Rh⁺²;

Ir⁺²;

Pd⁺⁴;

Pt⁺⁴;

Pd⁺²;

Pt⁺²;

Cu⁺;

Cu⁺²;

Cu⁺³;

Ag⁺;

Ag⁺²;

Ag⁺³;

Au⁺;

Au⁺²;

Au⁺³;

Zn⁺²;

Al⁺³;

Ga⁺³;

Ga⁺;

In⁺³;

In⁺;

Ge⁺⁴;

Ge⁺²;

Sn⁺⁴;

Sn⁺²;

Sb⁺³;

Sb⁺⁵;

Bi⁺³;

Bi⁺⁵;

organic compounds containing at least one N⁺ site;

organic compounds containing at least one phosphonium site;

organic compounds containing at least one stibonium site;

organic compounds containing at least one oxonium site;

organic compounds containing at least one sulfonium site;

organic compounds containing at least one iodonium site;

quaternary ammonium compounds having a formula NR₄⁺, where R is an alkyl, aromatic, or acyclic organic constituent;

or combinations thereof.

15. The corrosion-inhibiting seal of claim 12 wherein the solubility control agent is the anionic solubility control agent selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke'"'"'s salt, vanadates, or combinations thereof. perchiorates, bromides, bromates, jodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenoLates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chioroarsenates, selenates, selenites, fluorothallates, chiorothallates, iodomercury anions, chioromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke'"'"'s salt, vanadates, or combinations thereof.

16. The corrosion-inhibiting seal of claim 15 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chioromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chiorocobaltates, fluorozincates, chiorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chioroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchiorates, bromides, bromates, jodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.

17. The corrosion-inhibiting seal of claim 1 further comprising a lubricity agent.

18. The corrosion-inhibiting seal of claim 17 wherein the lubricity agent is selected from molybdenum disulfide, fluorinated hydrocarbons, perfluorinated hydrocarbons, graphite, soft metals, polymers, or combinations thereof.

19. The corrosion-inhibiting seal of claim 18 wherein the lubricity agent is the soft metal selected from tin, indium, silver, or combinations thereof.

20. The corrosion-inhibiting seal of claim 1 wherein the corrosion-inhibiting seal is colored.

21. The corrosion-inhibiting seal of claim 20 further comprising an agent which improves color-fastness of the corrosion-inhibiting seal.

22. The corrosion-inhibiting seal of claim 21 wherein the agent which improves color-fastness is selected from an active UV blocker, a passive UV blocker, a brightener, or a combination thereof.

23. The corrosion-inhibiting seal of claim 22 wherein the agent which improves color-fastness is the active UV blocker selected from carbon black, graphite, phthalocyanines, or combinations thereof.

24. The corrosion-inhibiting seal of claim 22 wherein the agent which improves color-fastness is the passive UV blocker selected from titanium oxide, tin oxide, lead oxide, silicon oxide, silicates, aluminosilicates, or combinations thereof.

25. The corrosion-inhibiting seal of claim 22 wherein the agent which improves color-fastness is the brightener selected from sulfonic acids, sulfonates, sulfonamides, sulfonic acids, sulfinates, sulfones, cyanides, nonionic surfactants, or combinations thereof.

26. The corrosion-inhibiting seal of claim 20 wherein the color is formed by a dye selected from vat dyes, mordant dyes, lake dyes, disperse dyes, azo dyes, triazine dyes, triphenylmethane dyes, azine dyes, formazan dyes, phthalocyanine dyes, Schiff Base dyes, naturally-occurring dyes, inorganic pigments, or combinations thereof.

27. The corrosion-inhibiting seal of claim 21 wherein the agent which improves color-fastness is an agent which prevents smudging.

28. The corrosion-inhibiting seal of claim 27 wherein the agent which prevents smudging is selected from phosphoric acid, metaphosphates, orthophosphates, pyrophosphates, polyphosphates, or combinations thereof.

29. The corrosion-inhibiting seal of claim 21 wherein the agent which improves color-fastness is a wetting agent.

30. The corrosion-inhibiting seal of claim 29 further comprising less than about 5 g/L of the wetting agent.

31. The corrosion-inhibiting seal of claim 29 wherein the wetting agent is a nonionic surfactant.

32. A solid corrosion-inhibiting seal formed on a coating selected from anodic coatings, phosphating coatings, or black oxide coatings, the solid corrosion-inhibiting seal comprising a rare earth element and an inorganic valence stabilizer combined to form a rare earth/valence stabilizer complex within the solid corrosion-inhibiting seal, wherein the rare earth element is selected from cerium, praseodymium, terbium, or combinations thereof at least one rare earth element is in the tetravalent oxidation state in the rare earth/valance stablizer complex, and the rare earth/valence stabilizer complex is sparingly soluble in water at about 25°

C. and about 760 Torr in the rare earth/valence stabilizer complex in the solid corrosion-inhibiting seal.

33. A solid corrosion-inhibiting seal formed on a coating selected from anodic coatings, phosphating coatings, or black oxide coatings, the solid corrosion-inhibiting seal comprising a rare earth element and a valence stabilizer combined to form a rare earth/valence stabilizer complex within the solid corrosion-inhibiting seal, wherein the rare earth element is selected from cerium, praseodymium, terbium, or combinations thereof, and at least one rare earth element is in the tetravalent oxidation state, wherein the rare earth/valence stabilizer complex has a central cavity containing a cerium, praseodymium, or terbium ion and an additional ion, and wherein the additional ion is B⁺³, Al⁺³, Si⁺⁴, P⁺⁵ , Ti⁺⁴, V⁺⁵, V⁺⁴, Cr⁺⁶, Cr⁺³, Mn⁺⁴, Mn⁺³, Mn⁺², Fe⁺³, Fe⁺², Co⁺², Co⁺³, Ni⁺², Ni⁺³, Ni⁺⁴, Cu⁺², Cu⁺³, Zn⁺², Ga⁺³, Ge⁺⁴, As⁺⁵, As⁺³, or Zr⁺⁴.

34. The corrosion-inhibiting seal of claim 33 wherein the rare earth/valence stabilizer complex has a solubility in water of between about 5×

10<sup>−

1</sup> and about 1×

10<sup>−

5</sup> moles per liter of cerium, praseodymium, or terbium at about 25°

C. and about 760 Torr.

35. The corrosion-inhibiting seal of claim 34 wherein the solubility in water of the rare earth/valence stabilizer complex is between about 5×

10<sup>−

2</sup> and about 5×

10−

5 moles per liter of cerium, praseodymium, or terbium at about 25°

C. and about 760 Torr.

36. The corrosion-inhibiting seal of claim 33 wherein there is an electrostatic barrier layer around the rare earth/valence stabilizer complex in aqueous solution.

37. The corrosion-inhibiting seal of claim 33 wherein the rare earth/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.

38. The corrosion-inhibiting seal of claim 33 wherein the anodic coatings, phosphating coatings, or black oxide coatings comprise a compound selected from oxides, hydroxides, phosphates, carbonates, oxalates, silicates, aluminates, borates, polymers, or combinations thereof.

39. The corrosion-inhibiting seal of claim 33 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, carbonates, antimonates, stannates, phosphates, nitrates, bromates, sulfates, titanates, zirconates, bismuthates, germanates, arsenates, selenates, borates, aluminates, silicates, or combinations thereof.

40. The corrosion-inhibiting seal of claim 39 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, carbonates, antimonates, stannates, phosphates, nitrates, bromates, sulfates, or combinations thereof.

41. The corrosion-inhibiting seal of claim 33 further comprising a solubility control agent.

42. The corrosion-inhibiting seal of claim 41 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.

43. The corrosion-inhibiting seal of claim 42 wherein the solubility control agent is the cationic solubility control agent selected from H⁺;

Li⁺;

Na⁺;

K⁺;

Rb⁺;

Cs⁺;

NH₄⁺;

Mg⁺²;

Ca⁺²;

Sr⁺²;

Be⁺²;

Ba⁺²;

Y⁺³;

La⁺³;

Ce⁺³;

Ce⁺⁴;

Nd⁺³;

Pr⁺³;

Sc⁺³;

Sm⁺³;

Eu⁺³;

Eu⁺²;

Gd⁺³;

Tb⁺³;

Dy⁺³;

Ho⁺³;

Er⁺³;

Tm⁺³;

Yb⁺³;

Lu⁺³;

Ti⁺⁴;

Zr⁺⁴;

Ti⁺³;

Hf⁺⁴;

Nb⁺⁵;

Ta⁺⁵;

Nb⁺⁴;

Ta⁺⁴;

V⁺⁵;

V⁺⁴;

V⁺³;

Mo⁺⁶;

W⁺⁶;

Mo⁺⁵;

W⁺⁵;

Mo⁺⁴;

W⁺⁴;

Cr⁺³;

Mn⁺²;

Mn⁺³;

Mn⁺⁴;

Fe⁺²;

Fe⁺³;

Co⁺²;

Co⁺³;

Ni⁺²;

Ni⁺³;

Ni⁺⁴;

Ru⁺²;

Ru⁺³;

Ru⁺⁴;

Rh⁺³;

Ir⁺³;

Rh⁺²;

Ir⁺²;

Pd⁺⁴;

Pt⁺²;

Pd⁺²;

Pt⁺²;

Os⁺⁴;

Cu⁺;

Cu⁺²;

Cu⁺³;

Ag⁺;

Ag⁺²;

Ag⁺³;

Au⁺;

Au⁺²;

Au⁺³;

Zn⁺²;

Cd⁺² ;

Hg⁺;

Hg⁺²;

Al⁺³;

Ga⁺³;

Ga⁺;

In⁺³;

In⁺;

Tl⁺³;

Tl⁺;

Ge⁺⁴;

Ge⁺²;

Sn⁺⁴;

Sn⁺²;

Pb⁺⁴;

Pb⁺²;

Sb⁺³;

Sb⁺⁵;

As⁺³;

As⁺⁵;

Bi⁺³;

Bi⁺⁵;

organic compounds containing at least one N⁺ site;

organic compounds containing at least one phosphonium site;

organic compounds containing at least one arsonium site;

organic compounds containing at least one stibonium site;

organic compounds containing at least one oxonium site;

organic compounds containing at least one sulfonium site;

organic compounds containing at least one selenonium site;

organic compounds containing at least one jodonium site;

quaternary ammonium compounds having a formula NR₄⁺, where R is an alkyl, aromatic, or acyclic organic constituent;

or combinations thereof.

44. The corrosion-inhibiting seal of claim 43 wherein the cationic solubility control agent is selected from H⁺;

Li⁺;

Na⁺;

K⁺;

Rb⁺;

Cs⁺;

NH₄⁺;

Mg⁺²;

Ca⁺²;

Sr⁺²;

Y⁺³;

La⁺³;

Ce⁺³;

Ce⁺⁴;

Nd⁺³;

Pr⁺³;

Sc⁺³;

Sm⁺³;

Eu⁺³;

Eu⁺²;

Gd⁺³;

Tb⁺³;

Dy⁺³;

Ho⁺³;

Er⁺³;

Tm⁺³;

Yb⁺³;

Lu⁺³;

Ti⁺⁴;

Zr⁺⁴;

Ti⁺³;

Hf⁺⁴;

Nb⁺⁵;

Ta⁺⁵;

Nb⁺⁴;

Ta⁺⁴;

Mo⁺⁶;

W⁺⁶;

Mo⁺⁵;

W⁺⁵;

Mo⁺⁴;

W⁺⁴;

Mn⁺²;

Mn⁺³;

Mn⁺⁴;

Fe⁺²;

Fe⁺³;

Co⁺²;

Co⁺³;

Ru⁺²;

Ru⁺³;

Ru⁺⁴;

Rh⁺³;

Ir⁺³;

Rh⁺²;

Ir⁺²;

Pd⁺⁴;

Pt⁺⁴;

Pd⁺²;

Pt⁺²;

Cu⁺;

Cu⁺²;

Cu⁺³;

Ag⁺;

Ag⁺²;

Ag⁺³;

Au⁺;

Au⁺²;

Au⁺³;

Zn⁺²;

Al⁺³;

Ga⁺³;

Ga⁺;

In⁺³;

In⁺;

Ge⁺⁴;

Ge⁺²;

Sn⁺⁴;

Sn⁺²;

Sb⁺³;

Sb⁺⁵;

Bi⁺³;

Bi⁺⁵ organic compounds containing at least one N⁺ site;

organic compounds containing at least one phosphonium site;

organic compounds containing at least one stibonium site;

organic compounds containing at least one oxonium site;

organic compounds containing at least one sulfonium site;

organic compounds containing at least one iodonium site;

quaternary ammonium compounds having a formula NR₄⁺, where R is an alkyl, aromatic, or acyclic organic constituent;

or combinations thereof.

45. The corrosion-inhibiting seal of claim 33 further comprising a lubricity agent.

46. The corrosion-inhibiting seal of claim 45 wherein the lubricity agent is selected from molybdenum disulfide, fluorinated hydrocarbons, perfluorinated hydrocarbons, graphite, soft metals, polymers, or combinations thereof.

47. The corrosion-inhibiting seal of claim 46 wherein the lubricity agent is the soft metal selected from tin, indium, silver, or combinations thereof

48. The corrosion-inhibiting seal of claim 33 wherein the corrosion-inhibiting seal is colored.

49. The corrosion-inhibiting seal of claim 48 further comprising an agent which improves color-fastness of the corrosion-inhibiting seal.

50. The corrosion-inhibiting seal of claim 49 wherein the agent which improves color-fastness is selected from an active UV blocker, a passive UV blocker, a brightener, or a combination thereof.

51. The corrosion-inhibiting seal of claim 50 wherein the agent which improves color-fastness is the active UV blocker selected from carbon black, graphite, phthalocyanines, or combinations thereof.

52. The corrosion-inhibiting seal of claim 49 wherein the agent which improves color-fastness is an agent which prevents smudging.

53. The corrosion-inhibiting seal of claim 52 wherein the agent which prevents smudging is selected from phosphoric acid, metaphosphates, orthophosphates, pyrophosphates, polyphosphates, or combinations thereof.

54. The corrosion-inhibiting seal of claim 49 wherein the agent which improves color-fastness is a wetting agent.

55. The corrosion-inhibiting seal of claim 54 further comprising less than about 5 g/L of the wetting agent.

56. The corrosion-inhibiting seal of claim 54 wherein the wetting agent is a nonionic surfactant.