Compositions – Preservative agents – Anti-corrosion
Reexamination Certificate
2002-12-23
2004-03-16
Anthony, Joseph D. (Department: 1714)
Compositions
Preservative agents
Anti-corrosion
C252S389220, C252S389230, C252S391000, C252S395000, C252S400210, C252S400220, C252S400230, C252S402000, C252S406000, C106S014120, C106S014160, C106S014370, C427S388200, C427S385500, C536S020000
Reexamination Certificate
active
06706214
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to compositions and processes for providing corrosion protection for metal substrates, particularly substrates comprised of aluminum or aluminum alloys, using treatment solutions comprising chitosan, which has been reacted with selected acids.
BACKGROUND OF THE INVENTION
Many metals are susceptible to corrosion. In this regard, atmospheric corrosion is of particular concern. Corrosion may affect the performance and/or appearance of the metals affected, and the products produced therefrom. In addition, when polymer coatings such as paints, adhesives or sealants are applied to the metal, corrosion of the underlying metal may cause loss of adhesion between the polymer coating and the base metal.
Aluminum and aluminum alloys frequently require corrosion protection and improvements in adhesion between the base aluminum (or aluminum alloys) and subsequent polymer coatings. Aluminum alloys, in particular, can be susceptible to corrosion since the alloying elements used to improve the aluminum's mechanical properties may decrease corrosion resistance.
Specifications for testing the effectiveness of the corrosion inhibition and adhesion promotion of various treatments have been established. Examples of such specifications include ASTM standard D3359-87, ASTM standard B117 and Military specification MIL-C-5541D.
Prior art techniques for improving corrosion resistance of metals widely employ the use of chromate conversion coatings to passivate the surface. Such chromate treatments are undesirable however, because the chromium used is highly toxic, carcinogenic, and environmentally undesirable. Various attempts have been made to reduce the toxicity of these chromium treatments, including the use of trivalent chromium in place of the more toxic hexavalent chromium, but these attempts have proven less than completely successful.
Phosphate conversion coatings are also used, but generally provide substantially less corrosion protection than is typically desired. More recently the use of treatment compositions comprising silicates and/or silanes has been proposed. However, these treatments have also fallen short of corrosion protection expectations in many cases.
As a result, there remains a real need for non-toxic treatment solutions which are safe to handle and provide the level of corrosion protection typically demanded in a variety of applications. The composition and process of the current invention are meant to address the foregoing needs.
Thus it is an object of this invention to provide an improved method of inhibiting corrosion of metals, especially aluminum and aluminum alloys, which is simple to employ, cost effective and environmentally friendly. It is a further object of this invention to provide a treatment for metals which improves the adhesion of subsequent organic coatings to the metal while at the same time improving the corrosion resistance of the metal.
SUMMARY OF THE INVENTION
The foregoing objectives can be accomplished by treating a metal, particularly aluminum or aluminum alloys, with a treatment composition which comprises an aqueous solution of chitosan which has been reacted with an additive selected from the group consisting of phosphorus-containing additives, sulfur-containing additives, and mixtures thereof. The presence of phosphorus as a phosphonic acid and/or sulfur as a mercapto, thio, or thienyl group, or as a mercapto functional silane is especially preferred. The treatment composition is applied directly to a clean metal surface by immersion, spray, flood or other means of direct contact. The treatment solution is preferably applied to the metal at a temperature of from 70° F. to 150° F. Preferably the treatment solution is acidic enough to solubilize the acid modified chitosan.
Preferably, the metal surface is cleaned, deoxidized, and/or etched prior to treatment with the chitosan based treatment solution. A variety of known cleaners, deoxidizers and/or etchants may be employed for this purpose, with the appropriate choice being made with the specific metal surface to be prepared in mind.
Once the chitosan treatment is applied to the metal surface the treated surface should be allowed to dry. Drying may occur at room temperature or upon baking the surfaces at temperatures that preferably do not exceed about 200° C.
The compositions and processes of this invention are particularly suitable for treating aluminum and aluminum alloys. The inventor has found that treating aluminum or aluminum alloys with the modified chitosan solution of this invention provides both increased corrosion resistance and enhanced adhesion of subsequent organic coatings to the treatment surfaces.
DETAILED DESCRIPTION OF THE INVENTION
Chitosan, a derivative of the polysaccharide chitin, is a polymer obtained from the shells of crustaceans such as crabs, lobsters and shrimp. The major issue with utilizing chitosan as a barrier against corrosion protection is its affinity to absorb atmospheric moisture, which transforms the polymer into a non-protective gel. This problem can be satisfactorily circumvented by reacting the chitosan with additives containing either phosphorous or sulfur. Such reactions are desirable because they tend to bridge between chitosan strands within the glucosamine ring structure, resulting in bonds that are hydrophobic in nature. The presence of phosphorous as a phosphonic acid and sulfur as a mercapto, thio or thienyl group is most desired. This effectively reduces the permeability of the chitosan polymer matrix.
Chitosan is the product of deacetylation of chitin. Generally chitosan is an amorphous solid which is soluble in aqueous solutions with pH less than about 6. Chitosan is of nearly identical structure to chitin, except that it is de-acetylated. The chemical structure of chitosan is as follows:
where n represents the number of repeating units in the polymer chain. Because chitosan is more easily solubilized than chitin, chitosan is preferred for use in the process of the invention. Chitosan is also a low cost polymer, since its source, chitin, comes from the shells of marine crustaceans.
The inventor herein has discovered that although aqueous solutions of chitosan, itself, do not adequately function as corrosion prevention treatments for metallic surfaces, certain modified chitosans do provide desirable levels of corrosion protection for metals. Specifically the inventor herein has discovered that aqueous solutions of chitosan which has been reacted with an additive selected from the group consisting of phosphorus-containing additives, sulfur-containing additives, and mixtures thereof, provide an excellent corrosion protection treatment for metals. The presence of phosphorus as a phosphonic acid and/or sulfur as a mercapto, thio, or thienyl group or a mercapto functional silane is most preferred.
Without being bound by theory, it is believed that when the phosphorus and/or sulfur-containing additive(s) are reacted with the chitosan, they tend to form amide bonds with the glucosamine ring structure, thereby bridging between chitosan strands. The resulting modified chitosan structure is more hydrophobic in nature than the unmodified chitosan structure, thereby reducing the permeability of the modified chitosan matrix. It is believed that this reduction in permeability of the modified chitosan matrix provides better corrosion protection for the treated metal.
As noted above, the modified chitosan is created by reacting chitosan with an additive selected from the group consisting of phosphorus-containing additives, sulfur-containing additives, and mixtures thereof. Preferably, the additive is a phosphonic acid or sulfur as a mercapto, thio, or thienyl group or a mercapto functional silane.
Mercapto functional silanes have been used to inhibit corrosion on aluminum or aluminum alloy surfaces, as described in U.S. Pat. No. 6,461,682 to Crotty et al., the subject matter of which is herein incorporated by reference in its entirety. However, mercapto functional silanes have not previously been used to m
Anthony Joseph D.
Carmody & Torrance LLP
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