CA2273249C

CA2273249C - Method of preventing corrosion of metals using silanes

Info

Publication number: CA2273249C
Application number: CA002273249A
Authority: CA
Inventors: Wim J. Van Ooij; Vijay Subramanian; Chunbin Zhang
Original assignee: University of Cincinnati
Current assignee: University of Cincinnati
Priority date: 1997-01-09
Filing date: 1998-01-08
Publication date: 2006-12-05
Anticipated expiration: 2018-01-08
Also published as: PL334657A1; HUP0001015A2; US6261638B1; CN1242805A; US5750197A; JP2001507755A; DE69823847T2; IL130282A0; EA001588B1; EA199900628A1; KR20000069926A; EP1015662A2; AU5862498A; ATE266749T1; AR011382A1; JP4376972B2; EP1015662B1; TR199901568T2; CA2273249A1; WO1998030735A3

Abstract

A method of preventing corrosion of metals using silanes. The method compris es applying a first treatment solution directly onto the surface of the metal, wherein the first treatment solution contains at least one multi-functional silane having at least two trisubstituted silyl groups, and wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy. An optional second treatment solution containing an organofunctional silane may also be employe d, particularly if the metal is to be painted.

Description

METHOD OF PREVENTING CORROSION
OF METALS USING SILANES
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a method of preventing corrosion of metal. More particularly, the method comprises applying a solution containing one or more multi-functional silanes to a metal substrate. If the metal is to be painted, this treatment may be followed by applying a solution of an organofunctional silane. The method is particularly useful for the treatment of cold-rolled steel, aluminum and aluminum alloys.
DESCRIPTION OF RELATED ART
Most metals are susceptible to corrosion, in particular atmospheric corrosion. Such corrosion will significantly affect the quality of such metals, as well as that of the products produced therefrom. Although this corrosion may sometimes be removed from the metal, such steps are costly and may further diminish the utility of the final product. In addition, when polymer coatings such as paints, adhesives, or rubbers are applied to the metal, corrosion of the base metal material may cause a loss of adhesion between the polymer coating and the base metal. A
loss of adhesion between the polymer coating and the base metal can likewise lead to corrosion of the metal. Aluminum alloys are particularly susceptible to corrosion as the alloying elements used to improve the metal's mechanical properties (e. g., copper, magnesium and zinc) will decrease corrosion resistance.
Prior art techniques for improving corrosion resistance of metal, particularly metal sheet, include passivating the surface by means of a heavy chromate treatment. Such treatment methods are undesirable, however, because the chromium is highly toxic, carcinogenic and a , CA 02273249 1999-OS-28 environmentally undesirable. It is also known to employ a phosphate conversion coating in conjunction with a chromate rinse in order to improve paint adherence and provide corrosion protection. It is believed that the chromate rinse covers the pores in the phosphate coating, thereby improving the corrosion resistance and adhesion performance. Once again, however, it is highly desirable to eliminate the use of chromate altogether. Unfortunately, the phosphate conversion coating is generally not effective without the chromate rinse.
Recently various techniques for eliminating the use of chromate have been proposed. These include the steps of providing an aqueous alkaline solution comprising an inorganic silicate and a metal salt in an amount to coat a steel sheet, followed by treating the silicate coating with an organofunctional silane (U. S. Patent No. 5,108,793).
U.S. Patent 5,292,549 teaches the rinsing of metal sheet with an aqueous solution containing low concentrations of an organofunctional silane and a crosslinking agent, such as bistrimethoxy silylethane in order to provide temporary corrosion protection. The crosslinking agent cross links the organofunctional silane to form a denser siloxane film.
One significant drawback to the methods of this patent is that the organofunctional silane will not bond well to the metal surface, and thus the coating may be easily rinsed off.
US Patent No. 5,393,353 describes a method for preparing a chromium-free black zinc-nickel alloy surface containing at least about 8% nickel in the alloy. The J:
method comprising contacting said surfaces with an aqueous acid solution of an inorganic acid, preferably a phosphorus acid, the solution optionally additionally containing at least one silane, such as bistrimethoxysilylethane.
US Patent No. 4,689,085 describes coupling agent and primer compositions comprising a conventional silane couplying agent and a disilyl cross linker compound in the same composition solution.
0~2 embec~~,m~~. an or ano~unc~ona,~ silane 5o~~~~ar~ ~W u5e~
4 me1-u~ Su,r~ Followed 0.pp~lCG~~~0Y1 O O~
AMENDED SHEETseccnd ~-r-ea1-t,r~e,~~ ~~~~.~~ ~~~Q~~~~ ~a u. ssl~nk~ ~ er~-P _ ___ __ _ ..._~. _ .s....._..~. _ _ ° _ __.~_... 'n9 a9 ..__ 2a US Patent No. 5, 433, 976 teaches the rinsing of a metal sheet with an alkaline solution containing a dissolved silicate or aluminate, an organofunctional silane and a cross-linking agent in order to form an insoluble composite layer containing siloxane.
The water solubility of some silanes may be limited creating solubility problems in the aqueous solution.
Additionally, some metal substrates are particularly prone to corrosion upon contact with water, thus, an aqueous solution may be undesirable in some circumstances.
Various other techniques for preventing the corrosion of metal sheets have also been proposed. Many of these i:

AME,vDEJ SHEET
IP~AiEP

proposed techniques, however are ineffective, or require time-consuming, energy-inefficient, multi-step processes.
Thus, there is a need for a simple, low-cost technigue for preventing corrosion of metals, particularly metal sheet and cast aluminium or aluminium alloys, including those instances wherein a polymer coating such as paint is to be applied to the metal.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved method of preventing corrosion of metals.
It is another object of the present invention to provide a method of preventing corrosion of metals, wherein the treatment compositions employed need not be removed prior to painting or coating with another polymer such as adhesives or rubber coatings.
The foregoing objects can be accomplished, in accordance with one aspect of the present invention, by providing a method of pretreating a metal substrate to improve corrosion resistance, comprising the steps of:
(a) providing a metal substrate; and (b) applying a first treatment solution directly onto the surface of the metal, the first treatment solution containing at least one multi-functional silane having at least two trisubstituted silyl groups wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, wherein the multi-functional silane has been at least partially hydrolyzed.
The first treatment solution has a pH of less than about 7 to ensure proper hydrolysis. One significant advantage of the present invention is that the first treatment solution may be applied directly onto the surface of the metal without an underlying layer of a silicate, aluminate or other coating as required by many of the prior art treatment methods.

More than one multi-functional silane may be employed, and each may comprise:
OR
X Sli- OR
OR
n wherein X is either a bond, an aliphatic or aromatic group, each R is an alkyl or acetyl group, and n is 2 or 3.
Preferably each R is individually chosen from the group consisting of: ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl. X may be chosen from the group consisting of: Cl - C6 alkyl, C1 - C6 alkenyl, C1 - C6 alkyl substituted with at least one amino group, C1 - C6 alkenyl substituted with at least one amino group, benzyl, and benzyl substituted with C1 - C6 alkyl.
The preferred multi-functional silane is 1,2-bis-(triethoxysilyl)ethane (BTSE).
The multi-functional silane coating is also preferably cured at a temperature of between about 60° C and about 250° C for between about one minute and about 2 hours.
After curing, the first treatment solution may be reapplied, and cured if desired.
If the metal substrate is to be painted or coated with another polymer such as an adhesive or rubber, a second treatment solution may be applied after application of the first treatment solution. This second treatment solution contains at least one (and possibly multiple) organofunctional silane which has been at least partially hydrolyzed. The organofunctional silane preferably has a trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, and at least one organofunctional group. The organofunctional group may be chosen from the group consisting of: amino (with any number of amino moieties), vinyl, ureido, epoxy, mercapto, cyanato, methacrylato, and SUBSTITUTE SHEET (RULE 26) __ __ _ ____ .-.._ ~ _..__ . .. _ _ _ _. _T __.._.~. _ _ ___.

vinylbenzyl. Particularly preferred organofunctianal silanes include: Y-APS, y-MPS, Y-UPS, y-GPS, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane. The methods of the present 5 invention are particularly suitable for treating aluminum and aluminum alloys (both in sheet form and cast). For these materials the preferred organofunctional silane (when employed) is a vinyl silane. In the first treatment solution, the total concentration of unhydrolyzed, multi-functional silanes employed to, prepare the treatment solution should be greater than about 0.1% by volume (more preferably greater than about 10, and ideally between about 2% and about 5%), based upon the total volume of treatment solution components. Curing may be performed at a temperature of between about 60° C and about 250° C for between about one minute and about 2 hours.
The methods of the present invention may also be effectively employed on cold-rolled steel (CRS), particularly when the CRS is to be painted. For CRS the preferred organofunctional silane is Y-APS. The total concentration of ,unhydrolyzed multi-functional silanes employed to prepare the first treatment solution may be between about 0.1% and about 10% by volume, based upon the total volume of first treatment solution components, and the total concentration of unhydrolyzed, organofunctional silanes employed to prepare the second treatment solution may be between about O.lo and about loo by volume, based upon the total volume o~ second treatment solution components. The pH of the first treatment solution should be less than about 7, and the total concentration of unhydrolyzed, multi-functional silanes employed to prepare the first treatment solution is preferably between about 1%
and about 5%.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Applicants have found that corrosion of metal, particularly cold-rolled steel ("CRS"), aluminum and aluminum alloys, can be prevented by applying a treatment solution containing one or more multi-functional silanes having either two or three trisubstituted silyl groups to the metal, wherein the multi-functional silane(s) has been at least partially hydrolyzed. This may be followed by a treatment solution containing one or more organofunctional silanes which have also been at least partially hydrolyzed, particularly when the metal is to be coated with a polymer such as paint. The corrosion protection provided by these coatings is surprisingly superior to conventional chromate based treatments, and avoids the chromium disposal problem.
In addition, when the second solution employing an organofunctional silane is applied to the metal, the organofunctional silane coating need not be removed prior to painting or application of another polymer (such as adhesives or rubbers). To the contrary, the organofunctional silane coating offers improved paint adhesion, and, together with the multi-functional silane, provides excellent corrosion protection beneath the layer of paint.
As used herein, the term "multi-functional silane"
means a silane having two or three trisubstituted silyl groups (i.e., bis- or tris-functional) wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy. The term "organofunctional silane" refers to a silane which has a single trisubstituted silyl group, and an organofunctional moiety which will react with the paint or other polymer coating (such as adhesives or rubbers) which may be applied over top of the organofunctional silane.
While not wishing to be bound by theory, it is believed that the silanol groups of the hydrolyzed multi-functional silane bonds very strongly and very quickly to the oxides on the surface of the metal. In addition, the multi-functional silane coats the metal surface well, therefore further improving the ability of the multi-functional silane to passivate the metal surface.

The organofunctional silanes of the present invention, on the other hand, do not bond well to the metal surface, even when crosslinked in the manner described in U.S. Patent No.
5,292,549 discussed above. These organofunctional silanes, however, will bond to a coating of a mufti-functional silane of the present invention which has previously been applied to the metal surface (primarily through the silanol groups of the hydrolyzed organofunctional silane). the.
organofunctional moiety is then free to bond to paint, or other polymer coatings (such as adhesives and rubbers).
Thus, Applicants have found that when an organofunctional silane of the present invention is employed, it should be applied to the metal only after a coating of a mufti-functional silane of the present invention has been applied to the metal.
The treatment methods of the present invention may be used on any of a variety of metals, including CRS, aluminum (both in sheet form and cast), and aluminum alloy (both in sheet form and cast). It should be noted that the term "metal sheet" includes both continuous coil as well as cut lengths.
The preferred mufti-functional silanes which may be employed in the present invention each have two or three trisubstituted silyl groups, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy. Thus, the mufti-functional silanes which may be used in the present invention may have the general structure of:
OR
X Sli - pR
OR
n wherein X is either a bond ,an aliphatic (saturated or unsaturated) or aromatic group, n is 2 or 3, and each R is an alkyl or acetyl group. Each R within the mufti-functional silane can be the same or different, and thus the mufti-functional silane may include both alkoxy and acetoxy moieties. For example, each R may be individually chosen from the group consisting of: ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl. X is preferably chosen from the group consisting of: a bond, C1 - C6 alkyl (linear or branched), C1 - C6 alkenyl (linear or branched), C1 - C6 alkyl substituted with one or more amino groups, C1 - C6 alkenyl substituted with one or more amino groups, benzyl, and benzyl substituted with C1 - C6 alkyl. In the case where X is a bond, the mufti-functional silane comprises two trisubstituted silyl groups which are bonded directly to one another, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy (such as hexamethoxydisilane). One particularly preferred mufti-functional silane is 1,2-bis-triethoxysilyl)ethane (hereinafter referred to as "BTSE"), which has the following formula:
i CH2CH3 H i CH2CH3 CH3CH20-Sli-H-C2-S'i-pCH2CH3 '2 OCH2CH3 OCHzCH3 Other suitable mufti-functional silanes include 1,2-bis-(trimethoxysilyl)ethane (TMSE), and 1,6-bis-(trialkoxysilyl)hexanes (including 1,6-bis-(trimethoxysilyl)hexanes), 1,2-bis-(triethoxysilyl)ethylene, 1,4-bis-(trimethoxysilylethyl)benzene, and 1,2-bis-(trimethoxysilylpropyl)amine.
The above-described mufti-functional silanes must be at least partially, and preferably fully hydrolyzed so that the silane will bond to the metal surface. During hydrolysis, the alkyl or acetyl groups (i.e., the "R"
moiety) are replaced with a hydrogen atom. As used herein, SUBSTITUTE SHEET (RULE 26) the term "partially hydrolyzed" simply means that only a portion of the alkyl or acetyl groups on the silane have been replaced with a hydrogen atom. The multi-functional silanes should be hydrolyzed to the extent that at least two of the alkyl or acetyl groups on each molecule have been replaced with a hydrogen atom. Hydrolysis of the multifunctional silane may be accomplished merely be mixing the silane with water, and optionally including a solvent such as an alcohol in order to improve solubility. The pH
of the solution is also preferably maintained below about 7, and, in the case of BTSE, more preferably between about 4 and about G, in order to improve hydrolysis. The pH may be adjusted, for example, by the addition of an acid, such as acetic, oxalic, formic or propionic acid. If the pH is permitted to increase above about 7, the hydrolyzed multi-functional silane may begin to polymerize via a condensation reaction. If this is permitted to occur, the corrosion resistance will be significantly reduced since the silane may not bond strongly to the metal surface.
The concentration of multifunctional silanes such as BTSE in the solution should be between about 0 . 1 o and about 100, preferably greater than 1%. More preferably, a concentration of between about 2% and about 5% is preferred. Although a more concentrated solution will provide a greater film thickness on the metal, this comes at the expense of increased cost. In addition, thicker films are often weak and brittle. It should be noted that the concentration of silanes discussed and claimed herein are all measured in terms of the ratio .between the amount of unhydrolyzed, multi-functional silanes employed (i.e., prior to hydroiyzation, and the total volume of treatment solution components (i.e., silanes, water, optional solvents and pH adjusting acids). In addition, the concentrations refer to the total amount of unhydrolyzed multi-functional silanes added, as multiple silanes may optionally be employed in this treatment solution.

Since the solubility in water of some of the silanes used may be limited, the treatment solution may optionally include one or more solvents, such as alcohols, in order to improve silane solubility. The alcohol may also improve the 5 stability of the treatment solution, as well as the wettability of the metal substrate. The use of alcohols or other non-aqueous solvents such as acetone is also particularly useful for metal substrates which are prone to corrosion upon mere contact with water (such as galvanic 10 corrosion of certain alloys, including CRS). Particularly preferred alcohols include: methanol, ethanol, propanol, butanol and isomers thereof. The amount employed will depend upon the solubility of the particular multi-functional silanes in the treatment solution and thus the concentration range of alcohol to water in the treatment solution of the present invention is in the ratio of 1:99 to 99:1, (by volume). There should be sufficient water to ensure at least partial hydrolysis of the silane, and thus it is preferable that at least 5 parts of water be employed for every 95 parts of alcohol. Alcohols may, however, be omitted entirely if the silane(s) is soluble in water. When alcohols are employed, methanol and ethanol are the preferred alcohols.
The treatment method itself is straightforward. The unhydrolyzed multifunctional silane(s), water, alcohol (if needed), and a small amount of acetic acid (as needed to adjust the pH) are combined with one another. Other acids may alternatively be employed to adjust the pH as needed.
The solution is then stirred at room temperature in order to at least partially hydrolyze the silane(s). This hydrolysis may take up to several hours to complete, and its completion will be evidenced by the solution remaining completely clear when water is added to a small sample of the solution.
The metal substrate to be treated is preferably solvent and/or alkaline cleaned (by techniques well-known in the prior art) prior to application of the _._._ __..__ ~.__ _ ._.._ _..

above-described treatment composition of the present invention, and then allowed to dry. The metal may be preheated (preferably to a temperature between about 60°C
and about 250°C) prior to coating with the multi-functional silane, particular in the case of aluminum alloys, as this preheating has been found to significantly improve the corrosion protection provided by the present invention. The treatment solution, however, can be maintained at room temperature. The treatment solution may then be applied directly onto the cleaned metal (i.e. , with no other layers between the metal and the treatment composition of the present invention) by either dipping the metal into the solution (also referred to as "rinsing"), spraying the solution onto the surface of the metal, or even wiping or brushing the treatment solution onto the metal substrate .
When the preferred application method of dipping is employed, the duration of dipping is not critical, as it will generally not affect the resulting film thickness. It is preferred that the dipping time be between about 2 seconds and about 30 minutes, preferably between about 1 and 2 minutes to insure complete coating of the metal.
If the metal is not to be coated with a polymer such as paint, and particularly in the case of aluminum and aluminum alloys, the multi-functional silane coating should be cured following the application process described above.
Curing will polymerize the hydrolyzed silanol groups. The coated metal need not be dried prior to curing, as the curing itself will dry the surface. Alternatively, the metal may be blown dry or dried in place. Curing may be performed at temperatures between about 60°C and about 250°C, for between about 1 minute and 2 hours, however curing will eventually take place even at room temperatures over a sufficient period of time. Preferably curing is performed at a temperature of about 200°C for about 10 minutes.
Following the cure, a second coating of the multi-functional silane(s) is preferably applied, and then cured in the same manner. The metal substrate may be cooled prior to application of the second coating, however applicants have achieved excellent results by applying the second coating without first cooling the substrate (i.e., by merely quenching the cured metal substrate by dipping the heated substrate into the room temperature treatment solution). Additional coatings may be similarly applied, however two coatings has been found to provide more than sufficient protection which is at least equal to that provided by conventional chromate pretreatments.
The above treatment method has been shown to perform better than that of the sol-gel technology proposed by others, and in fact approaches the performance of a heavy chromate coating. This technique has been found to be particularly advantageous for aluminium alloys, including 2024-T3, 7075, 356 and 380. The silane film is typically between about 100 and about 1000 Angstroms thick (depending upon silane concentration and the solvents employed), and, in the case of aluminium 2024-T3 alloy, provides corrosion resistance to immersion in a 3o aerated salt solution of 175 hours or more. By way of comparison, an untreated 2024-T3 sheet provides corrosion resistance for less than 12 hours. The film is believed to form covalent, non-hydrolyzable bonds with the metal oxide, and is also highly hydrophobic, which contributes to the corrosion performance. The film is completely stable in air, is colourless, is pore free (particularly when a second coating is applied), and provides unexpectedly excellent corrosion protection.
If the metal is to be painted or coated with another polymer (such as adhesives or rubbers) application of the multi-functional silane(s) treatment solution is preferably followed by the application of a second treatment solution containing one or more organofunctional silanes which have been at least partially hydrolyzed. The organofunctional silane(s) will not only bond with the multi-functional silane coating, but the organofunctional moiety will also WO 98/30735 PCT~~B~~~

bond with the paint or other polymer coating applied over top of it. Multiple layers of the multi-functional silane(s) may be first applied, however, the final layer of the multi-functional silane(s) should be only partially cured (or not cured at all) in order to insure that the organofunctional silane(s) will bond to the multi-functional silane layer (by means of the silanol group on the hydrolyzed organofunctional silane). In other words, if two coatings of a multi-functional silane such as BTSE is applied, the first coating may be cured as described above, while the second coating is left uncured.
An organofunctional silane is then applied over top of the second, uncured layer of BTSE. In this manner, the organofunctional silane coating will react with, and therefore bond to the multi-functional silane coating, and paint or other polymers will bond to the organofunctional silane coating. This technique is particularly suitable for CRS, aluminum and aluminum alloys.
Numerous types of organofunctional silanes may be employed for this top coating, particularly those containing a trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, and at least one free organofunctional moiety which will react with the paint or other polymer coating (such as adhesives or rubbers). More preferably, the trisubstituted silyl group is at one terminus of the organofunctional silane, and the organofunctional moiety is at the opposite terminus. The organofunctional -moiety may be, for example, amino (with any number of amino moieties), vinyl, ureido, epoxy (including glycidoxy), mercapto, cyanato, methacrylato, vinylbenzyl. Particularly suitable organofunctional silanes include: Y-aminopropyltriethoxysilane (Y-APS);
Y-mercaptopropyltrimethoxysilane (y-MPS);
Y-ureidopropyltrialkoxysilane (y-UPS);
Y-glycidoxypropyltrimethoxysilane (YGPS); and any of a variety of vinyl silanes (i.e., an organofunctional silane wherein the organofunctional moiety is a vinyl group) including vinyltrimethoxysilane (VS), vinyltriethoxysilane, vinyltriacetoxysilane. For aluminum and aluminum alloys any of the above-mentioned vinyl silanes are preferred (particularly VS), while Y-APS is preferred for CRS.
Application of the organofunctional silanes may be accomplished in a manner similar to that described for the multi-functional silanes. Thus, the organofunctional silane should be at least partially, and preferably completely hydrolyzed. This may be accomplished by merely mixing the organofunctional silane(s) with water, and proper maintenance of the pH. For some organofunctional silanes, hydrolysis will occur at an alkaline pH, and thus the pH
should be maintained at the optimum level which promotes hydrolysis and limits condensation of the organofunctional silane. For example, the "natural" pH of an aqueous solution of Y-APS is 10.4. The term "natural pH" refers to the pH of a to (by volume) aqueous solution of Y-APS. At this pH, the y-APS is fully hydrolyzed, and therefore the pH need not be reduced. Similarly, the natural pH of Y-UPS
is about 8.1, and the y-UPS is fully hydrolyzed. For y-MPS, Y-GPS and vinyl silanes, the pH should be maintained below about 7. Once again an acid such as acetic, oxalic, formic or propionic acid may be used to maintain the pH, and various types of solvents such as alcohols may be employed to improve solubility. Concentrations of the organofunctional silanes are calculated in the manner previously described, and it is preferred that between about 0.1% and about 10% of organofunctional silane{s) be employed in this second treatment solution. More preferably, between about 1o and about 5% organofunctional silane(s) is employed. It should be pointed out that as was the case previously, multiple organofunctional silanes may be employed.
The method of application of the organofunctional silane is similar to that previously described. Thus, immediately after the final layer of multi-functional silane(s) has been applied and preferably only partially cured, the second treatment solution containing the organofunctional silane(s) is applied to the metal.
Application may be accomplished by spraying, dipping or 5 other means well known to those skilled in the art. A
single coating of the organofunctional silane(s) is sufficient, and the substrate may then be dried at room temperature prior to application of paint or other polymer coating.
10 By employing this dual-coat of a multi-functional silane(s) followed by an organofunctional silane(s), not only is excellent corrosion protection provided, but also excellent paint adherence. The paint or other polymer coating may be applied directly on top of the 15 organofunctional silane(s). In addition, the organofunctional silane may be chosen depending upon the type of paint or polymer to be employed, and thus the methods of the present invention can be precisely tailored to the particular application.
The examples below demonstrate some of the superior and unexpected results obtained by employing the methods of the present invention.

A 3o solution of hydrolyzed BTSE was prepared as follows. 3 ml of BTSE was added to 0.3 ml of acetic acid with magnetic stirring. 3 ml of water was then added to this solution, followed by 94 ml of methanol. This order of addition is preferred, as the early use of acetic acid helps prevent condensation of the BTSE. Samples of 2024-T3 (2.5 cm x 10 cm) were then ultrasonically solvent cleaned for 15 minutes in hexanes, 15 minutes in acetone, and 15 minutes in methanol. The samples were then dipped (at room temperature) into the 3o BTSE solution for approximately 100 seconds, and then blown dry with air. After drying, the coated samples were then cured at 100° C for 15 minutes.
The dipping/drying/curing steps were then repeated two additional times, such that a total of three layers of BTSE
were deposited on the samples.
The BTSE-coated samples (prepared as above), untreated samples, and samples treated by a conventional chromating process were then partially immersed in a 3 o NaCl solution, and the water line was monitored for evidence of corrosion.
Corrosion began to appear on the untreated samples in less than 12 hours, and in 10o to 150 hours for the chromated samples. The BTSE-coated samples exhibited no corrosion after 175 hours.
EXAMPhE 2 The steps of Example 1 were repeated, however the number of coats applied, and the use of a cure step and cure temperature were varied in the manner shown in the table below. Samples were also preheated to the indicated temperature prior to-application of the first coating of BTSE. The corrosive protection provided by the BTSE coating was then measured by conducting standard electrochemical polarization tests using a 3% NaCl solution. The voltage range was varied from -200 mV to +200 mV, with a scan rate of 1 mV/s. The results of these tests are shown below, wherein the rate of corrosion is reported in millimeters per year. In these examples, the samples were preheated to the cure temperature prior to application of the first BTSE
coating, and were not cooled between curing and the application of a second coating of BTSE.

~._d_.__._ . __.~~._._. T

ample Corr.
Rate(mpy) 00'C ingle coat 0.578 (1.83x10-emm/sec) reheat ingle coat with cure 0.038 (1.20x10-9mm/sec) nd ouble coat with cure 0.221 (1.70x10-9mm/sec) etween coats ure ouble coat with cure .021 (6.60x10-1mm/sec) fter each coat 50'C ingle coat 0.134 (4.24x10-9mm/sec) reheat ingle coat with cure .013 (4.12x10-1mm/sec) nd ouble coat with cure .031 (9.83x10-1mm/sec) etween coats ure ouble coat with cure .015 (4.71x10-'mm/sec) fter each coat 00'C ingle coat 0.043 (1.36x10-9mm/sec) reheat ingle coat with cure .017 (5.39x10-1mm/sec) nd ouble coat with cure .004 (1.27x10-1mm/sec) etwee n ts coa ure ouble coat with cure .004 (1.27x101mm/sec) fter each coat hromated 0.004 (1.27x10''mm/sec) (Standard 0.003 (9.51x10-llmm/sec) hromate .007 (2.22x10-1mm/sec) reatment) .003 (9.51x10-llmm/sec) .~Filiform corrosion occurs on metallic surfaces which have~been coated with a thin organic film (s~a~h as paint).
The pattern of attack is characterized by the appearance of fine filaments emanating from one or more sources in semi-random directions. The source of initiation is usually a defect or mechanical scratch in the coating. The filaments are fine tunnels composed of corrosion products underneath the bulged and cracked coating.
Samples of cast A1356 alloy known to be sensitive to filiform corrosion were treated with a BTSE solution in the AMEf~DED S~IE'E ~
~p =~'./E~' manner described above and as indicated in the table below.
A 3% BTSE solution at a pH of 5 was employed. In addition, one of the samples was coated with a 3% solution of vinyl silane (at a pH of 5), after application of BTSE. The dried samples were then painted with a clear polyester powder coating and subjected to GM 4476P Copper Accelerated Acetic Acid-Salt Spray Test. The samples were periodically observed for filiform corrosion. As indicated in the table below, the treatment methods of the present invention provided excellent protection against filiform corrosion, even exceeding the results obtained with a standard chromate treatment (CHEM COTE 3530 chromate treatment available from Brent America, Inc.}
Treatment Method Initiation of Filiform Corrosion No treatment prior to painting <1 day Standard chromating 1 week Coat with BTSE solution, cure at 100C for none after 15 minutes, cool to room temperature, weeks coat with BTSE, cure at 100C for 15 minutes, cool to room temperature Preheat to 200C for 15 minutes, coat with none after BTSE solution, cure at 200C for 15 weeks minutes, coat with BTSE, cure at 200C for 15 minutes Preheat to 200C for 15 minutes, coat with none after BTSE solution, cure at 200C for 15 weeks minutes, coat with vinyl silane, cure at 200C for 15 minutes EgAMPLE 4 Samples of CRS (10 cm x 15 cm x 0.5 mm) were treated according to the methods of the present invention, coated with a polyurethane powder paint (6570 um thick), and then SUBSTITUTE SHEET (RULE 26) cured for 10 minutes at 200° C. In order to measure creepage, which in turn is indicative of the degree of paint adhesion and corrosion protection, a carbide-tipped pencil-type scribing tool was used to create a 7 cm long scribe in each of the samples. The scribe was sufficiently deep to expose the base metal. The scribed panels were then subjected to a cyclic corrosion test (GM9540P) for two weeks and/or a salt spray test (ASTM B117) for 25 days. At the end of that time, a piece of strong, industrial adhesive tape was secured atop each scribe and then pulled off of the panel. The average width of the area of paint delamination was then measured, and the following results obtained:
Treatment Method (prior to painting) Scribe Creep (mm~

alkaline cleaning only 30.0(GM 9540P) alkaline cleaning only 23.1(ASTM B117) alkaline cleaning followed by an iron 14.5(GM 9540P) phosphate treatment alkaline cleaning followed by an iron 51.0(ASTM B117) phosphate treatment alkaline cleaner, water rinse, iron 5.0(GM 9540P) phosphate, water rinse and chromate rinse alkaline cleaner, water rinse, iron 2.2(ASTM B117) phosphate, water rinse and chromate rinse dipped in 2% BTSE solution (pH 6) for 2.5(GM 9540P) 2 minutes blown dry, dipped in 5%

y-APS (pH 10.5) for 30 seconds, blown dry dipped in 2% BTSE solution (pH G) for 2.6(ASTM B117) 2 minutes blown dry, dipped in 5%

Y-APS (pH 10.5) for 2 minutes, blown dry, cured for 10 minutes at 200 C

CHEM CLEAN 1353* alkaline cleaner, CHEM COTE 3029* iron phosphate and CHEM SEAL 3603* chromate rinse were employed in the above examples. All of these products are commercially available from Brent America, Inc.
5 The above results clearly demonstrate that the treatment methods of the present invention are effective in treating CRS prior to painting.

10 The methods of Example 4 were repeated, however a polyester powder paint was applied (60 ~cm thick), and was then cured for 10 minutes at 200° C.
The results are as shown below.
15 Treatment Method (prior to painting) scribe Creep (mta) alkaline cleaning only 32.0(GM 9540P) alkaline cleaning only 34.1(ASTM B117) alkaline cleaning followed by an iron 23.0(GM 9540P) phosphate treatment 20 alkaline cleaning followed by an iron 52.4(ASTM Bii7) phosphate treatment alkaline cleaner, water rinse, iron 4.0(GM 9540P) phosphate, water rinse and chromate rinse alkaline cleaner, water rinse, iron 2.2(ASTM B117) phosphate, water rinse and chromate rinse dipped in 2% BTSE solution (pH 6) for 3.0(GM 9540P) 2 minutes blown dry, dipped in 5%

Y-APS (pH 10.5) for 2 minutes, blown dry dipped in 2% BTSE solution (pH 6) for 1.4(ASTM B117) 2 minutes blown dry, dipped in 5%

Y-APS (pH 10.5) for 2 minutes, blown dry * trade-mark The above results once again show the effectiveness of the treatment methods of the present invention. In addition, Applicants have also found that slight variations in the pH, dipping time, concentrations, and age of the solutions had no effect on the performance of the treatment methods of the present invention. In addition, the treated CRS panels can be stored in ambient for at least 30 days prior to painting without a loss of performance. It is believed that the BTSE/y-APS treatment passivates the steel, and therefore prevents the format on of corrosion.
in the atmosphere.
As indicated by the above results, the treatment methods of the present invention provide significant protection against corrosion as compared to both untreated panels as well as those treated with the phosphate/chromate treatment method of the prior art. These results clearly indicate that the treatment methods of the present invention not only provide excellent corrosion resistance, but also excellent paint adhesion.
The foregoing description of preferred embodiments is by no means exhaustive of the variations in the present invention that are possible, and has been presented only for purposes of illustration and description. In addition to providing corrosion protection, the treatment methods of the present invention also improve paint or polymer adhesion, and hydrophobicity. The coatings are also colourless, homogeneous, and relatively soft (i.e., non-brittle). Obvious modifications and variations will be apparent to those skilled in the art in light of the teachings of the foregoing description without departing from the scope of this invention. For example, various types of polymer coatings other than paint may be applied on top of the coatings of the present invention. In addition, BTSE is but merely one exemplary multi-functional silane which may be employed. Thus, it is intended that the scope of the present invention be defined by the claims appended hereto.

Claims

CLAIMS:

1. A method of treating a metal substrate, comprising the steps of:
(a) providing a metal substrate;
(b) applying a coating of at least a first treatment solution directly onto the surface of said metal, said first treatment solution having a silane content of between 0.1% and 10% by volume and consisting solely of at least one multi-functional silane having two or three trisubstituted silyl groups wherein the substituents are individually alkoxy or acetoxy, wherein said multi-functional silane has been at least partially hydrolyzed, and wherein said first treatment solution has a pH of less than 7.

2. A method of treating a metal substrate, comprising the steps of:
(a) providing a metal substrate;
(b) applying at least one coating of at least a first treatment solution onto the surface of said metal to afford a coated metal surface, said first treatment solution having a silane content of between 0.1% and 10% by volume and consisting solely of at least one multi-functional silane having two or three trisubstituted silyl groups wherein the substituents are individually alkoxy or acetoxy, wherein said multi-functional silane has been at least partially hydrolyzed, and wherein said first treatment solution has a pH of less than 7; and (c) applying a polymer coating onto the coated metal surface.

3. The method of claim 2, wherein the polymer coating is paint, adhesive or rubber coating.

4. The method of any one of claims 1 to 3, wherein said at least one multi-functional silane comprises:

wherein X is a bond, an aliphatic group or an aromatic group; each R is an alkyl or acetyl group; and n is 2 or 3.

5. The method of claim 4, wherein each R is individually ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl or acetyl.

6. The method of claim 5, wherein X is a bond, C1 - C6 alkyl, C1 - C6 alkenyl, C1 - C6 alkyl substituted with at least one amino group, C1 - C6 alkenyl substituted with at least one amino group, benzyl, or benzyl substituted with C1 - C6 alkyl.

7. The method of claim 6, wherein said multi-functional silane is 1,2-bis-(triethoxysilyl)ethane.

8. The method of claim 6 or claim 7, wherein said metal is cold-rolled steel, aluminum or aluminum alloy.

9. The method of any one of claims 1 to 8, further comprising the step of curing said coating after step (b), at a temperature of between 60° C and 250° C for between one minute and 2 hours.

10. The method of claim 9, further comprising the step of applying a second coating after step (b) of said first treatment solution after said curing step.

11. The method of claim 10, further comprising the step of curing said second coating.

12. The method of any one of claims 1 to 10 further comprising the step of applying a second coating after step (b) comprising a second treatment solution after application of said first treatment solution, said second treatment solution containing at least one organofunctional silane which has a single trisubstituted silyl group and an organofunctional moiety, said organofunctional silane having been at least partially hydrolyzed.

13. The method of claim 12, wherein said at least one organofunctional silane has one trisubstituted silyl group, wherein the substituents are individually alkoxy or acetoxy, and at least one organofunctional group.

14. The method of claim 13, wherein said organofunctional group is amino, vinyl, ureido, epoxy, mercapto, cyanato, methacrylato, or vinylbenzyl.

15. The method of claim 14, wherein said at least one organofunctional silane is:
.gamma.-aminopropyltriethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-ureidopropyltrialkoxysilane, .gamma.-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltriacetoxysilane.

16. The method of any one of claims 4 to 7, wherein said metal is preheated to a temperature of between 60°C and 250°C prior to application of the first treatment solution.

17. The method of any one of claims 1 to 16 wherein the metal substrate is aluminum or aluminum alloy.

18. The method of claim 17, wherein the total concentration of said multi-functional silanes in said treatment solution is in the range from 0.2 % to 10% by volume, based upon the total volume of treatment solution components.

19. The method of claim 18, wherein the total concentration of said multi-functional silanes in said treatment solution is between 2% and 5%.

20. The method of claim 12, further comprising the step of applying a final coating of a solution after step (b) containing at least one organofunctional silane which has been at least partially hydrolyzed.

21. The method of any one of claims 12 to 16 for pretreating cold-rolled steel, comprising the steps of:
(a) providing said first treatment solution consisting essentially of at least one multifunctional silane which has been at least partially hydrolyzed, wherein said~
multi-functional silane has at least two trialkoxysilyl groups;
(b) providing said second treatment solution comprising at least one organofunctional silane which has been at least partially hydrolyzed;
(c) applying a coating of said first treatment solution directly onto the surface of the steel; and (d) thereafter applying a coating of said second treatment solution onto said steel.

22. The method of claim 21, wherein the total concentration of said multi-functional silanes in said first treatment solution is between 0.1% and 10% by volume, based upon the total volume of first treatment solution components, and wherein the total concentration of said organofunctional silanes in said second treatment solution is between 0.1%
and 10% by volume, based upon the total volume of second treatment solution components.

23. The method of claim 21 or claim 22, wherein said at least one organofunctional silane is .gamma.-aminopropyltriethoxysilane, and the total concentration of said multi-functional silanes in said treatment solution is between 1 and 5% by volume.

24. A treatment solution composition having a silane content of between 0.1% and 10% by volume and consisting solely of at least one multi-functional silane having two or three trisubstituted silyl groups wherein the substituents are individually alkoxy or acetoxy, in an aqueous alcohol solution, wherein the concentration range of alcohol to water is in the ratio of 1:99 to 99:1 by volume, and wherein the total concentration of multi-functional silanes in said treatment solution is between 2% and 5% by volume, based upon the total volume of said treatment solution components.

25. The composition of claim 24, wherein an amount of a weak acid is added to the solution to adjust the pH.

26. The composition of claim 24, wherein the concentration range of alcohol to water is in the ratio of 5:95 to 95:5 by volume.

27. The composition of claim 25, wherein the weak acid is acetic acid.