Abstract:
A non-chrome process for the pretreatment of substrate surfaces to simultaneously clean them and improve their bonding strength for organic coatings such as adhesives, protective primers, sealants, paints, composites and similar materials conventionally bonded to such substrates, including non-chromated or chromated curable organic resin protective coatings applied directly to bare aluminum substrates. The invention involves the use of novel wipe solvent compositions containing a major volume of an environmentally-safe volatile organic solvent which has a low composite vapor pressure or is otherwise exempt from federal, state or local regulations, and a minor volume of a polyfunctional coupling agent, preferably of the silane type.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to wipe solvent compositions for application to various substrates, including metal finishes/coatings such as anodized, Alodined, deoxidized, abraded, bare metals, fiberglass, plastic films, organic coatings, composites, glass and other substrates, for purposes of cleaning the substrate surface to improve the receptivity and bonding properties of the substrate relative to organic coatings, adhesives, adhesive coatings, primers, adhesive primers, sealants, paints, honeycomb structures and similar materials conventionally bonded to such substrates. 
     2. State of the Art 
     It is known to improve the receptivity of substrates for paints, primers and adhesive layers by treating the substrate surface with mechanical abrasive operations such as blasting followed by cleaning with an organic solvent such as methyl ethyl ketone following by brush-coating with a dilute aqueous silane solution and drying. Reference is made to U.S. Pat. No. 5,312,520. The process according to the patent is objectionable because methyl ethyl ketone is a hazardous air pollutant, dangerous to worker safety, and the process requires three separate steps, with the silane brushing step being repeated three times using alternating brush strokes. 
     Reference is also made to U.S. Pat. No. 5,424,133 for its disclosure of a process for preparing a plastic film or composite substrate surface for adhesive bonding coating operations by applying to the surface an abrasive composition containing abrasive particles such as silicon-containing particles and rubbing the coating into the surface to fix the abrasive particles thereto. The surface is first degreased by wiping with a solvent such as isopropanol. 
     It is known to treat or coat aluminum and other substrates to improve their bonding properties relative to primers, paints, adhesive coatings and other substrates such as composites, metals, glass, etc. Such process typically requires the use of a chemical conversion coating (CCC), such as Alodine, over the aluminum surface to improve the bonding properties of the substrate for paints, adhesives, etc., while enhancing the corrosion resistance of the coating system. The chemical conversion coating composition typically contains chromic acid, a fluoride acid salt and accelerators. 
     Chromium is an environmentally-objectionable chemical targeted by the EPA for reduction or elimination, and the replacement of chromium-containing plating and treatment baths with non-chromated baths has been the subject of extensive academic and industrial research. 
     Alternative chromium-free coating compositions have been developed but the process of applying such compositions requires multiple steps, each of which usually requires a different heated process tank as opposed to the single heated process tank required for the conventional chromated chemical conversion coating (CCC) process. The energy and facility requirements of this alternative process create substantial difficulty and expense from the standpoint of implementation into a production facility. 
     Another alternate chemical conversion process involves the use of a cobalt-amine oxidizing composition such as Alodine 2000 to form a chemical oxide film on aluminum substrates. Such process requires the use of two separate heated process tanks. In the first step a chemical oxide layer is formed on the surface of the aluminum using a cobalt-amine oxidizing bath to form an oxide layer about 1000 angstrom units in thickness. In the second step the oxidized aluminum substrate is immersed in a second tank containing a composition which seals the oxide layer to impart corrosion resistance to the substrate. The first step increases the bonding properties of the aluminum substrate while the second step is required to impart corrosion resistance. 
     Clearly, it is highly desirable to provide a process which eliminates the need for chemical conversion steps which require the use of chromium or require the use, of several heated baths and several steps to enhance adhesion properties to the substrate. 
     Such processes are tedious, time-consuming and/or dangerous, and are unsatisfactory for use on certain substrates, where abrasion or blasting cannot be used, and are ineffective for certain coatings and bonding operations. 
     SUMMARY OF THE INVENTION 
     The present invention is based upon the discovery that environmentally-safe non-chrome surface treating wipe solvent compositions can be produced by incorporating conventional silane or coupling agents in effective, environmentally-safe organic solvents such as naphtha, methyl propyl ketone, isopropyl alcohol, acetone and similar safe, non-carcinogenic volatile organic solvents, or blends of such solvents, having a composite vapor pressure below about 45 mmHg, or a volatile organic compound considered exempt by federal, state or local regulations, and that such compositions can be wiped onto various substrate surfaces to simultaneously clean the surfaces and deposit the coupling agent thereon for subsequent bonding to an applied primer, paint, adhesive layer and/or to another substrate such as of composite, metal, glass, plastic or honeycomb composite. 
     An advantage of the present process resides in the elimination of the conventional chemical conversion coatings that are applied to substrates, such as aluminum, to improve the bonding properties and corrosion-resistance of such substrates. The present process enables the direct application of novel surface treating wipe solvent(s) coatings to the surface of the substrate to simultaneously clean the substrate surface with environmentally-friendly organic solvents and to deposit thereon and bond thereto a coupling agent which functions as a bonding link between the substrate surface and the reactive organic groups contained in the corrosion-resistive primer composition to provide excellent bonding properties therebetween. 
    
    
     THE DRAWING 
     FIG. 1 is a chart showing the steps of the present process for preparing the surface of aluminum substrates for the application of paint primer compositions, preferably non-chromated primer compositions. 
    
    
     DETAILED DESCRIPTION 
     The novel process of the present invention involves the addition of conventional silane type polyfunctional coupling agents to major amounts by volume of environmentally-safe organic wipe solvents generally having a low vapor pressure to form novel wipe solvent compositions for cleaning the surface of a substrate such as that of metal, composite, glass, plastic or other material prior to the application of coatings of primer, paint, adhesive and/or similar layers and/or prior to the lamination of such substrates to each other or to support structures such as honeycomb bodies, while simultaneously depositing and bonding the coupling agent to the cleaned surface of the substrate. Such process avoids the use of environmentally-objectionable volatile organic solvents which are dangerous to the environment and to the health of workers, eliminates the need for separate cleaning steps and coating agent-application steps, and eliminates the need for conventional chemical conversion or oxidation coating steps on metal substrates such as aluminum, enabling the direct application and bonding of corrosion-resisting coatings such as chromated or unchromated primers, paints, adhesive resin layers, sealant layers, etc., to the substrate to impart corrosion resistance thereto, while coupling the coating directly to the substrate to avoid peeling, flaking or other separation of the coating and top coatings or laminates from the substrate. The present process targets the coupling agent directly to the area of the substrate to be coated, and eliminates the need for the coupling agent to migrate through a resin matrix to couple to the substrate as in the case where the coupling agent is present in an after-applied resinous primer, paint, adhesive or other layer, such as of curable epoxy resin or curable polyurethane resins from polyester resins and isocyanate curing agents. 
     The present novel surface treatment wipe solvent compositions comprise dilute solutions of one or more polyfunctional coupling agent(s) in one or more environmentally-safe volatile organic solvents. Such compositions contain from about 0.1% up to about 10% by volume of the coupling agent. 
     Preferred volatile organic solvents include naphtha, methyl propyl ketone, acetone, isopropyl alcohol and commercially available solvents and blends such as Shell Tolu-Sol® WHT, (mixed aliphatic (c 7  -c 8  cycloparoffins)solvents), Eco Solv® 1, 20 and 25, Prep Solv®, Enviro Sol® 655(isoparaffins), Oxsol® 100 (fluorochlorobenzene), and mixtures or blends or such environmentally and/or legally acceptable solvents. 
     Suitable silane-type polyfunctional coupling agents include silane coupling agents listed in Dow Corning Bulletin Form No. 23-012C-90. A preferred silane additive to the present wipe compositions comprises a 0.1 to 5% solution of hydroxyl- or lower alkoxy-terminated silane compound, such as 3-glycidoxy-propyltrimethoxy silane which is commercially-available under the trade designation Dow Corning Z-6040. This is an organofunctional silane which hydrolyzes to form silanol groups capable of bonding with inorganic surfaces such as metal and having an affinity for organic coatings applied thereover. Also suitable is a composition available under the trademark Rain-X® which is a 9% solution of a mixture of siloxane silanes in water-miscible alcohols, essentially ethyl alcohol, as well as aminoalkoxy silane reaction products. 
     A preferred embodiment of the present invention involves the application of the wipe solvent/coupling agent composition directly to the substrate surface being coupled, such as aluminum. In cases where the aluminum surface is oxidized, Alodined or anodized, the surface is lightly treated with an abrasive pad such as Scotch-Brite™ No. 7447 pad (silicon carbide/aluminum oxide) to remove the oxide, Alodine or anodized layer, or is soaked in an alcoholic phosphoric acid bath for about 10 minutes to etch away the oxidized layer and rinsed in water to remove all traces of the bath, or is deoxidized according to other standard methods of deoxidation. 
     In the preferred processes of the present invention, illustrated by FIG. 1 of the drawing, the aluminum substrate is surface-prepared in a series of sequential steps in which it is first degreased if necessary, such as by cleaning with acid, alkali or solvent wipe, rinsed and then deoxidized by one of the indicated methods 1 to 4. If method 1 is used, the substrate is then wiped with the novel wipe solvent composition of the present invention, containing a polyfunctional coupling agent, and is then coated with paint primer composition, preferably non-chromated. If deoxidation methods 2, 3 or 4 are used, the substrate is then rinsed before application if the wipe solvent and paint primer coating. 
     The following comparative tests demonstrate the improvement in bonding strength of resinous primer coatings to various aluminum substrates, and to graphite epoxy composite laminates, as measured by the conventional Lap Shear Test, ASTM D-1002. In each that the shear strength values represent the average of five specimens. 
     EXAMPLE 1 
     The substrate was bare aluminum in the form of coupons 4&#34;×6&#34; and 0.063&#34; thickness. The test panel surfaces designated 1A and 2A were pretreated with a deoxidation treatment according to Northrop/Grumman Document No. MEPS 4000-47 whereas the test panel surfaces 3A and 4A were not pretreated. 
     The test panel surfaces 1A and 3A were wiped clean with 50% naphtha/50% methyl propyl ketone (MPK) solvent, dry wiped, coated with a GM 4004 221 (Hysol EA 9394) epoxy resin adhesive layer and bonded within 30-40 minutes to identical 1A and 3A panel surfaces, respectively. 
     The test panel surfaces 2A and 4A were wiped clean with the present novel wipe solvent/coupling agent compositions comprising 95% by volume of the 50:50% by volume mixture of naphtha and methyl propyl ketone and 5% by volume of Dow Corning Z-6040 silane coupling agent, dry wiped, coated with a GM 4004 221 (Hysol 9394) adhesive layer and bonded within 30-40 minutes to identical 2A and 4A panel surfaces, respectively. 
     All of the bonded test panels were allowed to cure for 72 hours at room temperature and then baked for 2 hours at 150° F., cooled to room temperature and then band sawed into lap shear test specimens. All testing was conducted in accordance with ASTM D 1002 titled &#34;Strength Properties of Adhesives in Shear by Tension Loading (Metal to Metal) Test&#34; at room temperature (75° F.), with the following test results: 
     
         __________________________________________________________________________Spec. Width                    Shear Strength,Inches  Overlap Inches          Bondline Inches                  Fail Load lbs.                          psi    Mode of Failure__________________________________________________________________________Wiped With Naphtha/MPK-Panels 1A1 0.991 0.50   0.005   287     579    100% Adhesive2 0.989 0.50   0.005   381     770    100% Adhesive3 0.986 0.50   0.005   353     716    100% Adhesive4 0.990 0.50   0.005   339     685    100% Adhesive5 0.987 0.50   0.005   264     535    100% Adhesive                  AVERAGE 657Wiped With Naphtha/Z-6040-Panels 2A1 0.981 0.50   0.005   489     997    100% Adhesive2 0.986 0.50   0.005   395     801    100% Adhesive3 0.989 0.50   0.005   530     1072   100% Adhesive4 0.986 0.50   0.005   621     1260   100% Adhesive5 0.988 0.50   0.005   647     1310   100% Adhesive                  AVERAGE 1088                  IMPROVEMENT                          65.6%Wiped With Naphtha/MPK-Panels 3A1 0.986 0.50   0.005   251     509    100% Adhesive2 0.986 0.50   0.005   295     598    100% Adhesive3 0.983 0.50   0.005   267     543    100% Adhesive4 0.986 0.50   0.005   261     529    100% Adhesive5 0.988 0.50   0.005   273     553    100% Adhesive                  AVERAGE 546Wiped With Naphtha/Z-6040-Panels 4A1 0.986 0.50   0.005   385     781    100% Adhesive2 0.990 0.50   0.005   357     721    100% Adhesive3 0.987 0.50   0.005   313     634    100% Adhesive4 0.988 0.50   0.005   324     656    100% Adhesive5 0.990 0.50   0.005   343     693    100% Adhesive                  AVERAGE 697                  IMPROVEMENT                          27.7%__________________________________________________________________________ 
    
     As demonstrated by the test results, both the deoxidized Panels 2A and the non-pretreated Panels 4A have substantially-improved bonding strength as compared to Panels 1A and 3A, and the only difference to account for the improvement is the addition of the Z-6040 silane coupling agent to the wipe solvent to provide both cleaning of the substrate and bonding to the adhesive layer in a single step. The test results also demonstrate that the bonding strength provided by the present novel wipe solvent compositions is greatest when the compositions are directly applied to aluminum substrate surfaces which are pre-treated to remove surface oxidation, to enable the coupling agent to couple to and more intimately bond to the newly formed aluminum oxide surface. 
     EXAMPLE 2 
     This example demonstrates the improved bonding strength imparted to anodized aluminum substrates, pre-treated by lightly abrading with Scotch-BriteTM pads (No. 7447) to partially remove the superficial aluminum oxide, and then wiped with naphtha solvent which, contains no coupling agent (Panel 1B) or which contains various amounts of Z-6040 silane coupling agent (Panels 2B, 3B, 4B, 5B and 6B). In each case the panels are dry wiped and adhesive bonded within 30-40 minutes, using GA 100 BD12 epoxy resin adhesive (Hysol EA9394), and cured at 150° F. for two hours following 24 hours at room temperature. The panels were then subjected to lap shear testing according to ASTM D-1002 with the following results: 
     
         __________________________________________________________________________Width Overlap     Bondline          ShearInches Inches     Inches          Z-6040%               Fail Load lbs.                       Strength, psi                             Mode of Failure__________________________________________________________________________PANEL 1B1 1.017 0.50     0.005          0.0  559     1099  100% Adhesive2 1.014 0.50     0.005          0.0  524     1034  100% Adhesive3 1.016 0.50     0.005          0.0  581     1144  100% Adhesive4 1.016 0.50     0.005          0.0  569     1120  100% Adhesive5 1.015 0.50     0.005          0.0  551     1086  100% Adhesive               AVERAGE 1096PANEL 2B1 1.011 0.50     0.005          0.20 791     1565  100% Adhesive2 1.016 0.50     0.005          0.20 733     1443  100% Adhesive3 1.016 0.50     0.005          0.20 787     1549  100% Adhesive4 1.016 0.50     0.005          0.20 892     1756  100% Adhesive5 1.015 0.50     0.005          0.20 807     1590  100% Adhesive               AVERAGE 1581               IMPROVEMENT                       44.3%PANEL 3B1 1.016 0.50     0.005          0.50 683     1895  100% Adhesive2 1.013 0.50     0.005          0.50 683     2154  100% Adhesive3 1.016 0.50     0.005          0.50 733     1919  100% Adhesive4 1.014 0.50     0.005          0.50 759     1957  100% Adhesive5 1.016 0.50     0.005          0.50 604     2038  100% Adhesive               AVERAGE 1993               IMPROVEMENT                       81.8%PANEL 4B1 1.015 0.50     0.005          1.00 958     1888  100% Adhesive2 1.016 0.50     0.005          1.00 948     1866  100% Adhesive3 1.015 0.50     0.005          1.00 988     1947  100% Adhesive4 1.016 0.50     0.005          1.00 1080    2126  100% Adhesive5 1.017 0.50     0.005          1.00 965     1898  100% Adhesive               AVERAGE 1945               IMPROVEMENT                       77.4%PANEL 5B1 1.013 0.50     0.005          2.00 960     1895  100% Adhesive2 1.015 0.50     0.005          2.00 1093    2154  100% Adhesive3 1.017 0.50     0.005          2.00 976     1919  100% Adhesive4 1.015 0.50     0.005          2.00 993     1957  100% Adhesive5 1.013 0.50     0.005          2.00 1032    2038  100% Adhesive               AVERAGE 1993               IMPROVEMENT                       81.8%PANEL 6B1 1.015 0.50     0.005          4.00 1026    2022  100% Adhesive2 1.015 0.50     0.005          4.00 1014    1998  100%Adhesive3 1.014 0.50     0.005          4.00 1035    2041  100% Adhesive4 1.017 0.50     0.005          4.00 1036    2037  100% Adhesive5 1.012 0.50     0.005          4.00 924     1826  100% Adhesive               AVERAGE 1985               IMPROVEMENT                       81.1%__________________________________________________________________________ 
    
     As demonstrated by these test results, Panel 2B wiped with a novel wipe solvent composition containing as little as 0.2% by volume of the silane coupling agent, based upon the total volume of the composition imparts an average shear strength of 1581 psi for five samples compared to the average shear strength of 1096 psi for the five sample panels wiped with the naphtha solvent containing no silane coupling agent, an increase of 44.3%. Substantially greater improvement is obtained through the use of greater amounts of the silane additive in the wipe solvent compositions used to treat Panels 4B, 5B and 6B. 
     Similar results are obtained with Alodined substrates, pre-treated with Scotchbrite® pads to remove the Alodine. The use of wipe solvent compositions containing 0.2% by volume and 0.5% by volume of Z-6040 silane coupler increases the average shear strength to 1904 psi and 2334 psi, respectively , compared to similar panels treated with the same wipe solvent which does not contain any silane coupling agent and which have an average shear strength of only 1613 psi. 
     EXAMPLE 3 
     This example demonstrates the improved bonding strength imparted to deoxidized aluminum substrates primed with curable epoxy resin coatings commercially-available under the trademark Spraylat® containing an activator. The substrates are deoxidized in the same manner as Panels 1A and 2A of Example 1. 
     The deoxidized aluminum panels are rinsed with water, dry wiped, solvent wiped, dried and coated with Spraylat epoxy primer 30-40 minutes after final wiping. The primed panels are cured for six days at room temperature, and then cured for 24 hours at 150° F. The cured panels are wiped with methyl ethyl ketone solvent, and dry wiped. The primed panels are bonded with GA100BD12 epoxy adhesive (Hysol EA 9394) 30-40 minutes after dry wiping, cured for 20 hours at room temperature, following by 2 hours at 150° F. The panels are then subjected to lap shear testing according to ASTM D-1002. 
     For Panels 1C, the first solvent wipe applied directly to the deoxidized aluminum panels, prior to priming, consists of a naphtha solvent, whereas the first solvent wipe applied directly to the deoxidized aluminum panels 2C, 3C, 4C and 5C consists of a novel wipe composition containing various amounts by volume of Z-6040 silane coupling agent, as indicated. The average shear strength psi values are: 
     
         ______________________________________% Silane   Shear Strength, psiPanels Z-6040   Minimum  Maximum                          Average                                Improvement %______________________________________1C    0         819      945    874  Baseline2C    0.1      1097     1247   1175  343C    0.2      1109     1190   1151  324C    1.0       920     1313   1207  385C    2.0      1363     1448   1401  60______________________________________ 
    
     The following Example 4 demonstrates the improved shear strength imparted to graphite epoxy laminates bonded to each other by means of epoxy resin adhesive. 
     EXAMPLE 4 
     A plurality of graphite epoxy composite panels are provided by removing the peel ply, solvent wiped, dry wiped, sanded with 220 grit silicon carbide paper, solvent wiped, dry wiped, and coated with epoxy resin (Hysol EA 9391) adhesive within 30-40 minutes after final wipe. The composite panels are cured for at least 20 hours at room temperature, following by 2 hours at 150° F. The cured panels are tested for shear strength according to ASTM D 1002. The solvent wipe applied to Panels 1D consists solely of naphtha solvent whereas the wipe solvent composition applied to Panels 2D and 3D comprises a novel wipe solvent composition consisting of naphtha and 2% by volume of Z-6011 silane and 2% by volume of Z-6040 silane, respectively. The test results are as follows: 
     
         ______________________________________      Shear Strength, psi (5 Coupons Per Solvent)PanelSolvent     Minimum  Maximum                            Average                                  % Increase______________________________________1D   Tolu-Sol WHT            1578     2074   1790  --Only2D   Tolu-Sol WHT +            1755     2118   1921  7.32% Z-60113D   Tolu-Sol WHT +            1679     2402   1989  11.12% Z-6040______________________________________ 
    
     The test results demonstrate an improvement in average shear strength obtained by the use of the present novel wipe solvent compositions for the bonding of composite laminates to each other. 
     EXAMPLE 5 
     This example demonstrates the cleaning properties as well as the adhesion promoting properties of the present solvent wipe compositions when applied to bare aluminum substrates soiled with various lubricating oils and pastes. 
     A plurality of test panels of bare 2024-T3 aluminum were soiled with a mixture of lubricant drilling, press forming and cutting oils and pastes and allowed to stand for 24 hours. After 24 hours the panels were dry wiped with clean dry cloth, solvent wiped, dry wiped, abraded with Scotch-Brite™#7447 (silicon carbide/aluminum oxide), solvent wiped, dry wiped, and within 1-2 hours bonded with GA100BD12 epoxy adhesive to form lap shear test panels per ASTM D1002. The panels were allowed to cure at room temperatures for 7 days, followed by baking at 150° F. for 2 hours. The panels were then band-sawed into lap shear test specimens per ASTM specification. 
     The following tables illustrate the comparative shear strength psi values for the different lap shear test panels cleaned and coated with the indicated wipe solvents with and without the addition of the present silane compiling agents. 
     
         __________________________________________________________________________WIDTH     OVERLAP           BONDLINE                 FAIL LOAD                       SHEAR STRENGTH                                 MODE OFSPEC NO.INCHES     INCHES           INCHES                 LBS   PSI       FAILURE__________________________________________________________________________MPK1    1.003     0.50  0.005 556   1109      100% ADHESIVE2    1.000     0.50  0.005 562   1124      100% ADHESIVE3    1.000     0.50  0.005 686   1372      100% ADHESIVE4    1.006     0.50  0.005 710   1412      100% ADHESIVE5    0.999     0.50  0.005 692   1385      100% ADHESIVE                 AVERAGE                       1280MPK 5%Z-6040 SILANE1    1.002     0.50  0.005 1300  2595      100% ADHESIVE2    1.002     0.50  0.005 1460  2917      100% ADHESIVE3    1.002     0.50  0.005 2458  2910      100% ADHESIVE4    1.003     0.50  0.005 1598  3186      100% ADHESIVE5    1.003     0.50  0.005 1048  2090      100% ADHESIVE           AVERAGE                 2740NAPHTHA/MPK TECH GRADE1    1.002     0.50  0.005 618   1234      100% ADHESIVE2    1.003     0.50  0.005 632   1260      100% ADHESIVE3    0.998     0.50  0.005 608   1218      100% ADHESIVE4    1.002     0.50  0.005 654   1305      100% ADHESIVE5    1.005     0.50  0.005 638   1270      100% ADHESIVE                 AVERAGE                       1257NAPHTHA/MPK TECH GRADE 5% Z-6040 SILANE1    1.000     0.50  0.005 1540  3080      100% ADHESIVE2    1.002     0.50  0.005 1076  2148      100% ADHESIVE3    0.999     0.50  0.005 1122  2246      100% ADHESIVE4    1.002     0.50  0.005 1256  2507      100% ADHESIVE5    1.003     0.50  0.005 1186  2365      100% ADHESIVE                 AVERAGE                       246982% TECH GRADE MPK, 15% IPA,3% D.I. WATER1    1.001     0.50  0.005 740   1478      100% ADHESIVE2    1.005     0.50  0.005 780   1552      100% ADHESIVE3    1.002     0.50  0.005 822   1641      100% ADHESIVE4    1.002     0.50  0.005 840   1677      100% ADHESIVE5    1.004     0.50  0.005 868   1729      100% ADHESIVE                 AVERAGE                       1615(82% TECH GRADE MPK, 15% IPA,3%0.1. WATER) 5% Z-60401    1.006     0.50  0.005 1638  3260      100% ADHESIVE2    1.002     0.50  0.005 1638  3269      100% ADHESIVE3    1.003     0.50  0.005 1536  3063      100% ADHESIVE4    1.005     0.50  0.005 1634  3261      100% ADHESIVE5    1.001     0.50  0.005 1636  3269      100% ADHESIVE                 AVERAGE                       3224__________________________________________________________________________ 
    
     The first wipe solvent MPK (methyl propyl ketone) is commercially-available under the trademark Eastman® Methyl Propyl Ketone. 
     The second wipe solvent Naphtha/MPK is commercially-available as a 50:50 mixture under the trademark Tolu-Sol® WHT and MPK. 
     The third wipe solvent comprises a blend of methyl propyl ketone, isopropyl alcohol and deionized water. 
     Each of these wipe solvents is compared to corresponding wipe solvent compositions containing 5% by volume of Dow Corning Z-6040 silane coupling agent to produce substantial increases in the average shear strength equal to 114%, 96% and 99%, respectively. 
     The present process also can be used to replace the need for the conventional protection of aluminum and its alloys with chromate conversion coatings such as Alodine® coatings, while still achieving the required properties for paint adhesion, salt spray protection, filiform corrosion protection, etc., as illustrated by the comparative data in the following Example and table. 
     EXAMPLE 6 
     This Example illustrates the comparative adhesion properties and corrosion resistance properties of bare aluminum substrates QQ-A-250/4 and QQ-A-250/12 and aluminum alloy-clad aluminum substrates (250/4 and 250/12) which are (1) Alodined (MIL-C-5541), (2) Anodized (PAA) or (3) untreated prior to surface preparation and priming with chromated primer and non-chromated primer, respectively. 
     
         __________________________________________________________________________                                 Non-                           Chromated                                 Chromated  Test Method              Primer                                 Primer  (MIL-P-      Surface  # of                           (Deft (DeftProperty  85582)  Substrate               Prep     Spec                           44GN36)*                                 46GN05)*                                        Comments__________________________________________________________________________Adhesion  Fed Std 141B          QQ-A-               1. Deoxidize-                        3  1A-pass                                 1A-pass                                        1/ Immerse test panel for 2A. Dry-RT  Method 6301          250/5               See 1/      1B-pass                                 1B-pass                                        minutes in corrosionB. Wet ASTM D3359          (T3) 2. PAA-See 2/                           1C-pass                                 1C-pass                                        removing compound to MIL-C-C. Dry-350° F.               3. NGC Nonchrome                           2A-pass                                 2A-pass                                        38334, Type 1, Class 1,See Note 3/    2B-pass               2B-pass  then remove test panel and                           2C-pass                                 2C-pass                                        rinse with distilled water.                           3A-pass                                 3A-pass                                        Apply the primer coating                           3B-pass                                 3B-pass                                        within one hour.                           3C-pass                                 3C-pass                                        2/ Phosphoric Acid Anodize                                        (PAA) In accordance BAC                                        5555                                        3/ See FIG (1)Adhesion-  N/A     QQ-A-               1. MIL-C-5541                        3  1-pass                                 1-fail Spec requires No AdhesionCross Hatch    250/4               2. PAA      2-pass                                 (5%)   Loss &gt; 2%; Adhesion of          (T3) 3. NGC Nonchrome                           3-pass                                 2-pass Nonchrome Primer Improved                                 3-pass w/NGC Surface TreatmentAdhesion-  Fed Std 6301          QQ-A-               1. Deoxidize-See                        3  1-pass                                 1-pass Allow Primer to Dry for aIntercoat      250/5               1/          2-pass                                 2-pass minimum of two hours prior          (T3) 2. PAA      3-pass                                 3-pass to topcoat application               3. NGC NonchromeFlexibility  Fed Std 141          QQ-A-               1. MIL-C-5541                        3  1A-pass                                 1A-pass-1&#34; Mandrel  Method 6221          250/4               2. PAA      1B-pass                                 1B-passA. RT          (T3) 3. NGC Nonchrome                           2A-pass                                 2A-passB. 350° F.               2B-pass                                 2B-pass                           3A-pass                                 3A-pass                           3B-pass                                 3B-passStrippabil-  MIL-P-85582          QQ-A-               1. MIL-C-5541                        3  1-pass                                 1-pass 90% of Coating Must Beity    para 4.6.4          250/4               2. PAA      2-fail                                 2-fail Removed w/MIL-R-81294;          (T3) 3. NGC Nonchrome                           3-fail                                 3-fail Failure to Remove Coating                                        w/PAA and NGC Surface                                        Treatment Indicates                                        Enhanced AdhesionWater  MIL-P-85582          QQ-A-               1. MIL-C-5541                        3  1-pass                                 1-pass 4 Day Immersion @ 120  F.Resistance-  para 4.6.6          250/4               2. PAA      2-pass                                 2-passPrimer Only    (T3) 3. NGC Nonchrome                           3-pass                                 3-passWater  MIL-P-85582          QQ-A-               1. MIL-C-5541                        3  1-pass                                 1-pass *One Small Blister on 1 ofResistance-  para 4.6.6          250/4               2. PAA      2-pass                                 2-fail*                                        3 Test PanelsPrimer +       (T3) 3. NGC Nonchrome                           3-pass                                 3-passTopcoatHumidity  ASTM D2247          QQ-A-               1. MIL-C-5541                        3  Pass  Pass   30 Days @ 140° F.;                                        100% RHResistance     250/4               2. PAA          (T3) 3. NGC NonchromeSalt Spray  ASTM B117          QQ-A-               1. MIL-C-5541                        10 1-3024                                 1-3024 hrs                                        3000 Hour ExposureCorrosion      250/4               2.PAA       hrs   2-3024 hrs(A1)           (T3) 3. NGC Nonchrome                           2-3024                                 3-3360 hrs                           hrs                           3-3024                           hrsSalt Spray  ASTM B117          QQ-A-               1. MIL-C-5541                        10 1. No 1-3360 3000 Hour Exposure UsingCorrosion      250/12               2. PAA      Test  2-3360 7075-T6(A1)           (T6) 3. NGC Nonchrome                           2. No 3-3360                           Test                           3-3024Filiform  MIL-P-85582          QQ-A-               1. MIL-C-5541                        10 1-pass                                 1-pass 1000 Hour ExposureCorrosion  para 4.6.7.2          250/5               2. PAA      2-pass                                 2-pass  ASTM D2803          (T3) 3. NGC Nonchrome                           3-pass                                 3-passFluid  MIL-P-85582          QQ-A-               1. MIL-C-55441                        3  1A-pass                                 1A-passResistance  para 4.6.9          250/4               2. PAA      1B-pass                                 1B-passA. MIL-L-      (T3) 3. NGC Nonchrome                           2A-pass                                 2A-pass23699                           2B-pass                                 2B-passB. MIL-H-                       3A-pass                                 3A-pass83282                           3B-pass                                 3B-pass__________________________________________________________________________ 
    
     The stated number of specimens were treated and tested, as indicated, to provide the indicated results. As shown, the NGC Nonchrome specimens #3, which are neither anodized nor Alodined, but are surface treated in accordance with the novel solvent wipe process of the present invention, illustrated by FIG. 1 of the drawing, provide equal or better primer adhesion and corrosion-resistance than the corresponding Alodined specimens #1 (MIL-C-5541) and phosphoric acid anodized specimens #2 (PAA). Thus the present process provides a useful alternative to the use of chromium-containing conversion coatings (Alodine) and to proprietary PAA anodized coatings, and enables the use of non-chromated primer compositions (DEFT 46GN05 -chrome-free epoxy resin) primer paint composition or chromium-containing primer composition (DEFT 44GN36 strontium chromate polyamide resin). Thus the present process enables the elimination of chromium from the surface preparation prior to priming to meet certain enviromental considerations and military specification requirements. 
     Many variations of the present invention will suggest themselves to those skilled in this art in light of the above, detailed description. All such obvious variations are within the full intended scope of the appended claims.