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Sol for coating metals
Sol for coating metals
Patent Drawings:
(8 images)
Blohowiak, et al.
Date Issued:
September 29, 1998
November 4, 1996
Blohowiak; Kay Y.
(Issaquah, WA)
Krienke; Kenneth A.
(Seattle, WA)
Osborne; Joseph H.
(Tacoma, WA)
The Boeing Company
(Seattle, WA)
Primary Examiner:
Lovering; Richard D.
Assistant Examiner:
Attorney Or Agent:
Hammar; John C.
U.S. Class:
Field Of Search:
International Class:
U.S Patent Documents:
Foreign Patent Documents:
Other References:
Abstract, Method for Improving Durability of Electrode Tip, Japanese Appl. 63-86129 (Kawamoto) Jan. 1990..
A surface treatment, especially for titanium and aluminum alloys, forms a sol-gel film covalently bonded on the metal surface to produce strong, durable adhesive bonds between the metal and an organic adhesive without using toxic chemicals and while significantly reducing or eliminating rinse water requirements of traditional anodizing or etching processes. An aqueous sol containing an zirconium and an organosilane with an organic acid catalyst and alkoxyzirconium stabilizer is applied to etched or grit blasted substrates by dipping, spraying, or drenching, to produce bonds in a single application comparable in strength and performance to standard anodize controls. Parameters affecting performance include the sol composition, the Si/Zr ratio, the ratio of sol ingredients, the concentration of the sol, the carrier solvent, solution age, catalysts, surface pretreatment, application method, curing process, and primer used.
We claim:
1. A sol suitable for surface treatment of a metal to improve corrosion resistance and adhesion, comprising:
a) a dilute aqueous mixture of alkoxyzirconium, free of alcohol, for covalently bonding to the metal through the zirconium to form a metal-to-organic interface on the metal surface;
b) an organosilane coupling agent dissolved in the mixture;
c) an organic acid as a catalyst and as a stabilizer of the hydrolysis rate of the alkoxyzirconium; and
d) an effective amount ammonia or ammonium hydroxide to disrupt the the Zr-acetate complex that otherwise forms.
2. The sol of claim 1 wherein the organosilane includes a reactive functionality adapted to covalently bond with an adhesive when the sol is applied to a metal surface to form a sol-gel film with enhanced adhesion.
3. The sol of claim 1 wherein the ratio of alkoxyzirconium to organosilane is about 1 part alkoxyzirconium to about 2 or about 3.4 parts organosilane by volume, and wherein the organic acid is acetic acid.
4. The sol of claim 3 wherein the organosilane is glycidoxypropyltrimethoxysilane.
5. The sol of claim 3 wherein the acetic acid is no more than 1 vol % of the sol.
6. The sol of claim 1 wherein the alkoxyzirconium is tetra-n-propoxyzirconium.
7. The sol of claim 6 wherein the organosilane is
vinyltriethoxysilane, or
8. The sol of claim 6 wherein the organosilane is glycidoxypropyltrimethoxysilane.
9. The sol of claim 8 wherein the alkoxyzirconium comprises about 1 vol % of the sol.
10. The sol of claim 1 further comprising an effective amount of a cerium, yttrium, titanium, or lanthanum organometallic for bonding to the metal, the organometallic being together with or in place of the alkoxyzirconium.
11. The sol of claim 1 wherein the alkoxyzirconium is (R--O).sub.4 --Zr wherein R is lower aliphatic having 2-5 carbon atoms, alicyclic, or aryl.
12. The sol of claim 11 wherein the organosilane is
vinyltriethoxysilane, or
13. The sol of claim 1 wherein the water is deionized.
14. A sol suitable for surface treatment of a metal to improve corrosion resistance and adhesion, comprising:
in a deionized water carrier, a mixture made from,
(a) about 1 vol % (R--O).sub.4 --Zr wherein R is a straight chain aliphatic having 2-5 carbon atoms for covalently bonding to the metal through the zirconium to form a metal-to-organic interface on the metal surface;
(b) about 2 or about 3.4 vol % organosilane coupling agent selected from the group consisting of:
vinyltriethoxysilane, and
(c) an effective amount of acetic acid as a catalyst and hydrolysis rate stabilizer of the (R--O).sub.4 --Zr; and
(d) an effective amount of ammonia or ammonium hydroxide to disrupt the Zr-acetate complex that otherwise forms.
15. The sol of claim 14 wherein the (R--O).sub.4 --Zr is tetra-n-propoxyzirconium.
16. The sol of claim 15 wherein the organosilane is glycidoxypropyltrimethylsilane or aminopropyltrimethoxysilane.
17. An aqueous sol for coating titanium, made by mixing in deionized water without the addition of alcohol:
(a) about 1 vol % (R--O).sub.4 --Zr wherein R is aliphatic having 2-5 carbon atoms, alicyclic, or aryl with
(b) about 2 or 3.4 vol % of an organosilane from selected from the group consisting of:
vinyltriethoxysilane, and
vinyltrimethoxysilane; and with
(c) an effective amount of a hydrolysis rate stabilizer for the (R--O).sub.4 --Zr the deionized water being a carrier.
18. The sol of claim 17 wherein the hydrolysis rate stabilizer is acetic acid and further comprising an effective amount of base to disrupt the Zr-acetate complex that otherwise forms.
A sol-gel surface coating of the present invention is applied to metal, especially through a waterborne reactive sol, to provide a stable oxide surface that results in corrosion resistance and enhanced organic matrix resin adhesion with the goalof achieving adhesion equivalent to conventional wet-chemical surface treatment methods.
Conversion coatings for titanium, aluminum, or other metals are electrolytic or chemical films that promote adhesion between the metal and an organic adhesive resin, especially for adhesive bonding. Anodizing is a conventional process for makingelectrolytic films by immersing titanium or its alloys in chromic acid or an alkaline earth hydroxide or aluminum in chromic, sulfuric, or phosphoric acid. Anodizing produces a porous, microrough surface into which primer (a dilute solution of adhesive)can penetrate. Adhesion results primarily from mechanical interlocking between the rough surface and the primer. Chemical films include either a phosphate-fluoride conversion coating or films made with alkaline peroxide or other alkaline etchants fortitanium substrates and alodyne films for aluminum substrates.
Using strong acids or strong bases and toxic materials (such as chromates) in immersion tanks, these surface treatment processes are disadvantageous from an environmental viewpoint. They require significant amounts of water to rinse excessprocess solutions from the treated parts. The rinse water and spent process solutions must be treated to remove dissolved metals prior to their discharge or reuse. Removing the metals generates additional hazardous wastes that are challenging tocleanup and dispose. They greatly increase the cost of using the conventional wet-chemical processes. A process that will produce adhesive bonds with equivalent strength and environmental durability to these standard processes without generatingsignificant hazardous wastes while eliminating the use of hazardous or toxic materials would greatly enhance the state-of-the-art. The present invention is one such process. In addition, the process of the present invention can be applied by sprayingrather than by immersion. It, therefore, is more readily used for field repair and maintenance.
Surface anodizing chemically modifies the surface of a metal to provide a controlled oxide surface morphology favorable to receive additional protective coatings, such as primers and finish paints. The surface oxides function as adhesioncoupling agents for holding the paint lacquer, an organic adhesive, or an organic matrix resin, depending on the application. Anodizing improves adhesion between bonded metals. It also improves adhesion between the metal and a fiber-reinforcedcomposite in hybrid laminates, like those described in U.S. Pat. No. 4,489,123 or U.S. patent application Ser. No. 08/585,304. We incorporate this patent and patent application by reference. Structural hybrid laminates have strengths comparable tomonolithic metal, and have better overall properties than the metal because of the composite layers. At higher temperatures (like those anticipated for extended supersonic flight), conventional anodized treatments are inadequate in addition to beingenvironmentally unfriendly. The thick oxide layers that anodizing produces become unstable at elevated temperatures. The oxide layer dissolves into the base metal to produce surface suboxides and an unstable interfacial layer.
Obtaining the proper interface for the organic resin at the surface of the metal is an area of concern that has been the focus of considerable research. For example, cobalt-based surface treatments are described in U.S. Pat. Nos. 5,298,092;5,378,293; 5,411,606; 5,415,687; 5,468,307; 5,472,524; 5,487,949; and 5,551,994. U.S. Pat. No. 4,894,127 describes boric acid-sulfuric acid anodizing of aluminum.
Standard surface treatments yield a surface that lacks many sites that are friendly with the bonding sites traditionally available in the binder. Such bonding sites bind through covalent bonds, hydrogen bonds, or van der Waals forces. Acoupling agent for the resin and metal often is required to improve adhesion. The present invention improves adhesion by creating a sol-gel film at the interface between the metal and resin. A metal-to-resin gradient occurs through a monolayer oforganometallic coupling agents. Generally we use a mixture of coupling agents. The organometallic compounds preferably have zirconium or silicon active moieties to interact with, react with, or bond to the metal surface. Some mechanical interactionmay result from the surface porosity and microstructure. The organic portion of the organometallic compounds usually has a reactive functional group for covalently bonding with the adhesive or matrix resin. A preferred sol-gel film is made from a solhaving a mixture of organometallic coupling agents. One component (usually containing the zirconium) bonds covalently with the metal while a second component bonds with the resin. Thus, the sol-gel process orients the sol coating having ametal-to-resin gradient on the surface.
Situations involving extended exposure to hot/wet conditions where polyimide adhesives hold promise do not allow the adhesion surface preparation to continue to be the standard anodize processes or oxide surface preparations, especially fortitanium. At high temperatures, the solubility of oxygen in titanium is high and the oxide layer simply dissolves with the oxygen permeating through the base metal. The result is interfacial failure at the metal-adhesive interface. To alleviate thistype of bond failure, the surface oxygen needs to be tied up in a stronger bond that will not dissociate in bonding or during operation of the system. A zirconate-silicate sol coating of the present invention is useful at these extended hot/wetconditions because the Zr--O bond that forms between the coating and the metal surface is stronger than a Ti--O bond. Both Zr--O and Ti--O bonds are stronger than Si--O bonds. The higher bond strength prevents dissolution of the oxide layer, so the Zrcomponent in our sol coating functions as an oxygen diffusion barrier. We can use yttrium, cerium, or lanthanum in addition to or as a replacement for the Zr, because these elements also produce high strength oxide bonds that function as an oxygendiffusion barrier. The high cost of these compounds, however, dictates that they be used sparingly. Hence, we have developed a hybrid coating having Zr and Si to produce the desired metal-to-resin gradient needed for good adhesion in structuraladhesive bonds, hybrid laminates, or paint adhesion applications. The hybrid coating integrates the oxygen diffusion barrier function of the Zr (or its alternatives) with an organosilicate network desirable for superior bonding performance.
The present invention is a surface treatment for metal surfaces, especially aluminum or titanium alloys, using a sol-gel film to produce a metal surface coating suitable as an interface to improve adhesion between the metal and an organic matrixresin or adhesive. The sol-gel film or sol coating provides corrosion resistance to a limited degree and promotes adhesion through a hybrid organometallic coupling agent at the metal surface. We use a sol to produce the sol-gel film on the metal'ssurface. The sol is preferably a dilute solution of a stabilized alkoxyzirconium organometallic salt, such as tetra-i-propoxy-zirconium or tetra-n-propoxyzirconium, and an organosilane coupling agent, such as 3-glycidoxypropyltrimethoxysilane for epoxyor polyurethane systems or a corresponding primary amine for polyimide systems, with an acetic acid catalyst for aqueous formulations. The sol-gel film is applied by immersing, spraying, or drenching the metal in or with the sol without rinsing. Key tothe sol-gel film are bonding sites with the metal and separate sites to bond (or otherwise affiliate) with the resin. The sol-gel film produces a gradient changing from the characteristics of metal to those of organic resins. Good adhesion results fromclean, active metal surfaces with sol coatings that contain the organometallic coupling agents in the proper orientation. After application, the sol coating is dried at ambient temperature or, more commonly, heated to a temperature between ambient and250.degree. F. to complete the sol-gel film formation.
Ideally, covalent bonding occurs between the metal surface and a zirconium compound in the sol. Successful bonding requires a clean and chemically active metal surface. The strength and durability of the sol coating depends upon chemical andmicro-mechanical interactions at the surface involving, for example, the metal's porosity and microstructure and on the susceptibility of the sol coating to rehydrate. Our preferred sol coating provides high temperature surface stability for paintadhesion, adhesive bonding, or fabrication of structurally superior hybrid laminates.
FIG. 1 is a block diagram of the typical steps in the surface treatment process of the present invention.
FIG. 2 is a graph showing wedge crack extension for a sol-coated titanium alloy of the present invention compared with a chromic acid anodize standard.
FIG. 3 is a graph showing wedge crack extension for a sol-coated aluminum alloy of the present invention compared with a phosphoric acid anodize standard.
FIG. 4 is a chart showing lap shear ultimate stress test results for several coupons of titanium-6Al-4V alloy adhered with Cytec FM-5 polyimide adhesive.
FIG. 5 is a chart showing floating roller peel resistance test results for sol-coated 2024 and 7075 aluminum alloys compared with phosphoric acid anodize standards.
FIG. 6 is a graph showing cumulative crack growth of alcohol-based and water-based sol coatings on a titanium alloy as a function of the duration of exposure to hot/wet conditions.
FIG. 7 is a graph showing the effect of surface cleaning and pretreatment by plotting cumulative crack growth against the duration of exposure to hot/wet conditions for samples with differing surface treatments.
FIG. 8 is a graph showing the effect of drying time at 230.degree. F. on the time to failure of wedge crack extension test samples.
FIG. 9 is a graph showing the effect of spraying versus dipping (immersing) to apply the coating, plotting cumulative crack growth against the duration of exposure to hot/wet conditions.
FIG. 10 is a graph showing cumulative crack growth as a function of extended exposure to hot/wet conditions comparing sol-coated metals with chromic acid anodized standards.
FIG. 11 is an isometric view of a typical hybrid laminate.
FIG. 12 is an isometric view of a sandwich panel having hybrid laminate skins and a honeycomb core as typically used in an aerospace skin panel.
FIG. 13 is a sectional view showing the typical layers in a sol coated metal product, here illustrated as a lap joint having an adhesive bond.
FIG. 14 is a schematic sectional view of the sol coating.
FIG. 15 is another schematic sectional view of the sol coating for paint adhesion showing the interfaces at the metal and resin interfaces and the peptizing within the sol coating between the Zr and Si.
In describing the invention, we will first discuss some generally applicable aspects of the sol and of the sol coating. Then, we will discuss representative tests we conducted for sol coatings on titanium for forming strengthened adhesive bondsusing an epoxy adhesive. Finally, we will discuss our preferred applications for the sol coating in hybrid laminates and in adhering paint to metal.
1. The sol coating
Sol coating of metals achieves resin-to-substrate bonding via chemical linkages (covalent bonds, hydrogen bonds, or van der Waals forces) while minimizing environmental impacts otherwise caused by the traditional use of highly diluted hazardousmetals. A preferred sol for making the sol coating (also called a sol-gel film) on the metal includes an organozirconium compound (such as tetra-n-propoxyzirconium) to covalently bond to the metal through Zr and an organosilane (such as3-glycidoxypropyltrimethoxysilane) to covalently bond to the organic primer, adhesive, or resin (with an acetic acid catalyst in water-based formulations as a catalyst and Zr hydrolysis rate stabilizer).
In a successful surface treatment, the typical failure mode for adhesively bonded specimens in a hot/wet environment is cohesive failure in the organic adhesive layer. In such cases, the sol-gel film is stronger than the bulk adhesive, so theadhesive bond is as strong as possible.
We use sol-gel chemistry to develop binder coatings about 20-500 nm thick that produce a gradient from the metallic surface through a hybrid organometallic sol-gel film to the adhesive. Bond strength and durability in our preferred sol coatingis increased by including organosilanes and organozirconium compounds. The organosilanes covalently bond to or otherwise associate with the organic adhesive resin or primer. Ideally, covalent bonding also occurs at the interface between the sol-gel andmetal surface. Mechanical interactions may also play a role depending on the design (i.e., porosity, microstructure) of the sol coating. Durability of the sol-gel film in humid conditions depends on whether the film rehydrates. If the film is toothick, it becomes glassy.
The term "sol-gel," a contraction of solution-gelation, refers to a series of reactions where a soluble metal species (typically a metal alkoxide or metal salt) hydrolyzes to form a metal hydroxide. The soluble metal species usually containorganic ligands tailored to correspond with the resin in the bonded structure. The metal hydroxides condense (peptize) in solution to form an hybrid organic/inorganic polymer. Depending on reaction conditions, the metal polymers may condense tocolloidal particles or they may grow to form a network gel. The ratio of organics to inorganics in the polymer matrix is controlled to maximize performance for a particular application.
Many metals are known to undergo sol-gel reactions. Silicon and aluminum sol-gel systems have been studied extensively. Representative sol-gel hydrolysis and condensation reactions, using silicon as an example, are shown in equations (1) and(2).
wherein Et is CH.sub.3 CH.sub.2 --. The hydrolysis and condensation reactions can be complete, resulting in complete conversion into the metal oxide or a hydrous metal hydroxide. They can be partial, leaving more of the alkoxide functionalitiesin the finished gel. Depending upon the reaction conditions, reactions (1) and (2) can produce discrete oxide particulates, as demonstrated in the synthesis of nanoscale particles, or they can form a network gel, which can be exploited in filmformation. The solubility of the resulting gel in a solvent will depend upon the size of the particles and degree of network formation.
We prefer a clean and chemically active metal surface to bond a sol-gel film from the sol by spraying, immersing, or drenching. Cleaning is a key factor toward obtaining good adhesion. If the surface is dirty, bonding is blocked by the dirt oroccurs between the sol and the dirt rather than between the sol and the surface. Obtaining a chemically active surface is not trivial. Titanium produces a passive oxide surface. A bare, pure titanium surface will immediately oxidize in air or dryoxygen to form a barrier titanium oxide film which has a thickness of 2-4 nm (20-40 521 ). Titanium surface oxides do not hydrolyze as readily as aluminum surface oxides to form active metal hydroxides. Water will, however, chemisorb onto the surfaceof the titanium oxide. Aluminum oxidizes as quickly, or more quickly in air.
HNO.sub.3 --HF etching of titanium alloys removes TiO.sub.2 alpha case, but creates a smooth surface which is difficult to bond to. Traditional alkaline etches like TURCO 5578 or OAKITE 160, produce a roughened surface better suited for adhesivebonding, but produce a tenacious smut layer. The smut causes adhesion to be reduced dramatically. Extended soaking in hot HNO.sub.3 after the alkaline etch still leaves some smut. In our preferred process, we clean and rinse the surface, etch withHNO.sub.3 -HF, rinse again, and alkaline etch. Again after another rinse, we desmut the surface with BOECLENE once or in multiple stages to produce a clean and active surface best suited for adhesive bonding through the sol coating of the presentinvention.
Our model of the formation of a sol-gel film on titanium involves Lewis acid/base interaction of a hydrolyzed zirconium alkoxide, an organosilane, or both in the sol with the titanium oxide surface. This interaction is possibly assisted bychemisorbed water to cause the formation of a coupled Zr--O--Ti or Si--O--Ti linkage and a new Ti--OH bond on the surface. A similar reaction occurs on aluminum. The ability of the metal alkoxides to covalently bond with the metal surface most likelyrequires more energy in the case of titanium than aluminum. Complete coupling and formation of covalent bonds with titanium alloys may not occur until the part reaches higher temperatures, such as they usually experience during adhesive curing.
Sol-gel chemistry is quite versatile. Reaction conditions (for example, concentration of reagents and catalyst type) control the relative rates of the hydrolysis and condensation reactions. Sol-gel solutions can be prepared which readily formthin films or which condense to fine colloidal particles. Starting materials and reaction conditions can produce films with morphology similar to surface coatings achieved with anodize and etch processes. Density, porosity, and microstructure can betailored by controlling the chemistry of the sol.
Sol-gel condensation reactions are affected by the acid-base character of the metal/oxide surface. The isoelectronic point (IEP, a measure of surface pH) for titanium is more acidic (IEP=6.0) than an aluminum surface (IEP=9.2), which changes thesurface chemistry of the metal with the sol.
2. Screening studies on sol coatings
We conducted screening studies on test panels of titanium-6Al-4V (Ti-6-4) alloy sized 6".times.6".times.0.50" initially prepared by degreasing the surface with an aqueous detergent (11, FIG. 1). The panels were then either grit blasted with #180grit alumina (13) followed by a final aqueous detergent cleaning to minimize the presence of loosely adhered grit or acid etched in a HNO.sub.3 -HF immersion tank (not shown in FIG. 1). Our preferred sol for these tests consisted of a dilute aqueousmixture of 3-glycidoxypropyltrimethoxysilane (GTMS) and tetra-n-propoxyzirconium (TPOZ) with an acetic acid catalyst. Typically, the panels were dip-coated with a 10 minute immersion time (15), held under ambient conditions for 15 to 30 minutes (17),and dried in a 230.degree. F. oven for 15-30 minutes (19). With the sol coating complete the specimens were ready for accepting primer (21) and then an epoxy adhesive (23). We also tested corresponding formulations using alcohol as the carrier orsolvent. These epoxy sols typically have a pH around 4-5.
Our test specimens were primed with BMS 5-89 chromated adhesive primer (American Cyanamid BR127). Two sol coated panels were then bonded together to form an adhesive lap joint in an autoclave using BMS 5-101 Type II Grade (Dexter-Hysol EA 9628)250.degree. F. cure epoxy adhesive.
Screening level testing used the ASTM D 3762 Wedge Test with exposure at 140 .degree. F. and greater than 95% relative humidity to test the bond strength. The bonded panels were cut into five 1".times.6" strip specimens and wedges were driveninto the bondline. Progress of the crack along the bondline was measured after the initial driving of the wedge, and after exposure to 140.degree. F. and greater than 95% relative humidity for one hour, 24 hours, one week, and longer. Samples weremonitored in the humidity chamber for over 2500 hours total exposure time. Typical test results compared with conventional chromic acid anodizing (CAA) are shown in FIG. 2. Test data for comparable aluminum specimens with 7075 or 2024 aluminum alloysare shown in FIG. 3. Here, the standard surface treatment for comparison was phosphoric acid anodizing (PAA).
FIG. 4 reports test results of the ultimate strength of Ti-6-4/FM-5 polyimide adhesive lap joints. FIG. 5 reports the average roller peel resistance of aluminum/epoxy specimens similar to those made for the crack growth tests reported in FIG. 3.
Additionally, lap shear testing was carried out on panels which showed good wedge crack screening characteristics. Finger panels were primed and lap bonded with the 5-101 adhesive. Measurements were taken at -65.degree. F. room temperature,and 165.degree. F.
A water-based system alleviates many of the flammability, safety, toxicity, and environmental concerns associated with the process when the sol is alcohol-based. We chose a glycidoxysilane (an epoxy) because of its stability in solution and itsability to crosslink with common, aerospace epoxy or urethane (cyanate ester) adhesives. The silane is acid-base neutral (pH.apprxeq.7.0) so its presence in the sol mixture does not increase the relative hydrolysis and condensation rates of thealkoxides. Sols including the organosilanes are relatively easy to prepare and to apply with reproducible results.
The choice of the organosilane coupling agent was a significant factor in improving hot/wet stability of the BMS epoxy bonding system. The GTMS included an active epoxy group which can react with the bond primer. GTMS did not form strong Lewisacid-base interactions with the hydrated titanium oxide substrate. The titanium oxide surface was more accessible to the zirconium organometallic when GTMS was used, allowing the desired stratification of the sol-gel film in essentially a monolayer withthe epoxy groups of the silane coupling agents oriented toward the primer. The ideal concentration will depend upon the mode of application. A higher concentration may be preferred for drench or spray applications. We believe this orientation allowedstrong covalent bonding to develop between the titanium substrate and zirconia and silica (i.e. M--O--M bonds), as well as maximizing bonding between the epoxy moiety of the GTMS to the epoxy adhesive.
For polyimides (including bismaleimides), we usually replace GTMS with an aminoalkylsilane or an aminoarylsilane to match the silane coupling chemistry with the resin system. In these sols which operate best at a pH 8-9, we add ammoniumhydroxide in small amounts to disrupt the Zr-acetate complex that otherwise forms.
Physical size of the silane coupling agent also has an effect on adhesion. Aluminum studies revealed that both the initial adhesion and hydrolytic stability decreased when epoxycyclohexylpropyltrimethoxysilane was used instead of GTMS as thecoupling agent. We attribute the difference in performance to a difference in size of the organic functionality. This size effect is most likely the result of physical interference of both hydrolysis and condensation reactions by the bulky alkyl groupattached directly to the silicon. Hydrolysis was incomplete and the silicon hydroxide could not effectively condense with the aluminum surface. These results suggest that the most effective coupling agents for a spray or drench coating application willbe smaller so as not to sterically hinder hydrolysis and condensation reactions.
The concentrations of the reactants in the sol were generally determined as volume percentages. In the screening tests, a 2 vol % of GTMS and 1 vol % of TPOZ was used. This concentration corresponds to a molar ratio of silicon to zirconium of3.7:1. Related studies suggest that a slightly higher concentration of reactants, namely a total of (Si +Zr)=4.4 volume % may yield better results, so the ratio of GTMS to TPOZ might need further adjustment to obtain the optimal performance (strongestsurface adherence). We believe that a higher adhesion will occur with a mixed (Zr+Si) sol because of the more chemically active Zr. The sol might also include cerium, yttrium, titanium, or lanthanum organometallics, such as yttrium acetate trihydrateor other hydrates, yttrium 2-ethylhexanoate, i-proproxyyttrium, methoxyethoxyyttrium, yttrium nitrate, cerium acetate hydrate, cerium acetylacetonate hydrate, cerium 2-ethylhexanolate, i-propoxycerium, cerium stearate, cerium nitrate, lanthanum nitratehexahydrate, lanthanum acetate hydrate, or lanthanum acetylacetonate, together with the Zr or in its place.
The organozirconium compound serves to minimize the diffusion of oxygen to the surface and to stabilize the metal-resin interface. As a variation to the sol coating process, a stabilizer might be applied to the surface to form a barrier filmprior to applying the hybrid organometallic sol to form the sol-gel film.
Alcohol-based sols allow us to precisely control the amount of hydrolysis. Optimization of the water-based system, however, actually yielded better hot/wet durability results than the alcohol-based system, as demonstrated by comparing similaralcohol and water-based coatings (FIG. 6).
Aging of the sol which we call the "induction time" is another important factor in using our sols. Complete hydrolysis and condensation of the organometallic in the sol-gel film is important to develop a hydrolytically stable metal oxide film inthe metal. The presence of hydrolyzable alkoxides in the sol-gel film will have two adverse effects. First, every residual alkoxide represents an incomplete condensation site between the metal and the coupling agents. Incomplete condensation,therefore, decreases the ultimate bond strength of the sol-gel film. Second, in a humid environment, these alkoxide residues can hydrolyze. The structural changes accompanying hydrolysis cause stress in the sol-gel film which, we believe, promotesfailure to occur within the sol-gel film or at one of the interfaces (metal/film or film/primer or adhesive).
Aging is a function of the rates of the hydrolysis reaction of the zirconium alkoxides and the organosilane. Tetra-n-propoxyzirconium reacts more rapidly with water or other active hydrogens than the silane. The zirconate hydrolyzes rapidlyusing ambient moisture and condenses with itself or with absorbed water on the titanium surface. If not properly controlled, this zirconate hydrolysis self-condensation reaction can produce insoluble zirconium oxyhydroxides which will precipitate andbecome nonreactive.
If, however, the sol is applied too short a time after being made, the organosilane may not be fully hydrolyzed. As the sol ages, the hydrolyzed silicon and zirconium components may condense among themselves, forming oligomers and networks. These networks will eventually become visible to the naked eye and become insoluble. The ideal solution age is at the point that the zirconium and silicon are hydrolyzed sufficiently that zirconium and silicon react with the metal surface. At thispoint, generally some metal polymers and networks have formed in the sol and they will give the sol-gel film some structure.
We made the zirconium and silicon components hydrolyze on a similar time scale by mixing the zirconium alkoxide with glacial acetic acid to stabilize the fast reacting four-coordinate zirconate center and to enable a water-based system. Thismixing effectively changed the geometric and electronic nature of the zirconium component. We use the minimum amount of acetic acid necessary to form the zirconium-acetic acid complex. Other organic acids, like citric acid, can be substituted for theacetic acid. We might also use glycols, ethoxyethanol, H.sub.2 N--CH.sub.2 --CH.sub.2 --OH, or the like.
Extended X-ray fine structure (EXAFS) analysis to interpret the X-ray absorption near edge structures (XANES) identified zirconium polymers in the sol where the terminal alkoxy groups are substituted by acetyl groups. Bridging alkoxide groupsexisted in an equilibrium placing the Zr-atom in a 6-fold coordination. The zirconium thereafter hydrolyzed more slowly, putting it on a hydrolysis time scale similar to the preferred organosilane. IR measurements indicated that the acetatecoordination was monodentate.
The relative rates of the hydrolysis and condensation reactions involved in the sol coating process are controlled by the type of catalyst (either acid or base), the concentrations of the reagents in the reactions, the metal alkoxide selected,and the water available for hydrolysis. An acidic catalyst promotes the hydrolysis reaction over condensation while a basic catalyst does the opposite. We examined the effects of various acidic catalysts, such as acetic acid and nitric acid, and basiccatalysts, such as ammonium hydroxide and triethylamine. For these formulations, the basic catalysts promoted the condensation reactions too vigorously, which shortened the pot-life of the solution. Colloidal zirconate-silicate particles precipitatedtoo soon after the sol was mixed. The nitric acid was effective as a catalyst, but did not stabilize the zirconate via a coordinating ligand like the acetate ion in acetic acid, so aging of the sol produced differing, unpredictable results. Thus,acetic acid was chosen as the preferred catalyst. We make the sols dilute to control the self-condensation reactions, thereby extending the pot life. Still, the sols must be used soon after they are prepared.
The amount of acetic acid also plays a major role in the sol because the acetic acid functions as a catalyst for the hydrolysis and a hydrolysis rate stabilizer for the zirconium complex. In general throughout our screening tests, we added 0.13moles of glacial acetic acid to 0.091 moles of the organosilane before combining the organosilane with the organozirconium. Doubling the amount of acetic acid to 0.26 moles improved bonding performance; tripling the amount of acid to 0.39 moles made itworse. More studies are necessary to understand this correlation completely, especially the relationship between the acetic acid concentration and the gelation rate. We try to minimize the amount of acetic acid. Less is best for application tocorrosion sensitive airplane parts.
In our tests, we cleaned the metal surface using abrasive blasting or acid etching with HNO.sub.3 --HF in both liquid and paste form. Since the sol reacts directly with chemical moieties on the substrate surface, adhesion is sensitive to surfaceprecleaning. Residues or smut resulting from the cleaning processes can drastically effect the adhesive bond performance, because residues and smut are relatively loosely adhered to the surface.
FIG. 7 shows the wedge crack test results for Ti-6Al-4V panels given a variety of surface pretreatments and then coated with the same sol. Our results indicate that degreasing with an aqueous detergent with a gentle scrubbing action or agitationwas sufficient for removing most soils and grease from the metal surface. Subsequent grit blasting was generally better than acid etching for pretreatment of the surface. We believe that grit blasting enhanced mechanical interaction by producing amacrorough surface. The grit blasted surface may hold the sol on the surface longer during the ambient temperature flash, allowing a longer reaction time between the sol and surface, but the time difference is rather short. Prehydrolysis of the surfaceusing steamy or hot water may activate the metal by populating the surface with chemisorbed water. The water on the surface can turn into surface hydroxyls which are available for condensation with the sol. Surface hydroxyls are especially important fortitanium alloys.
The two best performing sets of samples were both grit blasted with #180 alumina and had the roughest surfaces. Of these two grit blasted samples, the set which was cleaned with Alconox detergent following grit blasting had better performancethan one wiped only with methyl ethyl ketone (MEK). Solvent wiping of the rough surfaces of grit blasted panels with lint free cloth frequently left small shreds or fiber residues snagged on the substrates. Cloth residues increased with higher pressureexerted on the wiping cloth.
Test results for panels etched for one minute in HNO.sub.3 --HF did not perform as well as the grit blasted panels. The poorest wedge crack test performance was obtained from panels abraded by hand with #80 and #150 grit silicon carbidesandpaper. The sandpaper produced a relatively non-uniform surface that typically was contaminated with silicon carbide. Detergent washing did not remove the contamination. Sanding does not produce the same mechanical surface as grit blasting.
A paste etch process was considered as an alternative to the HNO.sub.3 --HF acid etch bath for field repair. The paste consists of nitric and hydrofluoric acid in an emulsifier. It was applied with a brush on the surface of the titanium panels. Four 6".times.5" titanium panels were solvent wiped and prepared for the process. Hydrogen bubbles were produced on the surface of the metal during the process by the reaction of the acid and the metal surface. These bubbles became encapsulated in thepaste. A continuous brushing motion over the surface of the panel was necessary to keep the etchant in contact with the titanium. Without brushing, the etching was uneven.
TURCO 5578 alkaline etch produces a mat finish, similar to an anodize, resulting from the formation of a microrough surface. This pretreatment shows superior hot/wet durability.
The use of conventional dry grit blasting as a surface preparation pretreatment prior to sol coating has both advantages and disadvantages depending on the type of metal surface to be treated and the environment in which the process is beingcarried out. Grit blasting produced the highest strength and most durable adhesive bonds of the tested surface treatments over the course of this program. Grit blasting should work well in practice on thicker panels or parts requiring limited amountsof blasting. Care must be taken not to warp the panel as the result of stresses introduced during the blasting.
There are numerous disadvantages associated with grit blasting. First, it cannot be used on titanium foil or honeycomb core without serious risk of damage to the substrate or on fatigue critical parts. Blasting produces holes in the metal inthese cases. Complex parts might be difficult to access to produce a uniform finish. Although the equipment and materials required for grit blasting are not exotic, they may not be available at sites where sol coatings could otherwise easily beapplied.
We blasted titanium panels with different grit sizes of alumina #46 grit, #180 grit, and a very fine polishing alumina with an average size of 50 micrometers. All of the grit sizes evenly abraded the surface and yielded a uniform matte finish. Surface roughness was measured using a surface profilometer, using a half inch traverse and a 0.03 cutoff. The average roughness (Ra) was 144 microinches for the #46 grit panel, 30 for the #180 grit panel, and 22 for the panel blasted with the finegrit. Surface contaminants, like heavy greases or oils, were not easily removed during grit blasting using the fine alumina powders. The grit was simply imbedded into the contaminant and lost all velocity. The finest alumina grit was too friable andbroke down quickly during the blasting process. After a certain time period, the very fine particles were no longer effective at abrading the surface. The dust was hard to contain within the sandblasting apparatus.
We used scanning Auger microscopy to analyze the panels after blasting. The effective oxide thickness of the non-blasted area was measured at approximately 200 .ANG., while the total structured surface was about 2000 .ANG. for that of theblasted area. Bright particles were observed imbedded into the surface and were verified to contain primarily aluminum and oxygen, most likely as Al.sub.2 O.sub.3. Acid etching removed the embedded alumina particles from the titanium surface only afterthe titanium had been etched away and removed from around the particles. Unfortunately, post-blasting etching also removed the roughened texture of the surface. We do not know the role alumina particles play, if any, in adhesion to the grit blastedsurface.
No single surface pretreatment appears to provide optimum results over the full range of substrates. Various combinations of acid etch and alkaline etch treatments apparently work well on certain alloys, but questions remain as to whether theyintroduce hydrogen embrittlement problems for Ti foil or honeycomb core substrates. Our preferred cleaning and activation processes are prewetting, steam cleaning, alkaline etching to activate the surface, and BOECLENE or other acid etching (i.e.H.sub.2 SO.sub.4 --HNO.sub.3 -ammonium bifluoride) to desmut titanium alloys.
The drying cycle for the sol coating is another significant processing parameter to controlling adhesive bond performance. The drying cycle includes: (1) ambient air flash time after application of the sol; (2) oven dry time at temperature; and(3) storage time in air thereafter prior to application of the primer. As shown in FIG. 8, shorter drying times at 230.degree. F. tended to yield better results. An oven drying time of 15-30 minutes at 140.degree.-230.degree. F. in air lead to betterhot/wet durability.
FIG. 9 shows a difference we observed in performance arising from applying the sol by spraying or dipping. In this experiment, the sol was sprayed onto the substrates using a high velocity, low pressure (HVLP) spray gun. A coat consisted oflight, but complete, coverage of the surface. The coating was allowed to flash dry between coats. In all cases, the sprayed coatings did not perform as well as the dipped coatings. Specimens sprayed with an even number of coats did not perform as wellas specimens sprayed with an odd number of coats, this effect may be an artifact of how the gradient coating layered onto the surface. In applying an even number of coats, the GTMS may couple with the next layer's glycidoxy end of the GTMS in the nextlayer, the silica oriented away from the metal surface where it cannot bond with the metal and where it interferes with the sol-gel film/primer interfacial chemistry. Consequently, there would be fewer organic functionalities available for bonding tothe resin. With an odd number of coats, a glycidoxy edge would occur at the outer surface if this intermediate reaction occurs. Hence, we suspect, we achieve better performance. This gradient effect has been seen in multilayers of phospholipids and inother biochemical systems.
We also examined a drench method for applying the sol, which combines elements of both the dip and spray processes. In this application technique, the surface of the part is wetted with a continuous stream of solution for a given period of time. The solution surface is wet with the solution for longer than in the spray process, but not as long as the dip process. One of the advantages of this technique is that it does not require the precise skills of an expert sprayer. It also usessignificantly less solution than the dip (immersion) process. The coating thicknesses are controlled by the coating formulation itself and length of time that the surface is wet.
Our testing on epoxy systems was primarily conducted using solvent-based, chromated primer Cytec BR 127. We conducted tests with the nonchromated water-based
Cytec XBR 6757 primer. The water-based primer with a preferred sol-gel formulation yielded comparable results to the solvent-based primer.
Titanium samples (Table 1) were aqueous degreased, then grit blasted using 180 grit alumina abrasive powder, and treated with sol using a dip coating.
TABLE 1 __________________________________________________________________________ Titanium Specimens Prepared For Epoxy Adhesion Performance Testing Sample Size # of Surface Sample ID (inches) Panels Test Treatment Primer __________________________________________________________________________ GAB01 6 .times. 6 .times. 0.125 4 Wedge Crack GTMS/TPOZ BR 127 Extension GAB02 6 .times. 6 .times. 0.125 4 Wedge Crack GTMS/TPOZ Cytec 6757 Extension GAB03 6 .times. 6.times. 0.050 2 Wedge Crack GTMS/TPOZ BR 127 Extension GAB04 6 .times. 6 .times. 0.050 2 Wedge Crack GTMS/TPOZ Cytec 6757 Extension GAB05 4 .times. 7 .times. 0.063 12 Lap Shear, GTMS/TPOZ BR 127 Various Conditions GAB06 4 .times. 7 .times.0.063 8 Lap Shear, GTMS/TPOZ Cytec 6757 Various Conditions GAB07 finger panels 6 Lap Shear, GTMS/TPOZ BR 127 Various Conditions GAB08 finger panels 6 Lap Shear, GTMS/TPOZ Cytec 6757 Various Conditions GAB010 6 .times. 6 .times. 0.125 4Wedge Crack CAA/5V BR 127 Extension GAB011 6 .times. 6 .times. 0.125 12 Lap Shear, CAA/5V BR 127 Various Conditions __________________________________________________________________________
The chromic acid anodize (CAA) specimens displayed 100% cohesive failure. The failure modes of the sol-gel panels varied. Panels primed with the solvent-based BR127 tended to show between 10-50% cohesive failure and the remainder adhesivefailure at the adherent-sol interface, while the panels primed with the water-based XBR 6757 exhibited from 80-100% cohesive failure.
The results of crack growth tests during long term exposure to 140.degree. F. condensing humidity are shown in FIG. 10. H133-2 is a sol that had been aged for 1.9 hrs, while H133-3 had aged for 0.2 hrs prior to application. These solutionsproduced coatings having crack growth comparable with the chromic acid anodize standards even after 2000 hours hot/wet exposure. The crack growth rate had leveled off at approximately 0.1 inches crack extension. Abrupt jumps in the data are due to thedifficulty in visually measuring minute changes in the crack extension. Ideally, a smooth curve could be drawn into the raw data representing the growth rate over time. These results show that the hot/wet durability of these water-based sol coatingscompares well with the CAA controls.
Lap shear data were collected on an Instron Series IX Automated Materials Testing-System 6.04. The sample rate was 9.1 pts/sec with a crosshead speed of 0.05 in/min. Lap shear data is listed in Table 2. Results are an average of five fingertest specimens per data point.
TABLE 2 ______________________________________ Lap Shear Data CAA Control Boeing SG Boeing SG with with Cytec BR 127 with Cytec BR 127 Cytec XBR 6757 Ultimate Failure Ultimate Failure Ultimate Failure Stress Mode Stress Mode Stress Mode (psi) (% coh) (psi) (% coh) (psi) (% coh) ______________________________________ -65.degree. F. 7988 80 7900 100 8822 100 Lap Shear RT 5935 100 6278 100 6015 100 Lap Shear 180.degree. F. 3722 100 4123 100 3586 100 Lap Shear ______________________________________
The lap shear failure mode is predominantly cohesive within the adhesive layer in all of the specimens at all of the temperatures. The data for the CAA control and the sol-gel surface preparations with both primers was essentially the samewithin experimental error.
Lap shear coupons produced with a sol that had been aged for 150 hrs or one that had been aged for 338 hrs had essentially the same ultimate stress values. Exposure of the lap shear specimens made with sol in a hot/wet environment resulted in a14% decrease in ultimate stress after 168 hrs and 27% after 500 hrs. A 500 hour hot/wet exposure of the CAA control specimens resulted in a 7% degradation.
Electronic Spectroscopy for Chemical Analysis (ESCA) studies were conducted on an ethanol-based formulation to determine the mode of failure during hot/wet exposure. The bonding surfaces of two previously tested wedge crack sample coupons wereexamined using ESCA analysis techniques. The first sample, H83KAK-1, was a grit blasted Ti-6-4 panel which had been coated with an isopropanol solution of 2% GTMS, 1% TPOZ and 1% 80%-acetic acid. It was tested at 120.degree. F. and 95% relativehumidity for 864 hours and had an average increase in the initial crack length of 0.45 inches by the end of the test.
The sample was split in half and small mating surface section from adhesively failed areas of the coupon were examined The bare titanium surface of the adhesively failed sample section had high carbon, low titanium and small amounts of siliconand zirconium. As this surface was sputter-etched, the percentages of silicon, zirconium and chromium increased and reached a maximum before dropping off with continued sputtering. After 300 .ANG. of sputter etching, the carbon-content percentage hadreached a minimum and the titanium, aluminum and vanadium content percentages had reached a maximum. At this depth, the zirconium percentage was about 20% below its maximum value and the silicon content was more that 50% below its maximum value. Table3 shows the sputtering data for this system.
TABLE 3 ______________________________________ ESCA Sputter Data for Failed Surfaces adhesive metal atom (sputter) metal metal sputter ______________________________________ O 40.97 28.23 36.88 31.52 Ti 2.62 22.74 C 36.89 59.61 44.3619.06 Al 4.05 2.99 6.12 14.16 Si 11.9 4.45 3.42 5.38 Zr 2.81 0.51 0.63 2.34 Ar 2.2 N 1.1 0.91 0.95 1.45 V 1.15 Cr 2.29 1.43 1.82 ______________________________________
Aging studies with ESCA suggest that aging the solution does not alter the surface characteristics significantly.
Roughness of the etched titanium surface prevented accurate determination of the thickness of the sol coating. ESCA measures an area of the surface approximately 600 .mu.m in diameter. Table 4 shows the surface composition following varioussputter times on the coated sample. The etched titanium surfaces have "craters" approximately 15 .mu.m in diameter and 2-5 .mu.m deep. Therefore, the ESCA experiment will measure about 20 "craters" and associated ridges. The sol coating is likely tobe thinner on the ridges than in the craters, perhaps thin enough for the substrate material to have a measurable signal even without sputtering.
The ESCA data for both samples show a small amount of titanium at the surface indicating that some areas of the substrate are not coated or that sol coating on the ridges is thinner than about 130 .ANG.. Argon plasma sputtering the surfacegradually removes the sol coating, as indicated by the decrease in Si and Zr, but there is not a sharp change in surface composition. The data are consistent with a surface having roughness greater than the coating thickness.
TABLE 4 ______________________________________ ESCA Data for Unexposed Water-based Sol-Gel Specimens 24 hr old solution 1 hr old solution Sur- Light 345 .ANG. 430 .ANG. 430 .ANG. Atomic % face Sputter Sputtered Sputtered Surface Sputtered ______________________________________ Carbon 44.8 19.0 5.2 5.5 57.5 23.0 Oxygen 40.6 52.8 23.0 23.5 32.1 31.4 Titanium 3.1 9.2 51.0 54.0 2.4 31.3 Aluminum 0.6 2.4 9.8 8.3 0.6 5.8 Vanadium -- -- 2.8 2.4 -- 1.7 Zirconium 2.0 3.0 0.71.0 0.8 0.5 Niobium 0.5 1.0 0.3 -- 0.3 -- Moly- 0.2 0.5 0.2 -- 0.2 -- bdemun Fluorine -- 0.8 -- -- -- -- Silicon 8.1 10.8 -- -- 3.5 -- Nitrogen -- -- 3.3 1.8 1.1 2.4 Copper -- -- -- -- 0.3 0.3 Calcium -- -- -- -- 1.2 1.2 Argon -- 0.4 3.73.4 -- 2.4 ______________________________________
The theoretical composition of the fully hydrolyzed sol-gel film is 4 parts SiO.sub.1.5 Gly and 1 parts ZrO.sub.2 where Gly is the glycidoxy group attached to the silicon. The (silicon+zirconium):carbon:oxygen ratio for a homogeneous coatingformed from this sol is 1:4:4:3.2. The experimental value for the surface of the 24 hr old formulation specimen shows the (silicon+zirconium):carbon:oxygen ratio to be approximately 1:4:5:4.0, very close to the theoretical value. The ratio of(Si+Zr):C:O ratio becomes 1:1.2:3.8. Continued sputtering further reduces the carbon signal to near background levels and the oxygen signal decreases as well. We interpret the data to indicate that the deposited film is not homogeneous. Theglycidoxysilane is located primarily on the surface with the coating composition changing to zirconia and titania and finally the metallic substrate. This measured gradient is consistent with our model of formation of films from our sols andobservations of increasing water aversion of substrates as coatings are deposited. The thickness of the sol coating is not accurately determined by this measurement but it appears to be a minimum of 100-300 .ANG.. Considering the escape depth of ESCAbeing about 100 .ANG., the glycidoxy-rich surface layer is no more than about 75-150 .ANG. thick as indicated by the decrease in the carbon level.
The low carbon level in the coating after 450 .ANG. etch indicates that hydrolysis of the sol is essentially complete within 24 hours. Data for coatings deposited from the same sol aged for only 1 hour show significantly greater amounts ofcarbon both at the surface and at the 450 .ANG. level. Incomplete hydrolysis will leave alkoxy groups attached to both silicon and zirconium. In addition, acetate groups from the incomplete hydrolysis of the stabilized zirconate will also beincorporated throughout the coating. The ESCA data do not differentiate between acetate, glycidoxy, and alcohol carbon and oxygen.
We conducted experiments using aluminum substrates (alloys 7075 and 2024) similar to those for titanium. FIG. 3 shows the cumulative crack growth or extension as a function of time for an epoxy adhesive. Crack growth was the smallest for a solcoated 7075 alloy. The hot/wet durability of the sol coated specimens was comparable with the phosphoric acid anodized (PAA) controls for 1000 hrs of testing. The sol coated specimens were acceptable as measured by BAC 5555 PAA requirements, so the solcoating is an alternative and improvement to PAA for at least these aluminum alloys.
We collected lap shear data as well for the sol coated 7075 and 2024 alloys. Room temperature (RT) results surpass the minimum threshold specified in BAC 5555. Our tests indicate that specimens primed with a waterbased nonchromated primer(Cytec XBR 6757) performed as well as or better than specimens primed with the conventional chromated, oil-based primer (Cytec BR 127). Again, 7075 alloys had better performance than 2024 alloys. Floating roller peel test data (reported as the averageof five individual specimens) showed that sol coated aluminum specimens compared favorably with the bond strengths achieved with conventional PAA controls.
Our studies regarding the method of application (i.e., spraying v. drenching v. dipping) for aluminum substances suggest that the method of application has little effect on the bond strength. This fact makes the sol coating desirable for fieldrepair and depot maintenance because specialized equipment likely is not required to obtain the benefits of sol coating. Also, the data we collected suggests that the coating process is robust rather than a "craft." We also found little effect fromdrenching versus mist spraying.
Parameters such as concentration, acid catalyst, aging, hydrolysis/concentration, and the ratio of the reactants will need to be optimized for large scale and spray operation. We anticipate that these will be different than those optimized fordipping. The use of surfactants and thixotropic agents in the solution may improve the spray characteristics of the solution, but may adversely affect the bonding performance. These agents may help to provide a more uniform sprayed coating and improvethe manufacturability of the process.
There are fundamental differences in the manner of film formation between spraying and dipping. With dipping or immersion coating, the thermodynamically favored products of slower reactions can dominate. With the part immersed in the solution,reactant can reach to the metal surface through mechanical, thermal, and mass transport mechanisms. Reaction products can diffuse away from the surface. The most thermodynamically stable coating will develop. In the case of spraying, only a thin filmof the sol contacts the surface. Depletion of reactants can and likely does occur as the sol flows down the surface. Consequently, reaction products build up and may influence the chemistry that occurs. In addition, reaction products remain on thesurface when the film dries. The sol-gel film developed with spraying is dominated by kinetically accessible products. Advantages of spraying include coating thickness control and uniformity.
The preferred zirconium compounds for making the sol are of the general formula (R--O).sub.4 Zr wherein R is lower aliphatic having 2-5 carbon atoms, especially normal aliphatic (alkyl) groups, and, preferably, tetra-n-propoxyzirconium, becauseof its being readily available commercially. We believe that branched aliphatic, alicyclic, or aryl groups would also perform satisfactorily. For applications involving extended exposure to hot/wet conditions, we want the organo moiety on the zirconiumto have thermo-oxidative stability.
The preferred organosilane compounds (available from Petrarch or Read) for making the sol are:
vinyltriethoxysilane or
In these organometallics, the organo moiety preferably is aliphatic or alicyclic, and generally is a lower n-alkoxy moiety having 2-5 carbon atoms. The organosilane includes typically an epoxy group (for bonding to epoxy or urethane resins oradhesives) or a primary amine (for bonding to polyimide resins or adhesives).
If the sols are alcohol-based, the preferred alcohols are ethanol, isopropanol, or another lower aliphatic alcohol.
The sols can be used to make sol-gel films on the following aluminum and titanium alloys: Al 2024; Al 7075; Ti-6-4; Ti-15-3-3-3; Ti-6-2-2-2-2; and Ti-3-2.5. The sol coating method can also be used with copper or ferrous substrates, includingstainless steel or an Inconel alloy.
3. Hybrid laminates
Sol coated metals are useful in hybrid laminates like those described in U.S. Pat. No. 4,489,123 or U.S. patent application Ser. No. 08/585,304. These hybrid laminates are candidates for use as aircraft skin panels and other structuralapplications in subsonic or, especially, supersonic aircraft. The utility of these hybrid laminates hinges on a sound, strong adhesive bond between the metal and resin. The sol coating of the present invention provides a high strength adhesioninterface at relatively low cost compared with conventional alternatives in a reasonably simple manufacturing process.
Hybrid laminates should have a high modulus (absolute strength) and be fatigue resistant so that they have long life. They should exhibit thermomechanical and thermo-oxidative stability, especially in hot/wet conditions. They should have a highstrength-to-weight ratio while having a relatively low density as compared to a solid (monolithic) metal. They should be damage resistant and damage tolerant, but they should dent like metal to visibly show damaged areas long before the damage resultsin actual failure of the part. They should be resistant to jet fuel and aerospace solvents. Finally, they should be resistant to crack growth, preferably slower than monolithic titanium.
The hybrid laminates generally have alternating layers of titanium alloy foil 110 and a fiber-reinforced organic matrix composite 120 (FIG. 11). The foil typically is sol coated in accordance with the method of the present invention to enhanceadhesion between the foil and the matrix resin of the composite (and any intervening primers or adhesives). The sol coating may also provide corrosion resistance to the titanium. The foil typically is about 0.01-0.003 inches thick (3-10 mils) of.beta.- annealed titanium alloy having a yield strain of greater than about 1%. The composite typically is a polyimide reinforced with high strength carbon fibers. The polyimide is an advanced thermoplastic or thermosetting resin capable of extendedexposure to elevated temperatures in excess of 350.degree. F., such as BMI, PETI-5, or a Lubowitz and Sheppard polyimide. The composite is one or more plies to provide a thickness between the adjacent foils of about 0.005-0.03 inches (5-30 mils). Other configurations of the hybrid laminates, like metal reinforced resin composites, might be used.
The preferred composite is formed from a prepreg in the form of a tow, tape, or woven fabric of continuous, reinforcing fibers coated with a resin to form a continuous strip. Typically, we use a unidirectional tape. The fibers make up fromabout 50 to 70 volume percent of the resin and fibers when the fiber is carbon, and from about 40 to about 60 volume percent when the fiber is boron. When a mixture of carbon and boron fibers is used, total fiber volume is in the range 75 to 80 volumepercent. The plies may be oriented to adjust the properties of the resulting composite, such as 0.degree./90.degree. or 0.degree./-45.degree./+45.degree./0.degree., or the like.
Hybrid laminates of this type exhibit high open-hole tensile strength and high compressive strength, thereby facilitating mechanical joining of adjacent parts in the aircraft structure through fasteners. The laminates might also include Z-pinreinforcement in the composite layers or through the entire thickness of the laminate. Z-pinning techniques are described in U.S. patent application Ser. Nos. 08/582,297; 08/658,927; 08/619,957; 08/618,650, now U.S. Pat. No. 5,736,222 or08/628,879, now abandoned, which we incorporate by reference.
The hybrid laminates can be used in skin panels on fuselage sections, wing sections, strokes, vertical and horizontal stabilizers, and the like. The laminates are generally bonded as the skins 100 of sandwich panels that preferably aresymmetrical and include a central core 130 of titanium alloy honeycomb, phenolic honeycomb, paper honeycomb, or the like (FIG. 12), depending on the desired application of sandwich panel. Sandwich panels are a low density (light weight), high strength,high modulus, tailorable structure that has exceptional fatigue resistance and excellent thermal-mechanical endurance properties.
The hybrid laminates are also resistant to zone 1 lightning strikes because of the outer titanium foil.
Outer metal layers protect the underlying composite from the most severe hot/wet conditions and the cleaning solvents that will be experienced during the service life of the product, especially if it is used on supersonic aircraft.
To prepare the hybrid laminates, generally we pretreat cleaned, .beta.-annealed Ti-6Al-4V alloy foils in various concentrations (i.e. 20%, 60%, or 80%) of TURCO 5578 alkaline etchant (supplied by Atochem, Inc. of Westminster, Calif.). Afterwater rinsing the foils are immersed in 35 vol % HNO.sub.3 -HF etchant at 140.degree. F. to desmut the foil, they are rinsed again, and, then, are sol coated in accordance with the present invention.
For the strongest interaction between the sol-gel film and the composite, We prefer that the organic moiety of the silane correspond with the characteristics of the resin. For example, PETI-5 is a PMR-type or preimidized, relatively lowmolecular weight resin prepreg having terminal or pendant phenylethynyl groups to promote crosslinking and chain extension during resin cure. Therefore, the silane coupling group might include a reactive functionality, such as an active primary amine;an anhydride, carboxylic acid, or an equivalent; or even a phenylethynyl group, to promote covalent bonding between the sol coating and the resin. The organic moiety might simply be an aliphatic lower alkyl moiety to provide a resin-philic surface towhich the resin will wet or have affinity for to provide adhesion without producing covalent bonds between the organosilane coupling agent and the resin. The aliphatic moiety, however, would still provide hydrogen atoms for hydrogen bonding with thenumerous heteroatoms (oxygen) in the cured PETI-5 imide. If the resin includes a nadic or maleic crosslinking functionality, as Lubowitz and Sheppard suggest or as occurs in bismaleimides, then the organosilane coupling agent might include the samenadic or maleic crosslinking functionality or an amine, --OH, or --SH terminal group for covalent bonding through capping extension or the Michael's addition across the active unsaturated carbon-carbon bond in the resin's cap. For higher temperatureapplications, we recommend using an aromatic organometallics since these compounds should have higher thermo-oxidative stability.
Greater covalent interaction between the resin and sol-gel film is likely to occur if the resin is a PMR formulation at the time of layup onto the foil rather than a fully imidized resin of relatively high formula weight, such as Lubowitz andSheppard propose. Of course, PMR formulations have their processing limitations. Knowing which resin approach will provide the best overall performance in the hybrid laminates remains for further testing, as does selection of the absolute type of resinand its formulation. Ideally, the resin is easy to process because it has few adverse aging consequences from extended exposure to ambient conditions common during fiber placement. The resin prepregs should also have long shelf lives. Alternately, theresin should be suitable for in situ consolidation while being placed on the foil.
Tows of mixed carbon and boron fibers suitable for these hybrid laminates are sold under the tradename HYBOR by Textron Specialty Materials of Lowell, Mass. Boron fibers provide high compressive strength, while carbon fibers provide high tensilestrength. The preferred boron fiber has the smallest diameter (typically 4-7 mils) and the highest tensile elongation.
Hybrid laminates can have open-hole tensile strengths of about 150-350 ksi and an ultimate tensile strength in excess of 2.times.10.sup.6 psi/lb/in.sup.3.
4. Paint adhesion
A sol coating is particularly useful as an adherent for surface coatings (paints), especially urethane coatings, that are common in aerospace applications. Essentially the same aspects that make the sol coatings advantageous for hybrid laminatesmake them advantageous for paint adhesion. They convert the metal surface into a surface with high affinity for the paint binder. They preferably include components that covalently bond to the metal substrate as well as to the paint binder. In thisapplication, rather than applying on adhesive 33 (FIG. 13) over the primer 39, we apply the exterior surface coating or paint 55 (FIG. 15) typically pigments carried in a urethane binder. The sol coating provides long lasting durability for adherence ofthe primer and finish coating to the metal.
The sol coating of the present invention promises to improve paint adhesion and to simplify field repair and maintenance of painted metal surfaces, especially titanium or aluminum structure painted with epoxy or urethane paints. Because the solhas essentially a neutral pH, it can be easily used in the field for touch up without the precautions or special equipment necessary for anodizing. Through the sol coating 45, the paint 55 is essentially covalently bonded to the metal 65 as shown inFIG. 15 and adhesion is significantly enhanced. We obtain improved adhesion even for parts that have had acid surface etching several weeks prior to priming and painting.
The preferred sol coating process for paint adhesion improvement involves:
(a) cleaning the surface with an aqueous detergent or another cleaning solvent.
(b) wetting the surface for at least five (5) min prior to applying the sol;
(c) applying the sol by spraying or another suitable means while continuing to keep the surface wet for 1-2 min;
(d) drying the sol to form a sol coating at ambient conditions for 15-60 min;
(e) heating the sol coating to a temperature in the range from 160.degree.-250.degree. F. (preferably, 230.degree..+-.20.degree. F.) for 15-45 min to complete the drying; and
(f) applying the primer or paint, as appropriate, between 2-72 hours after completing drying steps (a) & (e).
The sol has a pot life of up to about ten hours. Of course, there is an induction time following mixing that reduces the period of time in which the sol can be applied.
We achieve the most consistent results using deionized water as the carrier or solvent. The deionized water should have a minimum resistivity of about 0.2M .OMEGA..
The sol might also be used as a coupling agent in polyimide resin composite bonds (especially BMI or KIIIB composites) to other resin composite parts or to metals.
The sol coating can be applied to advantage on sheet, plate, foil, or honeycomb. While described primarily with reference to Ti, the sol coating is also useful on Al, Cu, or Fe pure metals or alloys. One application for copper includes coatinga susceptor mesh or foil used in thermoplastically welded composite structures. Another application for coated copper includes protecting the metallic interlayers in multichip modules or multilayer chip module packaging. Suitable ferrous alloys aremild steel, cold rolled steel, stainless steel, or high temperature alloys, such as the nickel-iron alloys in the INCONEL family.
To prepare the sol according to the mixing procedure outlined in Table 5. The absolute volume mixed can vary as needed. Once mixed the sol should age for 4-6 hours to reach equilibrium.
TABLE 5 __________________________________________________________________________ Sol Preparation for Amino-based Silanes STEP __________________________________________________________________________ * Stir 500 ml deionized (DI) water into1000 ml flask Flask 1 (1000 ml) * Add 4 Drops NH.sub.4 OH * Verify pH around 7-8 (add more if appropriate) * Add 7.3 ml glacial acetic acid (GAA) to 50 ml flask Flask 2 (50 ml) * Add 10 ml TPOZ into 5 ml flask with GAA * Shake mixture * Add 34 mlorganosilane to 1000 ml flask, avoid drops on sides of Flask 1 (1000 ml) * Cover flask * Dwell for 20 to 30 minutes * Add about 300 ml DI to 500 ml flask Flask 3 (500 ml) * Add about 200 ml DI to 200 ml flask Flask 4 (200 ml) * Dilute contents of50 ml flask with equivalent volume of DI Flask 2 (50 ml) * Add entire contents of 50 ml flask to 500 ml flask (should be Flask 2 (50 ml) + Flask 3 (500 ml) * Add 3 ml of NH.sub.4 OH, squirt in while agitating violently pH should be about 5 (milkywhite) * Add contents of 500 ml flask to 1000 ml flask Flask 3 (500 ml) + Flask 1 (1000 ml) * Rinse 500 and 50 ml flasks with DI water from 200 ml flask (pH between 8-9) Flask 1 (1000 ml), Flask 2 (50 ml) into 1000 ml flask Flask 3 (500 ml), Flask 4(200 ml) * Allow solution to age for 4-6 hours under constant agitation prior to application __________________________________________________________________________
A presently preferred surface pretreatment for the metal (albeit one different from that schematically illustrated in FIG. 1) includes the steps outlined in Table 6.
TABLE 6 __________________________________________________________________________ Surface Treatments Pretreatment Process Steps Temp Time __________________________________________________________________________ Aqueous Degrease with SuperBee per BAC 5763 (optional) 150 .+-. 5F 20 to 30 minutes Water immersion rinse (optional) 100 .+-. 15F 3 to 5 minutes Alkaline Clean Brulin 815 GD per BAC 5749 140 .+-. 5F 20 to 40 minutes Water immersion rinse 100 .+-. 15F 3 to 5 minutes Water Spray Rinse Ambient NA Turco 5578 Alkaline Etch (80% concentration) 190 .+-. 5F 15 to 20 minutes DI Water Immersion Rinse Ambient 3 to 5 minutes HNO.sub.3 Desmut (35% concentration) 150 .+-. 5F 3 to 4 minutes DI Water Immersion Rinse withAgitation Ambient 3 to 5 minutes DI Water Spray Rinse Ambient NA Verify parts are water break free for greater than 60 seconds __________________________________________________________________________
BOECLENE desmutting can replace the HNO.sub.3. The composition and use of BOECLENE is described in U.S. Pat. No. 4,614,607, which we incorporate by reference.
While we have described preferred embodiments, those skilled in the art will readily recognize alternatives, variations, and modifications which might be made without departing from the inventive concept. Therefore, interpret the claimsliberally with the support of the full range of equivalents known to those of ordinary skill based upon this description. The examples illustrate the invention and are not intended to limit it. Accordingly, define the invention with the claims andlimit the claims only as necessary in view of the pertinent prior art.
* * * * *
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text:
"You can now sell your town to Tom Nook."
"^ I hear it happens when you go to delete your town, it'll appear "
"Also, anyone know where wisp's lamp is?"
"Does anyone know what the point of 'Invite over wifi' is for Harvey? Like, what is that option for?"
"Where are the RVs located?"
"I have no idea ... possibly to have people invite villagers over WiFi? "

subset: commoncrawl


text:
Man charged in 2 Triad bank robberies
Man charged in 2 Triad bank robberies
A man was arrested in Atlanta Wednesday on suspicion of robbing two Triad banks within the past month.
Kelvin James Crosby, 31, was arrested by federal marshals in connection with a robberies in High Point and Thomasville.
The first robbery took place Nov. 6 at the BB&T at 2105 Westchester Dr. in High Point, and the other happened Nov. 16 at the Bank of North Carolina at 831 Julian Ave. in Thomasville.
Crosby is facing charges of robbery with a dangerous weapon and common law robbery. He is being held in the Guilford County Jail under a $150,000 secured bond.


text:
A world leader in international student placement services
and a proud co-owner of IELTS
University of South Australia
The University of South Australia is a progressive international university with a 150 year history, supporting a vibrant student community from around the world. In 2013/14, the QS 'Top 50 under 50' ranked the University of South Australia at number 42 in the world for universities less than 50 years old. Highlights include: • A ranking of five QS Stars • Award winning teachers • Practice based learning and strong industry links • World class research • State of the art technologies in modern facilities • Excellent study support services and great student experiences
الحرم الجامعي الرئيسي:
South Australia
عدد الطلاب:
الطلاب الدوليون:
التجهيزات: Health Sciences; Business and Law; Education, Arts and Social Sciences; IT, Engineering and the Environment
نظرة عامة
The University of South Australia offers a unique educational experience that prepares students for professional and personal success.
The University's dedication to academic excellence through coursework, postgraduate research and practical based learning is evidenced by the quality of graduates, who have the knowledge and experience as well as the personal and practical skills to make an immediate impact in their chosen profession.
Five Star University
The 2014 QS World University Rankings recognised the University of South Australia as a Five Star university for teaching, innovation, access, internationalisation and facilities.
Award winning teachers
Teachers are experts in their fields and almost 70 per cent of academic staff hold doctorates, which puts the University in the top 10 universities in Australia on this measure. Many of the teaching staff have been actively involved in industry and practise what they teach.
Practise based learning
Students will get the chance to test their learning in real work environments. They will have the opportunity to participate in clinical or field placements, assist with industry-based projects or work alongside people from industry and the professions.
World-class research
The 2012 round of Excellence in Research for Australia (ERA) evaluation rated more than 86 per cent of the University's assessed research as world-class standard or above.
World-class facilities
Each campus is equipped with the latest facilities including modern lecture theatres, libraries, workshops, laboratories and areas that simulate how students will work once they graduate. This is all backed up by a fully interactive online learning environment.
Great career outcomes
Graduate employment rates are above the national average and the highest in South Australia. The Career Services unit offers employment and careers expos, networking and mentoring schemes.
Supportive services
Services are designed to help students succeed in their studies and manage student life. Among the 28 Australian institutions that participated in the 2013 International Student Barometer, the University of South Australia ranked number two nationally for support for international students.
The experience of a lifetimeStudents can enjoy a wonderful student experience as campuses come alive with events, entertainment, sports, clubs and social events. Opportunities for travel, volunteering, mentoring, career development and more are also on offer.
مناطق الدراسة
List of academic areas – i.e. Faculties/Schools/Colleges:
- Health Sciences
- Business and Law
- Education, Arts and Social Sciences
- IT, Engineering and the Environment
تجهيزات الحرم الجامعي
- City West - located in Adelaide's central business district, City West is home to the Business School as well as visual art, architecture and design, Australian and Indigenous studies.
- City East - located on North Terrace in the city centre, City East is home to the Division of Health Sciences and the School of Natural and Built Environments.
- Magill - eight kilometres from the city centre, the Magill campus is set among lush gardens and open spaces and is home to the Division of Education, Arts and Social Sciences.
- Mawson Lakes - located north of the city centre and home to the Division of Information Technology, Engineering and the Environment, this campus also offers science, civil aviation and education studies.
- The University also offers programs on regional campuses in Mt Gambier and Whyalla.


text:
Creating situations where you don't have a choice but to walk or bike is the easiest way to motivate yourself to walk or bike more.
The best motivation to bicycle is necessity. When bicycling is the fastest and easiest way to get where you want to go, you don't need any other reason. You don't need to convince yourself that it's good for you, that it saves money, or that it is good for the environment. You'll get on that bike because you want to go somewhere. Maybe you'll feel resentful that you don't have faster wheels. Or maybe you'll be happy that you don't have to walk.
We became a one-car family in 2004 and I rode my bike when I had to. It was only temporary, until we could afford a car payment. But the more I biked, the more I enjoyed it. The longer we lived without a car payment, the more we liked that, too!
I hear a lot of people say, "I ought to bike or walk more." I don't know what to tell them. As long as you have that car, walking and biking is something you have to make yourself do.
There are days when I suddenly realize, "I should have taken the car. That would have made this so much easier." I'm so stuck in the habit of biking that it doesn't occur to me to use the car. That's how most of us are about driving—so ingrained in the habit of driving that it takes quite a special effort to walk or bike once in a while.
My friend Amanda bought a bike recently. She and her husband share the car but when her hours changed, it wasn't convenient anymore. She's been bicycling to work even when the weather hasn't been too nice, because it's easier than sharing the car.
A budgeting guru I follow is considering selling his family's second car. Since he started walking to work, the car sits in the garage. While the financial argument is clear, he finds it hard to let go of that security.
In a story about families and exercise, NPR contrasted two moms. One mom spends hours driving her sons to sports practices. The other mom is car-free and selects her son's activities based on what is within walking or biking distance. Both she and her son get plenty of exercise without having to plan for it.
If you hear yourself saying, "I ought to walk or bike more," consider parking your car somewhere else for a week, at a friend's house or a parking lot (with permission) within walking distance. If you really need it, it will be there, and you'll discover that it's natural and easy to walk or bike when the car is a little further away.


text:
National Library of France
Emergency plan
Protecting collections in the event of an incident
An incident in a library is an unforeseeable and unexpected event that can severely disrupt the day-to-day lives of staff and users and damage collections.
A library emergency plan aims to make provision for the various risks associated with incidents affecting collections, and to make advance preparation for activities aimed at repairing the damage.
Emergency does not imply haste.
An emergency plan is a methodology governing intervention by the various departments and officers affected by a major incident. Relevant volunteers draw on knowledge gained through specific training on the practical use of techniques for saving materials so as to reduce the devastating effects of an incident.
le plan d'urgence [fichier .pdf – 207 Ko – 12/10/07 – 28 p.]
Thursday, June 30, 2016
ContactCéline Allain


text:
Follow RFF News on your cell phone. Text follow rff to 40404 you will receive txt messages with RFF News
0 Members and 1 Guest are viewing this topic.
My head was exploding from the Oscar Red Carpet coverage. Glad TAR is here for a bastion of sanity!!!
Make note of the #TahitianPriest
for a future episode #AmazingRace @NoOppWasted
Twins taking the 6 hour penalty because they are scared of the water!
I'm surprised they decided to take the 6-H Penalty so quickly. The other two teams are like...3 hours behind , right now?
Page created in 0.08 seconds with 33 queries.


text:
Event box
Submission Deadline - 20th Annual Clemens Library Art Contest
- Date:
- Thursday, April 19, 2018
- Time:
- All Day Event
- Library:
- Clemens Library (CSB)
- Description:
The Clemens Library of the College of Saint Benedict will once again be the venue for an Art Contest and Show sponsored by the joint libraries. The Libraries are inviting any student at CSB/SJU to submit artwork. The show will be juried by members of the Art Department and the Library, and the selected works will be awarded cash prizes and displayed in the gallery space of the Clemens Library. If you entered last year, do not hesitate to enter again this year!
Entries to the contest must be submitted by April 19, 2018 to Jim Parsons in Clemens Library (CSB) or to Kelly Kraemer in Alcuin Library (SJU). Students may submit up to three pieces unless it is a series which consists of more than 3 pieces. This contest is open to all CSB/SJU students, not just Art Majors!
Work in all two-dimensional and three-dimensional media will be accepted including but not necessarily limited to sculpture, painting, prints, drawings, photographs, jewelry, ceramics, video, computer or artist's books. Work created in classes is certainly eligible. All work should be suitably framed (in whatever way the artist thinks is appropriate to the piece) and ready for hanging. Some frames are available for your use on a first come, first serve basis.
The artwork should be accompanied by a typed statement relating the intentions, motivations, or themes of the artist. The statement should be approximately 100 words. The prizes include 1st place of $300, 2nd place of $200 and 3rd place of $100. The contest is sponsored by the Clemens Library of the College of Saint Benedict and the Alcuin Library of Saint John's University with the assistance of members of the CSB/SJU Art Faculty.
The work will be displayed in the Clemens Library. For more information contact Jim Parsons (firstname.lastname@example.com).
All reasonable care and precaution will be taken in the handling, storing, and installing of the artworks submitted for this contest. Neither the Libraries nor the jury committee will be responsible for damage to works while in our possession. Submission to this contest shall imply agreement to all conditions of the contest.


text:
When school's out or you have a big birthday party to plan, we've got your back! The Little Gym offers individually created birthday parties to celebrate your child's special day.
Awesome Birthday Parties at The Little Gym gives your birthday child and their friends the full run of the facility, filling the celebration with instructor-led games, music and fun activities created especially for your birthday boy or girl. And you don't have to worry about setup or cleanup, making it totally awesome for you too!
Download Parties Brochure


text:
Kotaku video editor Chris Person declares that the best part of New Super Mario Bros. U is the game's Boost Rush Mode, in which the sidescrolling game sidescrolls faster as you collect more coins.
Chris is a man of taste and a devotee of Dyad. Speed-racing is his thing. He hasn't played that much of NSMBU, so maybe he's missing something even cooler. For now.. please enjoy Chris' current favorite thing.
The clips here are short. Why? We can only show you 30 seconds of any level, because those are the rules/regulations/conditions mandated by Nintendo, the providers of our pre-release Wii U.


text:
– We noted earlier that Cody Rhodes participated in a post-RAW segment with The Rock in Lafayette earlier this week after the show went off the air. Cody actually volunteered for the segment and pitched the idea of him going out and taking a People's Elbow and Rock Bottom.
– WWE sources note that Jack Swagger was scheduled to win the World Heavyweight Title from Alberto Del Rio at WrestleMania 29. No word yet on what his arrest means for booking plans but WWE creative was working late on Wednesday night to come up with ideas, which doesn't sound good for Swagger and Zeb Colter.
There's talk that if WWE officials saw fit to change the direction of the match, then Dolph Ziggler would most likely get the WrestleMania match with Del Rio.
If Swagger ends up suspended and loses the WrestleMania match, the arrest altogether would cost him upwards of $250,000.
Source: Wrestling Observer Newsletter


text:
Gift Audiobook Memberships
You pick the duration—1, 3, 6, or 12 months—they pick the audiobooks. Buying gifts from Totem Books has never been so easy.Gift Now
Bookseller Recommendation
The Man Who Caught the Storm
"Tornado-chasing Tim Samaras lived life on his own terms continually pushing parameters wherever he traveled searching for the next superstorm. In "The Man Who Caught the Storm", Brantley Hargrove offers fast-paced insight into the mysteries of this meteorological phenomenon as well as the man obsessed with finding an explanation. When Samaras catches wind of a tornado forming by El Reno, Oklahoma, he realizes this is his opportunity of a lifetime. With son Paul and partner Carl Young in tow, Samaras speeds towards the subvortex determined to deploy sensor equipment in its deadly path. With devastating consequences. I highly recommend this heart-stopping narrative guaranteed to leave you in a wake of tears."Kristin, McLean & Eakin Booksellers
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#1 NEW YORK TIMES, WALL STREET JOURNAL, AND BOSTON GLOBE BESTSELLER • NAMED ONE OF THE TEN BEST BOOKS OF THE YEAR BY THE NEW YORK TIMES BOOK REVIEW • ONE OF PRESIDENT BARACK OBAMA'S FAVORITE BOOKS OF THE YEAR • BILL GATES'S HOLIDAY READING LIST • FINALIST FOR THE NATIONAL BOOK CRITICS CIRCLE'S JOHN LEONARD PRIZE FOR BEST FIRST BOOK • LONGLISTED... Read More »
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The runaway New York Times bestseller!
Named a Best Book of the Year by:
People, The Washington Post, Bustle, Esquire, Southern Living, The Daily Beast, GQ, Entertainment Weekly, NPR, Amazon, Barnes & Noble, iBooks, Audible, Goodreads, Library Reads, Book of the Month, Paste, Kirkus Reviews, St. Louis... Read More »
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A New York Times Top Ten Book of the Year and National Book Award finalist, Pachinko is an "extraordinary epic" of four generations of a poor Korean immigrant family as they fight to control their destiny in 20th-century Japan (San Francisco Chronicle).
NEW YORK TIMES NOTABLE BOOK OF 2017 * A USA TODAY TOP TEN OF 2017 * JULY PICK FOR THE PBS... Read More »
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The newest audiobook sensation from Kristin Hannah, bestselling author of The Nightingale.
This program is read by acclaimed narrator Julia Whelan, whose enchanting voice brought Gone Girl and Fates and Furies to life. Kristin Hannah reads the acknowledgements.
Alaska, 1974.
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For... Read More »
A Higher Loyalty
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"Comey's conversational tone instantly connects with the listener, and hearing him deliver the book's highly charged contents in his own voice brings authenticity and immediacy to the presentation...This greatly anticipated, revelatory memoir needs to be heard." — AudioFile Magazine
In his audiobook, A Higher Loyalty, former FBI director James... Read More »
A Wrinkle in Time
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Meg Murray, her little brother Charles... Read More »
The Immortalists
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A Gentleman in Moscow
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Narrated by: Nicholas Guy Smith
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"The book is like a salve. I think the world feels disordered right now. The count's refinement and genteel nature are exactly what we're longing for." —Ann Patchett
"How delightful that in an era as crude as ours this finely composed novel stretches out with old-World elegance." —The Washington Post
He can't leave his hotel. You won't want to.
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The Woman in the Window
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Instant #1 New York Times Bestseller!
"Astounding. Thrilling. Amazing." —Gillian Flynn
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