AU2007202368A1 - Activation method using modifying agent - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION Standard Patent Applicants: THE BOEING COMPANY and COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION Invention Title: ACTIVATION METHOD USING MODIFYING AGENT The following statement is a full description of this invention, including the best method for performing it known to me/us: la C ACTIVATION METHOD USING MODIFYING AGENT

FIELD

The present invention relates to a method of C activating an organic coating, a coated substrate having an activated coating and an activation treatment for an organic coating. In particular, the activation method 00 ND improves the adhesion of the organic coating to further e coating layers and/or to other entities.

BACKGROUND

C Organic coatings are generally used to protect the surface of materials from incidental damage, abrasion, chemical attack and from environmental or in-service degradation. Organic coatings are also used to enhance the aesthetics and/or optical properties of an object or component.

The surface properties of many coatings dramatically change on drying, curing and/or aging to become more inert than might be predicted based on the chemistry of their individual components alone. Whilst this phenomenon in part provides the coating with chemical resistance, impact strength, abrasion resistance and durability, it also complicates the process of applying additional coating layers, particularly when they are not applied within a predetermined reapplication window. The same problem arises with applying other entities such as sealants, pin hole fillers and surfacers such as those used on composite substrates, decals and logos applied with pressure sensitive adhesives and the like, to such coatings. In cases which require the application of additional coating layers and/or other entities, a mechanical abrasion or stripping process of the coating is generally necessary before the re-application procedure can take place.

In the specific example of aircraft coatings, it is well known that adhesion will not meet in-service performance requirements when fresh layers of coating are -2- Q)applied over layers which have aged beyond the acceptable c-I reapplication window. The acceptable window may be of the order of days under ambient conditions or potentially hours under certain conditions of high temperature or c-I C 5 extreme humidity. Once the reapplication window has been exceeded, the standard practice for applying additional 00 coating layers on aircraft involves mechanical abrasion of

\O

M the aged coating.

Both chemical stripping and mechanical abrasion have limitations. Mechanical abrasion is labor intensive, the Sreproducibility is variable, and it is ergonomically C costly due to the highly repetitive and vibratory nature of the work. As such there is a pressing need for the development of a surface treatment to improve the adhesion of aged or inert industrial organic coatings towards additional coating layers or other entities, for example, adhesives, sealants, fillers, stickers and the like.

Coating manufacturers have developed a method of improving the procedure of coating stripping through the development of barrier layers and intermediate coats which, for example, protect the primer and conversion coating of metal structures from the chemical stripping agents (US 6,217,945). Although this procedure would reduce the amount of infrastructure down time, it still relies on paint removal to provide a surface which will accept a fresh coating layer with acceptable adhesion.

Haack (Surface and Interface Anal, (2000), 29, p829) investigated the interaction of automotive polyurethane coatings using UV light to generate ozone. Promising results in terms of improved adhesion and reduced water contact angles were produced when paint formulations incorporating Ti02 were subjected to H 2 0 2 and UV light.

However, there are obvious practical difficulties associated with this strategy, particularly in terms of its commercial viability for application in areas susceptible to corrosion and for treating larger surfaces.

3 Also the occupational health and safety issues make it less suited to commercial application.

In the biological field, Park et al. (Biomaterials, (1998), 19, p851) employed the surface urethane NH group C< 5 to graft chemical species onto polyurethane rubber, whilst Levy et al. (Biomaterials (2001) 22, p2683) employed a 00 strong base to remove the surface urethane NH proton to

NO

Saccelerate such nucleophilic grafting reactions. Both strategies are unsuitable for activating organic coatings.

The chemical reaction kinetics of the first strategy would Sbe too slow to be practical, particularly since, considering the low surface energy and inertness to bonding of such coatings, the urethane NH groups may not be oriented towards the air-coating interface. The use of very strong bases, as per the second strategy, may degrade existing paint layers, resulting in a mechanically weak foundation for fresh coatings to adhere to. Furthermore, the latter strategy is also unacceptable for activating large areas due to corrosion and health and safety considerations.

Other strategies in the biological field have employed free radical techniques to graft molecules onto the surface of biomedical polyurethane surfaces (Matuda et al, J. Biomed. Res., (2002), 59, p386; Eaton et al, Biomaterials, (1996) 17, p1977) Although commercially viable, the main difficulty with this strategy lies in promoting actual grafting of the substrate.

Controlled glycolysis or aminolysis as described in Polymer Engineering Science (1978), 18, p844, and J.

Applied Polymer Science (1994), 51, p675) has very slow kinetics at room temperature and as such is not a practical solution. The use of reagents such as dimethyl phosphonate (Polymer Degradation and Stability, (2000), 67, p159) is also not appropriate since they are highly toxic and act too slowly at room temperature.

The strategies disclosed above do not adequately address the need for the development of a surface 4 Qtreatment to improve the adhesion of aged or inert organic

(N

coatings to additional coating layers and/or other entities. The problems of commercial viability, health and safety considerations, viable kinetics, applicability to 5 small and large surface areas still remain and need to be resolved.

OO It is to be understood that, if any prior art Spublication in the biological field is referred to herein, D such reference does not constitute an admission of a known application to the field of industrial and architectural coatings.

SUMMARY

We have now found a method which allows the activation of organic coatings to improve their adhesive properties towards further coating layers of the same or different type, and/or other entities without compromising coating integrity, via the use of mild reagents and conditions. The process of activation on aged coatings when they have exceeded the application window where adhesion will not meet in-service performance requirements when fresh layers of coating are applied over layers is also termed reactivation. Both activation and reactivation will be used interchangeably.

The term "mild" in this context refers to chemicals which are not known to be excessively corrosive, acidic, basic or toxic and are applicable for use in highly regulated industrial environments. One example of such an environment is a commercial aircraft paint hangar.

Additionally the mild reagents used in the preferred application methods do not adversely affect the bulk aircraft coatings, or underlying coatings, such as primers or selectively strippable coatings, or underlying substrates, such as aluminium and composite.

Advantageously, this method no longer requires the traditional methods of mechanical abrasion or chemical stripping of an organic coating to improve its adhesive 5 Qproperties towards additional coatings and/or other

(N

entities.

In a first aspect, the present invention provides a method of activating an aged or inert organic coating to C 5 enhance adhesion of the coating to a further coating and/or to other entities selected from adhesives, 00 sealants, pin hole fillers and pressure sensitive decals or logos comprising applying a solvent and a surface chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface CI modification and/or adds chemical functionality to the surface of the organic coating.

In another aspect, the present invention provides a coated substrate having an activated coating, wherein the adhesion of the coating to a further coating and/or other entities selected from adhesives, sealants, pin hole fillers and pressure sensitive decals or logos has been enhanced by application of a solvent and a surface chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface modification and/or adds chemical functionality to the surface of the organic coating.

The solvent and the agent may be applied either simultaneously, sequentially or separately.

Advantageously, the solvent and the agent are applied to the organic coating simultaneously in the form of an activation treatment.

The agent may act independently from the solvent or alternatively the combination of the solvent and the agent may be necessary to affect a change in coating surface chemistry and/or topography.

In a further aspect, the present invention provides an activation treatment for an organic coating to enhance adhesion of the coating to a further coating and/or to other entities selected from adhesives, sealants, pin hole 6 Sfillers and pressure sensitive decals or logos comprising a solvent and a surface chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface CI 5 exchange, light induced surface modification and/or adds chemical functionality to the surface of the organic OO coating.

M1 The invention also provides a method for the O preparation of the activation treatment defined above comprising the step of mixing the solvent with the surface chemistry and/or surface topography modifying agent which N facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface modification and/or adds chemical functionality to the surface of the organic coating.

DETAILED DESCRIPTION In this specification, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

As used in the specification the singular forms "a" "an" and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "a solvent" includes mixtures of solvents, reference to "an agent" includes mixtures of two or more such agents, and the like.

The method of the present invention involves activating an organic coating so as to enhance the adhesive properties of at least the surface of the coating towards additional coating layers and/or other entities, for example, adhesives, sealants, pin hole fillers, pressure sensitive decal or logo adhesives and the like.

The term 'activating' is used in this context to mean the 7 Qimprovement of the adhesive properties of the organic coating relative to the adhesive properties of that coating, prior to application of the solvent and the agent.

Cl 5 The word "coating" is used herein its broadest sense and describes decorative topcoats; undercoats; 00 intermediate coatings; primers; sealers; lacquers;

INO

a coatings which are pigmented or clear; coatings designed for specific purposes, such as, corrosion prevention, temperature resistance, or camouflage; coatings which are Shigh gloss, matte, textured, or smooth in finish; or CI coatings containing specialty additives, such as metal flakes.

In general, organic coatings which are cured, dried or aged beyond a certain time period develop resistance to forming strong adhesive linkages towards other entities.

Their surface properties become more inert than might be predicted, based on the chemistry of their individual components alone. Without wishing to be limited by theory, it is believed that this phenomena may result from a reduction in coating surface energy and amount of reactive surface functional groups in conjunction with a higher cross-link density as a function of cure time/aging which makes chemical interaction and/or the formation of strong adhesive linkages with other entities difficult.

The organic coatings which may be activated include, but are not limited to, fully or partially cross-linked organic coatings. Examples of organic coatings include, polyurethane, epoxy, polyester, polycarbonate and/or acrylic coatings, more preferably polyurethane and epoxy coatings. Due to their superior mechanical properties and resistance to abrasion, chemical attack, and environmental degradation, such organic coatings are widely used to protect infrastructure in the aerospace, marine, military, automotive, and construction industries. Many of these coatings show a marked reduction in adhesion to other entities, such as additional coating layers, adhesives, 8 F-q sealants, pressure sensitive decals or logos and the like, >with increased time of curing and/or aging.

The activation method involves applying the solvent and the agent to a surface of the organic coating. The I 5 surface treatment is not a conventional coating such as a primer coating or tie-coat, but rather a chemical method 00 of modifying the surface of the existing coating so that C it is more receptive to forming adhesive interactions with 0 further coatings and/or other entities.

Without wishing to be limited by theory it is believed that the interaction of the agent and/or solvent c combination with the coating modifies the coating surface chemistry and/or surface topography to enable it to be more receptive towards other entities including but not limited to additional coating layers. Such agents and/or solvents are chosen such that the bulk integrity of the coating and underlying coating and substrate structures are maintained.

Suitable agents include those which facilitate chemical and/or topographical modification of the coating surface such as but not limited to agents which facilitate surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface modification and/or add chemical functionality to the surface of the coating.

Examples of agents capable of affecting surface reduction include: Reductants such as sodium borohydride, potassium borohydride, lithium borohydride, zinc borohydride, calcium borohydride and alkoxy, acetoxy and/or amino derivatives thereof such as sodium methoxy borohydride or lithium dimethylaminoborohydride; sodium cyanborohydride, borane and borane complexes; aluminium hydrides such as lithium aluminium hydride and diisobutyl aluminium hydride; calcium hydride; sodium hydride; Red Al (sodium bis(2-methoxyethoxy)aluminiumhydride); selectrides such as K-selectride (potassium tri-sec-butylborohydride); 9 e< sodium dihydro-bis-(2-methoxy) aluminate; sodium >borohydride mixed with aluminium trichloride; lithium triethylborohydride; and lithium tri-tert-butoxy aluminium hydride.

C 5 Examples of agents capable of catalysing surface hydrolysis include: 0 Acids such as organic acids, for example, formic Sacid, acetic acid, benzoic acid, propanoic acid, malonic 0 acid, oxalic acid and kemp's triacid; and inorganic acids, 10 for example, phosphoric acid.

Examples of agents capable of affecting surface oxidation include: Oxidants such as trichloroisocyanuric acid, sodium hypochlorite, hydrogen peroxide, potassium permanganate, potassium chromate, periodic acid and lead tetra acetate.

Examples of agents capable of affecting surface exchange or transesterification include: metal alkoxides or chelates thereof, such as those outlined in "Alkoxides and alkylalkoxides of metals and metalloids" Mehrotra, Inorganic Chemical Actia, Reviews, (1967) p99, including titanium or zirconium alkoxides or chelates thereof, for example those marketed by companies such as DuPont or Gelest, i.e.tetraisopropyltitanate, tetra-n-propyl titanate, tetra-nbutyltitanate, tetra-2-ethylhexyltitanate, tetraethyltitanate, triethanolamine titanate chelate, tetra-n-propylzirconate, tetra-n-butylzirconate and triethanolamine zirconate chelate.

Examples of agents capable of affecting light induced surface modification include: Free radical initiators such as initiators which are activated by the presence of light, preferably visible light induced free radical initiators or combinations of free radical initiators with tertiary amines and/or mono or multi-functional unsaturated species.

10 Suitable light activated initiators include but are >not limited to camphorquinone and derivatives thereof; benzophenone and derivatives thereof, such as, diethylaminobenzophenone; and phenylphosphineoxide (C 5 derivatives, such as, Irgacure (CIBA).

Tertiary amine agents include species such as N,N- 00 dimethyl toluidine, N,N-dimethylamino ethylmethacrylate, C methyl imidazole, NNN'N'tetramethyl-l,4-butane diamine and 0 NNN'N'tetramethylphenylenediamine.

The multi-functional unsaturated species may be selected from acrylates, for example, hydroxyl ethyl (C acrylate; methacrylates, for example, polyethyleneglycol monomethacrylate, hydroxyl ethyl methacrylate, glycidyl methacrylate, N,N-dimethylamino ethylmethacrylate, ethyleneglycol dimethacrylate and butane diol dimethacrylate; and acrylamides, for example, hydroxyethyl acrylamide and bis acrylamide.

It will be appreciated that the agents may also be prepared in-situ from their constituent components. For example, LiBH 4 may be prepared in-situ from NaBH 4 and LiC1 and sodium methoxyborohydride from methanol and NaBH 4 The agent(s) are generally present in an amount more than about 0.001%, preferably more than about 0.01%, and most preferably about 0.01% to about 20% based on the total weight of the activation treatment, or the combination of solvent(s), agent(s) and any further optional additive(s).

Preferably the solvent and/or agent only interact with the surface of the organic coating so that the integrity of the coating is not compromised.

The solvent may be a single solvent or a combination of two or more solvents. Preferably the solvent is an organic solvent. Suitable organic solvents or solvent combinations depend on the surface modifying agent employed to above) and include but are not limited to: 11 S(a) ester based solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tertiary butyl acetate and glycol ether acetates; ketones such as methyl ethyl ketone, methyl CI 5 propyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl isobutyl ketone and acetone; 00 alcohols such as aromatic alcohols, for example,

NO

benzyl alcohol; aliphatic alcohols, for example, tertiary butanol, n-butanol, secondary butanol, isopropanol, nc 10 propanol, ethanol, methanol and cyclohexanol; and glycol Sethers, for example, those marketed by Dow under the trade C-I name Dowanol such as, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol and their monoethers such as mono-C 1 6 alkyl ethers including but not limited to those marketed by Dow under the trade name Downanol E-series and P-series glycol ethers.

ethers such as glycol diethers, for example, the di-C 1 -6 alkyl ethers of glycols such as diethers of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol including but not limited to diethylene glycol dimethylether, dipropylene glycol dimethyl ether or diethylene glycol methyl butyl ether such as those marketed by Dow under the trade name Downanol E-series and P-series glycolethers; and cyclic ethers such as tetrahydrofuran; amides such as N-methyl pyrrolidinone; aromatics such as toluene and xylene; halogenated solvents such as dichloromethane and tetrachloroethylene; and water In view of the toxicity and negative environmental impact of halogenated solvents it will be understood 12 that they should be used within the constraints of environmental, health and safety regulations.

Preferred solvents are ester based solvents such as ethyl acetate, ethoxyethyl acetate, isopropyl acetate C- 5 and/or tertiary butyl acetate; ketone solvents such as methyl propyl ketone, methyl amyl ketone, methyl isoamyl 00 ketone and/or methyl ethyl ketone; alcohols such as c ethanol, methanol, ethoxyethanol, n-propanol, isopropanol, butanol, tertiary butanol and secondary butanol; ether 10 solvents such as C 1 -6 alkyl ethers or combinations thereof S(i.e. mixed ethers) of ethylene glycols and propylene C-I glycols including but not limited to glyme, diglyme, triglyme, tetraglyme and dipropylene glycol dimethyl ether and cyclic ethers, for example, tetrahydrofuran; amide solvents such as N-methyl pyrrolidinone; and water.

Preferred solvent combinations include glycol ether acetate combinations such as dipropylene glycol dimethyl ether tertiary butyl acetate; ether: alcohol combinations such as diproplyene glycol dimethyl ether: isopropanol, n-propanol, methanol, isobutanol, secondary butanol, tertiary butanol, ethoxy ethanol and/or ethylhexanol; ethylene glycol monomethyl ether: ethanol, methanol, ethoxyethanol and/or isopropanol; glycols and monoether combinations such as dipropylenegylcolmonomethylether, dipropylenegylcol-monobutylether, and/or dipropylenegylcol; ether combinations such as tetrahydrofuran: triglyme and tetrahydrofuran: dipropylene glycol dimethylether; ketones and acetate combinations such as methylethyl ketone: ethoxyethyl acetate and methyl amyl ketone: ethoxyethyl acetate; N-methyl pyrrolidinone: ethyl acetate; ethyl acetate: benzyl alcohol; dipropylene glycol dimethyl ether: polyethylene; and methyl propyl ketone: methyl ethyl ketone. Typical solvent combinations include high and low boiling point solvent combinations.

The solvent(s) are generally present in an amount of less than about 99.999%, preferably greater than about most preferably in an amount of about 80% to about 13 99.99% based on the total weight of the activation treatment or the combination of solvent(s), agent(s) and any further optional additive(s).

One or more additives and/or inerts known in the art Cq 5 of coatings may also be used in the method or activation treatment of the present invention. Examples include: 00 rheology modifiers such as hydroxypropyl methyl m cellulose Methocell 311, Dow), modified urea (e.g.

Byk 411, 410) and polyhydroxycarboxylic acid amides (e.g.

Byk 405); S(b) film formers such as esters of dicarboxylic acid C1 Lusolvan FBH, BASF) and glycol ethers Dowanol, Dow); wetting agents such as fluorochemical surfactants 3M Fluorad) and polyether modified poly-dimethylsiloxane Byk 307, 333); surfactants such as fatty acid derivatives (e.g.

Bermadol SPS 2543, Akzo) and quaternary ammonium salts; dispersants such as non-ionic surfactants based on primary alcohols Merpol 4481, Dupont) and alkylphenol-formaldehyde-bisulfide condensates (e.g.

Clariants 1494); anti foaming agents; anti corrosion reagents such as phosphate esters ADD APT, Anticor C6), alkylammonium salt of (2benzothiazolythio) succinic acid Irgacor 153 CIBA) and triazine dithiols; stabilizers such as benzimidazole derivatives Bayer, Preventol BCM, biocidal film protection); leveling agents such as fluorocarbon-modified polymers EFKA 3777); pigments or dyes such as fluorescents (Royale Pigment and chemicals); organic and inorganic dyes such as fluoroscein; and 14 Lewis acids such as lithium chloride, zinc chloride, strontium chloride, calcium chloride and aluminium chloride.

C The additive(s) are usually present in an amount of C 5 less than about 10% based on the total weight of the activation treatment or the combination of solvent(s), 00 0O agent(s) and additive(s) SSpecific activation methods forming embodiments of the present invention (which may optionally be used in combination) are as follows: i. Surface reduction q This method involves using a solvent and an agent such as a reductant, for example, lithium borohydride to cause surface reduction or break down of the organic coating surface. While not wishing to be bound by any theory, it is believed that this method provides reactive entities or a suitable morphology to improve inter-coat adhesion with further coating layers and/or other entities. Suitable solvent or solvent combinations for use in this method are, for example, ether or alcohol based solvents and their combinations such as dipropylene glycol dimethylether and isopropanol.

2. Surface hydrolysis This method involves using a solvent and an agent such as a carboxylic acid, for example, acetic acid to cause surface hydrolysis or break down of the organic coating. While not wishing to be bound by any theory, it is believed that this method provides reactive entities or a suitable morphology to improve inter-coat adhesion with further coating layers and/or other entities. Suitable solvent or solvent combinations for use in this method are, for example, ester or amide based solvents such as ethyl acetate or N-methyl pyrrolidinone.

3. Surface oxidation This method involves using a solvent and an agent such as an oxidant, for example, trichloroisocyanuric acid to cause surface oxidation or break down of the organic 15 Scoating. While not wishing to be bound by any theory, it >is believed that this method provides reactive entities or a suitable morphology to improve inter-coat adhesion with further coating layers and/or other entities. Suitable 1 5 solvent or solvent combinations for use in this method are, for example, ester or amide based solvents such as 00 ethyl acetate or N-methyl pyrrolidinone.

C4. Surface Exchange 0 This method involves exposure of the coating surface 10 with a reagent capable of interacting (via Stransesterification or otherwise) with suitable chemical c-I functionality such as ester and/or urethane moities or otherwise to modify its chemistry or topography such that it improves the intercoat adhesion with subsequent coating layers. Suitable solvent or solvent combinations for use in this method are, for example, ether or alcohol based solvents and their combinations such as dipropylene gylcol dimethylether and isopropanol or dipropylene glycol dimethylether and n-propanol.

5. Light induced photo-grafting This method involves applying an agent such as a visible light activated free radical initiator, for example, camphorquinone and an unsaturated species, for example, acrylate or methacrylate to the surface of the organic coating in a solvent. The influence of visible light causes free radical reactions to occur which modify the surface of the coating to improve the inter-coat adhesion of the further coating and/or other entities.

Suitable solvents for use in this method include ketone or amide based solvents such as methyl amyl ketone and Nmethyl pyrrolidinone.

The substrate for the above methods having an activated coating may be of any type including metals such as aluminum; composites such as carbon fibre reinforced epoxy or glass reinforced epoxy; plastics such as polyimide; elastomers such as polysulfide elastomers; or materials containing glass, wood or fabric. There may 16 also be various "sub" coating layers beneath the coating requiring reactivation such as other decorative coating layers, primers, intermediate layers, conversion or anticorrosion coating layers and the like.

c 5 Although polyurethane and epoxy based coatings, particularly polyurethane based coatings are typical, it 00 will be understood that other organic coatings may be activated by the method of the invention.

c-i When the solvent and agent are combined and applied (Ni 10 in the form of an activation treatment this may take different physical forms such as solution, suspension, (Ni mixture, aerosol, emulsion, paste or combination thereof.

Treatments which take the form of a solution or emulsion are preferred.

The activation treatment may be prepared by mixing the components together with any mixing equipment known to those skilled in the art such as but not limited to stirrers, shakers, high speed mixers, internal mixers, inline mixers such as static mixers, extruders, mills, ultra-sound and gas dispersers. When the activation treatment is in the form of a solution, the solution may be prepared as a concentrate and diluted before use or prepared ready for use.

The activation treatment or the application of the individual components thereof may be applied via any method known to those skilled in the art such as but not limited to spray, brush, dip, knife, blade, hose, roller, wipe, curtain, flood, flow, mist, pipette or combinations thereof. Application by spray is typical.

The method of activation may be conducted at ambient temperatures or alternatively at higher temperatures if desirable. The activation treatment or individual components thereof may be applied to small or large areas, to sections of larger parts, components or full infrastructure such as infrastructure associated with the aerospace aircraft), automotive vehicles), marine ships), transportation trains), 17 military helicopter, missile) or construction industries buildings, factories, floors). The Csurface may have simple or complex geometry or may be at any orientation. Treatment may be conducted once or multiple times prior to interaction with the separate entity. The exposure time of the activation treatment on 00 the coating is more limited by the throughput and Sapplications requirements. As such the exposure time may be short for example one minute or extended for example 24 hours with no detriment to the integrity of the organic coating or materials that may be found on the organic Cl coating such as sealants, and underlying coating structures and substrates.

The organic coating may remain activated in a noncontaminated environment for extended periods of time. In some circumstances, the activation treatment can remove contaminants from the surface in addition to activating the coating.

It may also be preferable to remove excess agent and/or treatment solution from the surface. This process may be conveniently carried out by techniques such as solvent or water rinsing; dry, water or solvent wiping; air or gas knife; vacuum application; removal by squeegee; and/or natural or forced convection evaporation.

Optionally the water or solvent used to remove excess agent and/or treatment solution from the surface of the coating undergoing reactivation can contain additives for example to enhance the removal process, modify the drying time, or reduce corrosion. Such additives include but not limited to ionic and non-ionic surfactants, detergents, anticorrosion additives and wetting agents such as but not limited to those described above. The additives may also include cleaning agents commonly used to clean aircraft such as but not limited to those marketed under the trade names Isoprep, Turco, CeeBee, Ridoline, Formula and Daraclean by companies such as 18 Brulin, Elf Atochem North America, MacDermid, W.R. Grace, McGean-Rohco and Henkel.

After the coating surface is activated, separate entities such as additional coating layers or coating c-I cl 5 details, adhesives sealants, pressure sensitive decals or logos, and the like may be applied either immediately or 00 at a later time, providing the surface remains

NO

Spredominantly uncontaminated during storage or that the contamination can be conveniently removed. The activation solution may need to be reapplied in some cases.

SAny suitable method known to those skilled in the art Cl may be used to assess whether the adhesive linkage between the organic coating and further coatings and/or other entities is fit for purpose. Such tests include but are not limited to ASTM, ISO, and FAA standards, in-house test methods to simulate in-service performance, in-service performance itself, and durability testing either actual or accelerated. For the case of aerospace coatings, test methods based on water impact, such as whirling arm and the Single Impact Jet Apparatus (SIJA) (MIJA Limited, Cambridge, UK), have been found to be particularly useful for assessing inter-coat adhesion. In these cases, the amount of overcoat removal is related to the level of inter-coat adhesion.

For aerospace applications the activation method of the present invention offers the advantages of improved flow time for the process of reactivation, greater reproducibility and consistency over larger areas and between operators, and improved ergonomics of the process leading to reduced vibration or repetitive motion based injuries for completing the process of reactivation which added together provide a net cost saving.

DETAILED DESRIPTION OF THE ABBREVIATIONS In the Examples, reference will be made to the following abbreviations in which: 19

AFM

APP

BAC

BMS

C

Cl

DHS

F

F

FTIR

h

HH

HSS

IC

LH

IPA

LiBH 4

MAK

MEK

MPK

Mn Mw

MW

NBA

NPA

NPZ

NBT

NPT

OH&S

P

PACCS

Proglyde DMM

RH

SEM

SIJA

SOLO

SOWO

SOHO

SS

tBAC

TEAZ

THF

TPT

WARE

Wt% Atomic Force Microscopy Applications Boeing Approved Color Boeing Material Specification Celsius Class Concentration Desothane HS Fahrenheit Fail Fourier Transform Infrared Hour high humidity High strength Steel Intermediate Coating Low humidity Isopropanol Lithium borohydride Methyl amyl ketone Methyl ethyl ketone Methyl propyl ketone Number average molecular weight Weight average molecular weight Molecular weight n-butanol n-propanol tetra-n-propylzirconate tetra-n-butyl titanate tetra-n-propyltitanate Occupational Health and Safety Pass Pre-Applied Composite Coating System (abbreviated, proglyde) dipropylene glycol dimethyl ether Relative Humidity Scanning Electron Microscopy Single Impact Jet Apparatus Spray On Leave On Spray On Wipe Off Spray On Hose off Stainless Steel t-butyl acetate triethanolamine zirconate Tetra hydrofuran tetra-isopropyltitanate Whirling Arm Rain Erosion weight percentage 20 O XPS X-Ray Photoelectron Spectroscopy DETAILED DESCRIPTION OF THE DRAWINGS In the Examples, reference will be made to the q 5 accompanying drawings in which: 00 Figure 1 is photographs showing the impact on different pq metal alkoxide modifying agents and concentration on Sinter-coat adhesion. (Base coat: DHS BAC70846, C2. Base Cl 10 cure condition: 16h, 120F, ~8%RH. Over-coat: BAC50103, C.

0 Over-coat cure: 4 days, 120 F, 10% RH.); Figure 2 is photographs showing SIJA inter-coat adhesion.

(Base coat: DHS BAC70846, C2. Base cure condition: 16h, 120F, -8%RH. Over-coat: BAC50103, C. Over-coat cure: 4 days 120F, Figure 3 is photographs showing the impact of modifying agent dwell time on over-coat adhesion performance.

(Base coat: DHS BAC70846, C2. Base cure condition: 16h 120F, ~8%RH. Over-coat: BAC50103, C. Over-coat cure: 4 days 120F, Figure 4 is photographs showing the preliminary stencil interaction results and corresponding SIJA adhesion.

(Base coat: DHS BAC70846, C2. Base cure condition: 16h, 120F, ~8%RH. Modifying agent dwell time before overcoat Over-coat: BAC50103, C. Over-coat cure: 4 days, 120F, Figure 5 is photographs showing the preliminary stencil interaction results and corresponding SIJA adhesion.

(Base coat: DHS BAC70846, C2. Base cure condition: 16h.

120F, ~8%RH. Modifying agent dwell time before overcoat Over-coat: BAC50103, C. Over-coat cure: 4 days, 120F, 21 Figure 6 is photographs showing the preliminary water soak data: 3x applications each of modifying agent system in IPA. (Base coat: DHS BAC70846, C2. Base cure condition: 16h. 120F, ~8%RH. Over-coat: BAC50103, C. Over-coat cure: C 5 4 days, 120F, 00 O Figure 7 is photographs showing: a) SOLO treatment solution application on stencil letter O and premask diamond quality (Base coat: DHS BAC70846, C2.

0- 10 Base cure condition: 16h 120F, ~8%RH. Over-coat: 2 mil DHS SBAC50103, C2. Over-coat cure before removal: 16hr, 120F.); c b) Effect of solvent combination on stencil letter clarity employing, base coat (DHS BAC70846, C2 with cure condition: 16h, 120F, modifying agent(5wt% NPZ SOLO with dwell time lh), and over-coat(l mil DHS BAC50103, C with cure condition before removal: 16 hr, ambient); c) Image quality employing no modification agent or NPZ employing a 20:80 NPA:Proglyde combination.(Base coat: DHS BAC70846,C. Base cure condition: 3 Cycles of 4hr, 120F, 9%RH 8hr, 75F 36% RH. Stencil coat: DHS BAC701 Black, C2.); Figure 8 is photographs showing scribe adhesion. (Base coat: DHS BAC70846, C2. Cure condition: 16h, 120F, 8%RH.); Figure 9 is photographs showing stencil pull scribe adhesion base coat. (DHS BAC70846, C2. Cure conditions: 16h, 120F, 8%RH. Over-coat: DHS BAC50103, C2, Imil. Overcoat cure: ambient.); Stencil Pull Time (min) Scribe Test Time (h) 1 2 3 4 22 Figure 10 is photographs showing SIJA inter-coat adhesion S(DHS CA8000 paint); cure conditions as indicated.

CI 5 Figure 11 is photographs showing corresponding WARE results to Figure 12; cure conditions as indicated.

00 OO Figure 12 is photographs showing SIJA inter-coat adhesion C-I (DHS CA8800 paint); cure conditions as indicated.

(N Figure 13 is photographs showing SIJA inter-coat adhesion S(Eclipse paint); cure conditions as indicated.

Figure 14 is photographs showing SIJA inter-coat adhesion (DHS CA8000 paint); cure conditions as indicated.

Figure 15 is photographs showing Whirling Arm Rain Erosion data: Modification agent (alkoxide): 5wt% NPZ in 80%IPA: proglyde;.

DHS CA8800: Basecoat BAC70846, CTR Thinner, Overcoat BAC70281, CTR Thinner.

DHS CA8000: Basecoat BAC70846, C Thinner, Overcoat BAC707, C Thinner.

Eclipse: Basecoat BAC70846, TR109 Thinner, Overcoat BAC707, TR109 Thinner.

Base coat cure conditions as indicated. Overcoat cure conditions: 4 days at 120F; Figure 16 is photographs showing WARE data using DHS CA8800 paint.

a)Basecoat BAC707 Gray w/ varied thinners, Cure conditions: 3 Cycle Cure 4h, 120F, 18%RH 8h, Overcoat BAC70846 White w/ CTR thinner, Cure conditions: 4 days, 120F.

23 b) Basecoat BAC707 Gray w/ varied thinners, Cure >conditions: 3 Cycle Cure 4h, 120F, 18%RH 8 h, Overcoat BAC51265 Blue w/ CTR thinner, Cure conditions: 5 4 days, 120F; 00 Figure 17 is photographs showing WARE data.

cm a) Basecoat DHS CA8800 BAC70846 White w/ CTR thinner, 0 Cure Conditions: 3 Cycles of 4h, 120F, 18%RH 8h, S 10 Modification agents (alkoxides) cN 5Z-60i: 5wt% NPZ in 60wt% IPA and 40wt% proglyde, 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde.

Overcoat DHS CA8800 BAC70281 Gray w/ CTR thinner, Cure conditions: 4 days, 120F.

b) Basecoat DHS CA8000 BAC70846 White w/ C thinner, Cure conditions: 3 Cycles of 4h, 120F, 3%RH 8h, 75F, 12%RH.

Modification agents (alkoxides) 5Z-60i: 5wt% NPZ in 60wt% IPA and 40wt% proglyde, 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde.

Overcoat DHS CA8000 BAC707 Gray w/ C thinner, Cure conditions: 4 days, 120F; Figure 18 is photographs showing WARE data.

a) Basecoat Eclipse BAC70846 White w/ TR-109 thinner, Cure conditions: 3 Cycles of 4h, 120F, 18%RH 8h, Modification agents (alkoxides) 5Z-60i: 5wt% NPZ in 60wt% IPA and 40wt% proglyde, 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde.

Overcoat Eclipse BAC707 Gray w/ TR-109 thinner, Cure conditions: 4 days, 120F; b) Basecoat Eclipse BAC70846 White w/ TR-109 Thinner, Cure Conditions: LH or HH (See below).

Modification agents (alkoxides) 5Z-60i: 5wt% NPZ in 60wt% IPA and 40wt% proglyde, 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde.

24 SOvercoat Eclipse BAC707 Gray w/ TR-109 thinner, Cure conditions: 4 days, 120F.

Basecoat Cure LH: 4h, 120F, 3%RH 8h, 75F, 12% RH for 3 cycles, C 5 Basecoat Cure HH: 4h, 120F, 18%RH 8h, 75F 70%RH for 2 or 3 cycles; 00 c) Basecoat Eclipse BAC70846 White w/ TR-109 Thinner, m Basecoat Cure LH or HH (See below).

0 Modification agents (alkoxides) 5Z-60i: 5wt% NPZ in 60wt% IPA and 40wt% proglyde, 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde.

C Overcoat Eclipse BAC707 Gray w/ TR-109 thinner, Cure conditions: 4 days, 120F.

First TC Cure LH: 4h, 120F, 3%RH 8h, 75F, 12%RH for 3 cycles, First TC Cure HH: 4h, 120F, 18%RH 8h, 75F, 70%RH for 2 or 3 cycles; Figure 19 Basecoat DHS CA8000 BAC70846 White w/ C thinner, Cure conditions as indicated.

Modification agents (alkoxides) with 30 minute dwell: 5Z-60n: 5wt% NPZ in 60wt% NPA and 40wt% proglyde, 7Z-60n: 7wt% NPZ in 60wt% NPA and 40wt% proglyde, 9Z-60n: 9wt% NPZ in 60wt% NPA and 40wt% proglyde.

Overcoat cure conditions: 4days, 120F.

Overcoats: DHS CA8000 BAC5004 Blue w/ C thinner, Eclipse BAC5004 Blue w/ TR-109 thinner, Sky-Hullo FLV-II 900BL004 Blue w/ IS-900, Type III thinner; Figure 20 is photographs showing the shelf life of metal alkoxide reactivation treatment solutions on adhesion.

25 1^ 00 \O

CD

pq

(N

(N

oo kO mq

(N

0q

(N

1^ 0q Figure 21 is graphs showing soak and recovery experiments using BMS5-142 (polysulfide) sealant: a) Weight change, b) Volume change and c) Hardness change; 5 Figure 22 is graphs showing soak and recovery experiments using BMS1-71, CL1 (EPR) elastomer: a) Weight change, b) Volume change, and c) Hardness change; Figure 23 is graphs showing soak and recovery experiments 10 using BMS1-71, CL2 (Silicone) elastomer: a) Weight change, b) Volume change, and c) Hardness change; Figure 24 is graphs showing soak and recovery experiments using BMS1-57 (Silicone) elastomer: a) Weight change, b) Volume change and c) Hardness change; Figure 25 is photographs showing images of elastomers and sealants on recovery; Figure 26 is a graph and photographs results for titanium; Figure 27 is a graph and photographs results for 2024T3 bare aluminium; Figure 28 is a graph and photographs results for 2024T3 clad aluminium; Figure 29 is a graph and photographs results for high strength steel; Figure 30 is a graph and photographs results for stainless steel; showing immersion showing immersion showing immersion showing immersion showing immersion Figure 31 is photographs showing sandwich corrosion results a) lx magnification and b) 10x magnification; 26 Figure 32 is a graph and photograph showing immersion >results for BMS8-79 composite material; Figure 33 is a graph and photograph showing immersion c 5 results for BMS8-256 composite material; 00 Figure 34 is a graph and photograph showing immersion C results for BMS8-256 with Metlbond; 10 Figure 35 is a graph and photograph showing immersion results for BMS8-276 with SM905 composite material; Figure 36 is a drawing and photographs showing tapeline experiments: Untreated and treated with various modification agent formulations.

Figure 37 is a graph showing impact on colour shift for DHS BAC70846 treated with various modification agents not over-coated following accelerated exposure according to SAE J1960 relative to specimens left untreated and Figure 38 is a drawing showing the lab colour shift and system used to derive delta E.

Figure 39 is photographs showing WARE data.

Basecoat DHS CA8800 BAC900 clear with F thinner, Cure Conditions: 3 heat cycles (4h, 120F, 18% RH and 8h, Modification agent 5% NPZ, 80:20 NPA: Proglyde Post treatment of Modification agent none or tack rag Overcoat DHS CA8800, white or blue cured for 2 weeks at ambient -72F, 35% RH; Figure 40 is pencil hardness data for specimens left untreated prior to overcoat or treated with the modification agent prior to over-coating both prior to and following 30 day immersion into hydraulic fluid.

27 Figure 41 is Gardner Impact adhesion test results employing no modification agent or 5WT% NPZ alkoxide in isopropanol. (Base coat: DHS CA8800 BAC3613 Yellow, CTR c-I (q 5 thinner. Base cure condition: 3 Cycles of 4hr, 120F, 12%RH 8hr, 75F 36% RH. Over-coat: DHS CA8800 various colors, 00 CTR thinner. Overcoat Cure condition: 2 weeks ambient);

\O

cI

EXAMPLES

(C 10 The invention will now be described with reference to Sthe following non-limiting examples. Although the examples concentrate on coatings derived from polyurethane chemistries it will be understood that the same activation methodology could be applied to coatings such as but not limited to those based on epoxy, acrylic, polycarbonate, or polyester coatings through the appropriate choice of solvent(s), agent(s) and optional additives under appropriate activation conditions.

The specific "substrate" the polyurethane topcoat is applied to is not relevant. Hence the substrate can be metal (eg. aluminium), plastic (eg. polyimide), composite (eg. carbon fibre reinforced epoxy or glass reinforced epoxy) or an elastomer (eg. polysulfide elastomer). The substrate may be finished with surfacing materials, films, elastomers or coatings.

The polyurethane topcoat layer which requires reactivation may have topcoat, intermediate or priming layers beneath it and again these layers are not relevant.

Typical examples of build-ups employed in the aerospace industry include: Aluminium substrate: cleaned, surface prepared with anodize or conversion coat, epoxy based primer(s), optionally selectively strippable intermediate coating layer, and polyurethane topcoat layers.

Epoxy based composite: surface prepared/cleaned, epoxy based primer(s), optionally selectively 28 Qstrippable intermediate coating layer, and c-I polyurethane top-coating layers.

The reactivation treatment solution is designed in c-I such a way that it can be applied under industrial conditions and the integrity of the "substrate" or coating 00 layers beneath the polyurethane coating which is

\O

INDundergoing reactivation are not adversely effected to a point where they are unsuitable for their intended purpose by interaction of treatment solution which may O inadvertently come in contact with it for short periods.

Example 1 Hydrolysis Surface Activation Method The example demonstrates that improved SIJA intercoat adhesion relative to untreated specimens results from activation of the coating prior to over-coating. Intercoat adhesion provided in this case is similar to specimens reactivated by sanding.

Example 2 Oxidation Surface Activation Method The example demonstrates that improved SIJA intercoat adhesion relative to untreated specimens results from activation of the coating prior to over-coating. Intercoat adhesion provided in this case is similar to specimens reactivated by sanding.

Example 3 Reduction Surface Activation Method The example demonstrates that improved SIJA intercoat adhesion relative to untreated specimens results from activation of the coating prior to over-coating. Intercoat adhesion provided in this case is similar to specimens reactivated by sanding.

Example 4 Light induced photo-grafting Surface Activation Method The example demonstrates that improved SIJA intercoat adhesion relative to untreated specimens results from 29 F, activation of the coating prior to over-coating. Intercoat adhesion provided in this case is similar to specimens reactivated by sanding.

c-I Example 5 Reduction Surface Activation Method The example demonstrates that improved Scribe green 0 adhesion (predictor of possible problems during masking Stape removal) relative to untreated specimens results from activation of the coating prior to over-coating. Intercoat adhesion provided in this case is similar to specimens reactivated by sanding.

Example 6 Reduction Surface Activation Method Stripping study indicated that coatings reactivated by surface reduction methods strip quicker than specimens sanded prior to over-coating but slower than coatings over-coated without treatment.

Example 7 and 8 Evidence of Surface Chemistry Change Results indicate that a higher Specific contribution to surface energy results particularly to surfaces activated with the reduction strategy.

Examples 9 to 33 Reduction Surface Activation Method Examples 34 and 5: Surface Activation Method with Exchange Agents It is envisaged that suitable combinations of components of the activation treatment will differ depending on the type of coating to be activated. The appropriate choice of solvent(s), agent(s), optional additives and inerts, and activation conditions will differ depending on the type of coating to be activated.

30 q General Experimental Detail Painting Conditions and Protocol Spray painting of many flat panels was carried out c employing a Yamaha robotic painting arm incorporating a gravity fed Binks Mach 1A automatic spray gun configured with a 94 nozzle. Spray painting was conducted using an 00 inlet pressure of 40 PSI, a scan rate of 100 mm/s and a \O (f specimen to gun distance of 300 mm. The coating thickness was controlled by the gun's fluid needle control position and scan rates. These parameters were adjusted in line Swith paint thickness measurements and assessed using a c Fischer Isoscope (MPOD) on aluminium substrates. When coating was completed on composite substrates, the coating layer thickness was estimated by calibration with the isoscope readings from aluminium panels. An analogous strategy was employed for the application of the primers, optional intermediary and topcoat layers. For the majority of the examples, the painted films were overcoated following taping through the middle of the coupon with 3M vinyl tape (#471) to form a paint edge on its removal. This edge was the impact target for SIJA (Single Impact Jet Apparatus) analysis.

Spray painting of curved or larger surfaces (eg: rain erosion foils) and some of the smaller flat panels was typically conducted using a Binks Mi-H HVLP gun configured with a 94 nozzle. Occasionally, a similar gravity fed HVLP gun or a pressure pot fed HVLP gun was used. In these cases the aluminium or composite was prepared in the same manner as the flat plates prior to the first top-coat being applied. Following cure of the first coating layer the front of the foils were masked (Intertape Polymer Group, PG-777 tape) prior to over-coating to form a leading edge once the over-coating was applied and tape removed.

Cure protocols were undertaken in a computer controlled temperature humidity chamber, such as a 31 O Thermoline Environmental chamber and/or a conventional curing oven.

Table 1 Paint Material Information CN For the majority of the examples, the coatings used are listed in Table 1. In the examples, paint companies are 00 generally abbreviated:

\O

PRC-DeSoto International: PRC-DeSoto Akzo-Nobel Aerospace Coatings: Akzo-Nobel 0D 0D

(N

32 Table 1 Components Base: CA8000/BxxxxxX such as CA8000/B70846X Activator: CA8000B Thinner 1: CA8000C Thinner 3: CA8000C2 Or Base: CA8800/Byyyy Activator: CA8800Z Thinner 1:CA8800CTR Thinner 2: CA8800CT Thinner 3: CA8800CT2, Base: ECL-G-xxxx such as ECL-G-14 (BAC70846) Curing Sol: PC-233 Thinner TR-109 Thinner TR-1 12; Sky-Hullo FLV-II Base: 900YYxxx such as 900BL004 (Blue) Curing Sol: 900X001 CAT Thinner: IS-900, Tyll

L

Note: the thinner designation C and C2 are used to indicate the relative rate at which the paint cures. C thinners standard cure rate with C2 producing a correspondingly faster cure rate (from incorporation of high catalyst levels into the thinner). For Desothane CA8800 CTR is reduced rate, CT is standard rate and CT2 is fast rate cure thinner. For Akzo-Nobel fast cure thinner is designated TR-112 and standard thinner TR-109.

33 QD Painting Conditions and Protocol >Substrates were cleaned prior to priming and optionally Swhere appropriate treated with an alodine type conversion C coating or anodized.

Polyurethane topcoats, intermediate and primer layers were OO mixed and applied according to the paint manufacture Sinstructions.

O Primer:

(N

Typical conditions: For Composite or aluminium: application of common aerospace epoxy based primer optionally incorporating additives to aide corrosion resistance at 0.5 mil (12.5 micron) dry film thickness (dft) per manufacturer instructions.

Intermediate coat: SOptionally application of intermediate coat (IC) that is selectively strippable at 0.35 mils (10 microns) according to manufacturer instructions Polyurethane topcoat: Application of polyurethane topcoat (eg: Desothane HS topcoat containing CA8000/B70846X base (white color of this topcoat also designated as BAC70846. In examples it is typically designated as Desothane HS 70846X or DHS BAC70846) at 1.0 to 4.0 mil (typically 1.0 mil (25 micron)). Painted panels flash off for 1 hour prior to cure and accelerated aging.

Standard cure accelerated aging conditions employed for topcoats were: Cure painted panels in oven at 120 0 F, 5-10% RH (Relative Humidity) for 40 hours, followed by (ii) post cure in a humidity chamber at 120 0 F (49 0 C) and 50% RH for 48 hours, and then (iii) 34 oven cure at 160 0 F for 24 hours. Total cure time was 112 hours. Alternatively other "accelerated" aging protocols were employed as specified in the examples to C- render the polyurethane topcoat unreceptive to additional coating layers as indicated by poor adhesion under standard adhesion tests eg: 120°F and 2-3% RH for 00 NO 5 days or 120 0 F and 5% RH for 16 hours or as specified

(N

in the examples.

Surface Modification '1 The solvents and agents used for surface modification were purchased from the MERK and Sigma-Aldrich or Dow Chemical Companies. Purity was of an Analytical or Laboratory Reagent grade purity. Isopropanol and npropanol were generally of an anhydrous grade. However, alternative suppliers and grades of the reagents are known to be available.

35 CN Table 2 General Activation Protocol Treatment Spray application of the reactivation treatment C solution employed a Binks MI-H HVLP gun with a 92 or 94 nozzle and 20 psi inlet pressure or, on occasion, a similar HVLP gravity or pressure fed gun 00 or by a flood application where indicated.

\O

SThe active agent (eg: reducing agent such as LiBH 4 O was dissolved, dispersed or suspended in the solvent/s at a percentage based on weight and the hence 0prepared "reactivation treatment" applied to the 0 substrate for a given period Post-Treatment Spray on leave on application (SOLO) Optionally the polyurethane surface may be "post" treated Washed with water (or solvent) a period following treatment spray on-hose off (SOHO) or Wiped with an isopropanol, ketone (eg: methyl-propyl ketone) or water soaked cloth spray on wipe off

(SOWO)

Re-coating Samples were over-coated with polyurethane topcoat either: Same day (5 mins to 4 hours after treatment) Some period following reactivation.

Unless otherwise specified for SIJA or rain erosion adhesion testing, overcoat thickness was 100 micron employing Eclipse or Desothane HS coatings cured with standard thinners. Cure conditions were 120F under 8-20% RH for at least 48 hours unless specified.

Scribe test overcoat paint thickness was typically to 50 microns Analysis Table 3 provides the equipment and conditions used for testing for analytical purposes.

36 Table 3 Testing Equipment Conditions 00 IO Cc) r Ir-l-__IlI Equlpment Conaitions 1 SIJA Adhesion testing was completed using a Single Impact Jet Apparatus (SIJA, Cambridge). The initial equipment was typically configured using a 0.8 mm nozzle typically and employed 0.22 calibre 5.5 mm Crosman Accupell Pointed Pellets (#11246). Testing was completed following immersion in water for 16 to 18 hours, employing a line laser to locate the impact position, and using a 450 specimen to impact droplet geometry.

A single water jet was employed at each site to test adhesion with the pressure employed for the "shot" indicated below its impact. The velocity of each individual shot was recorded for future reference, but generally the pressure to velocity conversion is specified below m/s) Pressure (PSI) Velocity (m/s) 350 610 100 725 200 895 Alternatively the impact was dictated by a "dot" or via the velocity employed eg. 600 m/s.

In some cases the amount of overcoat removed, and hence the inter-coat adhesion was assessed employing image analysis techniques to quantify the area of paint removed. However regardless of the impact velocity relative to the unmodified reference more overcoat removed corresponded with inferior inter-coat adhesion.

-4- Scribe Adhesion Scribe adhesion was assessed according to (BOEING Specification Standard) BSS7225, Class This adhesion test is a five line crosshatch tape (3M tape, No. 250) pull test.

Briefly: Heat aged polyurethane coatings were reactivated and then over-coated (25 80 micron thickness) curing the over-coat for 16 hours at room temperature and 50% RH. The coatings were then scribed according to BSS7225 (C15 scribe cross-hatch) and the adhesion test performed.

The paint adhesion of specimens are rated on a scale of 10 to 1 with "10" being no paint removed and being all paint removed.

I

I

37 Equipment Conditions Whirling Arm Rain Erosion Testing -f

I

Rain erosion testing was completed on a whirling arm rain erosion apparatus employing a 52 inch zero lift helicopter like propeller run at 3600 rpm. Reference and activated polyurethane topcoat foils were over-coated (85 to 120 micron paint thickness) following masking to produce a leading edge. The foils were attached to the propeller at a distance along the propeller correlating to a velocity of 380 mile per hour at the mid point of the foil. The effective rain field density of 2 mm droplets used during the experiment was 1 inch per hour. After min the impact of rain erosion on the inter-coat adhesion of the foils was evaluated according to a 0.5 to 5 rating correlating with the amount of paint removed or tear length. The impact of water droplets on the leading edge of the overcoat formed on removal of the tape during the experiment erodes the over-coating layer relative to the strength of the inter-coat adhesion.(F or Fail or red markings indicate less then acceptable adhesion) Paint Stripping Procedure for the complete strip test is described in SAE MA4872, Annex A, pages 51 to 53.

In this Stage an abbreviated version was completed using benzyl alcohol based paint strippers without thermal cycling to compare how the activated and over-coated specimens to untreated and reference specimens.

ged specimens (Aluminium or composite substrate) were untreated, sanded, or activated, were overcoated (60-75 micron), and cured for 40 hours at 120 0 F. The edges were taped with Aluminium tape (such as 3M Scotch Brand No, 425) prior to commencing the test. Stripper was applied every 2 hours until the coating was removed. Lifting paint was removed just prior to reapplication of the stripper using a plastic squeegee.

Contact Angle Contact angle analysis was completed using "FIRST TEN ANGSTROMS" semi-automated video equipped contact angle analyser.

CH

2 1 2 and H 2 0 were employed as the reference solvents to calculate the dispersive and polar (yP) contributions to surface energy through the Young-Dupre relationship and Fowkes equation.

38

T

Equipment Conditions -4- FTIR FTIR analysis was carried out on a BRUKER FTIR/NIR spectrometer or Nicolet Instruments, employing NaCI plates or an ATR KRS-5 TiBr Til mixed crystal associated with the microscope. Extent of surface contamination was assessed by swabbing the surface with a "Q-tip" soaked with hexane. Following evaporation of the hexane solution onto NaC1, powder NaC1 plates suitable for FTIR analysis were prepared by compression moulding.

SEM SEM analysis of the polyurethane crosssections were collected on a Oxford Pentafet detector controlled by an Oxford ISIS system.

Cross-sections of the samples, prepared with a cut off saw appropriate for non-ferrous materials, were mounted in epoxy resin, ground and polished to a 1 micron finish and gold coated. Imaging and x-ray analysis was conducted using a 15 KV accelerating voltage and a 17 mm working distance. EDX analysis was specifically refined for carbon, nitrogen, oxygen, and chlorine.

Hydrogen Evolution Activity of reducing agent was determined by employing Hydrogen Evolution techniques. The activity of the reducing agent solution (eg.

LiBH 4 in Proglyde DMM) was determined by measuring the quantity of hydrogen evolved following interaction with dilute aqueous acid.

Accelerated UV exposure Equipment: Atlas (Xenon Arc) Weatherometer Outer filter borosilicate Inner filter quartz Light intensity: 0.55 W/m 2 /nm @340nm Operation Cycle (~SAE J1960): SPanels: Desothane HS 70846 White Test for: Colour shift of previously reactivated (but not over-coated) panels Reactivation potential of samples conditioned through aging protocol then a UV cycle.

39 Hydraulic fluid exposure Specimens were tested for coating pencil hardness prior to immersion into the fluid and rated in hardness according to the following protocol (soft to hard). After days immersion the specimens were re-tested.

Values reported are the softest pencil that would cut into the paint surface.

Hardness Scale (soft to Hard) 6B 4B 3B 2B

B

HB

F

H

2H 3H 4H 6H 7H 8H 9H Gardner Impact Adhesion Both sides of the test specimen were subject to varying impact forces in 10 inch pound increments using a Gardner 160 inch pound capacity impact testing machine with a 0.625 inch diameter hemispherical indenter. Values reported are the highest force recorded that produced no cracking of paint in either the forward or reverse impact. Maximum impact tested was 80 inch pounds.

2007202368 22 May 2007 Example 1 Hydrolysis Method SIJA inter-coat adhesion of Desothane HS 70846X white (30±5 im, CA8000C thinner) cured hour at 120 0 F RH) followed by 48 hour at 120 0 F (50% RH) followed by 24 hour at 160 0

F,

activated and over-coated with Desothane HS S601X blue (104+10 tm).

Untreated Sanded 1% acetic acid Ethyl acetate 1% acetic N-methyl pyrrolidinone Activation Treatment 30 min, horizontal application position (IPA wipe post treatment) 2007202368 22 May 2007 Example 2 Oxidation Method SIJA inter-coat adhesion of Desothane HS 70846X white (30±5 am, CA8000C2 thinner) cured hour at 120 0 F RH), followed by 48 hour at 120 0 F (50% RH) and 24 hour at 160 0 F, activated and over-coated with Desothane HS S601X blue (104±10 pm).

Ig Untreated Sanded 5% trichloroisocyanuric Acid Ethyl acetate 2%NaOC1/0.5% HC1 DI water 2% NaOC1/0.5% HC1 PEG 600, DI water Activation treatment time 30 min, (IPA wipe post treatment) 2007202368 22 May 2007 Example 3 Reduction Method SIJA inter-coat adhesion of Desothane HS 70846X white (30+5 4m CA8000C2 thinner) cured hour at 120 0 F RH) followed by 48 hour at 120 0 F (50% RH) and 24 hour at 160 0 F, activated and over-coated with Desothane HS S601X blue (104±10 im).

5% NaBH 4 EtOH Untreated Sanded 2% NaBH 4 EtOH Treatment 30 min, (SOHO post treatment).

2007202368 22 May 2007 Example 4 Light Grafting Method SIJA inter-coat adhesion of Desothane HS 70846X white (30±5 pm, CA8000C-thinner) cured hour at 120 0 F, RH), followed by 48 hour at 120 0 F, 50% RH and 24 hour at 160 0 F, activated 120 min, wiped (IPA) and over-coated with Desothane HS S601X blue (104±10 m).

methylamylketone N-methyl pyrrolidinone methylamylketone Apo

L

i-b untreated 10% hydroxy monomethacrylate 10% hydroxy ethylacrylate 10% PEG ethylacrylate Initiator System Camphorquinone w/w based on acrylate), Dimethyltoluidine (120% w/w based on camphorquinone) system placed under an 2x18W fluorescent desk lamp.

2007202368 22 May 2007 Example 5 Reduction Surface Activation Method Green scribe adhesion Green (scribe) inter-coat adhesion of Desothane HS 70846X white (30+5 im CA8000C2 thinner) cured 40 hour at 120 0 F RH), followed by 48 hour at 120 0 F (50% RH) and 24 hour at 160 0

F,

activated and over-coated with Desothane HS S601X blue (68+10 pm, 16h ambient cure). Green adhesion rating as per BSS7225.

4 n10 n Untreated Sanded 2% NaBH4 EtOH 2007202368 22 May 2007 Example 6 :Reduction Activation Method Stripping rate test B C B

I

K.

I

Time 0 Time 125min Time 245 min B C B C Time 365 min Time 485 min A Untreated, B Sanded, A -Unteatd, andd, C Treatment with NaBH 4 in ethanol, 30 min 2007202368 22 May 2007 Example 7 :Evidence of Surface Energy Change Surface energy results for activated surfaces employing a thermally aged Desothane HS 70846X substrate (CA8000C thinner) ondiio' i Cozfac t A n S face., -neg J/) 41 O d .cf~ 7 ip~~ie C Thinner Fresh 76.5 39.0 4.2 42.0 Aged Untreated 76.2 40.3 4.5 41.3 Aged IPA Wipe 75.8 35.0 4.0 44.0 Aged 2% Sodium EtOH /EtOH wash Borohydride 36.6 23.7 43.2 Aged 1% Acetic Acid 69.7 29.4 5.8 46.6 Aged Camphorguinone 2xl8W fluorescent 65.2 43.5 8.5 43.5 w/w based on acrylate), desk lamp, MAX wipe Dimethyltoluidine (120% w/w based on Camphorguinone) methylamylketone Fresh -4 hour at 120OF (-9o6 RH) Aged -40 hour at 120'F RH) 48 hour at 120OF (50% RH) and 24 hour at 160OF 0~ 2007202368 22 May 2007 Example 8 :Evidence of Surface Energy Change Surface energ results for activated surfaces employing a thermally aged Desothane HS 70846 substrate (C2 thinner) retmn 'iioditbdb 11; x1 ~,uac 6' Ener~y(J~Z W'zx %HX 2 tSpecifi1c 3~~tj~riey C2 Thinner Aeshnteae 71.4 27.6 5.0 47.3 Aged UntrWie e 74.6 45.5 5.7 38.5 ge IAWie73.9 36.3 4.9 43.4 Aged 2% Sodium Borohydride EtOH /EtOH wash 42.6 32.2 19.7 45.3 Aged 1% Acetic Acid EtOAc /IPA wipe 67.9 28.7 6.5 46.9 ged Camphorquinone 2xl8W fluorescent 68.6 27.3 6.0 47.4 (1i w/w based on acrylate), desk lamp, MAK wipe Dimethyltoluidine (120% w/w based on Camphorguinone) ethylamylketone__________ Fresh -4hour at 120OF RH) Aged -40hour at 120OF RH) 48 hour at 120OF (50% RH) and 24 hour at 160OF -1 2007202368 22 May 2007 Example 9. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified for 30min (SOHO) and over-coated with Desothane S400X red 3 hours following hose-off with water.

Untreated Sanded 7% NaBH 4 75 NaB(OMe)H 3 1% LiBH 4 Treatment solutions prepared in progylde (dipropylene glycol dimethyl ether).

Results indicated that improved inter-coat adhesion is possible employing "mild" reducing agents such as NaBH 4 and LiBH 4 2007202368 22 May 2007 Example 10. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified for 30min (SOHO) and over-coated with Desothane HS S601X blue 3 hours following hose-off with water.

Untreated Red-Al K-selectride Lithium pyrrolidinoborohydride Borane-THF complex Lithium dimethylaminoborohydride Treatment solutions prepared in dipropylene glycol dimethyl ether at 0.2% concentration.

Results indicate that reducing agents with different strengths may be employed for the purpose of reactivation.

2007202368 22 May 2007 Example 11. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified for 30min (SOHO) and over-coated with Desothane S400X red 3 hours following hose-off with water.

Untreated Sanded 1.0% 0.5% 0.25% 0.1% LiBH 4 Treatment solutions prepared in dipropylene glycol dimethyl ether.

Example illustrates that a variety of different concentrations may be employed to "activate" the surface of polyurethane based coatings towards over-coating to provide improved adhesion.

2007202368 22 May 2007 Example 12. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified (SOLO) for 3h and over-coated with Desothane HS 5070X blue.

Untreated Sanded 0.1% 0.05% 0.01% LiBH 4 Treatment solutions prepared in dipropylene glycol dimethyl ether.

Example illustrates that very low concentrations of the reducing agent may be employed to "activate" the surface of polyurethane based coatings towards over-coating using a spray on leave on approach.

2007202368 22 May 2007 (ii) Scribe adhesion of aged Desothane HS 70846X white reactivated under the conditions specified and over-coated with Desothane HS 5070X blue. The overcoat was allowed to cure under ambient conditions for 16h prior to conducting the test.

SOHO

N3

SOLO

(180min) Reference 0.01% 0.05% 0.1% LiBH 4 The example illustrates that excellent scribe adhesion results are possible employing low concentrations of reducing reagent under various application conditions.

2007202368 22 May 2007 Example 13. SIJA inter-coat adhesion of aged Eclipse BAC70846 white reactivated under the conditions specified (SOLO) for 3h and over-coated with Desothane HS 5070X blue.

c- Untreated 0.01% 0.05% 0.1% 0.5% 1.0% In Uj Sanded Treatment solutions prepared in Progylde (dipropylene glycol dimethyl ether) using LiBH 4 as the reducing agent.

Example illustrates that a variety of different reducing agent concentrations may be employed to "activate" the surface of polyurethane based coatings towards over-coating from different manufacturers and polyurethane chemistries.

2007202368 22 May 2007 (ii) Scribe adhesion of aged Eclipse BAC70846 white reactivated under the conditions specified and over-coated with Desothane HS 5070X blue. The overcoat was allowed to cure under ambient conditions for 16h prior to conducting the test.

SOLO

(180min)

SOHO

Untreated 0.01% 0.05% 0.1% 0.2% LiBH 4 The example illustrates that improved scribe adhesion results were possible employing low concentrations of reducing reagent to reactivate different types of polyurethane topcoats under various application conditions.

2007202368 22 May 2007 Example 14. SIJA inter-coat adhesion of aged Desothane HS70846X white reactivated with LiBH 4 (0.2 wt%) in the solvent/s specified (SOLO) for 3h and over-coated with various coloured Desothane HS polyurethane topcoats.

Untreated Sanded Triglyme Proglyde DMM THF t-BAC Untreated Sanded IPA Results indicate that different solvents may be employed for reactivation using reducing agents under appropriate conditions.

2007202368 22 May 2007 Example 15. SIJA inter-coat adhesion of aged Desothane HS 70846X white reactivated with LiBH 4 (0.2 wt%) in Proglyde DMM and co-solvent specified (SOLO) for 3 hours and over-coated with various coloured Desothane HS polyurethane topcoats.

Untreated Sanded 2% t-butylacetate 5% t-butylacetate Untreated Sanded 20% IPA 30% IPA 40% IPA 600- IPA 8006 IPA 2007202368 22 May 2007 (ii) Example incorporating different alcohols and alcohol combinations (20:20%).

Untreated t-butanol IPA: t-butanolethylhexanol dipropyleneglycol monobutylether dipropylene glycolmonomethylther Untreated Sanded 1% Polyethylene glycol Results indicate that under appropriate conditions a variety of solvent combinations may be employed for the purpose of reactivation with appropriate reducing agents.

2007202368 22 May 2007 Example 16. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified for 30min (SOHO) and over-coated with Desothane S400X red 3 hours following hose-off with water.

Li(OCH 3 )xBH 4 -x in Proglyde prepared by addition of 0 major component)),2(x=2, major component),and 3 major component)equivalents (Eq) respectively of methanol "in-situ".

Untreated Sanded 0 Eq 1.OEq 2.OEq 3.OEq MeOH Example illustrates that the active agent be conducted in the presence of more than may be prepared "in situ" and that reactivation can one different type of reducing reagent.

2007202368 22 May 2007 Example 17. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified for 30min (SOHO) and over-coated with Desothane S400X red 3hours following hose off with water.

Untreated Sanded 0.5wt% LiBH4 from 5wt% THF stock solution diluted with proglyde 0.5wt% LiBH 4 prepared from solid LiBH 4 in proglyde 0.5wt% LiBH 4 prepared insitu from NaBH 4 and LiCI in triglyme Example illustrates that different treatment solution preparation methods can be employed to manufacture the reduction based reactivations formulation taking into consideration the different ways in which reducing agents are packaged and sold commercially. In certain circumstances the reactive agent may be generated "in situ" if required.

2007202368 22 May 2007 Example 18. Rain erosion adhesion results for Desothane HS 70846X white (C2) aged as specified. Reactivated using the formulations and treatment time specified before overcoated with Desothane HS 50103X blue.

Ageing protocol: 4h (120F, 2-3% RH). SOLO based reactivation method 2007202368 22 May 2007 (ii) Ageing protocol: 5 Days (120F, 2-30 RH) SOLO based reactivation treatment 2007202368 22 May 2007 (iii) Ageing protocol: 4h (120F, 2-3% RH) SOHO based reactivation method T 4hr 2007202368 22 May 2007 (iv) Ageing protocol: 5 days (120F, 2-3% RH) SOHO based reactivation method Results illustrate that improved inter-coat adhesion is possible using reducing agents mixed into various reactivation treatment formulations and applied under various treatment times and protocols for substrates aged under various protocols.

2007202368 22 May 2007 Example 19. Rain erosion adhesion results for aged Desothane HS 70846X white (C-thinner) applied onto epoxy-carbon fibre composite incorporating primer, intermediate and topcoat layers reactivated under the conditions specified before being over-coated with Desothane HS S601X blue.

Untreated Sanded 0.1% LiBH 4 in Proglyde DMM SOLO (3h treatment time) SOHO Example illustrates that reactivation of aged polyurethane topcoats can be completed using the reducing methodology on "composite substrates" incorporating paint lay-ups including selectively strippable intermediate coating layers beneath the polyurethane topcoat.

Note: sanded and untreated reference in duplicate, chemically reactivated in triplicate 2007202368 22 May 2007 Example 20. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated with LiBH 4 (0.2 wt% in Proglyde DMM) for 2h under the post treatment conditions specified before being over-coated with Desothane HS S601X blue.

Untreated Sanded SOLO SOLO with dry tack rag wipe SOHO(water) SOHO(Water 0.1% FC4430 surfactant) SOHO(IPA) SOHO (IPA: water, 20:80) 2007202368 22 May 2007 Untreated Sanded SOWO (water) SOWO (IPA) SOWO (MPK) Example illustrates that various "post treatment" protocols may be employed depending on the application process requirements without negatively impacting adhesion.

2007202368 22 May 2007 Example 21. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated with LiBH 4 (0.1 wt% in Proglyde DMM) multiple times 30min apart under the conditions specified before being over-coated with Desothane HS S601X blue.

Untreated Ix application 2x application 3x application (SOLO) (SOHO) Ix application 2x application 3x application Example illustrates that multiple applications of the reactivation treatment solution does not diminish adhesion performance.

2007202368 22 May 2007 Example 22. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated with LiBH 4 (0.1 wt% in Proglyde DMM) for one hour before being subjected to the conditions specified and then washed (water) allowed to dry or (ii) for the treatment time specified before being over-coated with Desothane HS S601X blue or S400X red.

(i) Untreated (ii) Sanded 4h bake at 70 0 F 24h at ambient conditions Untreated 5 min 8 days ambient conditions The example demonstrates that reactivation can be conducted for a short (5min) or extended period (8 days) and that the reactivated surface retains its reactivity towards subsequent paint layers under a variety of conditions.

2007202368 22 May 2007 Example 23. SIJA inter-coat adhesion of aged Desothane HS 7084X6 white (C2) reactivated with LiBH 4 solutions themselves previously aged under ambient conditions for the period specified before being over-coated with Desothane HS S601X blue.

(i)Treatment solutions: 0.2% LiBH 4 in Progylde DMM the percentage IPA indicated stored for days before being used to reactivate the aged polyurethane topcoat.

Untreated Sanded 5% IPA 20% IPA 2007202368 22 May 2007 (ii) Treatment solutions: Various LiBH 4 concentrations stored in Proglyde DM14 tBAC for days prior to application T-9Odays Untreated 0.01% 0.05% Untrate 0.0% 005%0.1% LiBH 4 2007202368 22 May 2007 (iii) Treatment solution: LiBH 4 prepared as a stock 0.5wt% concentration in Proglyde DMM and stored for 6 months. Dilutions to the indicated concentrations and formulations were made just prior to application of the treatment solution for the purpose of reactivation in a SOLO format.

Untreated 0% IPA 20% IPA 40% IPA 0.15% LiBH 4 0.2% LiBH 4 Sanded 2007202368 22 May 2007 (iv) Rain erosion adhesion data from Desothane HS 70846X white cured at 120F (10%RH) 4 days prior to reactivation and over-coating with Desothane HS S601X blue. NOTE: Reactivated samples in triplicate, benchmark untreated and sanded in duplicate.

Treatment solutions (a)Aged for 25 days Aged for 25 days Stock solution in Proglyde DMM aged for 25 days and IPA added just prior to application to provide the given concentration prepared fresh prepared fresh.

0.2% LiBH 4 80% Proglyde 20% IPA 1 4tj70 r P Examples illustrate that reactivation treatment retain their activity thus providing shelf life solutions stored under ambient conditions and pot-life robustness.

2007202368 22 May 2007 Example 24. Example demonstrates that application of the treatment solution can assist in the mitigation of common surface contaminants (residues), produced by the manufacturing assembly which can reduce both the visual appearance and inter-coat adhesion particularly when the reactivation treatment solution is applied as a SOHO or SOWO application technique.

Illustration of application of common surface contaminates to the surface of an aged Desothane HS 70846X white topcoat prior to reactivation and over-coating with Desothane HS 5070X blue.

Microcut Diluted Cat Oil Silicone drips from bulb seal Paint appearance untreated Paint appearance following reactivation with 1.0% LiBH 4 solution in Proglyde DMM (30min) SOHO.

2007202368 22 May 2007 Corresponding SIJA inter-coat adhesion results from contaminant quadrants Quadrant: Blank Cat oil Microcut Silicone Not Reactivated Reactivated LiBH4 2007202368 22 May 2007 (ii) SIJA inter-coat adhesion of aged Desothane HS white 70846X topcoat contaminated with (a) petroleum jelly or Aeroshell 33 prior to reactivation employing 0.1% LiBH 4 in Proglyde DMM 2% tBAC. Activation treatment left on for (30 minutes) prior to application of the designated post treatment conditions specified. Subsequently over-coated with Desothane HS S601X blue.

Petroleum jelly contaminant Uncontaminated Contaminated Untreated SOHO Untreated SOHO SOWO (MPK/MEK) SOWO (IPA) 2007202368 22 May 2007 b) Aeroshell 33 Uncontaminated Contaminated Untreated SOHO Untreated SOHO SOWO (MPK/MEK) SOWO (IPA) The above example clearly demonstrates that improved inter-coat adhesion and paint appearance may be obtained when the Desothane HS coatings contaminated with common aerospace residues from manufacturing processes are reactivated prior to over-coating.

2007202368 22 May 2007 (iii) Supporting FTIR evidence for selected contaminants: Samples were swabbed with a hexane soaked "Q-tip" and the hexane containing sample absorbed onto NaC1. Following compression molding of the NaC1 into Plaques, FTIR spectra was obtained.

Petroleum Jelly Contaminant 0.05 0.03 0.01 -0.01 0.05 0.03 0.01 S-0.01 am 0 0.03 0.01 0.01 0.03 0.01 -0.o o.os o. 0 0.01 0 Uncontaminated topcoat Q-tip in isolation Petroleum Jelly Contaminated untreated Contaminated substrate following SOHO treatment Contaminated substrate following SOWO (IPA) treatment Contaminated substrate following SOWO (MPK/MEK) treatment o005 0.03 0011 -0.01 Aooo 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm NOTE: typical absorptions around 3000 cm 1 for the contaminant was removed or reduced following reactivation under the conditions listed.

2007202368 22 May 2007 Aeroshell 33 Contaminant 0.05 0.03 0.01 -001 0.05 0.03 0.01 -0.01 0.05 0.03 0.01 -0,.01 00 o 0o03 0.01 -0-01 005 0.01 -ooi 40o.o00 -0.01 0.0S 0.03 o.o01 4ooO Uncontaminated Topcoat Q-tip in isolation Aeroshell 33 Contaminated untreated Contaminated substrate following SOHO reactivation treatment Contaminated substrate following SOWO (IPA) reactivation 3500 3000 2500 2000 1 Contaminated substrate 1soo 0ooo soo following SOWO (MPK/MEK) reactivation Wavenumbers (cm 1 NOTE: typical absorptions around 3000 cm' for the contaminant was removed or reduced following reactivation under the conditions listed.

Examples illustrate that the level of contaminate is clearly reduced or removed following the reactivation treatment.

2007202368 22 May 2007 (iv) Supporting surface energy results for selected contaminants following no treatment, solvent wipe only and reactivation treatments of the contaminated aged Desothane HS 70846X white topcoat under the conditions specified.

C z n i11mI I No Treatment MEK/MPK Wipe Only 0.1% LiBH4 (Proglyde, 2% tBAc) MEK/MPK Wipe Dispersive Specific Dispersive Specific Dispersive Specific None 45 4.2 43 3.9 45 8.6 Microcut 48 3.2 45 4.2 45 6.9 Catoil 47 2.0 44 2.9 45 Boelube 37 6.0 46 3.5 46 5.9 Aeroshell33 43 2.2 44 2.8 46 Petroleum Jelly 49 3.0 41 3.9 43 The specific surface energy component of total surface energy is significantly reduced after contaminants are applied to the surface of the aged Desothane HS 70846X substrate. Wiping the surface with just solvent only marginally improved the specific contribution to surface energy (not back to untreated, non-contaminated) whilst specimens reactivated with LiBH. under the conditions listed provided a significant improvement in the specific contribution to surface energy above that for non-contaminated substrates indicating simultaneous cleaning and reactivation has occurred.

2007202368 22 May 2007 Example 25. Example 25. Example 25. SIJA inter-coat adhesion of aged Desothane HS 70846X white (C2) reactivated under the conditions specified one (thinapplication) or two (thicker application) applications followed by water hose-off after the 30 minute treatment time (SOHO) and over-coated with Desothane S400X.

Following cure of the over-coating the samples were immersed in Skydrol aviation fluid for a period of 30 days under ambient conditions prior to adhesion testing.

1 x 30 min treatment 2 x 30 min treatment I: 7U 0.1% LiBH4 0.25%LiBH4 In Proglyde DMM 0.1% LiBH4 0.25%LiBH4 Untreated Sanded 2007202368 22 May 2007 The example illustrates that the inter-coat adhesion between topcoat layers is resistant to hydraulic fluids.

(ii) SIJA inter-coat adhesion of aged Desothane HS 70846X white reactivated under the conditions specified (SOLO, 180 min) and over-coated with Desothane HS S601X blue. Following cure of the over-coating the samples were immersed in water under ambient conditions or placed in a condensing humidity chamber at 120F 98% RH for a period of 30 days prior to adhesion testing and visual appearance assessment.

0D ex Condensing Humidity Water Soak Untreated 0.1 0.15 LiBH4 in Proglyde (unfiltered solution) 0.2% 2007202368 22 May 2007 Condensing Humidity Water Soak Untreated 0.1 0.15 0.2% LiBH4 in Proglyde (unfiltered solution, tack rag following application time) 2007202368 22 May 2007 Condensing Humidity Water Soak

CO

Untreated 0.1 0.15 LiBH4 in Proglyde (Decanted solution) 0.2% 2007202368 22 May 2007 Condensing Humidity Water Soak Untreated 0.1 0.15 LiBH4 in Proglyde (filtered solution) 0.2% 2007202368 22 May 2007 Condensing Humidity Water Soak

I

1--j Untreated 0.1 0.15 LiBH4 in Proglyde (SOHO, water)) 0.2% Results indicate that excellent inter-coat adhesion was obtained after 30 days water soak under ambient conditions or 30 days conditioning at 120F and 95% RH. Paint appearance is also acceptable and further improved by either using sediment (precipitate free) treatment solutions obtained from filtering, or post treatment protocols such as a tack rag wipe, wash (SOHO) or wipe (SOWO) processes.

2007202368 22 May 2007 Example 26. The following example illustrates effects of spray application of 0.1% LiBH 4 Proglyde DMM reactivation solution onto bare polysulfide based sealant (PRC-Desoto PR 1772) that has been applied over primed carbon fiber reinforced epoxy.

Example illustrates that no lifting, bubbling of the sealant occurs even at thin sealant thicknesses.

Adhesion of the sealant to the substrate is maintained even through application of rubbing.

Prior Application On Application Post Application 2007202368 22 May 2007 (ii) The following example illustrates scribe adhesion results from polysulfide cured for 4h before treatment with a reactivation treatment solution comprised of time specified before overcoating with Desothane HS S601X Blue and curing for 16h sealant (PRC-Desoto PR 1772) 0.1% LiBH 4 in proglyde for the under ambient conditions.

Untreated 3h Prior to over-coating 24h Prior to over-coating The example illustrates that no deleterious effects occur following application of the treatment solution onto the sealant prior to over-coating even when the treatment solution is applied onto only moderately cured (young) sealants.

2007202368 22 May 2007 ((iii) The following example provide weight change data for polysulfide immersed into different solvents and reactivation treatment solutions.

sealant (PRC-Desoto PR 1772) when CgWater *MPK OProglyde 080:20 Proglyde:IPA 060:40 Progyde:IPA 00.1% LiBH4 Proglyde 00.1% LiBH4 80:20 Proglyde:IPA 00.1% LiBH4 60:40 Proglyde:IPA E0.2% LiBH4 Proglyde LiBH4 80:20 Proglyde:IPA 00.2% LiBH4 60:40 Proglyde:IPA The example illustrates that over periods of up to 8 days.

the reactivation solution may be formulated to provide only minimal weight change 2007202368 22 May 2007 (iv) The following example illustrates what impact application of LiBH 4 proglyde reactivation solutions has on selective strippable (intermediate) coating layers applied over primed composite panels.

0.55% LiBH 4 1.1% LiBH 4 2.2% LiBH 4 Untreated in Proglyde DMM The example demonstrates that no lifting or dissolution of the intermediate coating layer occurs through interaction of the reactivation treatment solution.

2007202368 22 May 2007 The following examples provide immersion weight change data up to 28 days of various aerospace substrate materials in various solvents, typical aerospace paint stripper, and reactivation treatment solutions. (a) BMS8-256 carbon fiber reinforced epoxy BMS8-79 glass fiber reinforced epoxy BMS8-276 carbon fiber reinforced epoxy with Metlbond 1515 adhesive film BMS 8-276 with Surface Master 905 adhesive film (e) Various metals, Al aluminum, Ti titanium, SS stainless steel, HSS high strength steel.

a. BMS8-256 4 2007202368 22 May 2007 BMS8-79 o 2 0: .Pill O MPK Stripper 0 0.15% LiBH4 Prog lyde 030.2% LiBH4 Proglyde N 0.15%o LBH4 80:20 Proglyde:IPA 0l0.2% LiBH4 80:20 Proglyde:IPA E*0.15% LiBH4 60:40 Proglyde:IPA 0 0.2% LiBH4 60:40 Proglyde:IPA 2007202368 22 May 2007 BMS8-276 with Metibond r 110 OMPK N Stripper 130.15% UBH4 Proglyde 0 0.2% UBH4 Proglyde 00.15%LiBH480:2OProglyde:IPAOO.2%LiBH480:2OProglyde:IPA 00.15%LiBH460:4OProgiyde:IPAOO.2%LiBH460:4OProglyde:IPA 2007202368 22 May 2007 BMS8-276 with SM905 0 MPK N Stripper 00.15% LiBH4 Proglyde 00.2% LiBH4 Progtyde EQ0 15% LiBH4 80:-20 Proglyde: IPA IN0.2% LiBH4 80:20 Proglyde IPA NO. 15% LiBH4 60.40 Proglyde: IPA 0 0.2% LiBH4 60:40 Proglyde: IPA 2007202368 22 May 2007 e. LiBH 4 in proglyde used for immersion 0.1 0J 2024 T3 Bare 0.075 U 2023 T3 Clad O Ti 6-4 0.05 SS T304 4130 HSS 0 0.025 S 0 hr 1 day ayH -0.025 -0.05 -0.075 -0.1 Time The examples demonstrate that the reactivation solutions may be formulated for minimal negative interaction with a range of materials from plastics, composites, elastomers, and metals relative to common solvents or chemical formulations often used in industries such as the aerospace sector. In the case of metals, weight loss is within measurement uncertainty.

95 Example 27. The following examples demonstrate the reactivation solution may be used in conjunction with materials such as stencils and design masks and tapes for the production of decorative painted finishes.

Reactivation (LiBH 4 in proglyde:IPA 40:60 SOLO application 30min) applied onto aged Desothane HS white 70846X topcoat (16h, 120F, 8%RH) with pre-applied vinyl based stencil prior to painting with Desothane HS S601X blue (C2) cured for 16h at ambient conditions.

Untreated 0.05% LiBH 4 0.15% LiBH4 Example illustrates that crisp non-distorted letters are maintained even when the treatment solution is applied over the top of the stencil.

96 (ii) Reactivation (LiBH 4 in proglyde:IPA 40:60 SOLO application 30min) applied onto aged Desothane HS white 70846X topcoat (16h, 120F, 8%RH) with pre-applied vinyl based stencil prior to painting with Desothane HS S601X (C)blue at 120F for 16h.

untreated 0.05% LiBH 4 U. IB LiBH4 Example illustrates that crisp non-distorted designs are maintained even when the treatment solution is applied over the top of the mask.

2007202368 22 May 2007 (iii) Reactivation (0.15% LiBH 4 in proglyde:IPA,30min, SOLO) applied onto aged Desothane HS white 70846X topcoat (16h, 120F) with pre-applied vinyl based stencil prior to painting with Desothane HS S601X blue (C2).

Scribe test 1 2 3 4h After blue application under abient conditions SStencil pull CON After blue application oilILY under abient conditions

ONLY

N LY 20:80 Proglyde:IPA Untreated 40:60 Example illustrates that excellent green adhesion, verified by scribe and stencil pull tests, is possible after lh with reactivated samples unlike untreated and excellent letter clarity is possible across a range of stencil pull times.

2007202368 22 May 2007 Example 28. Desothane HS 3613X yellow or S400X red (C2) cured aged under the standard aging protocol was reactivated using the LiBH 4 concentrations indicated for 30 min SOLO prior to overcoating with Desothane HS S601X blue.

Untreated Sanded 0.05% in Proglyde DMM 0.1% LiBH 4 2007202368 22 May 2007 Untreated Sanded 0.2% 0.1% LiBH 4 In Proglyde IPA, 80:20 The example illustrates that different coloured polyurethane coating may be reactivated using the reduction strategy.

2007202368 22 May 2007 Example 29 SEM pictures of Desothane HS 70846X white polyurethane coatings both and (C2) aged under the standard cure cycle aging conditions and low humidity conditions (120F, days, 2-3% RH) prior to and following reactivation with 0.1% LiBH 4 in proglyde.

Untreated "C2 9 Reactivated 66C99 Example a illustrates that the surface of the coating looks similar prior to and following reactivation.

2007202368 22 May 2007 Example b illustrates that the surface of the coating looks similar prior to and following reactivation.

Reactivate<

"C"

"C2"

I

2007202368 22 May 2007 (ii) (C2) Surface energy results for Desothane HS 70846X white polyurethane coatings both and aged using the standard cure conditions and low humidity cure conditions (120F das 2-3% RH) rior to and following reactivation with 0.1% LiBH 4 in proly d Ifl~lWUMI[IiM8W~hmnm2 Su s r t e Cure Treatment* Dispersive Specific Low Humidity Cycle (5 days, 120F, 2-3% RH) 44.2 5.4 0.1% LiBH 4 43.9 6.3 C2 41.5 5.5 "C2" 0.1% LiBH 4 42.4 7.3 Ageing Cycle: 120 0 F, 5% RH 40 h, (ii) 120oF 50% RH 48 h, and (iii) oven cure at 160°F for 24h 43.6 3.6 0.1% LiBH 4 45.4 5.9 "C2" 45.2 4.2 "C2" 0.1% LiBH 4 45.5 7.3 Example illustrates that increases in the Specific contribution to surface energy results from exposure to the reactivation treatment solution for the coatings aged under difference conditions and with catalyst levels (eg: C and C2).

2007202368 22 May 2007 (iii) FTIR-ATR results from Desothane HS 70846X white the standard conditions and reactivated as indicated.

polyurethane coatings (C2) aged under 0.0 4000 3500 3000 2500 2000 1500 1000 The example illustrates that similar FTIR-ATR traces result between untreated and treated samples, indicating that surface modification occurs primarily in the upper most portion of the coating combining the results from (ii) and (iii) and not deeply into the coating such that FTIR-ATR provides discernable differences in chemical structure.

2007202368 22 May 2007 (iv) SEM cross section images of cured aged Desothane HS 70846X white (C2) applied over primer and aluminium substrate untreated, sanded and (c)reactivated using 0.1% LiBH 4 in proglyde 30 min SOLO prior to over-coating with Desothane HS S601X blue.

(A)

2007202368 22 May 2007 2007202368 22 May 2007 (c) Examples illustrate that the over-coat does not wet the aged Desothane coating when untreated providing de-bonded regions. The de-bonded regions are not present in the sanded and chemically reactivated samples, providing evidence for improved interfacial 0 interaction between the two polyurethane topcoat coating layers (white and blue).

2007202368 22 May 2007 Example 30. Example illustrates the impact of accelerated UV exposure on aged Desothane HS 70846X polyurethane coating relative to untreated reference for different lengths of exposure time.

Change in colour for samples not over-coated.

Effect of time of UV on White Panels WJ 08 -0 06 a No UV SUV 210 hours 0 UV 420 hours UV 630 hours Untreated Sanded 0.1% SOHO 0.1% SOLO The example illustrates that the colour shift is similar for samples untreated, sanded, reactivated with 0.1% LiBH 4 in proglyde that is either removed after 30min (SOHO) or not removed (SOLO) if left not over-coated prior to various lengths of accelerated UV exposure time.

2007202368 22 May 2007 (ii) SIJA inter-coat adhesion results for Desothane HS 70846X white (C2) aged under the standard protocol and then accelerated UV conditions for 630h before reactivation and overcoating with Desothane S601X.

Prior UV Exposure: Untreated Sanded 0.1% LiBH4 (Proglyde) SOWO (MPK/MEK), 2007202368 22 May 2007 No UV Exposure: Untreated Sanded 0.1% LiBH4 (Proglyde) SOWO The example illustrates that the reactivation protocol provides improved inter-coat adhesion for samples exposed to accelerated aging and UV exposure with similar result provided to those samples not exposed to UV.

This example is relevant to polyurethane coating that has undergone UV exposure for extended periods before requiring reactivation and over-coating, for example, in-service airplanes.

2007202368 22 May 2007 Example 31. Example shows a comparative paint stripping experiment between composite panels incorporating a primer, intermediate and polyurethane topcoat layers. In the example the stripping behaviour of aged Desothane HS 70846X white (C2) reactivated with the reduction method under the conditions listed prior to over-coating with Desothane HS S601X relative to untreated and sanded references.

t initial Top row (from left to right): 17, 18, 19, Bottom row (left to right): 21, 22, 23, 24 17 Untreated 18 Sanded 19, 20 0.05% Lithium Borohydride t-Butyl Acetate: Proglyde 2:98 (SOHO) 21, 22 0.01% Lithium Borohydride t-Butyl Acetate: Proglyde 2:98 (SOLO) 23, 24 0.05% Lithium Borohydride t-Butyl Acetate: Proglyde 2:98 (SOLO) ill t 120 min t=120 min aft 112 00

\O

C.3 untreated references.

untreated references.

2007202368 22 May 2007 Example 32. The following example shows the impact on paint adhesion and appearance of Desothane HS S601X applied over untreated and reactivated aged Desothane HS 70846X coatings (themselves applied over primed aluminum) under cycling temperature and humidity for 500 cycles according to the protocol below.

120 100 tHumidity Temperature Thermal cycle: from -40 oC to 71°C: 1Hr, 7 1 C to -40'C: 2007202368 22 May 2007 Scribe adhesion was rated "10" for all samples 0.1% LiBH 4 in Proglyde 0.2 LiBH 4 in Proglyde Sanded Untreated

SOLO

SOHO (H20) SOWO( MPK) 2007202368 22 May 2007 (ii) SIJA adhesion testing provided improved inter-coat adhesion similar to sanded following the cycling protocol.

0.2 LiBH 4 in Proglyde Sanded Untreated SOLO SOHO (H20) SOwo (MPK) 2007202368 22 May 2007 (iii) No change of paint finish was noted in terms of "micro-cracking" or "pin head defect formation" following the cycling Untreated 0.2% LiBH4 Proglyde SOLO The examples illustrate that no apparent reduction in adhesion or over-coat appearance occurs following cycling of temperature and humidity.

117 S Example 33 Example demonstrates the paint adhesion and overcoat paint quality of rain erosion foils following C-q simulation of typical paint masking hangar operations and (C heat cure. The examples show rain erosion foils, (incorporating primer, intermediate coating, and) topcoated 00 with Desothane HS CA8000/B70846X base with C thinner cured \D /aged for 5 days at 3% RH and 120 0 F' which were reactivated for 1.5 hours using SOHO (prior to wash off) or the SOLO process indicated.

(N

Following reactivation the samples either underwent a 6 hour 120F thermal cycle directly (then left under ambient conditions overnight) or alternatively prior to the thermal treatment were wrapped with Kraft paper or had 4 bands of masking tape perpendicularly wrapped around the samples.

After removal of the paper and tape (wiping the tape lines with IPA) the samples were painted with Desothane HS CA8000/B50103 base with C thinner and following cure tested for adhesion and paint appearance relative to unreactivated and sanded controls.

2007202368 22 May 2007 SOHO Reactivation 3 applications 1 application Controls 0.10wt% LiBH 4 Proglyde -20% IPA 0.15wt% LiBH 4 Proglyde -40% IPA application 3 application refers to the number of times the reactivation solution was applied to the white paint.

2007202368 22 May 2007 (ii) SOLO Reactivation -3 applications 0.15wt% LiBH 4 Proglyde 40% IPA Controls 0.10wt% LiBH4proglyde 20% IPA application 3 application refers to applied to the white paint the number of times the reactivation solution was 120 O Results indicate: 0 All the foils except for a random SOLO foil passed Cwith good marks 0 Excellent paint appearance was noted: No ghosting seen Cq from the tape being on the foil that was cured for 6 C- hours and then being solvent wiped with IPA and no deleterious effects from application of Kraft paper were noted 00 \0 No significant difference from a 1 application Ssituation and a 3 application situation 2007202368 22 May 2007 121 Example 34. The following example illustrates the inter-coat adhesion of aged Desothane 70846X and S400X red untreated and reactivated with tetraisopropyl titanate or sanded reference prior to over-coating with S601X blue and 5070X light blue.

SIJA adhesion Untreated Sanded 5% IPA 2.5% IPA Untreated Sanded 5% in IPA 2007202368 22 May 2007 122 The example illustrates that treatment of the aged surface with tetraisopropyl titanate provides improved adhesion with different coloured aged polyurethane substrates and overcoatings.

(ii) The following example demonstrate the reactivation solution based on tetraisopropyl titanate may be used in conjunction with materials such as stencils and design masks and tapes for the production of decorative painted finishes.

Untreated reference *i h) 123 00

O

The example illustrates that the use of the treatment solution based on tetraisopropyl titanate applied as a treatment solution for aged Desothane HS 70846X prior to over-coating with Desothane HS 5070X improved adhesion compared with the untreated reference and also provided minimal letter swelling or figure distortion, when it is applied SOLO directly over the design stencil prior to over-coating with polyurethane.

124 Example Screening experiments assessed a variety of metal alkoxide modifying agents with different relative reactivities (moisture stabilities) as described in Table 4. Initial experiments employed SIJA methods to probe the change in CIl inter-coat adhesion with the type of metal alkoxide used in the activation treatment system and (ii) its concentration.

00 Under all conditions a SOLO approach was employed. Figure 1 ND provides the SIJA data employing 0.5, 3 and Sconcentrations of modifying agent. It should be pointed out that there was no true concentration parity in the I experiment although given the large concentration range investigated trends in performance could be assessed and (ii) all solutions were prepared in the one solvent system (IPA) to CI simplify the experiment even though it is known that alcoholysis is possible to provide mixed alkoxides. However, to counter this effect to some degree each solution was prepared freshly and applied directly. Considering that NPZ has a high molecular weight and was supplied as a 70% NPA solution the actual concentration was much lower than for similar titanium based reagents.

Metal alkoxides with small alkoxy groups (eg: TPT, NET, NPZ see Table 4) appeared to provide limited benefit at concentrations of 0.5wt% but under the reactivation conditions employed showed improved inter-coat adhesion at concentrations above 3wt%. A lower reactivity for TEAZ was observed probably due to its greater moisture stability (Table Closer investigation of concentration (Figure 2) indicated that around 6 7mmol of modifying agents per 100g was required to see paint removal comparable to sanded specimens with less paint removed as the concentration was increased.

A preliminary investigation was also undertaken to assess the activity of the substrate over time considering that along with a standard reactivation time (eg 30 to 60 minutes) there may also be a requirement in the paint hangar for the activated surface to remain active after a heat cycle or for shorter or longer periods. Preliminary assessment results are provided in Figure 3. The salient points from this study were that NPZ treatment solutions appear to build up adhesive forces faster than TPT, (ii) both versions provided about the same level of inter-coat adhesion after lh even though the respective molar concentration of NPZ was less, (iii) paint surfaces remain active after 24h at ambient conditions, and (iv) the surfaces remained active after a heat cycle. Point may be explained by the relative reactivity of the materials as provided by their difference in hydrolysis rate (Table This type of activation window was considered commercially attractive and appeared to provide some flexibility for paint hangar scheduling.

2007202368 22 May 2007 Table 4 -Properties Of Various Metal Alkoxides Promoter /Property fTetra-i-propyl Tetra-n- Tetra-n-butyl Tetra-n-propyl Triethanolamine Iti tanate propyl titanate zirconate zirconate titanate Formulaj Ti (O-i-C 3

H

7 4 Ti (O-n-C 3

H

7 4 Ti (O-n-C 4 Hq) 4 Zr (O-n-C 3

H

7 4 Zr (C 6

H

1 4 N0 3 4 MW 284 284 340 327 683 Abbreviation T TPT NPT NBT NPZ TEAZ supply 100% 1000% 100%; 70% (NPA) 100%- Density (g/rnL, 20 0 C) 1 0.965 1.05 1.0 1.07 1.34 Pour Point +17 (Melt -50 <-70 Point) Flash point 23-60 38 50 21-25 >100 Relative hydrolysis 0.5-2.0 0.5-2.0 1.0-2.5 0.02 >S00 rate (mL water added) Relative moles at 3.5 3.5 2.9 2.2 lwt'% in -1009 (mmcl) Table 5 Physical Properties of Various Solvents Solvent Material Boiling point* Vapor pressure Flash Point 0 c) (mmHg 20 0 OC) 0 c) Isopropanol (IPA) 82 33 12 n-Propanol (NPA) 97 14.9 22 n-Butanol (NBA) 116 4.5 Hexanol 156 -0.5 59 Ethylhexanol 184 0.36 73 Dipropylene glycol dimethylether 175 0.6 (Proglyde DMN) Methyl ethylketone (M4EK) 80 71 -l Methyl propylketone (MPK) 101 27 7 start of boiling point range provided 126 u Based on the results provided for LiBH 4 based modifying agents stencil and pre-mask swelling appeared to be more related to the physical properties of the solvent system employed rather than the low concentrations of the active agent. To confirm this with metal alkoxide modifying agents a brief study was undertaken with the results provided in Figures 4 and 5. As was shown for LiBH 4 00 treatments in 100% Proglyde DMM extensively swelled the D 0 vinyl mask whilst 100% IPA provided no swelling. Since slight swelling began at a ratio of approximately 60:40 IPA: proglyde this ratio was considered a reasonable upper limit for the amount of glycol ether in formulations to be used with stencils. The effect of modifying agent concentration for NPZ in NPA or TPT in IPA was also undertaken (figure 5) with the results confirming that in 100% alcohol at least the concentration range (0.5 to did not appear to negatively impact letter quality.

Preliminary 30 day water soak experiments were also undertaken with specimens reactivated and then overcoated. One to three applications of the modifying agent were investigated to simulate both thin and thick applications, over spray, multiple passes etc. Generally good over-coat appearance was observed even with high concentrations of TPT or NPZ (5wt%) at 1 to 3 applications (Figure 6) Pre-mask and Stencil Vinyl Swelling Based on the preliminary results for stencil swelling, full stencil and premask diamond studies were undertaken. Using 100% IPA or NPA in the solvent system did not appear to provide appreciable stencil or pre-mask swelling and as such letter clarity was crisp even when the reactivation solution was applied over vinyl mask materials SOLO (Figure 7a). Following encouraging whirling arm rain erosion results (see later) additional stencil swelling experiments were undertaken employing 5wt% NPZ in a range of solvents and combinations (Figure 7b). No negative impact was demonstrated by using a 20:80 ratio of proglyde DMM to IPA or NPA, although at a 40:60 ratio some slight wicking away from the edges of the stencil was noted. Considering the benefits provided by using a slightly higher proglyde concentration in terms of adhesion on thicker paint layers, this degree of stencil swelling may be acceptable and probably not observed on pre-mask vinyl considering its lower susceptibility to swelling or when applied for short dwell times (15min) 127 QAlternatively, different solvent formulations can be employed depending on whether the application is for stencils which typically uses paint layer thickness on the order of one mil or premask or large body area applications where the paint layer thickness is typically two to five mils.

Tests using a 5wt% NPZ are provided in Figure 7C. It should be pointed out that using difficult to remove oo00 Chinese characters letter quality was significantly D 10 improved compared to untreated specimens and there was no C- appearance of stencil swelling when a 5%NPZ 20:80 O proglyde:IPA solvent system was employed for reactivation.

Adhesion S 15 Leveraging the preliminary results provided in the initial screening experiments above, the majority of subsequent experiments were completed employing a 3wt% concentration of modifying agent in alcohol based solvents. Later, higher concentrations of modifying agent and the addition of proglyde to the solvent system was found necessary to provide acceptable whirling arm rain erosion results on thick layers of paint in certain circumstances. It should also be emphasised that as indicated in Figure 2, concentration parity was not maintained between TPT and NPZ with a 3wt% solution actually corresponding to a 10.5 and a 6.6 mmol/100g concentration respectively.

Scribe Adhesion Various scribe adhesion test results are provided in Figure 8. Although the 3.5h, 120F cure stencil results did not provide a reference material that failed BSS7225 (and as such it was not possible to discriminate between the reactivation treatments) the 12h ambient cure overcoats did with the reactivated samples providing a rating similar to sanded for in contract to untreated with a rating.

Stencil pull and scribe adhesion were also undertaken (Figure 9) and mirror that completed for LiBH 4 Regardless of the treatment dwell (30 or 90 min), the treatments provided excellent scribe results (10 in BSS 7225) after min under ambient conditions superior to that of both sanded and untreated In terms of stencil pull: pull times of 90 min (more severe) did provide a "thinner" letter for all the reactivations treatments. Results for TPT were somewhat superior to NPZ regardless of whether IPA or NPA was employed which might be attributed to the difference in effective concentration. However, stencil pull results were on the whole far better than untreated 128 Swith effectively a full letter present at a stencil pull time of 60min (similar to sanded specimens) where as untreated specimens only provided a full letter at a pull time of Cq SIJA and Rain Erosion Adhesion Based on those strategies WARE foils were prepared with the main aim of obtaining concentration parity 00 between TPT and NPZ, (ii) employing Desothane CA8000 base -1 10 coat cured with standard thinner, (iii) exploring the potential for using proglyde as a co-solvent, and (iv) probing the effect of multiple applications. In all the experiments a relatively long application time was employed (4h) to provide a sufficient time frame for the metal alkoxide to firstly react and then condense with the aged paint surface. Subsequent tests demonstrated that much shorter dwell (application) times, e. g. 30 minutes, were feasible.

The results from SIJA panels are provided in Figure 10 and the WARE results obtained from foils provided in Figure 11. Although reasonable paint removal was obtained for the untreated reference from the 16h, 120F heat cycle cure (at 8%RH or 0.59wt% air moisture), the 72 hr basecoat ambient cure (at 60%RH or 1.12wt% air moisture) provided an untreated reference with only marginal paint loss. As such it was again difficult to compare the relative performance of the reactivation treatments.

Table 6 provides tabular data for the WARE results given in Figure 11. All foils produced "passes" with the cured base coating under the 16h, 120F, 8%RH cure.

For the ambient cured foils, all the NPZ foils had superior WARE compared to the TPT foils. Fot the TPT foils, multiple applications appeared to help, although incorporation of 20% proglyde provided the greatest advantage with 2/3 foils passing the test (eg a marginal pass). The reason for this is complex: the addition of proglyde assists in spraying a more uniform treatment film, (ii) proglyde has a much lower vapour pressure than IPA or NPA and as such the surface remained "wet" somewhat longer which presumably also assisted in promoting surface chemical reactions, (iii) proglyde is known to soften the paint and as such probably promoted metal alkoxide penetration into the coating surface and hence chemical reactions with embedded chemical groups, and (iv) through that process favors the formation of a surface/subsurface interpenetrating network during condensation of the alkoxide prior to or during cure of the over-coat.

2007202368 22 May 2007 Table 6 WARE results for Figure 11 DHS BAC70846 Base coat: 16h, 120F, 8%RH, C2, Adhesion promoter 2h dwell, Overcoat BAC50103, 96h 120F, C2 Untreated Sanded 3%TPT in IPA 3%TPT in IPA 3%TPT in 5%NPZ in IPA 5%NPZ in x2 PG:IPA, 1:4 NPA 4.3 4.8 4.6 4.4 4.6 0.2 4.9 4.5 4.8 4.8 4.0 4.6 4.9 4.8 4.0 4.6 4.7 0.4 4.6 4.7 4.7 4.4 4.4 4.6 DHS BAC70846 Base coat: 72h, 75F, 60%RH, C2, Adhesion promoter 2h dwell, Overcoat BAC707, 96h 120F, C2 Untreated Sanded 3%TPT in IPA 3%TPT in IPA 3%TPT in 5%NPZ in IPA 5%NPZ in x2 PG:IPA, 1:4 NPA 4.9 2.0 2.4 4.1 4.8 4.8 2.4 4.9 2.3 3.5 3.7 4.5 4.9 2.3 3.3 4.0 4.9 4.9 2.2 4.9 2.2 3.1 3.9 4.7 4.9 The findings from the trials with Desothane CA8000 on metal alkoxides may be summarised generally as follows: NPZ is preferred over TPT (ii) NPA is preferred over IPA (iii) Small amounts of proglyde co-solvent appear to be helpful (iv) For maximum benefit, metal alkoxide concentrations should be >10 mmol/100g Multiple application provide a more limited benefit 130 (vi) Reactivation of high humidity cured specimens appeared to be more complex compared with low humidity cure (surface chem. related moisture present in coating etc) Based on those findings a SIJA screening experiment was completed with Desothane CA8800 and Eclipse coatings employing the same two cure scenarios albeit that the 00 ambient cure relative humidity was increased to N 10 (1.56wt%% air moisture). The results are provided in C-i Figures 12 and 13. Reactivation employing either TPT or NPZ using a variety of solvent systems provided improved levels of inter-coat adhesion under both cure conditions.

0 The extent of improvement was such that further discrimination between the alkoxides and solvent systems employed was difficult to assess, although introduction of proglyde into the formulation as an 80:20 blend did appear to further enhance the performance. Further SIJA screening was also completed on Desothane CA8000 using 5wt% NPZ and several proglyde to n-propanol and isopropanol solvent ratios as shown in Figure 14. Results using 5wt% NPZ in a solvent solution of proglyde and either IPA or NPA with 30 to 60 minute dwell time of the modifying agent prior to overcoat paint are provided in Figures 15 to 18.

Figure 15 shows the rain erosion results employing a 20:80 proglyde:IPA solution for different dwell times and for "high" humidity (1.31wt% air moisture) and "low" humidity (0.22wt% air moisture) cure scenarios. In all cases the modifying agent treatment provided excellent inter-coat adhesion to both Desothane CA8000 and CA8800 coatings with just the high humidity cure Eclipse providing failures.

Figure 16a explores the effect of Desothane CA8800 cure rates using reduced rate (CTR), standard rate and fast rate (CT2) cured overcoats and a CTR cured base coat employing the same reactivation treatment. For BAC70846 white over BAC707 gray good passes were obtained for the CTR and CT thinners. The faster CT2 cured over-coat did not provide so good a performance (2/3 foils rated above 4) although it should also be noted that sanded also failed under similar conditions. When BAC51265 Blue was used as the overcoat (CTR) and the BAC 707 gray base coat cured with the different thinners (Figure 16b), high passes were obtained for each of the cure rates. This suggests that reactivation of the basecoat is relatively insensitive to the cure rate (thinner) employed in the basecoat.

Figures 17a and b documents the effect of higher proglyde concentrations and the impact of NPA or IPA as the alcohol in the 5wt% NPZ formulation using difficult 131 to over-coat systems including Desothane CA8800 gray on C white cured under high humidity and CA8000 cured under low humidity conditions. In both cases excellent passes were obtained with little differentiation between the two types of alcohols employed.

C Given those results the treatments were applied to high humidity cured Eclipse base coats which had been previously shown to fail when exposed to 5wt% NPZ in 80:20 00 IPA:proglyde (Figure 18a). In the case of formulations D 10 employing 60% IPA no passes were obtained when three M- cycles of the humidity protocol were used even when two 0 application and longer adhesion promoter dwell times were employed although specimens cured at low humidity were Ssuccessfully reactivated (Figure 18b). Two cycles of the high humidity protocol, however, did provide good passes.

C In contrast the 60% NPA formulation provided passes with three cycles of the humidity cure protocol with 2/3 foils passing after only lx 30min application and with 2x 30 or treatment solution applications 3/3 foils passed the adhesion test (Figure 18c). From these results,

NPA

performed slightly better than IPA for intercoat adhesion.

This difference in NPZ formulations could be due to (i) longer dwell time re: vapour pressure or (ii) mixed alkoxides from the interaction of IPA in the solvent system not favouring reactivation of such materials.

Intuitively one might predict that steric hindrance would be greater in the mixed alkoxide system which could reduce the reaction rate with the substrate surface or ability for it to interpenetrate into the coating.

To determine if higher concentrations of modifying agent would show even further improvements in WARE, NPZ formulations up to 9wt% (19.8 mmol/100g) with a solvent of NPA 40wt% proglyde were tested using CA8000 basecoat cured at 120F under low RH, 0.22 wt% air moisture) and moderately high humidity (13%RH, 0.95wt% air moisture) conditions for eight days. Various paint lines CA8000 (Figure 19A), Eclipse (Figure 19B) and Sky-Hullo (Figure 19C) were used as overcoats. All foils (18/18) passed using 5wt% NPZ, 13/18 foils passed using 7wt%, and only 10/18 passed using 9 wt%. The Sky-Hullo overcoat was particularly discriminating with 6/6 foils passing using 4/6 using 7wt%, and 1/6 using 9wt%. Overall, the results in Figures 19A to 19C suggested that the optimum NPZ concentration is near 5 wt% and the optimum alkoxide concentration is near 0.11 mmol per gram.

Preliminary shelf life SIJA data is provided in Figure 20 and suggested that the modifying agent was not negatively affected by storage under ambient conditions.

After three months all of the solutions (stored in glass) 132 0 were precipitate free indicating a low level of hydrolysis l and hence polymerisation. Although the solutions were prepared in either NPA or IPA it was not anticipated that the addition of 20 to 40% proglyde would negatively impact storage stability, particularly since proglyde can be obtained essentially moisture free. Other storage containers such as high density polyethylene could be used. The modifying solution could also be stored as a two 00 part kit, similar to how many aerospace paints are D 10 packaged, where one part would contain the NPZ either at M, 70wt% or at diluted concentration and the second part Swould contain a proglyde/alcohol solvent solution.

D Sealant Elastomer Interaction Sealant and elastomer immersion results are provided in Figures 21 to 24. In those tests BMS5-142 sealant was immersed in modifying agent solutions with IPA or NPA as the solvent for a period of 24h, whilst elastomers were immersed for 7 days and the change in weight, volume and hardness monitored both during the immersion as well as on recovery relative to MPK and water reference solutions.

Figure 25 provides images of the sample following recovery and illustrates that the samples were not obviously eroded or negatively impacted visually. Considering that MPK has solubility parameters of [dispersion, polar, and Hbonding] [16.0, 9.0 and 4.7 J/cm 3 NPA [16.0, 6.8 and 17.4 J/cm'] and employing the rule of mixtures a 40:60 blend of Proglyde NPA [15.6, 5.0 and 12.0 J/cm 3 the proglyde NPA solvent blend should not provide a substantial interaction with these types of materials.

In the case of BMS5-142 (polysulfide non-chromate sealant) weight gain reported in Figure 21A was more significant for MPK relative to the reactivation treatment solutions and correspondingly the volume change in Figure 21B was also greater. This result indicated a relatively low interaction between the treatments and the polysulfide sealant. After 7 days recovery all modifying agent treatment solution immersed samples were within 5% of their initial pre-treatment hardness, whilst both the water and MPK immersed samples were less than 10% softer.

BMS1-71, CL1 (EPR) elastomers provided the greatest weight gain in MPK and material appeared to be extracted by the reference solutions. Weight loss on recovery in MPK was about 12% after 7 days compared to less than 4% for samples immersed in the treatments. Correspondingly shrinkage on recovery was greater for the MPK reference, whilst the 7 day recovery Shore A. hardness at -17% increase was slightly higher than the 9 to 12% increase for samples immersed in TPT or NPZ. Similar results in 133 Figure 23 were provided by BMSI-71, CL2 (Silicone) During immersion, that material also showed a great uptake of MPK after 7 days (70% weight increase) compared to the treatment and water solutions but weight and volume and hardness changes were all similar during recovery.

BMSI-57 (Silicone) was also less susceptible to treatment solution uptake than MPK weight gain re: 00 Weight and volume loss during recovery were less N1 0 than 10% (typically for all immersions, and presumably was caused by material extraction during immersion. Hardness increase for the treatment solutions upon recovery was about 20%, whilst for MPK it was The larger hardness increase could indicate a larger sensitivity of this elastomer to the treatment solutions than to MPK, a commonly used cleaning component. However, the treatment solutions are typically sprayed on as thin films rather than flooded or wiped on as is typical for cleaning solutions so the 7 day soak of the treatment solutions is an extreme condition.

Metal Interaction Commonly used aerospace metals were also investigated for weight change and visual appearance following 30 day immersion in the metal alkoxide solutions compared with water (Figures 26 to 30). As a general point weight loss or gain was very low (not much more than the resolution of the 4 decimal place balance) and generally much less than water which appeared for most substrates to be the most aggressive. Weight gain for titanium was less than -0.07% for the treatment solutions re: 0.14% for water although samples in the reactivation solution did appear to be more "tarnished". This colour shift was reversed for 2024-T3 aluminium with water providing significant discolouration and weight change of compared with less then 0.1% for the treatments. 2024-T3 clad samples accumulated a dull finish following immersion in water and less weight gain compared with the bare Al at just 0.8% increase.

However treatment solution samples produced less than a 0.05wt% increase. Weight gains for high strength and stainless steel immersed in treatment solutions were all less than 0.02 wt% and similar to or less than for water.

Interestingly NPZ in IPA did not appear to tarnish high strength steel the way the other systems (inc. water) did although this observation did not translate into a significant difference in weight gain. Sandwich corrosion was tested according to ASTM F1110 with the results provided in Figure 31. Without magnification both the reference water and treatment solutions appear to provide 134 surface discolouration without pitting to most of the surface.

Composite Interaction Immersion results for several composite systems are C- provided in Figures 32 to 35 relative to MPK and CEEBEE paint stripper. Samples were cut and immersed without any edge taping and as such, considering the small sample 0O size, represented a most severe immersion test since the cut edges are regions for easy treatment penetration for C example through pores fibre-matrix de-bonding from the cutting process and more generally from the effective "cut" surface to volume ratio. As general comments (i) Sthe CEEBEE paint stripper appeared to be the most aggressive towards all systems resulting in weight gains in the 1.5 to 4% range after a month immersion (ii) generally immersion in the treatment solution also led to weight gain rather than loss (apart from BMS8-276 with SM905), although in such cases the weight change was generally very low (less than 0.5% for all composites and about 0.1% for BMS8-276 with SM905. In several instances initial weight gain was larger (eg 24h 7 days) with this reducing after longer periods of immersion which may be possible if some material was extracted from the system over time or broke off.

Interaction with Tapes Preliminary tape interaction studies are provided in Figure 36 and were considered of critical importance to application of the modifying agent technology for decorative painting of aircraft. In this experiment the effect of tape line, tape ghosting, and IPA wipe to remove residue were evaluated. In general no more paint wicking was observed for samples reactivated prior to/following taping with generally crisp lines present regardless of the modifying agent formulation applied. With TPT a larger amount of modifying agent residue was expected considering its effective concentration at 5wt% was larger than the NPZ examples (17.5 mmol/100g re: llmmol/100g) However no appreciable ghosting effects were obvious meaning that even a 1 mil overcoat thickness was sufficient to hide the tape lines.

Interaction with Coatings During production there remains the potential for paints to be reactivated (eg through over-spray) but not overcoated. Considering that the process of reactivation modifies the surface of the paint, there remains the 135 Qpotential for some accelerated aging brought about via environmental factors such as heat, water and UV irradiation. To assess this, coupons painted with a white basecoat were subjected to accelerated aging according to SAEJ1960 protocols employing a weatherometer. Figure 37 provides the change in colour (delta E) over time for coupons treated with modifying agent, sanded, or untreated relative to an untreated, painted coupon stored in the OO dark and measured at each time increment. Both untreated D 10 and sanded, UV exposed samples showed colour shift values M- in the range of one delta E unit during the experiment C (see Figure 38). As expected treated coupons at zero time show some colour shift compared the untreated coupon at Szero time. Samples reactivated with titanium were slightly lighter and had a yellow green colour shift l prior to exposure. On exposure residue treatment not well bonded to the surface would be anticipated to be removed (washed away) due to the SAE J1960 protocol. This can account for the rapid change in delta E after the equivalent of three months exposure. However, in both 3/6 month cases the samples were shifted darker and after an initial drop in the yellow shift became more yellow at 6 months. Generally speaking colour shifts for Zr based modifying agents were less than the Ti based one. With increasing exposure leading naturally to a slight darkening and yellowing of the coating not dissimilar in magnitude to untreated samples.

Further performance Further application of the modification agent is provided in Figures 39 to 41. Figure 39 provides WARE results for clear coated samples (eg paints without pigment) either treated or non-treated prior to overcoating as well as the implication of the effects of any post-treatment process such as wiping with a tack rag prior to over-coating. In all cases the specimens treated with the modification agent provided superior inter-coat adhesion and on some occasions superior to sanded.

Figure 40 provides hardness measurements prior to and following immersion in hydraulic fluid. The results indicated that the adhesion promoting mechanism is compatible with hydraulic fluid with pencil hardness values either approximately the same as or harder than specimens left untreated prior to over-coating thus providing another benefit.

Figure 41 provides Gardner impact test results for treated and untreated specimens of various paint thickness. The test is used for predicting the ability of organic coatings to resist cracking or peeling caused by 136 impacts producing rapid deformation of the underlying (metal) substrate). The results show that the modifying agent does not increase the brittleness of the paint and could possibly reinfroce the some paint combinations at lower thickness.

00

IND

mq 0D 137 O It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without c. departing from the spirit or scope of the invention as C< 5 broadly described. The present embodiments are, therefore, to be considered in all respects as 00 illustrative and not restrictive.

ND

0q 0q

Claims (33)

1. A method of activating an aged or inert organic coating to enhance adhesion of the coating to a further C- 5 coating and/or to other entities selected from adhesives, sealants, pin hole fillers and pressure sensitive decals 00 or logos comprising applying a solvent and a surface \O 1 chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface C 10 oxidation, surface exchange or transesterification, light 0 induced surface modification and/or adds chemical C-q functionality to the surface of the organic coating.

2. A method according to claim 1, in which the agent which facilitates surface reduction is a reductant.

3. A method according to claim 2, in which the reductant is selected from sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, calcium borohydride and alkoxy, acetoxy and/or amino derivatives thereof; sodium cyanborohydride; borane and borane complexes; lithium aluminium hydride; diisobutyl aluminium hydride; calcium hydride; sodium hydride; sodium bis(2 methoxyethoxy) aluminiumhydride);and selectrides such as K-selectride (potassium tri-sec-butylborohydride.

4. A method according to claim 1, in which the agent which facilitates surface hydrolysis is an acid.

5. A method according to claim 4, in which the acid is an organic or inorganic acid.

6. A method according to claim 5, in which the organic acid is selected from formic acid, acetic acid, benzoic acid, propanoic acid, malonic acid, oxalic acid and kemp's triacid. 139

7. A method according to claim 5, in which the Sinorganic acid is phosphoric acid. C 5 8. A method according to claim 1, in which the agent which facilitates surface oxidation is an oxidant. 00 CO I 9. A method according to claim 8, in which the oxidant is selected from trichloroisocyanuric acid, sodium c- 10 hypochlorite, hydrogen peroxide, potassium permanganate, 0 potassium chromate, periodic acid and lead tetra acetate. A method according to claim 1, in which the agent which facilitates surface exchange or transesterification is alkyltitanate, alkyltitanate chelate, alkyl zirconate, alkylzirconate chelate or combinations thereof.

11. A method according to claim 10, in which the agent which facilitates surface exchange or transesterification is selected from tetra-ethyltitanate tetra-isopropyltitanate, tetra-n-propyltitanate, tetra-n- butyltitanate, tetra-2-ethylhexyltitanate, tetraethyltitanate, triethanolamine titanate chelate, tetra-n-propylzirconate, tetra-i-propylzirconate tetra-n- butylzirconate tetra-t-butylzirconate, tetra-t- pentylzirconate and triethanolamine zirconate chelate.

12. A method according to claim 1, in which the agent which facilitates light induced surface modification is a free radical initiator or a combination of a free radical initiator with a tertiary amine and/or a mono or multi- functional unsaturated species.

13. A method according to claim 12, in which the free radical initiator is a visible light activated initiator. 140

14. A method according to claim 13, in which the visible light activated initiator is selected from camphorquinone and derivatives thereof; benzophenone and 5 derivatives thereof; diethylaminobenzophenone; and phenylphosphineoxide derivatives. 00 IN 15. A method according to claim 12, in which the tertiary amine agent is selected from N,N-dimethyl (N 10 toluidine, N,N-dimethylamino ethylmethacrylate, methyl 0 imidazole, NNN'N'tetramethyl-l,4-butane diamine and C-i NNN'N'tetramethylphenylenediamine.

16. A method according to claim 12, in which the multi-functional unsaturated species is selected from acrylates, methacrylates and acrylamides.

17. A method according to claim 1, in which the modifying agent is present in an amount more than about 0.001% or about 0.01% to about 20% based on the total weight of the combination of solvent and agent.

18. A method according to claim 1, in which the modifying agent is prepared in-situ from its constituent components.

19. A method according to claim 1, in which the solvent is selected from an organic solvent and water.

20. A method according to claim 19, in which the organic solvent is selected from ester based solvents, ketones, alcohols, ethers, amides, aromatics and halogenated solvents. 141

21. A method according to claim 21, in which the Ssolvent is selected from ethyl acetate, ethoxyethyl acetate, isopropyl acetate, tertiary butyl acetate; methyl C 5 propyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl ethyl ketone; ethanol, methanol, ethoxyethanol, n- 00 propanol, isopropanol, butanol, tertiary butanol, IN secondary butanol, ethylene and propylene glycols and C 1 -6 alkyl ethers thereof, tetrahydrofuran, N-methyl CA 10 pyrrolidinone and water. C 22. A method according to claim 19, in which the solvent is a combination of dipropylene glycol dimethyl ether tertiary butyl acetate; diproplyene glycol dimethyl ether: isopropanol, n-propanol methanol, ethanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, ethoxy ethanol and/or ethylhexanol; ethylene glycol monomethyl ether: ethanol, methanol, ethoxyethanol, isopropanol and/or n-propanol; dipropyleneglycol- monomethylether, dipropyleneglycol-monobutylether, and/or dipropylenegylcol; combinations tetrahydrofuran: triglyme; tetrahydrofuran: dipropylene glycol dimethylether; methylethyl ketone: ethoxyethyl acetate; methyl amyl ketone: ethoxyethyl acetate; N-methyl pyrrolidinone: ethyl acetate; ethyl acetate: benzyl alcohol; dipropylene glycol dimethyl ether: polyethylene; and methyl propyl ketone: methyl ethyl ketone.

23. A method according to claim 1, in which the solvent is present in an amount less than about 99.999% or about 80% to about 9.99% based on the total weight of the combination of solvent and agent.

24. A method according to claim 1, in which an additive is also applied to the organic coating. 142 A method according to claim 24, in which the additive is selected from rheology modifiers, film formers, wetting agents, surfactants, dispersants, anti 5 foaming agents, anti corrosion reagents, stabilizers, levelling agents, pigments, dyes and Lewis acids. 00 \O IN 26. A method according to claim 24, in which the additive is present in an amount of less than about C( 10 based on the total weight of the combination of solvent, agent and additive.

27. A method according to claim 24, in which the solvent, agent and additive when present are applied either simultaneously, sequentially or separately.

28. A method according to claim 24, in which the solvent, agent and additive when present are applied simultaneously in the form of an activation treatment.

29. A method according to claim 26, in which the solvent, agent and additive when present are applied via a spray, brush, dip, knife, blade, hose, roller, wipe, curtain, flood, flow, mist, pipette or combinations thereof. A method according to claim i, in which the organic coating is a polyurethane, epoxy, polyester, polycarbonate and/or acrylic coating.

31. A method according to claim i, in which excess solvent and/or agent are removed by solvent or water rinsing; dry, water or solvent wiping; air or gas knife; vacuum application; squeegee; and/or natural or forced convection evaporation. 143

32. A coated substrate having an activated coating, wherein the adhesion of the coating to a further coating and/or other entities selected from adhesives, sealants, pin hole fillers and pressure sensitive decals or logos has been enhanced by application of a solvent and a 0O surface chemistry and/or surface topography modifying N agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light (N 10 induced surface modification and/or adds chemical Cfunctionality to the surface of the organic coating.

33. A substrate according to claim 32, in which the substrate is a metal, composite, plastic, elastomer or a material containing, glass, wood or fabric.

34. An activation treatment for an organic coating to enhance adhesion of the coating to a further coating and/or to other entities selected from adhesives, sealants, pin hole fillers and pressure sensitive decals or logos comprising a solvent and a surface chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface modification and/or adds chemical functionality to the surface of the organic coating. A method for the preparation of the activation treatment according to claim 34 comprising the step of mixing the solvent with the surface chemistry and/or surface topography modifying agent which facilitates surface reduction, surface hydrolysis, surface oxidation, surface exchange, light induced surface modification and/or adds chemical functionality to the surface of the organic coating. 144

36. A method according to claim 1, in which the agent t which facilitates surface exchange or transesterification is a metal alkoxide or a chelate thereof. (N

37. A method according to claim 36, in which the 00 metal alkoxide or chelate thereof contains a metal IN D selected from Groups 4A, 5A, 3A, 4B, 5B and 6B, Li Be, Mg, La, Fe, Zn, Nd and Gd. (C 0 38. A method according to claim 37, in which the C- metal alkoxide or chelate thereof contains a Group 4A metal.

39. A method according to claim 38, in which the Group 4A metal alkoxide is a titanium alkoxide or a zirconium alkoxide. A method according to claim 39, in which the titanium alkoxide or zirconium alkoxide is a tetra-C 1 salkyltitanate or a tetra-C 1 -_alkylzirconate.

41. A method according to claim 40, in which the tetra-C-.salkyl titanate or tetra-Ci-salkyl zirconate is tetra-propylzirconate or tetra-n-propyltitanate.

42. A method according to claim 41, in which the tetra-propyltitanate or tetra-propylzirconate is tetra-n- propyltitanate or tetra-n-propylzirconate.

43. A method according to claim 36, in which the metal alkoxide or chelate thereof is present in an amount of less than 20%, less than 10% or 3 to 10% based on the total weight of the combination of solvent and metal alkoxide or chelate thereof. 145 0 44. A method according to claim 1 or claim 36, in which the solvent is an alcohol or ether or combination thereof. 5 45. A method according to claim 44, in which the alcohol is selected from an alcohol having a molecular 00 weight of less than about 150 and the ether is selected IN from an ether having a molecular weight of less than about

300. 46. A method according to claim 45, in which the Cq alcohol is selected from isopropanol or n-propanol and the ether is dipropylene glycol dimethyl ether. 47. A method according to claim 46, in which the solvent is a combination of isopropanol or n-propanol and dipropylene glycol dimethyl ether. 48. A method according to claim 47, in which the dipropylene glycol dimethyl ether is present in an amount of less than 50% or 20 to 40% based on the total weight of the combination of isopropanol or n-propanol and dipropylene glycol dimethyl ether. 49. A method according to claim 36 or 44, in which an additive is also applied to the organic coating. A method according to claim 49, in which the additive is selected from rheology modifiers, film formers, wetting agents, surfactants, dispersants, anti foaming agents, anti corrosion reagents, stabilizers, levelling agents, pigments, dyes and Lewis acids. 51. A method according to claim 49, in which the additive is present in an amount of less than about based on the total weight of the combination of solvent, agent and additive. 146 52. A method according to claim 49, in which the Csolvent, agent and additive when present are applied either simultaneously, sequentially or separately. c- 53. A method according to claim 52, in which the 00 solvent, agent and additive when present are applied \O INDsimultaneously in the form of an activation treatment. C- 10 54. A method according to claim 49, in which the solvent, agent and additive when present are applied via a C-i spray, brush, dip, knife, blade, hose, roller, wipe, curtain, flood, flow, mist, pipette or combinations thereof. A method according to claim 36 or 44, in which the organic coating is a polyurethane, epoxy, polyester, polycarbonate and/or acrylic coating. 56. A method according to claim 36 or 44, in which excess solvent and/or agent are removed by solvent or water rinsing; dry, water or solvent wiping; air or gas knife; vacuum application; squeegee; and/or natural or forced convection evaporation. 57. A coated substrate having an activated coating, wherein the adhesion of the coating to a further coating and/or other entities selected from adhesives, sealants, pin hole fillers and pressure sensitive decals or logos has been enhanced by application of a solvent selected from an alcohol or ether or combination thereof and a surface chemistry and/or surface topography modifying agent which facilitates surface exchange or transterification selected from a metal alkoxide or a chelate thereof.