Patent Grant
9067821
Consumer and industrial products are made from a variety of materials including: metals and alloys, wood, glass, ceramics, cement and other masonry products, fabrics, plastics, paper, and composites. Composites of such materials can be composed of, for example, metals, masonry, or polymer based products. In all cases, surfaces of the products that are exposed to the environment may come into contact with a variety of agents, including dust, moisture, water, and oils. In industrial applications, surfaces may be exposed to a variety of agents such as water, aqueous salt solutions, solutions of aqueous acid or base, and chemicals that may be dissolved or suspended in aqueous compositions or other liquids that are used in manufacturing processes. Not only are product surfaces exposed to a variety of agents, but the temperatures to which surfaces are exposed can also affect their performance. For example, freezing liquids, such as water, can result in frozen deposits tightly attached to the surfaces exposed to the liquids, preventing access to the surface and preventing proper operation of equipment bound by the frozen liquids. In addition, elevated temperatures can accelerate processes such as corrosion or preferential surface leaching effects.
Highly durable coatings and surface treatments are provide having a variety of surface properties including, but not limited to: hydrophobicity/superhydrophobicity, oleophobicity, resistance to ice formation and/or ice deposition (adherence). Compositions that are hydrophobic and/or oleophobic and/or anti-icing (“HP/OP”) may be applied to a surface using single-step or multiple steps (e.g., two-step coating processes). Methods of applying such coatings and surface treatments also are provided, together with compositions for applying such coatings and surface treatments, and objects comprising coated and treated surfaces.
Coating methods and compositions/treatments are provided that impart a variety of desirable characteristics to objects and their surfaces, including hydrophobicity (e.g., superhydrophobicity), oleophobicity and anti-icing. Those characteristics can result in objects and surfaces with a variety of desirable properties including, but not limited to, resistance to: wetting, corrosion, swelling, rotting, cracking or warping, exfoliation, fouling, dust and/or dirt accumulation on surfaces (self cleaning), and surface ice formation adherence and accumulation. The coating compositions and treatments not only provide hydrophobicity and/or oleophobicity and/or anti-icing properties, but are durable in that they resist mechanical abrasion while retaining those properties
The coatings may be applied using a variety of techniques that can be grouped into three categories: one-step processes; two-step processes; and thermal deposition processes, which may in some instances be considered a special case of one-step or two-step processes. Within each of those categories numerous variations and embodiments are provided.
In some embodiments, the coatings may be applied using a one-step method, where a binder, first particles, and second particles are mixed to provide a coating composition that is then applied to the surface.
For example, a one-step method of applying a coating to a substrate may apply a coating composition to a substrate where the components include: i) a binder; ii) first particles having a size of about 30 microns to about 225 microns; and iii) second particles having a size of about 1 nanometer to 25 microns. Optionally, one or more independently selected alkyl, haloalkyl, or perfluoroalkyl groups may be covalently bound, either directly or indirectly, to the second particles. The composition optionally may contain 5% to 10% of a block copolymer on a weight basis. The composition may also contain any necessary solvents/liquids to assist in the application process.
Particles suitable for use in these compositions are described in detail below.
Where second particles are not HP/OP (e.g., untreated with a silanizing agent) prior to their incorporation into a coatings formed in one or two step processes, the coatings formed in those processes may be treated to apply chemical moieties (groups) such alkyl, haloalkyl, fluoroalkyl or perfluoroalkyl groups to the second particles at the surface of the coating (e.g., treating with silanizing agents such as compounds of formula (I), SIT7184.0 and the like).
In some embodiments, the coatings may be applied using two-step methods, where, in a first step, a binder and first particles are mixed to form a coating composition, which does not contain the second particles prior to the application of the coating composition to the surface. Once applied, the coating composition is termed a “substrate coating” or a “base coat.” Following the application of that coating composition, a composition comprising second particles is applied in a second step to the surface over the coating composition.
In some embodiments a two-step method of applying a coating to a substrate comprises:
In some embodiments of a two-step application method, the base coating is treated with the composition containing second particles after drying and curing the base coating at room temperatures (about 18-22° C.) or elevated temperatures (e.g., about 93° C.). In other embodiments, solvent used to apply the base coat is allowed to evaporate until the coating is no longer liquid and cannot be removed by contact; however, the base coating is not cured, when treated with the composition containing second particles. In still other embodiments, the composition comprising second particles may be applied directly to the base coat before solvents used in the application of the base coating have evaporated fully, substantially or even partly.
In one embodiment where HP/OP coatings are prepared using thermal spray processes, the process is a two step process. In such processes the metals and other materials applied to a substrate by thermal spray processes may be considered as binders for first particles added to the composition sprayed in the first step (e.g., Al2O3, silica or other metalloid oxides, or metal oxides). Alternatively the materials applied to the substrate may be considered as a binder for materials formed in the spraying process (e.g., metal or metalloid oxides formed in the spray process with oxidizing fuel). In addition to applying first particles, thermal spraying processes can also apply second particles and materials formed in the spraying process (e.g., metal oxides or metalloid oxides from the spraying composition). In each of those instances, following thermal spray treatment, the surface will contain materials (e.g., metal oxides) that can bind the materials or react with reagents that will enhance or impart HP/OP properties to the substrate's surface. Alternatively, the materials applied as a base coating, which form a rough surface, may be considered to comprise first particles formed from the materials applied in the partly melted and fused coating composition. In either case, following thermal spray deposition the surface is subject to a second treatment to enhance or impart HP/OP properties to the surface.
In one embodiment a method for thermal deposition of a coating to a surface may include the steps of:
Diverse binders, first particles, second particles and block copolymers may be employed in the methods and compositions described herein. In some embodiments, first particles may be considered filler particles. Similarly, in some embodiments second particles may be considered nanoparticles. In each instance, those materials are described more fully below.
A skilled artisan will understand that the selection of first particles and second particles needs to consider not only the desired properties of the coating and the ultimate conditions to which the coating will be subject in use, but also the process used to prepare the coating. Where, for example, particles must withstand elevated temperatures or specific solvents in the coating process, they need to be suitable for use in the required temperature ranges or in the required solvents. For example, in those embodiments where first and/or second particles are used with a thermoplastic binder, the particles need to be compatible with the elevated temperatures that are required to cure thermoplastic binders. In other embodiments where, for example, first particles or second particles are applied as part of a thermal spray composition, the particles need to withstand the high temperatures associated with those processes.
The one-step and two-step methods described herein can in some embodiments be used to produce coatings where the coating has (i) a surface in contact with said substrate and (ii) an exposed surface that is not is not in contact with the substrate where these surfaces bear different amounts of first particles, second particles, or both first and second particles. In such embodiments the exposed surface can have a greater amount of second and/or first particles on, at, or adjacent to the exposed surface, compared to the amount of first and/or second particles at or adjacent to the surface of the coating that is in contact with the substrate.
In other embodiments, the one-step and two-step methods described herein can be used to produce coatings where the coating has (i) a surface in contact with said substrate, (ii) an exposed surface that is not in contact with the substrate and a (iii) central portion of the coating that is between these surfaces. In such embodiments the exposed surface can have a greater amount of second and/or first particles on, at, or adjacent to the exposed surface, compared to the amount of first and/or second particles in the central region of the coating.
In embodiments where a greater amount of first and/or second particles may be present at the exposed surface, the coatings may be considered composite coatings. Such composite coatings may be formed using either one- or two-step application processes.
In one-step coating processes the incorporation of a block copolymer in a range selected from: about 35 to about 15%; from about 4% to about 13%; from about 5% to about 10% or 4% to about 7% (by weight of the final cured coating) can result in the movement of first or second particles to the surface of the coating. Without wishing to be bound by any theory, it is believed that block copolymers may form aggregates in the binder composition, which can cause localization of at least second particles, and may also cause localization of first particles as well.
In two step processes, composite coatings with a greater amount of first and/or second particles may be present at the surface as a result of their being applied to the exposed surface of the base coating. Furthermore, where the base coating composition comprises a block copolymer in the ranges listed above for one step applications, first and/or second particles present in the base coating may move to the surface, which will also create an unequal distribution of particles in the coating.
The amount of particles in any portion of a coating may be assessed by any means known in the art including, but not limited to, microscopy or electron microscopy. Using those techniques and cross or oblique sections of coatings, the amount (e.g., the number) of particles can be determined. In addition, where it is possible to remove coatings, or where the substrate permits (e.g., it is transparent), the surfaces can be examined directly using microscopy or electron microscopy to determine the amount of particles present at the surface adjacent to the coating.
The coatings described herein are durable and resistant to the loss of OH/OP properties as a result of abrasion. Resistance to abrasion may be measured using any method known in the art including assessment with a Taber abrasion testing instrument (e.g., a Taber “Abraser”). For the purpose of this application, wherever Taber testing results are recited, the tests were conducted on a Taber Model: 503 instrument using CS-10 wheels with 250 g or 500 g loads as indicated. Abrasion may also be measured using manual tests as described in Example 1. To provide an end point for the loss of hydrophobicity (and also oleophobicity and anti-icing properties) as a result of abrasion testing, surfaces are tested for their propensity to shed water droplets at an indicated angle of incline. Typically, twenty droplets are placed on the surface to be assessed, which is then inclined at the desired angle. End of life is indicated when more than half (ten or more drops) stay in place. While such measurements provide a consistent end point, a skilled artisan will understand that even after abrasion testing the abraded surfaces may still be quite hydrophobic, having water contact angles greater than 130 or 140° in many instances.
In addition to resistance to loss of OH/HP properties from abrasion, the compositions provided herein also provide durability in the form of resistance to other conditions. The coatings, which employ diverse binder systems, also display durability in:
The coatings, resulting from the application of the compositions provided for herein, have in some embodiments a surface with an arithmetical mean roughness in a range selected from: greater than about 3 microns to about 4 microns; from about 4 microns to about 6 microns; from about 4 microns to about 8 microns; from about 4 microns to about 12 microns; from about 4 microns to about 20 microns; from about 5 microns to about 10 microns; from about 5 microns to about 12 microns; from about 5 microns to about 20 microns; from about 6 microns to about 10 microns; or from about 6 microns to about 14 microns.
In other embodiments, the coatings, resulting from the application of the compositions provided for herein, have in some embodiments a surface with a ten point mean roughness selected from: greater than about 7 microns to about 60 microns; from about 7 microns to about 70 microns; from about 7 microns to about 80 microns; from about 7 microns to about 100 microns; from about 8 microns to about 60 microns; from about 8 microns to about 80 microns; from about 8 microns to about 100 microns; from about 12 microns to about 60 microns; from about 12 microns to about 100 microns; from about 15 microns to about 60 microns; or from about 15 microns to about 100 microns.
In some embodiments the coating surface has projections due to the presence of the first particles, with a maximum height above the level of the binder in a range selected from: from about 10 to about 180 microns; from about 15 to about 150 micron; from about 20 to about 100 microns; from 30 to 120 microns; from about 40 to 140 microns; from about 50 to about 150 microns, or from about 20 to about 80 microns.
A more complete discussion of the compositions and methods of their application and surface treatments follow. A skilled artisan will understand that the following description and examples are provided as guidance, and are not limiting to the scope of the methods and compositions described herein.
For the purposes of this disclosure a hydrophobic border or surface is one that results in a water droplet forming a surface contact angle exceeding about 90° and less than about 150° at room temperature (about 18 to about 23° C.). Similarly, for the purposes of this disclosure a superhydrophobic border or surface is one that results in a water droplet forming a surface contact angle exceeding about 150° but less than the theoretical maximum contact angle of about 180° at room temperature. Some authors further categorize hydrophobic behavior and employ the term “ultrahydrophobic.” Since for the purposes of this disclosure, a superhydrophobic surface has contact angles of about 150° to about 180°, superhydrophobic behavior is considered to include ultrahydrophobic behavior. For the purpose of this disclosure the term hydrophobic shall include superhydrophobic unless stated otherwise.
For the purposes of this disclosure an oleophobic material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding about 25° and less than the theoretical maximum contact angle of about 180° at room temperature.
Anti-icing (AI) surfaces are surfaces that are resistant to ice formation or prevent ice that forms from adhering to the surface (i.e., ice that forms can be removed with a minimum of force).
For the purpose of this disclosure HP/OP denotes hydrophobic (including superhydrophobic) and/or oleophobic behavior or properties as well as anti-icing properties. Durability, unless stated otherwise, refers to the resistance to loss of hydrophobic properties due to mechanical abrasion.
Alkyl as used herein denotes a linear or branched alkyl radical. Alkyl groups may be independently selected from C1 to C20 alkyl, C2 to C20 alkyl, C4 to C20 alkyl, C6 to C18 alkyl, C6 to C16 alkyl, or C6 to C20 alkyl. Unless otherwise indicated, alkyl does not include cycloalkyl. Cycloalkyl groups may be independently selected from: C4 to C20 alkyl comprising one or two C4 to C8 cycloalkyl functionalities; C4 to C20 alkyl comprising one or two C4 to C8 cycloalkyl functionalities; C6 to 20 alkyl comprising one or two C4 to C8 cycloalkyl functionalities; C6 to C18 alkyl comprising one or two C4 to C8 cycloalkyl functionalities; C6 to C16 alkyl comprising one or two C4 to C8 cycloalkyl functionalities. One or more hydrogen atoms of the alkyl groups may be replaced by fluorine atoms.
Haloalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by halogen atoms. Halogen atoms may be limited to chlorine or fluorine atoms in haloalkyl groups.
Fluoroalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by fluorine atoms.
Perfluoroalkyl as used herein denotes an alkyl group in which fluorine atoms have been substituted for each hydrogen atom present in the alkyl group.
For the purpose of this disclosure, when content is indicated as being present on a “weight basis” the content is measured as the percentage of the weight of components indicated, relative to the total weight of the binder system. When a liquid component such as a commercial binder product is used, the weight of the liquid component is used to calculate the weight basis, without regard to the relative amounts of solute and solvent that might be present in the commercial product. Thus, for example, when Polane is used as a binder, the weight basis is calculated using the weight of the Polane prepared as instructed by the manufacturer, without regard to the proportions of polyurethane solute and organic solvents. Optional solvents that are separately added to a composition merely to, for example, dilute the composition to a thickness suitable for spraying, are not included in the calculation of content on a weight basis.
Binders used to prepare durable superhydrophobic coatings may have a variety of compositions. Virtually any binder may be employed that is capable of adhering to the surface to be coated and retaining the desired first and second particles, both of which are described below. In some embodiments the binders employed are hydrophobic or superhydrophobic as applied in the absence of any added first or second particles, which can be advantageous in the preparation of durable HP/OP coatings.
In some embodiments the binders may be selected from lacquers, polyurethanes, fluoropolymers, epoxies, or powder coatings (thermoplastics). In other embodiments the binders may be selected from lacquers, polyurethanes, fluoropolymers, or thermoplastics. Binders may be hydrophilic, hydrophobic or superhydrophobic “as applied.” For the purposes of this disclosure, when binders or their properties are described “as applied,” it is understood that the binder(s) and properties are being described in the absence of the first and second particles described herein that alter the durability, hydrophobic/superhydrophobic and oleophobic properties of binder.
In one- or two-step processes, where the binders employed are hydrophilic, the coating will generally be given an application of a silanizing agent after it has been applied to the substrate.
In some instances, the binders are not comprised of materials (e.g., monomers or oligomers) that polymerize when exposed to UV light to form polymers. In another embodiment, the binders are not comprised of thermoset polymeric materials.
Regardless of what type of binder is employed, one consideration in choosing a suitable binder is the compatibility between the surface to be coated and any solvent(s) used to apply the binder. Other considerations are the environment to which the coating will be exposed after it is applied. Binders of the present disclosure provide resistance to a broad variety of chemical and ultraviolet light exposure (e.g., fluoropolymers such as in the LUMIFLON family of coatings are resistant to UV and light exposure from sunlight).
Durable HP/OP coatings formed with binders can have a broad range of thicknesses. In some embodiments the coatings will have a thickness in a range selected from about 10 microns to about 225 microns; about 15 microns to about 200 microns; about 20 microns to about 150 microns; about 30 microns to about 175 microns; or about 50 microns to about 200 microns.
2.1 Lacquer Binders
Lacquer binders typically are polymeric materials that are suspended or dissolved in carrier solvents and which dry to a hard finish, at least in part, by evaporation of the carrier solvents used to apply them. The polymeric binders present in lacquers include, but are not limited to, nitrocellulose and acrylic lacquers; each of which are suitable for use in preparing durable hydrophobic coatings.
In an embodiment, hydrophilic lacquers may be employed as binders; particularly where the coating will be given an application of a silanizing agent after it has been applied to the substrate. In another embodiment, lacquers that are hydrophobic or superhydrophobic as applied in the absence of first or second particles described below may be employed to prepare the coatings described herein.
In addition to the polymeric materials and solvents present in lacquers, a variety of other materials that enhance the properties of lacquers may be present. Such materials can provide not only color but also increased adhesion between the lacquer and the substance upon which it is applied.
A variety of commercial lacquer preparation may be used to prepare the durable coatings described herein. Among the commercial acrylic lacquers that may be employed are “Self-Etching Primer” (Eastwood Co. Pottstown, Pa.); Dupont VariPrime 615S (Dupont Performance Coatings, Wilmington, Del.) and Nason 491-17 Etch Primer (Dupont Performance Coatings Wilmington, Del.)
Lacquers may be used on a variety of surfaces and are particularly useful in forming coatings on plastics, woods and metals, including, but not limited to, steel, stainless steel, and aluminum.
2.2 Polyurethane Binders
Polyurethanes are polymers consisting of a chain of organic units joined by urethane (carbamate) linkages. Polyurethane polymers are typically formed through polymerization of at least one type of monomer containing at least two isocyanate functional groups with at least one other monomer containing at least two hydroxyl (alcohol) groups. A catalyst may be employed to speed the polymerization reaction. Other components may be present in the polyurethane coating compositions including, but not limited to, surfactants and other additives that bring about the carbamate forming reaction(s) yielding a coating of the desired properties in a desired cure time.
In some embodiments, the polyurethane employed in the durable coatings may be formed from a polyisocyanate and a mixture of —OH (hydroxyl) and NH (amine) terminated monomers. In such systems the polyisocyanate can be a trimer or homopolymer of hexamethylene diisocyanate, see e.g.,
Some solvents compatible with such systems include n-butyl acetate, toluene, xylene, ethyl benzene, cyclohexanone, isopropyl acetate, and methyl isobutyl ketone and mixtures thereof.
A wide variety of polyurethanes may be used to prepare the durable HP/OP coatings described herein. In some embodiments, polyurethanes that are hydrophobic or superhydrophobic as applied in the absence of first or second particles described below may be employed to prepare the coatings described herein. Among the commercial polyurethanes that may be employed are the POLANE® family of polyurethanes from Sherwin Williams (Cleveland, Ohio).
Polyurethanes may come as a single component ready to apply composition or as a two or three part (component) system, as is the case with POLANE products. For example POLANE B can be prepared by mixing POLANE® B (typically six parts), to catalyst (e.g., typically one part of V66V27 or V66V29 from Sherwin Williams), and a reducer (typically 25-33% of R7K84 from Sherwin Williams) The “pot life” of mixed POLANE® B prepared in that manner is typically 6-8 h.
Polyurethane coatings are compatible with, and show good adhesion to, a wide variety of surfaces. Using polyurethane binders durable HP/OP coatings may be formed on virtually any surface, including but not limited to, those of metals, glass, ceramics, concrete, wood, and plastics.
2.3 Fluoropolymer Binders
Fluoropolymers are polymers comprising one or more fluoroalkyl groups. In some embodiments, the fluoropolymers employed in the durable coatings may be formed from Fluoroethylene/vinyl ether copolymer (FEVE).
A wide variety of fluoropolymer coatings may be used to prepare the durable HP/OP coatings described herein. Fluoropolymers that are hydrophobic or superhydrophobic as applied in the absence of first or second particles, which are described further below, may be employed to prepare the coatings described herein. Among the commercial fluoropolymers that may be employed to prepare HP/OP coatings are LUMIFLON® family polymers (Asahi Glass Co., Toyko, Japan).
Fluoropolymers that may be employed as binders typically come as a two or three component system, as is the case with LUMIFLON® products. For example LUMIFLON® LF can be prepared by mixing 58 parts of LUMIFLON® LF-200, 6.5 parts of DESMODUR® N3300A, (Bayer Material Sciences,) 2.5 parts of catalyst (DABCO T12 (1/10,000 part), DABCO (1,4-diazabicyclo[2.2.2]octane, 1/10,000 part), 1 part xylene), with 33 parts xylene. Unless otherwise noted, references to LUMIFLON®, particularly in the Examples, refer to LUMIFLON® LF.
Fluropolymer coatings such as LUMIFLON® can be applied to variety of surfaces including wood, metal and concrete. Many fluoropolymers offer resistance to UV light and can therefore be used in exterior applications where the coatings are exposed to the potentially damaging effects of sunlight.
2.4 Powder Coatings
Powder coatings typically are thermoplastic or thermoset coatings that are applied on surfaces (often metal) to give a variety of desirable characteristics (e.g., colorful and slick appearance and functionalities such as corrosion protection, etc.). Powder coatings can be applied by a variety of means, including electrostatic spraying of thermoplastic or thermoset powders onto substrate surfaces. Once applied to the surface, the powder coats are subject to thermal treatment at nominal temperatures (about 400° F. or 200° C.), which melt the polymers, permitting their polymerization. The melting and solidification occur quickly, resulting in the formation of a very tenacious and durable continuous coating. Powder coat materials can be used as binders for the formation of superhydrophobic, hydrophobic, or oleophobic coatings.
In some embodiments the powder coating is mixed with first particles, at the time the coating is applied to the substrate. First particles may be present in a range that is about 5% to 40%, or 10% to 30%, 10% to 35%, 15% to 30%, or 20% to 40% by weight. In one embodiment, the first particles mixed with the powder coat are Extendospheres (P.A. Industries, Inc., Chatanooga, Tenn.), which may be used at 10% to 30% by weight.
2.5 Binders and Durable Hydrophobic, Superhydrophobic and Oleophobic Compositions Applied by Thermal Spray Processes
In addition to the preparation of durable HP/OP coatings using polymeric binders to form attachments between substrates and second particles (e.g., fumed silica nanoparticles) that are capable of forming linkages to moieties that impart one or more of hydrophobic, oleophobic or anti-icing properties (e.g., alkyl, fluoroalkyl, or perfluoroalkyl moieties), it is possible to prepare durable HP/OP coatings using thermal spray processes.
Thermal spray processes permit the formation of durable HP/OP coatings in which it is possible to immobilize materials capable of directly or indirectly forming linkages to chemical groups imparting HP/OP behavior to the surface (e.g., silica or alumina particles capable of binding alkyl, fluoroalkyl, or perfluoro alkyl moieties upon silanization). In an embodiment, particles impregnated into the surface with thermal spray coating can be particles of carbides, metal oxides, or oxides of metalloids (e.g., B, Si, Sb, Te and Ge) such as silicates (e.g., fumed silica). The particles may be directly impregnated into the surface by employing thermal spray processes
In addition, thermal spray processes also permit the formation and immobilization of materials that can be modified to give the surface OH/OP properties (e.g., the formation of metal oxides bound to, or incorporated into, the surface of a coating applied by an oxidizing thermal spray process). By way of example, thermal spray processes include High-Velocity OxyFuel (HVOF), thermal spray, and Twin-Arc spray (e.g., methods using a ROKIDE® ceramic spray systems). In each case, it is the thermal energy that either bonds particles of metals, alloys, oxide, carbides or nitrides, or a combination of them to metallic substrates. When metals and alloys are sprayed by thermal processes, because of the high temperatures involved and the presence of air or oxygen in the environment, the top layer of the deposited metals and alloys typically is oxidized. The oxidized materials (e.g., metals) may be used to attach moieties providing HP/OP properties (e.g., by reaction with silanizing agents such as compounds of formula (I), SIT8174.0 and the like).
While durable coatings employ binders as a means of immobilizing second particles (e.g., nanoparticles) bearing hydrophobic moieties to the surfaces, first particles may advantageously be added to the binder composition to, among other things, improve the durability of the hydrophobic coatings. A wide variety of first particles (also known as extenders or fillers) may be added to the binder to alter the properties and improve coating durability over coating compositions made in their absence. First particles that may be employed in the durable SP/OP coatings include, but are not limited to, particles comprising: wood (e.g., wood dust), glass, metals (e.g., iron, titanium, nickel, zinc, tin), alloys of metals, metal oxides, metalloid oxides (e.g., silica), plastics (e.g., thermoplastics), carbides, nitrides, borides, spinels, diamond, and fibers (e.g., glass fibers). Some commercially available first particles that may be employed in the formation of the durable HP/OP coatings described herein include those in the accompanying Table I.
In addition to the chemical nature of the first particles, other variables may be considered in the selection of first particles. These variables include, but are not limited to, the effect the first particle is expected to have on coatings, their hardness, their compatibility with the binder, the expected resistance of the first particle to the environment in which coating will be employed, and the environment the first particles must endure in the coating process, including resistance to temperature and solvent conditions. For example, where a first particle is applied in a thermoplastic binder that requires heating to cure the coating, the first particle must be capable of withstanding the temperatures required to cure the coating. In another example, where particles are applied to surfaces using a thermal spray process, the particles must be capable of withstanding the temperatures and environment presented in that process.
In an embodiment, first particles have an average size in a range selected from: greater than about 5 microns (μm) to about 50 μm; about 10 μm to about 100 μm; about 10 μm to about 200 μm; about 20 μm to about 200 μm; about 30 μm to about 100 μm; about 30 μm to about 200 μm; about 50 μm to about 100 μm; about 50 μm to about 200 μm; about 75 μm to about 150 μm; about 75 μm to about 200 μm; about 100 μm to about 225 μm; about 125 μm to about 225 μm; or about 100 μm to about 250 μm.
In another embodiment, first particles have an average size in a range selected from: about 30 μm to about 225 μm (microns); about 30 μm to about 50 μm; about 30 μm to about 100 μm; about 30 μm to about 200 μm; about 50 μm to about 100 μm; about 50 μm to about 200 μm; about 75 μm to about 150 μm; about 75 μm to about 200 μm; about 100 μm to about 225 μm; about 100 μm to about 225 μm or about 100 μm to about 250 μm.
First particles may be incorporated into binders at various ratios depending on the binder composition and the first particle's properties. In some embodiments, the first particles may have a content range selected from: about 1% to about 50%; from about 2% to about 40%; from about 4% to about 30%; from about 5% to about 25%; from about 5% to about 35%; from about 10% to about 25%; from about 10% to about 30%; from about 10% to about 40%; from about 10% to about 45%; from about 15% to about 25%; from about 15% to about 35%; from about 15% to about 45%; from about 20% to about 30%; from about 20% to about 35%; from about 20% to about 40%; from about 20% to about 45%; from about 20% to about 55%; from about 25% to about 40%; from about 25% to about 45%; from about 25% to about 55%; from about 30% to about 40%; from about 30% to about 45%; from about 30% to about 55%; from about 30% to about 60%; from about 35% to about 45%; from about 35% to about 50%; from about 35% to about 60%, or from about 40% to about 60% on a weight basis.
In some embodiments, where the first particles comprises or consist of glass spheres, the first particles may be present in a content range selected from: about 30% to about 40%; from about 30% to about 45%; from about 35% to about 45%; or from about 35% to about 50% on a weight basis. In other embodiments where the first particles are a polyethylene or modified polyethylene, the particle may be present in a content range selected from: 35% to about 45%; from about 35% to about 50%; or from 35% to about 50% on a weight basis.
First particles may have a size range selected from: about 1 μm to about 225 μm (microns); 30 μm to about 225 μm (microns); about 25 μm to about 50 μm; about 30 μm to about 50 μm; about 10 μm to about 100 μm; about 10 μm to about 200 μm; about 20 μm to about 200 μm; about 30 μm to about 100 μm; about 30 μm to about 200 μm; about 50 μm to about 100 μm; about 50 μm to about 200 μm; about 75 μm to about 150 μm; about 75 μm to about 200 μm; or about 100 μm to about 225 μm.
In one embodiment first particles have an average size in a range selected from: about 1 μm to about 225 μm (microns); greater than about 5 μm to about 50 μm; about 10 μm to about 100 μm; about 10 μm to about 200 μm; about 20 μm to about 200 μm; about 30 μm to about 100 μm; about 30 μm to about 200 μm; about 50 μm to about 100 μm; about 50 μm to about 200 μm; about 75 μm to about 150 μm; about 75 μm to about 200 μm; about 100 μm to about 225 μm; or about 125 μm to about 225 μm. In another embodiment, the coatings may contain first particles in the above-mentioned ranges subject to either the proviso that the coatings do not contain only particles (e.g., first or second particles) with a size of 25 microns or less, or the proviso that the coatings do not contain particles with a size of 25 microns or less.
In another embodiment, first particles have an average size greater than 30 microns and less than 250 microns, and do not contain non-trivial amounts of particles (e.g., first and second particles) with a size of 30 microns or less. And in still another embodiment, the coatings do not contain only particles (e.g., first and second particles) with a size of 50 microns or less, or particles with an average size of 50 microns or less in non-trivial amounts.
The incorporation of first particles can lead to a surface that is textured due to the presence of the first particles. In such embodiments, the presence of the first particles results in a surface texture that has elevations on the level of the coating formed. The height of the elevations due to the presence of the first particles can be from 0 (where the first particle is just below the line of the binders surface) to a point where the first particles are almost completely above the level of the binder coating (although they may still be coated with binder). Thus, the presence of first particles can result in a textured surface wherein the first particles cause elevations in the binder that have maximum heights in a range selected from: from about 10 to about 80 microns; from about 15 to about 80 microns; from about 20 to about 100 microns; from 30 to 70 microns; or from about 1 to 50 microns.
The surface texture of coatings may also be assessed using the arithmetical mean roughness (Ra) or the ten point mean roughness (Rz) as measure of the surface texture. In an embodiment, a coating described herein has an arithmetical mean roughness (Ra) in a range selected from: about 0.2 microns to about 20 microns; from about 0.3 microns to about 18 microns; from about 0.2 microns to about 8 microns; from about 8 microns to about 20 microns; or from about 0.5 microns to about 15 microns. In another embodiment, a coating as described herein has a ten point mean roughness (Rz) in a range selected from: about 1 micron to about 90 microns; from about 2 microns to about 80 microns; from about 3 microns to about 70 microns; from about 1 micron to about 40 microns; from about 40 microns to about 80 microns; from about 10 microns to about 65 microns; or from about 20 microns to about 60 microns.
First particles may optionally comprise moieties that make them hydrophobic or superhydrophobic and/or oleophobic. Where it is desirable to introduce such moieties the particles may be reacted with reagents that covalently bind moieties that make them hydrophobic, superhydrophobic, or oleophobic. In some embodiments, the reagents may be silanizing agents, such as those that introduce alkyl, haloalkyl, fluoroalkyl or perfluoroalkyl moieties (functionalities). In some embodiments the silanizing agents are compounds of formula (I) (i.e., R4-nSi—Xn), and the various embodiments of compounds of formula (I) described below for the treatment of second particles. The surface of many types of first particles can be activated to react with silanizing agents by various treatments including exposure to acids, bases, plasma, and the like, where necessary to achieve functionalization of the particles.
In any embodiment described herein, first particles may be employed that do not contain functional groups that impart one or more of hydrophobic, superhydrophobic, and/or oleophobic properties to the particles (e.g., properties beyond the properties inherent to the composition forming the particles). In one such embodiment, first particles do not contain covalently bound alkyl, haloalkyl, fluoroalkyl or perfluoroalkyl functionalities (moieties). In another such embodiment the first particles are not treated with a silanizing agent (e.g., a compound of formula (I)).
A variety of second particles can be used to prepare the durable coatings displaying HP/OP properties. Suitable second particles have a size from about 1 nanometers (nm) to 25 microns and are capable of binding covalently to one or more chemical groups (moieties) that provide the second particles, and the coatings into which they are incorporated, one or more of hydrophobic, oleophobic and anti-icing properties.
In some embodiments the second particles may have an average size in a range selected from about 1 nm to about 100 nm; about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns; about 1.0 micron to about 10 microns; about 2.0 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns; or about 100 nm to about 15 microns.
In one embodiments, such as where the second particles are prepared by fuming (e.g., fumed silica or fumed zinc oxide), the second particles may have an average size in a range selected from about 1 nm to about 50 nm; about 1 nm to about 100 nm; about 1 nm to about 400 nm; about 1 nm to about 500 nm; about 2 nm to about 120 nm; about 5 nm to about 150 nm; about 5 nm to about 400 nm; about 10 nm to about 300 nm; or about 20 nm to 400 nm.
Second particles having a wide variety of compositions may be employed in the durable coatings described herein. In some embodiments the second particles will be particles of metal oxides (e.g., aluminum oxides, zinc oxides, nickel oxide, zirconium oxides, iron oxides, or titanium dioxide) such as alumina, or oxides of metalloids (e.g., oxides of B, Si, Sb, Te and Ge) such as silicates (e.g., fumed silica) or particles comprising one or more metal oxides, oxides of metalloids or combination thereof, such as second particles of glasses. The particles are treated to introduce one or more moiety (group) that imparts HP/OP properties to the particles either prior to incorporation into the compositions that will be used to apply coatings or after they are incorporated into the coatings. In one embodiment, second particles are treated with silanizing agents to incorporate groups that will give the particles HP/OP properties.
In one embodiment second particles are silica (silicates), alumina (e.g., Al2O3), a titanium oxide, or zinc oxide, that are optionally treated with a silanizing agent.
In another embodiment, the second particles are comprised of fumed silica; and in a further embodiment, the second particles are comprised of fumed silica and have an average size in the range of 1 nm to 100 nm or 2 nm to 200 nm; wherein the silica is optionally treated with a silanizing agent.
In yet another embodiment second particles are comprised of one or more metals, metal oxides (e.g., zinc oxide, titanium dioxide, Al2O3), metalloids (e.g., B, Si, Sb, Te and Ge), oxides of a metalloid (e.g., SiO2 and silicates), or glasses. In such an embodiment the one or more independently selected second particles have average sizes in ranges independently (separately) selected from about 1 nm to about 100 nm; about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns; about 1.0 micron to about 10 microns; about 2.0 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns; or about 100 nm to about 15 microns. Second particles in such an embodiment may be employed in coatings prepared using thermal spray processes.
In any of the above-mentioned embodiments, the lower size of second particles may be limited to particles greater than 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or 60 nm. Similarly, in any of the above-mentioned embodiments, the upper size of second particles may be limited to particles less than 20, 10, 5, 1, 0.8, 0.6, 0.5, 0.4, 0.3 or 0.2 microns. Limitation on the upper and lower size of second particles may be used alone or in combination with any of the above-recited size limits on particle composition, percent composition in the coatings, etc.
4.1 Hydrophobic and Oleophobic Components of Second Particles
Second particles employed in the preparation of the durable coatings described herein comprise one or more independently selected chemical groups (moieties or functionalies) that impart HP/OP properties to provide the second particles, and the coatings into which they are incorporated. Second particles typically will be treated with agents that introduce such moieties before being incorporated into the durable coatings described herein, however, it is also possible to treat the coating after it is applied to a surface with agents that modify the second particles and introduce or more of hydrophobic, superhydrophobic or oleophobic properties. In such circumstances, other components of the coating (e.g., the binder or first particles) may also become modified by the agent.
In some embodiments, the second particles will be treated with an agent that introduces one or more hydrophobic, superhydrophobic or oleophobic properties.
In another embodiment the second particles will bear one or more alkyl, haloalkyl, fluoroalkyl, and perfluoroalkyl moieties. Such moieties can be covalently bound directly or indirectly bound to the second particle, such as through one or more intervening silicon or oxygen atoms.
In still another embodiment the second particles will bear one or more alkyl, fluoroalkyl, and perfluoroalkyl moieties of the formula R4-nSi—, where n is from 1-3, that are directly or indirectly bound (e.g., covalently bound) to the second particle, such as through one or more intervening atoms.
4.1.1 The Use of Silanizing Agents
A variety of silanizing agents can be employed to introduce R4-nSi—, moieties into second particles prior or subsequent to their introduction into the durable coatings described herein. Suitable silanizing agents have both leaving groups and terminal functionalities. Terminal functionalities are groups that are not displaced by reaction of a silanizing agent with silica second particles (e.g., R groups of compounds of the formula (I)). Leaving groups are those groups that are displaced from silanizing agents upon reaction to form bonds with the second particles.
Prior to reacting first or second particles with silanizing agents, the particles may be treated with an agent that will increase the number of sites available for reaction with the silanizing agent (e.g., SiCl4, SiCl4, Si(OMe)4, Si(OEt)4, SiCl3CH3, SiCl3CH2SiCl3, SiCl3CH2CH2SiCl3, Si(OMe)3CH2Si(OMe)3, Si(OMe)3CH2CH2 Si(OMe)3, Si(OEt)3CH2Si(OEt)3, or Si(OEt)3CH2CH2 Si(OEt)3 and the like). Treatment with such agents is conducted with a 1% to 5% solution of the agent in a suitable solvent (e.g., hexane), although higher concentrations may be employed (e.g., 5% to 10%). Subsequent reaction with silanizing agents is typically conducted using a silanizing agent at in the range of 1%-2% w/v, although concentrations in the range of 2%-5% w/v may also be used. Depending on the reagents employed, the reaction, which can be conducted at room temperature, can are typically conducted for 1 hour to 6 hours, although reaction for as long as 24 hours may be desirable in some instances.
In one embodiment, silanizing agents are compounds of the formula (I):
R4-nSi—Xn (I)
where n is an integer from 1-3;
In one embodiment, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms.
In another embodiment, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms.
In another embodiment, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms.
In another embodiment, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms and n is 3
In another embodiment, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms and n is 3
In another embodiment, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms and n is 3.
In another embodiment, R has the form —Z—((CF2)q(CF3))r, wherein Z is a C1-12 divalent alkane radical or a C2-12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1-4.
In any of the previously mentioned embodiments of compounds of formula (I) the value of n may be varied such that 1, 2 or 3 independently selected terminal functionalities are present in compounds of formula (I). In one embodiment, n is 3. In another embodiment, n is 2, and in still another embodiment n is 1.
In any of the previously mentioned embodiments of compounds of formula (I), all halogen atoms present in any one or more R groups may be fluorine atoms in some embodiments.
In any of the previously mentioned embodiments of compounds of formula (I), X may be independently selected from H, Cl, —OR2, —NHR3, —N(R3)2, or combinations thereof in some embodiments. In another, embodiment, X may be selected from Cl, —OR2, —NHR3, —N(R3)2, or combinations thereof. In still another embodiment, X may be selected from, Cl, —NHR3, —N(R3)2 or combinations thereof.
Any durable coating described herein may be prepared with one, two, three, four or more compounds of formula (I) employed alone or in combination to modify the first or second particle, and or other components of the coating (e.g., first particles and binder).
The use of silanizing agents of formula (I) to modify first or second particles or any of the other components of the coatings or coating compositions will introduce one or more R3-n XnSi—, groups (e.g., R3Si—, R2X1Si—, or RX2Si— groups) where R and X are as defined for a compound of formula (I), n is 0, 1, or 2 (due to the displacement of at least one “X” substitutent and formation of a bond between the particle and the Si atom), and the bond with the particle is the silcon atom is indicated by a dash “—” (e.g., R3Si—, R2X1Si—, or RX2Si— groups).
In another embodiment, specific reagents that can be employed to prepare first or second particles with hydrophobic, superhydrophobic, or oleophobic properties include silanizing agents (e.g., compounds that are commercially available from Gelest, Inc., Morrisville, Pa.). Such silanizing agents include, but are not limited to, the following compounds, which are identified by their chemical name followed by the commercial supplier reference number (e.g., their Gelest reference in parentheses): (tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane (SIH5840.5); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane (SIH5841.7); n-octadecyltrimethoxysilane (SI06645.0); n-octyltriethoxysilane (SI06715.0); and nonafluorohexyldimethyl(dimethylamino)silane (SIN6597.4).
The two attributes of silanizing agents important for the purposes of forming suitable first or second particles are the leaving group (e.g., X groups of compounds of the formula (I)) and the terminal functionality (e.g., R groups of compounds of the formula (I)). Silanizing agent leaving groups determine the reactivity of the agent with the first or second particle. Where, the first or second particles are a silicate (e.g., fumed silica) the leaving group can be displaced to form Si—O—Si bonds. The terminal functionality determines the level of hydrophobicity that results from application of the silane to the surface. Leaving group effectiveness is ranked in the decreasing order as chloro>methoxy>hydro (H)>ethoxy (measured as trichloro>trimethoxy>trihydro>triethoxy). This ranking of the leaving groups is consistent with their bond dissociation energy.
In addition to the silanizing agents recited above, a variety of other silanizing agents can be used to alter the properties of first or second particles and to provide hydrophobic, superhydrophobic or oleophobic properties. In some embodiments second particles may be treated with an agent selected from dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In further embodiments, the first or second particles are silica second particles. Silica second particles treated with such agents may have an average size in a range selected from: about 1 nm to about 50 nm; about 1 nm to about 100 nm; about 1 nm to about 400 nm; about 1 nm to about 500 nm; about 2 nm to about 120 nm; about 5 nm to about 150 nm; about 5 nm to about 400 nm; about 10 nm to about 300 nm; about 20 nm to 400 nm; or about 50 nm to 250 nm.
In addition to the silanizing agents recited above, which can be used to modify any one or more components of coatings (e.g., first and/or second particles) other silanizing agents can be employed including, but not limited to, one or more of: gamma-aminopropyltriethoxysilane, Dynasylan® A (tetraethylorthosilicate), hexamethyldisilazane, and Dynasylan® F 8263 (fluoroalkysilane), any one or more of which may be used alone or in combination with any other silanizing agent recited herein.
A variety of agents can be employed to introduce hydrophobic or oleophobic behavior into the coatings described herein. However, the use of agents to introduce alkyl functionalities (e.g., silanizing agents) does not generally prove as effective as their fluorinated or perfluorinated counterparts. The introduction of fluorinated or perfluorinated functionalities typically produce surfaces with the highest hydrophobicity.
4.1.3 Use of Compounds Other than Silanizing Agents
Other agents t can be used to introduce hydrophobic, superhydrophobic or oleophobic moieties into second particles. The choice of such agents will depend on the functionalities available for forming chemical (covalent) linkages between hydrophobic/oleophobic component and the functional groups present on the second particles surface. For example, where second particle surfaces have, or can be modified to have, hydroxyl or amino groups, then acid anhydrides and acid chlorides of alkyl, fluoroalkyl, and perfluoroalkyl compounds may be employed (e.g., the acid chlorides: Cl—C(O)(CH2)4-18CH3; Cl—C(O)(CH2)4-10(CF2)2-14CF3; Cl—C(O)(CF2)4-18CF3 or the anhydrides of those acids).
4.1.4 Preparation of Surfaces with Oleophobic Properties.
In addition to the hydrophobicity displayed against aqueous based solutions, suspension, and emulsions, and the anti-icing properties of the coatings described herein, the coatings described herein also have the ability to display oleophobic behavior. This is true particularly where the coatings comprise fluorinated or perfluorinated alkyl groups (e.g., where the terminal functionality, that is the R group(s) of a silane of the formula R4-nSi—Xn are fluorinated alkyl or perfluoroalkyl. Coatings comprising fluorinated or perfluorinated alkyl groups (e.g., as functionalities on second particles) can also be used to form spill-resistant borders that display the ability to retain oils, lipids and the like.
4.1.5 Sources of Second Particles
Second particles such as fumed silica may be purchased from a variety of suppliers, including but not limited to: Cabot Corp., Billerica, Mass. (e.g., Nanogel TLD201, CAB-O-SIL® TS-720, and M5 (untreated silica)): Evonik Industries, Essen, Germany (e.g., ACEMATT® silica such as untreated HK400, AEROXIDE® TiO2 titanium dioxide, AEROXIDE® alumina).
Some commercially available second particles are set forth in the accompanying scheme.
aData from Cabot Corp. website.
Hexamethyldisilazane
Polydimethylsiloxane
Octyltrimethoxysilane
As purchased the second particles may be untreated (e.g., M5 silica) and may not posses any HP/OP properties. Such untreated particles can be treated to covalently attach one or more groups or moieties to the particles that give them HP/OP properties with, for example, silanizing agents discussed above.
Durable hydrophobic/superhydrophobic coatings can be applied to any surface to which a binder can adhere. The surfaces may be flexible or rigid. In some embodiments the surface can be made from a material selected from glass, metal, metalloid, ceramic, wood, plastic, resin, rubber, stone, concrete or a combination thereof. In another embodiment the surface may be made from a material selected from the group consisting of glass, ceramic and a combination thereof. In other embodiments, the surfaces may be comprised of metalloids (e.g., B, Si, Sb, Te and Ge).
Any glass can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation: soda lime glass, borosilicate glass, sodium borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, optical glasses, lead crystal glass, fused silica glass, germania glasses, and germanium selenide glasses, and combinations thereof.
Any metal can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation: iron, nickel, chrome, copper, tin, zinc, lead, magnesium, manganese, aluminum, titanium silver, gold, and platinum or combinations thereof, or alloys comprising those metals. In one embodiment, the metal forming the surface comprises steel or stainless steel. In another embodiment, the metal used for the surface is chromium, is plated with chromium, or comprises chromium or a chromium coating.
Any ceramic can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation: earthenware (typically quartz and feldspar), porcelain (e.g., made from kaolin), bone china, alumina, zirconia, and terracotta. For the purpose of this disclosure, a glazing on a ceramic may be considered either as a ceramic or a glass.
Any wood can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation, hard and soft woods. In some embodiments, woods may be selected from alder, poplar, oak, maple, cherry apple, walnut, holly, boxwood, mahogany, ebony teak, luan, and elm. In other embodiments woods may be selected from ash, birch, pine, spruce, fir, cedar, and yew.
Any plastic or resin can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation polyolefins (such as a polypropylene and polyethylene), a polyvinylchloride plastics, a polyamides, a polyimides, a polyamideimides, a polyesters, aromatic polyesters, polycarbonates, polystyrenes, polysulfides, polysulfones, polyethersulfones, polyphenylenesulfides, a phenolic resins, polyurethanes, epoxy resins, a silicon resins, acrylonitrile butadiene styrene resin/plastic, methacrylic resins/plastics, acrylate resins, polyacetals, polyphenylene oxides, polymethylpentenes, melamines, alkyd resins, polyesters or unsaturated polyesters, polybutylene terephthlates, combinations thereof, and the like.
Any rubber can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation: styrene-butadiene rubber, butyl rubber, nitrile rubber, chloroprene rubber, polyurethane rubber, silicon rubber, and the like.
Any type of stone, concrete, or combination thereof can be employed as a substrate for durable hydrophobic or superhydrophobic coatings including, without limitation, igneous, sedimentary and metamorphic stone (rock). In one embodiment the stone is selected from granite, marble, limestone, hydroxylapatite, quartz, quartzite, obsidian and combinations thereof. Stone may also be used in the form of a conglomerate with other components such as concrete and/or epoxy to form an aggregate that may be used as a surface upon which a durable hydrophobic coating may be applied.
The coatings described herein can be applied to surfaces using any means known in the art, including but not limited to, brushing, painting, printing, stamping, rolling, dipping, spin-coating, spraying, or electrostatic spraying. Generally, the surfaces will be rigid or semi-rigid, but the surfaces can also be flexible, for example in the instance of wire and tapes or ribbons.
The coatings described herein can be applied to virtually any substrate to provide HP/OP properties. The choice of coatings and coating process that will be used may be affected by the compatibility of the substrate and its surface to the coating process and the component of the coating compositions. Among the considerations are the compatibility of the substrate and its surface with any solvents that may be employed in the application of the coatings and the ability of a desired coating to adhere to the substrate's surface. In addition, where the coating process will expose the substrate, and especially its surface, to heating (e.g., where binders are thermoplastics, thermoset plastics, or where thermal spraying is employed) the ability to withstand the effects of temperature are considerations that must be taken into account.
Coatings may take any desired shape or form, limited only by the manner and patterns in which they can be applied. In some embodiments, the coating will completely cover a surface. In other embodiments the coatings will cover only a portion of a surface, such as one or more of a top, side or bottom of an object. In one embodiment, a coating is applied as a line or strip on a substantially flat or planar surface. In such an embodiment the line or strip may form a spill-resistant border (see e.g., Example 18).
The shape, dimensions and placement of coatings on surfaces can be controlled by a variety of means including the use of masks which can control not only the portions of a surface that will receive a coating, but also the portions of a surface that may receive prior treatments such as the application of a primer layer or cleaning by abrasion or solvents. For example, where sand blasting or a chemical treatment is used to prepare a portion of a surface for coating, a mask resistant to those treatments would be selected (e.g., a mask such as a rigid or flexible plastic, resin, or rubber/rubberized material). Masking may be attached to the surface through the use of adhesives, which may be applied to the mask agent, the surface, or both.
In another embodiment a coatings applied to a ribbon, tape or sheet that may then be applied to a substrate by any suitable means including adhesive applied to the substrate, the ribbon or tape, or both. Ribbons, tapes and sheets bearing a superhydrophobic coating may be employed in a variety of application, including forming spill proof barriers on surfaces (see e.g., Example 18). Ribbons, tapes, and sheets of coated material may be made from any flexible substrate. Ribbons, tapes, and sheets are generally formed of a substantially flat (planar) flexible material where one side (the top) is made hydrophobic or superhydrophobic. This includes metal tapes such as aluminum tape or other tapes (e.g., metal adhesive tape, plastic adhesive tape, paper adhesive tape, fiber glass adhesive tapes), wherein one side is coated with an HP/OP coating and adhesive on the other side. Such ribbons, tapes, and sheets can be applied to any type of surface including metal, ceramic, glass, plastic, or wood surfaces, for a variety of purposes.
To improve the adherence of coatings to a surface, the surface may be treated or primed such as by abrasion, cleaning with solvents or the application of one or more undercoatings of primers. In some embodiments where metals can be applied to surfaces (e.g., by electroplating, vapor deposition, or dipping) and it is deemed advantageous, surfaces maybe coated with metals prior to the application of a coating described herein.
6.1 One-Step Coating Applications
In some embodiments, the coatings may be applied using methods wherein binder, first particles, and second particles are mixed prior to the application of the coating composition to the surface. For the purpose of this disclosure, such methods are termed one-step methods or processes.
In one embodiment, a one-step process of applying a coating to a substrate may comprise:
In one-step methods the binders, first particles, second particles and silanizing agents described above may be employed. First particles may be less than 30 microns, and may be particles with an average size in the range of about 1 μm to about 225 μm as described above.
In one embodiment, coatings are prepared in a one step process with fumed silica second particles (TS-720), where the second particles are present in the range of 10-15% on a weight basis in the coating. In another embodiment, coatings are prepared in a one step process with fumed silica second particles treated with SIT8174), where the second particles are present in the range of 10-15% on a weight basis in the coating. In such embodiments, prior to treatment with silanizing agents such as SIT8174, the silica may be treated with SiCl4, SiCl4, Si(OMe)4, Si(OEt)4, SiCl3CH3, SiCl3CH2SiCl3, SiCl3CH2CH2SiCl3, Si(OMe)3CH2Si(OMe)3, Si(OMe)3CH2CH2 Si(OMe)3, Si(OEt)3CH2Si(OEt)3, or Si(OEt)3CH2CH2 Si(OEt)3 to increase the modification by the silanizing agent,
Although coatings applied by one-step processes do not necessarily require subsequent treatments in order to create coatings with the HP/OP properties described herein, they may be subject to subsequent treatments. Such treatments may enhance, for example, one or more of the hydrophobicity, superhydrophobicity, oleophobicity or anti-icing properties, and may be made either before or after curing (e.g., by heating) the coatings applied using a one-step process.
In one embodiment, a one-step process may further comprise applying a composition comprising a silanizing agent (e.g. a compound of formula (I)). In another embodiment, a one-step process may further comprise applying a composition comprising a silicon containing reagent that can increase the number of site that can react with silanizing agents, followed by a composition containing a silanizing agent. Reagents that will increase the number of sites on silica particles and other components of coatings that can react with silanizing agents include, but are not limited to: SiCl4, SiCl4, Si(OMe)4, Si(OEt)4, SiCl3CH3, SiCl3CH2SiCl3, SiCl3CH2CH2SiCl3, Si(OMe)3CH2Si(OMe)3, Si(OMe)3CH2CH2 Si(OMe)3, Si(OEt)3CH2Si(OEt)3, or Si(OEt)3CH2CH2 Si(OEt)3. Where those reagents contain chlorine, they may react with water or moisture to convert residual Cl, bound to Si atoms that is not displaced in the reaction with the coating components, into SiOH groups, which in addition to other groups, may also subsequently react with a silanizing agent.
In another embodiment, a one-step process may further comprise applying a composition comprising one or more second particles over the coating formed in the one step process. In such embodiments, the second particles can be applied to the coating formed in the one step process in a suitable binder compatible solvent (e.g., hexane in many instances). The second particles (e.g., TS-720 or TLD-720, or TLD201) may be suspended in a suitable solvent in a concentration range (e.g., 2% to 10%; 4% to 12%; 5%−15%, or 5% to 20% w/v) for application to the coating.
In an embodiment where the coating applied to a substrate in a one-step process did not contain second particles treated so that they are hydrophobic, superhydrophobic, or oleophobic (i.e., have HP/OP properties), the one step process can further comprise applying a composition comprising either: a silanizing agent; or a composition comprising a silicon containing reagent that will increase the number of sites that can react with silanizing agents, followed by a composition containing a silanizing agent.
In another embodiment, where the coating applied in a one-step process does not contain second particles treated so that they are hydrophobic, superhydrophobic, oleophobic, the one step process can further comprise applying one or more second particles treated so that they are hydrophobic, superhydrophobic, or oleophobic. In such an embodiment, the second particles may comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl groups.
6.1.1 Block Copolymers
A wide variety of block copolymers may be employed in the one and two step coating systems described herein. Where they are employed, they are typically present in a range selected from: of 1% to 15%, 1% to 3%, 1% to 5%, 6%-10% 5, or 11% to 15% by weight. The block copolymers may be one or more of hydrophobic block copolymers, diblock copolymers, triblock copolymers, tetrablock copolymers and combinations thereof.
Block copolymers may be prepared or purchased from a variety of sources. For example Kraton.® D series block copolymers are available from Shell Chemical Company (Houston, Tex.), Europrene® Sol T block copolymers are available from EniChem (Houston, Tex.), Vector® block copolymers are available from Exxon (Dexco) (Houston, Tex.), and Solprene® block copolymers from Housmex® (Houston, Tex.).
6.2 Two Step Coating Processes
In some embodiments, the coatings may be applied using methods where, in a first step, a binder and first particles are mixed to form a coating composition, which does not contain the second particles, prior to the application of the coating composition to the surface. Following the application of that coating composition, a second step is conducted wherein a composition comprising second particles is applied to the surface over the coating composition. For the purpose of this disclosure, such methods are termed two-step method or processes.
The second step may be conducted either before or after curing the coating composition applied in the first step. In one embodiment, the composition comprising second particles is applied after any solvents in the coating composition have evaporated, but before the composition has been cured. In another embodiment, the composition comprising second particles is applied after the coating composition has been cured.
In one embodiment, a two-step process of applying a coating to a substrate may comprise the steps:
In two-step methods the binders, first particles, second particles and silanizing agents described above may be employed. First particles may be less than 30 microns, and may be particles with an average size in the range of about 1 μm to about 225 μm as described above.
Although coatings applied by two-step processes do not necessarily need to undergo subsequent treatments in order to create coatings with the HP/OP properties described herein, they may be subject to subsequent treatments. Such treatments may enhance, for example, one or more of the hydrophobicity, superhydrophobicity, oleophobicity or anti-icing properties, and may be made either before or after curing (e.g., by heating) the coatings applied using a two-step process.
In one embodiment, a two-step process may further comprise applying: a composition comprising either: a silanizing agent (e.g. a compound of formula (I). In another embodiment, a two-step process may further comprise applying a composition comprising a silicon-containing reagent that will increase the sites that can react with silanizing agents, followed by a composition containing a silanizing agent. Reagents that will increase the number of sites on silica particles and other components of coatings that can react with silanizing agents include, but are not limited to: SiCl4, SiCl4, Si(OMe)4, Si(OEt)4, SiCl3CH3, SiCl3CH2SiCl3, SiCl3CH2CH2SiCl3, Si(OMe)3CH2Si(OMe)3, Si(OMe)3CH2CH2 Si(OMe)3, Si(OEt)3CH2Si(OEt)3, or Si(OEt)3CH2CH2 Si(OEt)3.
Where the coating applied in a two-step process does not contain second particles treated so that they are hydrophobic, superhydrophobic, or oleophobic (i.e., have HP/OP properties), the two-step process can further comprise applying a composition comprising either a silanizing agent or a composition comprising silicon containing reagent that will increase the number of sites that can react with silanizing agents followed by a composition containing a silanizing agent.
6.3 Thermal Deposition Processes.
Thermal spray processes including Plasma Spraying, Warm Spraying Wire Arc Spraying, High Velocity Oxyfuel (HOVF), Rockide® process, and Twin-Arc spraying may be employed to prepare coatings that have one or more of hydrophobic, superhydrophobic, oleophobic, or anti-icing characteristics. Thermal spray coating processes as used herein are a form of a two-step coating process in which a base coat material is applied to the substrate, alone or in combination with a second particle.
In one embodiment, a thermal deposition process for applying a coating to a substrate may comprise the steps:
Due to the high temperature, oxidizing conditions, and the composition of the base coating spray composition, the base coating will contain a variety of functionalities that may be modified to impart HP/OP characteristics to the coating. The base coat can be treated as in step (b) to produce surfaces with water contact angles measured at room temperature of about 120° to about 170°. In some embodiment the contact angle of the surface with water will be in a range selected from about 120° to about 140°, about 130° to about 150°, about 140° to about 160°, or about 150° to about 170°.
In one embodiment the thermal spray process is selected from High Velocity OxyFuel (HOVF) and Twin-Arc spray. The size of the first particles that may be applied in a base coating spray composition varies depending on the thermal spray process employed. For HVOF, first particles have a size in a range selected from: about 1 to about 75 microns, or about 5 to about 50 microns, or about 25 microns to 70 microns, or about 10 to about 40 microns. For plasma spray processes the particles are typically in the range of about 15 microns to about 45 microns, and for combustion processes, the range is from about 45 microns to about 100 microns. Thermal spraying using the Rockide® process, where particles to be sprayed are prepared in the form of ceramic rods and thermal spraying employing Twin-Arc Processes, which spray metallic materials feed in the form of a wire are less sensitive to the starting particle sizes.
In one embodiment the base coating spray composition comprises one or more metals, metal alloys, metal oxides, metalloids, metalloid oxides, carbides (e.g., SiC) or nitrides (e.g., Si3N4). In another embodiment, the base coating spray composition comprises one or more metals in combination with one or more metal oxides, metalloid oxides or carbides. In an embodiment, the base coating spray composition comprises one or more of: zirconia, Al2O3, Ni—Cr (e.g., 80%-20%), stainless steel (e.g., a 316 stainless), tungsten carbide/cobalt, chromium carbide/nickel and nickel/aluminum.
In an embodiment, one or more independently selected carbides, silicates, metal oxides or metalloid oxides can be bonded to, or impregnated into, the surface of a substrate using thermal spray processes as a base coat. In another embodiment, one or more independently selected compositions comprising: a silicate (e.g., silica); zirconia (ZrO2), alumina (Al2O3), 80%-20% Ni—Cr, 316 Stainless Steel, tungsten carbide/cobalt, chromium oxide, chromium carbide/nickel, and nickel aluminide (IC-50) and the like can be bonded to, or impregnated into, the surface of a substrate to form a base coat using thermal spray deposition. In another embodiment the base coating comprises one or more metals, metal alloys, metal oxides, metalloids, metalloid oxides, carbides or nitrides, in combination with one or more metal oxides, metalloid oxides, or one or more alloys formed by thermal spray deposition. Such base coat compositions may optionally comprise one or more second particles.
Where base coating spray compositions comprise one or more independently selected second particles, the particles need to be compatible with the thermal spray process conditions (e.g., the high temperature). In an embodiment, the second particles are comprised of one or more materials independently selected from metals, metal oxides, metalloids, oxides of a metalloid, silicates, or a glass (e.g., silica or alumina)
In an embodiment, the second particles have an average size in a range selected from: about 100 nm to about 50 microns; about 500 nm to about 50 microns; about 500 nm to about 25 microns; about 1 micron to about 50 microns; about 1 micron to about 25 microns; about 5 microns to about 25 microns; about 5 microns to about 50 microns; about 10 microns to about 25 microns; about 10 microns to about 35 microns, or about 10 microns to about 50 microns. In a further embodiment the second particles are particles of silica or alumina.
Once bonded to the substrate, groups present on the surface (including groups on the surface of first or second particles) that are capable of binding functionalities imparting OH/OP properties (e.g., metal or metalloid oxides on the substrate's surface) can subsequently bemodified by the application of reagents (e.g., silanizing agents) that alter the surface properties. In an embodiment, metal or metalloid oxides bound via the thermally bonded materials are modified with silanizing reagents bearing one or more alkyl, haloalkyl, fluoroalkyl, or perfluoroalkyl functionalities to the surface of the coating. Additionally, coatings applied by thermal spray processes may also be modified to increase their HP/OP properties by treatment with second particles bearing one or more functionalities that provide HP/OP properties (e.g., silica particles treated with a silanizing agent such as SIT8174 or polydimethylsiloxane treated fumed silica such as TS-720). It is also possible to use a combination of a silanizing agent and a second particle (e.g., fumed silica second particles untreated or treated with a silanizing agent) to treat the coatings applied by thermal spray processes.
In one embodiment, the silanizing agents are compounds of formula (I) and embodiments thereof describe above.
In another embodiment, the silanizing reagent is selected from tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane (SIH5840.5); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane (SIH5841.7); n-octadecyltrimethoxysilane (SI06645.0); n-octyltriethoxysilane (SI06715.0); and nonafluorohexyldimethyl(dimethylamino)silane (SIN6597.4).
In another embodiment, the silanizing reagent may be selected from dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane.
In another embodiment the silanizing agent comprises (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0).
In another embodiment, the second particles applied to thermal spray coated surfaces are treated with one or more agents that provide HP/OP properties. In an embodiment, the agents are selected from compositions comprising one or more silanizing agents of formula I. In other embodiments, the agents are compositions comprising one or more of tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane (SIH5840.5); (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane (SIH5841.7); n-octadecyltrimethoxysilane (SI06645.0); n-octyltriethoxysilane (SI06715.0); and nonafluorohexyldimethyl(dimethylamino)silane (SIN6597.4). In an embodiment, the second particles applied in step (b) are treated with hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In another embodiment, the second particles applied in step (b) are comprised of silica and treated with one or more of hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In some embodiments the silane is tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane which may also be used to treat second particles, such as silica particles, and any metal oxides formed in the thermal spray process.
Prior to the application of silanizing agents it is possible to modify the coatings applied by thermal spray processes using a composition comprising a silicon containing reagent that increases the number of sites on silica particles or other components of thermal spray coatings that can react with silanizing agents. In one embodiment silicon containing reagents that increases the number of sites on silica particles comprise one or more of: SiCl4, SiCl4, Si(OMe)4, Si(OEt)4, SiCl3CH3, SiCl3CH2SiCl3, SiCl3CH2CH2SiCl3, Si(OMe)3CH2Si(OMe)3, Si(OMe)3CH2CH2 Si(OMe)3, Si(OEt)3CH2Si(OEt)3, or Si(OEt)3CH2CH2 Si(OEt)3. The number of sites on silica particles or other components of thermal spray coatings that can react with silanizing agents can also be increased by other treatments including, but not limited to: etching the surfaces with acids such as HF, HCl, H2SO4 and by electropolishing.
Following application of either or both of a silanizing agent or second particles, the coatings are cured. Curing may be accomplished at room temperature (about 18 to about 22° C.) for 24 hours; however, it may be desirable to use elevated temperatures and/or to adjust the curing time depending on the silane or second particles employed.
Thermal deposition process for applying a coating may be applied to a variety of substrates. Such substrates include, but are not limited to, metals, metalloids, ceramics, and glasses. In some embodiments the surfaces will be in the form of metal plates, metal sheets or metal ribbons.
Depending on the coating composition employed and the application process, deposits formed will have different thicknesses and widths. The material deposited by thermal spray deposition, which consist of flattened splatters or lamellae, are formed by flattening of the liquid droplets and can have a wide range of dimensions. Individual lamellae often have thickness in the range from a 1 or 2 microns to 40, 60, 80 or even 100 microns. The same lamellae may have widths that range from a 10 microns to 1,000 microns or more.
The performance of coatings described herein may be measured by any of a variety of means, which are relevant to a coating's ability to perform under a variety of circumstances.
The coatings described herein provide high levels of hydrophobicity, easily reaching into the range of superhydrophobicity as assessed by the contact angle of water with the surface. In addition, the coatings also display oleophobicity, which is most pronounced when fluoroalkly moieties (groups) are employed to introduce hydrophobicity into the coatings.
Coatings described herein have the ability to resist the loss of hydrophobicity when challenged in a mechanical abrasion test. The mechanical durability of the coatings described herein may be assessed in either manual or automated tests (e.g., Taber Abraser testing). Overall, the coatings offer high resistance to the loss of HP/OP properties in manual tests and in tests on a Taber apparatus, with two step application processes using polymeric binder systems out performing one-step processes. Two-step coatings are capable of withstanding more that 5,000 cycles in manual abrasion tests, as compared to several hundred for one-step process and thermal spray processes. Polyurethane compositions with glass second particles (e.g., POLANE binders with glass spheres used as base coat, with a top coating of silica gel(silica nano tubes) treated with SiCl4 and silanized with SIT 8174.0) offer some of the highest resistance to mechanical abrasion-induced loss of HP/OP properties. Mechanical abrasion tests show that such coatings can withstand more than 700 cycles of Taber abrasion testing.
The coating compositions described herein are compatible with a wide variety of surfaces. Moreover, the diversity of the binder systems (e.g., thermal spray, polymeric binders, thermoplastic binders) offers a wide range of properties in addition to hydrophobicity that may be advantageously employed. For example, coatings such a fluoropolymers not only show high resistance to the loss of HP/OP properties in mechanical abrasion tests, but those coating compositions tend to be UV resistant due the stability of the fluoropolymers employed.
The coatings described herein are also stable to environmental conditions including low temperatures, wetting, salt resistance, ice formation and the like, indicating they can be employed, in a variety of harsh environments for purposes such as the prevention of ice formation and accumulation.
In addition to the other forms of compatibility the coating described herein are flexible, which permits coating materials such as cables (e.g., high voltage electric transmission lines), and flexible tapes that can be used in a variety of applications, including rapidly forming spill-resistant barriers on a diversity of surfaces. The coatings are resistant to separation from their substrates even upon repeated heating and cooling or on exposure to liquid nitrogen. Moreover, the coatings also display a significant ability to remain attached to surfaces even when they are bent at temperatures well below freezing (0° C.).
The combination of the durable hydrophobicity, stability under a variety of conditions including exposure to salt water solution, good surface adherence and flexibility, and the ability to reduce drag, demonstrates the suitability of the coatings for high performance coatings on boat hulls. Water droplet contact angle hysteresis measurements suggest the coatings maintain a significant air fraction associated with their surfaces when submerged, which lead to the reduction in drag.
Water droplet hysteresis data, along with the air bubble observed on surfaces subject to drag measurements, typically 0.1-0.3 mm in size, suggest the use of bubbler systems to maintain the surface air associated with the coatings to obtain the maximum drag reduction by the coatings, particularly when applied to boat hulls.
The HP/OP properties of the coatings described herein give rise to numerous diverse applications for the coatings, some of which are set forth in the exemplary applications recited below. Applications in addition to those set forth below will be immediately apparent, and as such, the exemplary applications of the coatings are in no way intended to be limiting on the scope of the uses envisioned for the coatings.
The HP/OP properties of the coatings, and particularly their ability to resist the formation and/or adherence of ice to surfaces, gives rise to a variety of uses including, but not limited to:
The HO/OP properties of the coatings described herein, which resist the wetting of surfaces to which they are applied, can be used to reduce the friction at the water/substrate interface. The use of the coatings described herein to reduce of friction at the water/substrate interface has a variety of uses including, but not limited to:
The HO/OP properties of the coatings described herein, which resist the wetting of surfaces to which they are applied, can be used to reduce the corrosion of materials, particularly metals. The use of the coatings described herein in corrosion reduction has a variety of uses, including but not limited to:
Due to the HO/OP properties of the coatings described herein, the coatings may be used to prevent water penetration into the wood, which causes swelling that can be exaggerated under subzero conditions, warping, exfoliation, which can lead to rotting. The use of the coatings described herein in corrosion reduction finds a variety of uses, including but not limited to, wood and particle board resistant to the damaging effects of water.
Other uses of the HO/OP coatings described herein include a variety of applications, that include, but are not limited to:
8.1 Spill Resistant Borders
A spill-resistant border is a portion of a surface forming a perimeter around an area of a surface that has a lower hydrophobicity and/or lower oleophobicity than the border. Spill-resistant borders can prevent water and other liquids from spreading or flowing beyond the position of a border on a planar or substantially planar surface that is placed in a substantially level horizontal position (see
The HP/OP coatings described herein may be used to prepare spill resistant borders either by directly applying an HP/OP coating to a portion of a surface (with or without the use of a mask) or by applying a tape or ribbon to the surface where one surface of the tape or ribbon is treated with an HP/OP coating.
Where the surface, or a portion of the surface, is substantially planar, the spill-resistant border may be placed at or near the edges of the planar surface or near the edge of the portion that is substantially planar, such that the spill-resistant border surrounds a region of the surface that has a lower hydrophobicity or lower oleophobicity than the spill-resistant border. Alternatively, the border may be placed so as to form a boundary encompassing one or more portions of the surface that have a lower hydrophobicity or oleophobicity than the border. Thus, borders may, in some cases, be placed at the edges of (e.g., at or near the edges of the treated surface) or form one or more barriers separating regions of a surface that have lower hydrophobicity than the borders or bathers.
One embodiment provides surfaces comprising a hydrophobic and/or oleophobic spill-resistant border, wherein the border forms a perimeter around at least one area of the surface that has a lower hydrophobicity and/or lower oleophobicity than the border. In another embodiment, the surface may comprise a hydrophobic and/or oleophobic spill-resistant border, wherein said border forms a perimeter around at least two, or at least three, or at least four, areas of the surface that have a lower hydrophobicity and/or lower oleophobicity than the border.
In some embodiments a border may be placed at the edge of a surface, in which case it may be referred to as an “edge.” In other embodiments a border may be placed near an edge of a surface, such as in the form of a strip parallel or substantially parallel to one or more edges of a surface. In some embodiments a border may be placed on a surface at a position that is not the edge such that the border forms a perimeter around one or more areas that are have a lower hydrophobicity and/or lower oleophobicity than the border.
Where a border is not placed at the edge it may be termed a “barrier.” Barriers may divide a surface into several regions that have a lower hydrophobicity and/or lower oleophobicity than the border. Each area having a barrier as a perimeter will separately prevent the spreading of liquid between different areas of the surface. The regions separated by barriers may be in variety of forms. For example, the regions may be in the form of a series of concentric circles or a series of regular quadrilaterals (e.g., squares or rectangles, hexagons, or triangles). Barriers may retain liquids at the same height as a spill-resistant border placed at an edge or optionally may have a lesser ability to retain liquids than the border at the edge.
In some embodiments a border in the form of an edge, or a border located at or near the edge of the surface, may be employed with borders in the form of barriers. In such an embodiment the surface will not only prevent the spread of liquids between regions separated by barriers, but also may prevent or stop liquids from flowing off the surface by blocking passage of the liquid over the border at the edge. Where the barriers have a lesser ability to retain liquids than the border, aspill that overwhelms a barrier will spread to the next area before overflowing the edge. Some examples of spill-resistant borders, including those with edges and barriers, and combinations thereof, may be seen in
Spill-resistant borders (including borders in the form of edges and barriers), regardless of the pattern in which they are formed, are substantially 2-dimensional structures. The width of the HP/OP regions of a surface forming spill-resistant borders can vary depending on the specific application in which the borders are intended to be used. In some embodiments, the borders may be from about 0.2 to about 2 inches in width, or alternatively, about 0.2, 0.25, 0.3, 0.4. 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3 1.4, 1.5, 1.75 or 2.0 inches (about 5 mm to 50 mm) in width. In one embodiment, where the borders are intended for use on food preparation or storage surfaces, (e.g., cutting boards, glass shelving for refrigerators, or countertops) the borders in the range of 0.2 to 2.0 inches. In other embodiments, such as where the spill-resistant borders are intended for use on food preparation or storage surfaces, the borders can be about 0.4 to 1 inch wide, or alternatively, about, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, or 1.0 inches wide. Border width does not have to be uniform, and where borders on a surface comprise an edge and barriers, the edge and barriers may be of different widths or even varying widths on the same surface.
Where a combination of a border, such as a border in the form of an edge, and a barrier are used, the hydrophobicity of the barrier and edge may be controlled such that liquids will be prevented from spreading between different areas of the surface, but the highest resistance to liquid spreading (the highest height of liquid retained) will be at the edge. Thus, in the case of a spill that overflows an area surrounded by a barrier, the spill would flow to an adjacent area, rather than over the edge.
Spill-resistant borders and barriers may be used to direct liquid toward one or more drains in a surface and can be arranged to channel spilled liquids toward a drain (see e.g.,
In an embodiment, a spill resistant border can be formed on a surface that has a contact angle with water at room temperature that is less than about 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 100, 110, or 120 degrees, and where the border has a contact angle with water at room temperature that is greater than the contact angle of water with the surface on which it is formed by about 7, 8, 9, 10, 20, 30, 40, 50, or 60 degrees measured at room temperature (about 68°-72° F.).
Spill-resistant borders, may be employed for a variety of purposes, including, but not limited to, glass shelving for refrigerators, or countertops, laboratory work benches, or cutting boards.
The tapes and ribbons (and sheet) described above may be made from a variety of materials including, but not limited to, metal (e.g., aluminum), plastic, paper, fiber glass and the like. Such tapes and ribbons may be employed for variety of other purposes than preparing spill resistant borders, including but not limited to, their use as anti-icing tapes, and to provide corrosion resistance.
Three 4-inch×4-inch aluminum plates (0.062-in.thick) are cleaned with acetone. Each plate is spray-coated with a base coat (2 ml) of one of the following binders: Self-Etching Primer (a lacquer based primer from Eastwood Co., Pottstown, Pa.); POLANE® B (a polyurethane based binder from Sherwin Williams, Harrisburg, Pa.) or LUMIFLON® (a solvent soluble fluoropolymer from Asahi Glass Co., Exton, Pa.).
Following application of the binder base coat, and before the base coat dries, each of the plates was top-coated with CAB-O-SIL TS-720 (Cabot Corp., Billerica, Mass.) fumed silica second particles (e.g., second particles) having a nominal BET surface area of 200 m2/g treated with polydimethylsiloxane. The plate coated with Self-Etching Primer was top coated with 2 ml of a TS-720 suspension (4.2 g TS-720 per 100 ml of ethanol). Plates coated with POLANE® B or LUMIFLON® are top coated with 2 ml of TS-720 suspension (4 g per 100 ml of hexane). Plates coated with Self-Etching Primer are cured for 30 min, at 200° F., and plates coated with the other two binders are cured for 1.5 h at 200° F. in an electric oven.
Coatings are assessed for their hydrophobicity (contact angel with water), submerged water durability, mechanical durability and chemical durability.
The hydrophobicity of the coatings is assessed by measuring the contact angle of water with the coating. Measurements are made using a T200 Theta Optical Tensiometer on newly prepared coatings and after durability testing using a Taber unit (see below).
Mechanical durability can be assessed by a variety of methods, including manual abrasion with preset weights or on commercial apparatus such as those available from Taber Industries (North Tonawanda, N.Y.).
For the purpose of this disclosure manual abrasion testing (hand rub method) is conducted using a cylindrical 800-g weight with a flat bottom (about 1.75 pounds) having a base diameter of about 4.45 cm (1.75 inches) covered with a 50:50 cotton/polyester fabric. Testing is conducted by moving the weight with a reciprocating motion (1 rub or abrasion cycle is equivalent to 1 pass of the weight across the surface). The roll-off angle for water is checked at incline angles of 3°, 6°, and/or 9° by placing 20 water droplets on the portion of the surface (e.g., the portion subjected to manual abrasion testing). The end of life of the coating determined by manual abrasion testing is considered the point when most (more than 10) of the 20 droplets do not roll off the surface at the indicated degree of incline.
Abrasion testing is also conducted using a Taber Rotary Platform Abraser (Abrader), which employs two “wheels” to abrade a surface under 250-gm loads or 500-gm loads on each wheel. Each cycle counted by the instrument is equivalent to two rubs, one each from each of the wheels. The end of life for coatings subjected to Taber testing is measured using run-off angle as described for manual abrasion.
Results for the analysis of three different coatings are summarized in Table 1. In addition to the measurements describe above, plates are also assessed for their loss of coatings by directly measuring their change in weight following assessment.
bAfter Taber testing with 250 g load using 9° roll-off to determine end of life.
Data from the analysis of the three coatings indicates that as prepared each coating has superhydrophobic properties (the water contact angle exceeds 150°). The lacquer based Self-Etching Primer as a binder produced slight more durable coatings than either the polyurethane or fluoropolymer binder in manual abrasion testing at 3, 6 and 9° inclines. In contrast, abrasion analysis using the Taber instrument indicates that fluoropolymer binders give slightly more durable coatings
Aluminum plates (4-inch×4-inch 0.062-in.thick) are cleaned with acetone and are coated in a two step process comprising applying a base coat followed by application of a top-coat (second coat). Each plate is spray-coated with a base coat (2 ml) of one Self-Etching Primer (SEP) (Eastwood Co., Pottstown, Pa.) containing the indicated amount of the first particles listed below. After drying in air, this base coat is top-coated with 2 ml of TS-720 treated with polydimethylsiloxane suspended in ethanol (4.2 g/100 ml). After drying in air, the coated plates are dried in air and cured at 200° F. for 30 minutes (“min”) in an electric oven. Manual abrasion testing is conducted as described in Example 1. Data from the plates is shown in Tables 2a-2f.
The filler 512 black, (Xiom Corp., West Babylon, N.Y.) a thermoplastic powder is added to SEP at 0% to 40% weight to volume. The mixture was sprayed on as the base coat and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2a.
The filler Nulok 390 (Kamin LLC, Macon, Ga.) is added to SEP at 0% to 40% weight to volume. The mixture was sprayed on as the base coat and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2b. The maximum abrasion cycles tolerated with a 17% addition of Nulok 390 were about four times the number of cycle achieved in the absence of that filler.
First particles in the XT family (XT-600, XT-700, XT-750, and XT-765) (Xiom Corp, West Babylon, N.Y.) are added at 30% or 35% weight to volume. The mixture was sprayed on as the base coat and top coated with TS-720 as described above. Manual abrasion data is shown in Table 2c. The maximum number of abrasion cycles tolerated with additions of XT first particles to SEP are about five times that achieved without any filler addition.
The filler 200 White, (Xiom Corp, West Babylon, N.Y.), a thermoplastic bond coat powder of 10-100 microns mean diameter, is added to SEP as a filler at 15% or 30% weight to volume. The mixture was sprayed on as the base coat and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2d. The maximum number of abrasion cycles tolerated with additions of 200 White filler to SEP is about four times that achieved without any filler addition.
It can be stated from the thermoplastic filler study that all of them resulted in a positive effect and improvement varied somewhat, which is obviously dependent on filler size and to some extent on filler chemistry.
Wood powder of the indicated size is added to SEP at 10% or 15% weight to volume. The mixture is sprayed on as the base coat and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2e. The maximum abrasion cycles tolerated by coatings with 15% of 53 micron wood dust is over 4 times that of the coating in the absence of filler.
Aluminum powder of the indicated size (100 or 325 mesh) or (149 or 44 microns respectively) is added to SEP at 30% or 40% weight to volume. The mixture is applied as the base coat by spraying and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2f. The maximum abrasion cycles tolerated by coatings with the addition of 100 mesh aluminum filler is over three times that number of abrasion cycles tolerated by the coatings in the absence of any filler.
MULLITE, which is a spinal oxide of Al2O2 and SiO2 (powder −325 mesh or 44 microns mean diameter,) is added to SEP at 10% to 40% weight to volume. The mixture is sprayed on as the base coat and top coated with TS-720 treated with polydimethylsiloxane as described above. Manual abrasion data is shown in Table 2g. The maximum abrasion cycles tolerated by coatings with the addition of MULLITE is about three and a half times the number of abrasion cycles tolerated by the coatings in the absence of any filler.
Aluminum plates (4-inch×4-inch×0.062-in.thick) are cleaned with acetone are coated in a two step process comprising applying a base coat (2 ml) of Self-Etching Primer (SEP, Eastwood Co., Pottstown, Pa.) containing 30% weight to volume of Filler 512 White (the counter part of the 512 black filler used in Example 2). After drying in air, this base coat is top-coated with (2, 3, 4, 5 or 6 ml) of TS-720 treated with polydimethylsiloxane suspended in ethanol (4.2 g/100 ml) or suspended in hexane at 4.2 g/100 ml. After drying in air, the coated plates are dried in air and cured at 200° F. for 30 min in an electric oven. Manual abrasion testing is conducted as described in Example 1. Data from the plates is shown in Table 3.
This table clearly demonstrates that with 30% 512 filler, the rub resistance can be increased to over 500 rubs with the top layer consisting of 5 ml/plate. Ethanol and hexane are equally effective in preparing the top coat of TS-720.
aAll plates were cured at 200° F. for 30 min.
The data table demonstrates that with 30% 512 filler, it is possible to reach 500 abrasion cycles in the manual test with a top coat of 5 ml/plate of TS-720 treated with polydimethylsiloxane (about 2 mg of polydimethylsiloxane treated TS-720 per cm2 of surface).
Triplicate aluminum plates (4-inch×4-inch×0.062-in.thick) are cleaned and coated in a two step process comprising applying a base coat (2 ml) of POLANE® containing 20% weight to volume of: S60 glass bubbles (3M™, St. Paul, Minn.); Filler 512 Black (Xiom Corp, West Babylon, N.Y.), or Corvel Black (Rohm & Haas, Philadelphia, Pa.). After drying in air, this base coat is top-coated with 5 ml of polydimethylsiloxane treated TS-720 suspended in hexane at 4.2 g/100 ml. After drying in air, the coated plates are dried in air and cured at 200° F. for 90 min in an electric oven. Manual abrasion testing is conducted as described in Example 1. Data from the plates is shown in Table 4.
Aluminum plates (4-inch×4-inch×0.062-in.thick) are cleaned and a base coat (5 ml) of POLANE® B containing 20% weight to volume of Filler 512 Black (Xiom Corp, West Babylon, N.Y.) is applied to each plate in preparation for top coating. Top coatings of a second particle selected from (1) polydimethylsiloxane treated TS-720, (2) untreated M-5 fumed silica, or (3) hexamethyldisiloxane treated Nanogel TLD201 (Cabot Corp, Billerica, Mass.) are applied immediately after the base coating (e.g., after the bulk of solvent had evaporated).
Top coats of polydimethylsiloxane treated TS-720 (5 ml of 4.2% w/v) are applied in ethanol.
Top coats of M5 are applied by spraying 10-15 ml a 1.5% M-5 (w/v) suspension in hexane.
Top coats of Nanogel TLD201 are applied by spraying 10-15 ml of a 1.5% or 2% TLD201 suspension in hexane as indicated in the data.
In all cases, the plates were cured at 200° F. for 90 min in an electric oven. For the top coat of TS-720 the plates are ready for testing after a 90-min curing. Plates treated with For M-5 coated plates, are treated by one of two methods (method (A) or (B)) to produce superhydrophobic behavior.
In some instances Nanogel TLD201 treated plates are also treated with SIT8174 or SiCl4+SIT8174 using Method (A) or Method (B) as described above for M-5 coated plates and the amounts of the Nanogel and SIT8174 indicated in Table 5.
Data for manual abrasion testing of plates bearing the coatings from each treatment is given in Table 5 along with a control comparison. The rub data on all of the samples discussed above are summarized in Table 15.
Aluminum plates (4-inch×4-inch×0.062-in.thick) are cleaned and a base coat (3-5 ml) of POLANE® B containing 20% weight to volume of the indicted filler. Top coatings of second particles of polydimethylsiloxane treated TS-720 or untreated M-5 fumed silica (Cabot Corp, Billerica, Mass.) are applied after the base coating in the indicted solvents. Plates were dried and cured at 200° F. Where indicted, coatings were treated with Gelest silane SIT8174 or SiCl4 followed by treatment with SIT8174 using methods A or B described in Example 5. Table 6a sows the data with S60 filler (3M™, St. Paul, Minn.) and Table 6b for Corvel Black.
Plates coated with SIT8174 are both superhydrophobic and oleophobic, and perform show increased durability when pretreated with SiCl4.
Two 4 inch×4 inch aluminum plates with coatings having superhydrophobic and oleophobic behavior are prepared by the procedures in Examples 5 and 6.
After curing, both plates are checked for superhydrophobic performance and then placed in a boiling water bath. The water contact angle of the coatings is checked at periodically after removing the plates from the bath and cooling to room temperature. The plates are returned to the boiling water bath after each measurement. After hours in boiling water both plates are found to show superhydrophobic performance. A final measurement on the plates shows that they also show oleophobic behavior as well.
Aluminum plates measuring 4 Inches by 4 inches are coated with POLANE® B containing 20% 512 Black as filler. These plates are top-coated with untreated fumed M5 silica (Cabot Corp., Billerica, Mass.) suspended in hexane at 0.5, 1.0, 1.5, or 2% weight/volume. At higher percentages of M5 dispersed in hexane it becomes difficult to spray the mixture. The amount of each M5 suspension applied as top coat was also monitored by the volume applied to plate (ml/plate). The amounts applied are varied in increments of 5 ml/plate from 5 to 20 ml/plate. After the top coat is applied, the plates are cured for 90 min at 200° F. Following curing, half of the plates are treated with silane SIT8174 and the other half with SiCl4, followed by SIT8174, thereby converting the untreated M5 silica into hydrophobic/superhydrophobic and/or oleophobic particles. Following treatment with SIT8174 or SiCl4+SIT8174 plates are cured for 30-60 min at 200° F. and subjected to assessment of water contact angle and Taber testing. Taber testing is conducted with a 250 g weight on the wheels. The end of superhydrophobic behavior was measured at roll-off angles of 6° and 9° as shown in Table 8a.
The contact angle data for before and after Taber testing is shown in Table 8b. Data for 6° water roll-off angle tests (see Example 1) after the indicated number of abrasion cycles on the Taber Abraser is plotted in
Initial water contact angle and Tabor Abraser durability measurements are conducted on 4 inch×4 inch aluminum plates base coated with POLANE® B and top coated with M5 silica suspended at a concentrations of 0.5 or 2% w/v. After curing the plates are treated with either SIT8174 or SiCl4+SIT8174 (SIT8174 10% solution in hexane and SiCl4 1% solution in hexane using 1 to 2 ml per 4×4 plate) as described above in Example 8a. Contact angle data for the plates with water droplets before Taber testing (250 g load) is plotted in
Coatings displaying superhydrophobic and oleophobic behavior can applied to surfaces in a single step process. Such processes may employ a binder to which second particles bearing an alkyl or haloalkyl group (covalently attached directly or indirectly, such as through a Si atom or a series of bonds through oxygen and silicon atoms) are added to the binder in the presence of about 5% of a block copolymer described below and an optional first particle (e.g., filler). Such compositions typically require thinning with a binder compatible solvent for spray application.
For this example, a block copolymer is prepared by reacting 3.13 g styrene, 1.92 g butyl acrylate, 12.32 g butyl methacrylate, 4.25 g glycidyl methacrylate, and 100 ml toluene in a reaction flask with stirring at 85° C. A solution of 0.2 g AIBN in 2.5 ml toluene is added into the flask and mixture is maintained at 85° C. for 3 hours. A second amount of AIBN in toluene is added and the reaction is continued for anther 3 hours. The reaction mixture is cooled at room temperature and the resulting acrylic polymer is precipitated with hexane, filtered, and dried under vacuum at 40° C. for 24 hr prior to use.
Specific details of exemplary durable superhydrophobic/oleophobic coatings prepared on 4 inch by 4 inch aluminum plates employing a one-step process using the components given in Table 9a-1. Two plates employ fumed silica second particles (TS-720) treated with polydimethylsiloxane, two employ Nanogel TLD201, which is treated with hexamethyldisiloxane, and two employ Nanogel TLD201 and S60 glass particles as a filler. All plates are cured at 200 F for 90-120 min after air drying.
aAll plates were cured for 90-120 min at 200° F. in an electric oven.
All plates are tested for their durability and water contact angle. The durability is tested with the manual abrasion method (see Example 1) and also with a Taber machine employing a 250-g load. Data are summarized in Table 9a-2.
The durability data were taken for three roll-off angles of 3°, 6°, and 9°. The contact angle was measured before and after durability assessment with a Taber “Abraser”. The contact angle before abrasion testing for all six plates is between 161°-163°, implying that all of them are superhydrophobic as the contact angle with water exceeds 150° at room temperature. The coatings substantially retained their water repellant nature after abrasion, which was measured in two areas of the plates (left and right) before and after Taber abrasion testing.
Coatings displaying superhydrophobic and oleophobic behavior are prepared with a urethane binder (POLANE® B) to which are added the indicated second particles and a filler a described below. The compositions are thinned as required with a binder compatible solvent for spray applications.
HK400T nanaoparticles (second particles) are prepared by treating ACEMATT® HK400 nanopaticles (Evonick Industries, distributed by The Cary Co., Addison, Ill.) with Gelest silanizing agent SIT8174.0 (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane. The particles (50-g) are prepared by stirring with a 400-ml of a 1% w/v solution in hexane for 6 hours. Hexane is allowed to evaporate away and residual hexane is removed by heating the mixture to 200° F. for 6 hours.
HK400T particles may also be prepared by pre-treating a 50 g sample of HK400 particles with 2 grams of Gelest silanizing agent SIT8174.0 (tridecafluoro-1,1,2,3-tetrahydrooctyl)trichlorosilane by blending the materials together in a mixer for 30 seconds. An additional 2 grams of the silanizing agent is added to the mixture and it is blended for 45 seconds further. The treated powder was placed in a PYREX® dish and dried at 200° F. for 12 hours.
Particles of TLD201 Nanogel, which are treated with hexamethyldisiloxane are used as purchased from Cabot Corp., Billerica, Mass.
First particles are selected from 512 Black (Size microns, Xiom Corp., West Babylon, N.Y.) and S60 glass bubbles (15-65 microns, 3M Corporation). For this Example, S60 glass bubbles are prepared by treating a 50-g batch of the glass bubbles with 1.25 ml of SIT8174.0 in 50 ml of solvent. The mixture is blended for about 1 to 2 hours followed by a baking for 3 hours at 200° F.
The details of the preparation of six 4 inch by 4 inch aluminum plates coated with a one-step process are set forth below (coatings 9b-1 to 9b-6). For each coating, the coated plates are tested for contact angle and coating durability using both the manual abrasion method (see “hand rubs” see Example 1) and on the Taber Abraser unit with a 250-g load. Roll off angle data is obtained for both the manual abrasion and Taber sample testing at a 6° angle. Data for coatings 1-6 are summarized in Table 9b.
Coating 9b-1—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (5 ml), HK400T second particles treated with SIT8174.0 (2 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A and POLANE® reducer (6:1:5) is mixed thoroughly and the HK400T is mixed into the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
Coating 9b-2—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (8 ml), HK400T second particles treated with SIT8174.0 (1 g) and TLD201 second particles (0.75 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A and POLANE® reducer (6:1:8), is mixed thoroughly and the HK400T and TLD201 are subsequently added to the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
Coating 9b-3—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (3 ml), HK400T second particles treated with SIT8174.0 (1 g) and 512 Black filler (1 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A and POLANE® reducer (6:1:3), is mixed thoroughly and the HK400T and 512 Black filler are subsequently added to the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
Coating 9b-4—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (3 ml), HK400T second particles treated with SIT8174.0 (1.35 g) and S60 glass bubbles as a filler (1.35 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A and POLANE® reducer (6:1:3), is mixed thoroughly and the HK400T and S60 filler are subsequently added to the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
Coating 9b-5—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (3 ml), HK400T second particles treated with SIT8174.0 (1 g) and S60 glass bubbles as a filler (1 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A and POLANE® reducer (6:1:3), is mixed thoroughly and the HK400T and S60 filler are subsequently added to the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
Coating 9b-6—A mixture of POLANE® B (6 ml), POLANE® A (1 ml), POLANE® Reducer (2 to 3 ml), POLANE® Accelerator (3 ml), HK400T second particles treated with SIT8174.0 (1.25 g) and S60 glass bubbles as a filler (0.7 g) is prepared. For preparation of the mixture POLANE® B, POLANE® A, POLANE® reducer and POLANE® Accelerator, is mixed thoroughly and the HK400T and S60 filler are subsequently added to the mixture. After the coating composition is mixed thoroughly, two aluminum plates are each sprayed with about 3.5 ml of the mixture and immediately cured at 200° F. for 2 hours.
A set of 4 inch×4 inch aluminum plates are prepared by coating with a base coat comprising a mixture of POLANE® A and POLANE® B (1:6) containing the indicated amounts of either S60 glass beads (3M™, St. Paul, Minn.) or XIOM-512 black (Xiom Corp, West Babylon, N.Y.) filler (from 10% to 60% w/w). After the base coat applied to the plates had air dried, they were top coated with 10 ml per plate of untreated M5 fumed silica (particle size, Cabot Corp., Billerica, Mass.) as a 2% w/v suspension in hexane. The top coated palates are dried for 90 min at 93° C. After cooling, the plates are first treated with 1-2 ml of 10% SiCl4 in hexane, and after the hexane has evaporated with 1-2 ml of the silanizing agent SIT 8174.0 (1% in hexane). All coating applications were made using an air spray gun. After all visible hexane evaporates, the plates are given a final thermal curing at 93° C. for 2-8 hours.
After the final thermal cure samples are tested for durability by using a Taber Abraser with a 250 g load. All samples are also tested to for end-of-life by determining the roll-off angle with a plate set a 6° incline at 25 abrasion cycle increments. End-of-life is determined by the propensity of more than half of a set of water drops (typically 20 drops per test set) to stick to the area subject to abrasion testing when the plate is set at a 6° degree angle from level.
Data for coatings prepared with S60 filler is summarized in Tables 10a and 10b. Table 10a gives the coating compositions leading to a S60 content from 10 to 60%. Table 10b sets forth the weight change as a measure of abrasion resistance obtained after the indicated number of abrasion cycles on a Taber Abraser apparatus. Data for coatings prepared with 512 Black filler is summarized in Tables 10c and 10d. Table 10c gives the coating compositions leading to a 512 Black content from 10 to 60%. Table 10d sets forth the weight change as a measure of abrasion resistance obtained after the indicated number of abrasion cycles on a Taber Abraser apparatus.
Aluminum plates, 4 inches by 4-inches are used as test objects for assessment of powder coating binder systems. Table 11a summarizes some results obtained from the use of two powder coatings as binders for the preparation of HP/OP coatings and surfaces; GLSS70, a clear powder from Innotek Powder Coatings LLC (Big Spring, Tex.) and Tiger 39/80170 Black wrinkle powder (TIGER Drylac U.S.A., Reading, Pa.).
In each case, dry powders are sprayed on the aluminum plates as a base coat, followed by heating until the powder coatings begin to melt (details of the application are given in Table 11a). At the melt point, a top coat comprising fumed silica treated with polydimethylsiloxane (TS-720 CAB-O-SIL TS-720, Cabot Corp., Billerica, Mass. as a 4.2% or 2.1% suspension in acetone is applied to the base coat by spraying. The top-coated plates are heated to 400° F. (about 200° C.) for 10 min Plates treated with Innotek powder coating resulted in superhydrophobic behavior and achieved about 325 cycles (rubs) in the manual abrasion test conducted as in Example 1. Manual abrasion testing of sample 3, which was prepared with a top coating that contained 5% TS-720 and 20% of the Innotek base coat powder by weight, resulted in similar abrasion behavior (resistance to 325 abrasion cycles in the manual test). Tiger Black wrinkle powder also produced superhydrophobic coatings with lower abrasion resistance the manual abrasion test described in Example 1 (about 50 abrasion cycles). Overall, the highest durability based on this data arises when surfaces are heated to just above the powder coat melting point prior to applying the base and top coats, and curing of the top coat at a temperature near the melting point of the powder coat for about 2-3 min.
Table 11b summarizes further results with powder coatings. Again, aluminum plates, 4 inches by 4-inches are used as test objects for assessment of powder coating binder systems employing white Innotek powder coat G17SG101S70, (Innotek Powder Coatings LLC, Big Spring, Tex.). Plates are coated with G17SG101S70 applied to a cold plate, which is heated 10 min at the indicated temperatures, followed by a top coating with suspension of 4.2% TS-720 (fumed silica treated with polydimethylsiloxane) in the indicated solvent, and a final cure of at about 400° F. (see table). Manual abrasion testing conducted as in Example 1 indicated that some samples could resist over 900 abrasion cycles. When heating and cooling cycles are used prior to top coat application, some variation in the abrasion resistance can arise due to the extent of cooling the surfaces have experienced at the time of the top coat application (see e.g., samples 8 and 9).
Results of testing 90-1009R-H under similar conditions indicated that while superhydrophobic and oleophobic surfaces can be formed with that the material did not perform as well in abrasion testing. (data not shown)
Aluminum plates, 4 inches by 4-inches, are coated with Innotek G17SG101S70 containing the indicated first particles as a base coating. The first particles employed are selected from (1) extend spheres SL-150 (3M™, St. Paul, Minn.), (2) S60 HS glass bubbles (3M™, St. Paul, Minn.), (3) R&H 90-1009 Kynar plastic (Rohm & Haas, Philadelphia, Pa.), and (4) S/G extendo spheres (3M™, St. Paul, Minn.). The base coat was heated to 200-210° F., prior to applying a top coat of 4.2% TS-720 (fumed silica treated with polydimethylsiloxane) suspended in hexane. Plates bearing the topcoat are given a final cure at 400° F. for 6 min
Table 12b: The Preparation and Performance of G17SG101S70 Powder Coating as a Binder
Aluminum plates, 4 inches by 4-inches, preheated to 210° F. are coated with a base coat of Innotek G17SG101S70 containing SL-150 extendo spheres, 25% weight to volume at the indicated coverage rates (weight after drying at 200-210° F.). After top coating with TS-720 as indicated the plates are cured at about 400° F. and subject to abrasion testing. All abrasion testing data are obtained using the manual abrasion test described in Example 1, see Table 12b.
Aluminum or carbon steel plates 6 inches×6 inches×0.25 inches are sprayed with one of the materials recited in Table 13 using thermal (high-velocity oxyfuel (HVOF)) application processes. In all cases, excellent bonding of the sprayed materials to both aluminum and steel substrates is noted. The deposited surface was resistant to scratched, even when pressed with a sharp hardened metal objects (e.g., scissors). As deposited, coatings uniformly covered the surface giving rise to a sandpaper-like texture with the degree of coarseness depended on the size of the powder employed.
The surfaces prepared using the HVOF-spray process are treated by brushing on SIT8174 silane (Gelest, Inc., Pottstown, Pa.) as a 1% solution in hexane. Alternatively, the surfaces of some plates are sprayed with a suspension of polydimethylsiloxane treated fumed silica (TS-720, 4.2% w/v in hexane) as opposed to treatment with the silanizing agent SIT8174. Following application of the indicated silane or fumed silica, the plates are cured at room temperature for 24 h. After curing, all metal surfaces are found to be superhydrophobic, irrespective of the metallic or metal oxide coating applied. The surface treatment given to plates and the results from manual abrasion testing determined as in Example 1 are given in Table 13b.
The polymer coatings described herein may be applied by spraying, brushing or dipping objects to be coated. Using such methods polymer based coatings may be applied to both simple and complex shaped surfaces;
Coatings applied to simple and complex surfaces by spray-on processes include both one step and two step coatings. The coatings can be applied to surfaces for a variety of purposes including corrosion resistance and reduced resistance to water flow (drag). The SH coating can be applied to reduce water film formation and accumulation of condensation, even on surfaces with complex shapes such as steam turbine blades. The SH coatings can also be applied where high durability and corrosion resistance is desired, such as on slip resistant flooring in demanding environments
Coatings may also be applied by dipping object including electrical switches of the type used in food industry processing and packaging lines. Non-wetting SH coatings are particularly suitable for such facilities as they are typically cleaned by washing on a daily basis, and water seepage into switches can cause current leakages or shorts leading to unwanted production line shutdowns. The switches may be coated in a two step process with Self-Etching Primer or POLANE® as the binders.
Where dipping is not a suitable alternative, coatings may be applied by painting or brushing coatings on the surface. One example of an object that is suited to coating by brushing or painting of coatings is heat exchanger for clothes dryers. A coating of Self-Etching Primer with a top coat of 4% of TS-720 in ethanol is applied by a two step process and is anticipated to keep lint from accumulating on the heat exchanger.
Aluminum plates 4 inches by 4-inches are prepared and one is coated with a superhydrophobic coating of POLANE® B containing 20% S60 glass bead filler as base coat with 4% TS-720 in hexane as top coat applied in a two step process. Both plates are cooled to about −20° C. for 1 hour in a refrigerated enclosure. Water is cooled to until ice formation starts (0° C.). The cooled water is dropped on to the uncoated and coated plates so that it runs down the surface to determine if the cooled surfaces permit ice formation and adherence. Significant amounts of the cooled water freeze on to the uncoated aluminum plate. In contrast, water running down the surface of the plate coated with the superhydrophobic coating has little if any ice form on it. Moreover, the ice which does form on the coated plate is not tightly bound and readily comes loose, which contrast to the results observe with the uncoated aluminum plate.
16a) Individual segments (12-inches long) of 19 strand aluminum electrical transmission cables are spray coated using a two-step coating process. The first coat consisted of POLANE® A: POLANE B® (1:6 v/v) and POLANE® reducer as needed for ease of spraying) to which 20% w/v of 512 black thermoplastic filler is added. The top coat consisted of a 4% M5 (w/v) silica that is pretreated with Gelest Silane SIT8174.0 (Example 5, Method B) suspended in hexane. After coating, the cables were cured at 93° C. for 60 min in an electric oven.
The coated cable segments are all superhydrophobic with contact angles exceeding 150° (visual examination).
A segment of cables prepared in 16a is bent to 35° to simulated coiling operation. Bending to a 35° angle does not produce any delamination, cracking, chipping, or pealing of the coating, or degradation of superhydrophobic performance
A segment of the coated cable prepared in 16a is cooled in the freezer to about −29° C. (about −20° F.) for about 1.5 hours and then bent to an angle of 48°. Bending to that angle does not produce any flaking or delamination. Bend angles exceeding 35°, however, do tend to cause the individual strands of the cable to separate, and create openings large enough for water to enter the cable.
An unbent (straight) segment of the coated cable is subjected to a thermal cycling test. The cable is placed on a hot plate and the cable temperature is monitored by a non-contact temperature gun. When cable surface temperature reaches 170° C., it is removed from the hot plate and cooled to room temperature (about 18° to 23° C.) using an air gun. The same cycle is repeated 10 times with no loss of superhydrophobicity. Thermal cycling testing data is presented in Table 16.
Superhydrophobic, hydrophobic and/or oleophobic tapes, ribbons and sheets can be prepared using any flat, essentially two-dimensional material. In some embodiments the sheets can have an adhesive applied to one surface (see Example 17a) prior to applying the hydrophobic, superhydrophobic, or oleophobic coating, or can be coated with adhesive on the opposing surface after superhydrophobic, hydrophobic and/or oleophobic coating applications have been conducted (see Example 17b). The two dimensional materials can be in the form of sheets or narrow strips (e.g., adhesive strips that can be formed into rolls after their preparation or “tapes”) or even patterns, that can be made out of any suitably flexible material including, but not limited to, metals such as aluminum or tin, fiberglass, or plastic.
The materials are treated to increase the hydrophobicity/oleophobicity of at least a portion of one (or possibly both surfaces(and even the edges, which have nominal area).
Tapes and sheets (e.g., adhesive sheets) may be prepared from materials essentially two dimensional materials that are have an adhesive coating on one side (“pre-glued”). In some embodiments the pre-glued surface is covered with paper or other film that can be pealed away to expose the adhesive.
The surface(s) of the materials not bearing the adhesive are treated to increase the hydrophobicity and/or oleophobicity. In some embodiments hydrophobicity and/or oleophobiocity is increased using polymer coatings employing binders such as those described in Examples 2 through 12. In such process, tape surfaces are sprayed with polymeric binders including Self-Etching Primer, POLANE® B, LUMIFLON® using one-step or two step processes. Where two-step processes are employed, the top surface of the binder layer (base coat) is coated with either a treated fumed silica or silica nanogel (e.g., silicas such as TS-720 treated with agents that produce hydrophobic or oleophobic behavior). Where a fumed silica or silica nanogel is untreated with agents that provide hydrophobic or superhydrophobic properties, the fumed silica or silica nanogel can be treated with a reagent (e.g., silanizing agent such as SIT8174 from Gelest, Pottstown, Pa.) to increase the hydrophobicity and/or oleophobicity of the surface after silica application to the binder. The application of agents to increase the hydrophobicity and/or oleophobicity of untreated fumed silica or silica nanogels applied to the binder is typically conducted after 24 hours of room temperature curing of the binder/silica composite. The agents (e.g., silanizing agents such as SIT8174) may be applied by any suitable method including brushing or spraying as described above.
Where the polymer binder contains one or block copolymer polymers and particles of fumed silica or silica nanogel treated with agents that produce hydrophobic, superhydrophobic and/or oleophobic behavior (e.g., TS-720 or other silicas treated with silanizing agents bearing hydrophobic functionalities) the materials may be coated in a one-step process. In such a process the binder, block copolymer and treated silica(s) are mixed in and the entire blend is applied to the desired materials surface and cured under ambient (room temperature) conditions.
To speed the curing process the tapes, ribbons or sheets may be warmed to temperatures that do not affect the adhesive or binder (e.g., causing either the adhesive or binder to melt, flow to locations where it was not originally applied, or become brittle).
The surfaces of tapes, ribbons and sheets treated in the above-described manner will generally be hydrophobic if silanizing agents bearing alkyl functionalities are employed. The same surfaces will generally display superhydrophobic and oleophobic behavior where silanizing agents have fluorinated alkyl groups at the end furthest from the Si atom to which they are attached.
Ribbons and sheets of hydrophobic, superhydrophobic, and oleophobic materials may be prepared from essentially two dimensional materials that are have an have no adhesive coating on any side prior to the application of hydrophobic, superhydrophobic and/or oleophobic coatings (“non-glued” sheets and ribbons). Ribbons and sheets may be used with out the application of adhesives or may have adhesives applied subsequent to the applications of coatings (e.g., converting ribbons into tapes). The same processes may be used for making sheets and ribbons of materials hydrophobic, superhydrophobic and/or oleophobic that are employed for the preparation of pre-glued tapes and sheets described in Example 14a can be employed. When applied, adhesives can be applied by any known means, including spraying, brushing or rolling the materials on surfaces. Surfaces having adhesives applied may be protected by the application of an easily removable material such as a separating paper applied to the adhesive coated surfaces.
The Use of Durable HP/OP Coatings or Tape or Ribbons Comprising a Durable HP/OP Coating to Form Spill-Resistant Borders.
Around the outer perimeter of a 4 inch by 4 inch glass plate, a one half-inch border of Polane B containing first particles of XIOM 512 thermoplastic (10-100 microns) about 20% by weight is applied as a base coat. A top coat of TS-720 silica (Cabosil, Billerica, Mass.) as a 4.5% w/v suspension in ethanol is applied. The plate is air dried in followed by curing at 200° F. for 30-60 min. The plate retains water to a height greater than 5 mm as determined by the method in part b of this example.
Aluminum tape, about one-half inch wide coated with the Polane based coating is applied around the top outside edge of a 4 inch by 4 inch square aluminum plate to form a spill-resistant border. The plate is tested for its water retaining capacity, by filing the plate at its center with water until the water overflowed the tape border. The height of water retained by the tape barrier was determined by dividing the volume of water retained by the plate by the area of the plate within the border. A water height of about 5.7 mm, can be retained on aluminum plates prepared as described. In the absence of a hydrophobic/superhydrophobic tape border, or in the presence of an untreated aluminum tape border, aluminum plates will not retain significant amounts of water.
Two 24 inch×48 inch×⅜ inch aluminum plates (Plate A and Plate B) for drag reduction testing were prepared as follows:
Both Plates A and B were prepared using Self-Etching Primer as the binder with 4% w/v of 512 thermoplastic (10-100 μm) as the filler. The base coat used 18 ml of binder/filler mixture per square foot. Following the air gun spraying of the base coat, the plates were sprayed with a top coat of 4.2% of TS-720.
Plate A was heated at 400° F. for 10 min in a continuous infrared oven. This plate had a brownish surface appearance.
Plate B was air dried and tested in this condition. This plate had a gray-white color after drying.
The plates are assessed for water droplet contact angle hysteresis, surface air fraction, hydrodynamic drag reduction, and related parameters.
Water droplet contact angles and hysteresis are determined using deionized water (−5 μL in volume, ˜2 mm in diameter for a spherical droplet) on both Plate A and Plate B using a KSV CAM 100 contact angle meter. Table 19a summarizes the results.
The surface morphologies of the coatings on Plates A and B are also examined using a scanning electron microscope. The surface morphology of Plate A is rougher than that of Plate B, suggesting that the higher contact angle on the Plate B is due to its higher surface roughness.
Projected surface air fraction was determined based upon the contact angle assessment in Examples 19a by using the Cassie-Baxter equation (cos θ=fSL cos θ0−1+fSL, where θ denotes an apparent contact angle on an interface of solid and gas, fSL a fraction of wet surface (i.e., solid-liquid fraction), and θ0 a contact angle on a referential smooth rolled aluminum surface).
The estimated air (gas) fraction (fLG=1−fSL) on the superhydrophobic surface of Plates A and B, which is a critical factor influencing hydrodynamic drag reduction, is summarized in Table 19b. That table summarizes the expected surface air fraction of the coated plates. The surface air fractions are estimated for varying referential contact angles (θ0=80−110°) for a smooth surface. The results suggest that higher drag reduction effect would be achieved with Plate B due to the higher air fraction.
The hydrodynamic drag reduction of plates A and B are measured in a high-speed water towing tank system employing a monorail supported, cable driven, sample support capable of speeds of 0-60 ft/s).
The measured drag and the drag reduction observed for the plates relative to the control plate is plotted
Drag reduction at lower speed is tested on Plate B beginning at lower speeds than the data used in
Inspection of Plates A and B following hydrodynamic drag measurements reveals the presence of air bubbles, typically 0.1-0.3 mm in size, were retained on Plate B. In contrast to Plat B, Plate A did not retain a coating of such bubbles.
Samples are coated using a two step process. The base coat employs POLANE B® as a binder and Corvel Black as filler; and is followed by a top coat of M5 silica pretreated with Geleast silanizing agent SIT8174 (Example 5, Method B) suspended at 4% w/v in hexane. The coated sample is submerged in tetrahydrafuran (THF) and sonicated for 10 min using a UP400S Sonicator from Hielscher-Ultrasound Technology, Ringwood, N.J., (400 W, 24 kHz unit run at 100% amplitude and for a single 10 min cycle). Following sonication, the coatings are dried and found to be completely intact with no loss of superhydrophobic performance (water contact angles of at least 150°).
Two aluminum plates are coated using a two step process. The first plate (A) is coated with POLANE® B and S60 glass beads as base coat, followed by the application of M5 pretreated with Gelest silane SIT8174 (Example 5, Method B) suspended at 4% w/v in hexane as the top coat. A second aluminum plate (b) is coated in an identical fashion as the first substituting 512 thermoplastic beads for the S60 glass beads as the filler.
The plates are cooled in liquid nitrogen (−196° C.) and subjected to a bend test in which the plates are bent several degrees at a time as rapidly as possible with repeated cooling in liquid nitrogen to reach the indicated angles. The first plate was successfully bent to an angle of 120° without noting any delamination or cracking of the coating. The second plate was successfully bent to an angle of 140° without delamination or cracking of the coating. Both plates retain their superhydrophobicity after liquid nitrogen cooling and bending.
As a test of the ability to coat flexible surfaces, a toilet plunger with a rubber end is coated using a two step process using POLANE® B and S60 glass beads as base coat, followed by the application of M5 pretreated with Gelest silane SIT8174 (Example 5, Method B) as the top coat. The coating is applied to the plunger's rubberized end (both inside and outside) and the adjacent portion of the handle to the extent that it will become wet in use. The coated plunger is cured at room temperature for 24 hours.
The plunger is subject to repeated cycles of plunging (50 uses) without showing any wetting or damage to the coating on the plunger head or the handle area. The coated plunger minimized or eliminated dripping and surface contamination by materials that could adhere to the plunger in use.
A bed pan made from polypropylene is coated using a two step process using POLANE® B and S60 glass beads as base coat, followed by the application of M5 pretreated with Gelest silane SIT8174 (Example 5, Method B) as the top coat. The coating is applied both inside and outside.
A bedside commode made of high density polyethylene is coated in the same fashion as the bed pan.
The coated bed pan and commode do not become wet during use and avoids the adherence of fecal matter to their surfaces. Treated pans and commodes are easier than their untreated counterparts to clean, which avoids the need for pressure washing and the spreading of bacteria from incompletely cleaned surfaces.
The superhydrophobic phenomenon may not only be employed in many useful and interesting applications, but it also serves the purpose of science education and training in areas including: Second particles and nanotechnology; surface tension; contact angles and their measurement; solvents; and methods of preparing and applying superhydrophobic coatings.
Kits are assembled comprising a one-step coating composition and instructions Alternatively kits are assembled to comprise the materials needed to applying a superhydrophobic coating in a two-step process and instruction.
Kits may further include on or more of: applicators, such as paint brushes; mixing implements; and containers.
In addition to providing coating materials and instructions on how to apply the coating, the instructions may also include information on how to observe superhydrophobic phenomena and/or the basic scientific method.
A series of coatings prepared by the methods described herein are evaluated for roughness using a Mahr PocketSurf PS1 from Mahr Federal Inc. (Providence, R.I. 02905) and for thickness using a Positector 6000 from Delfelsko Corp. (Ogdensburg, N.Y). Both the arithmetical mean roughness (Ra) and the ten point mean roughness (Rz) are obtained. The average roughness Ra values of several coatings vary from 0.3-17.69 microns. The average roughness Rz values of several coatings vary from 1.91-78.53 microns. For each plate, both the low and high coating thickness values were measured. The low values of the coating thickness varied from 17.5-147.5 microns. The high values of thickness vary from 35-185 microns. Details are provide in Table 25.
Aluminum plates, 4 inches×4 inches, are coated with one of three different binders in the absence of any added first or second particles. After curing at 200° F. for 30-60 min, contact angle for each of the plates with water at about 18 to about 22° C. is measured. The results indicate the following contact angles are found for the binders.
Self Etching Primer: Contact angle varies from 80.69-83.27°.
Polane B: Contact angle varies from 69.39-71.3°.
Lumiflon: Contact angle varies from 75.76-80.70°.
Details are provided in Table 26.
Plates were also tested for roll-off angle, in each case the binders have roll-off angles greater than 60 and less than 90 degrees and leave residual water on the surface.
Fabric samples are treated with a silanizing agent alone, or with either SiCl4 or Si(OEt)4 followed by treatment with a silanizing agent, as indicated in Table 26. Two different silanizing were employed, (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane, which is a fluorinated silane, and n-octadecyltrichlorosilane, which is a not fluorinated. The treatment process comprised applying 10% solutions of either SiCl4 or SiOEt4 in hexane, or combinations thereof, to fabric samples by brushing the solutions on the fabric, Following treatment with SiCl4 SiOEt4 the fabric is cured at about 93° C. (about 200° F.) for 60 minutes (min). Silanes are then brushed on the fabric as a 1% solution in hexane, and the fabric samples are again cured at about 93° C. (about 200° F.) F for 60 min. Where acetic acid is employed it is used as a catalyst. Ten different fabrics having a variety of compositions are treated in this manner.
As an alternative to applying the agents by brushing, either the SiCl4 or Si(OEt)4, can also be applied by immersing the fabric in 10% solution of those agents in hexane under a pressure of 20 psi (pound per square inch) for 5 min. This step was carried out to enhance the attachment of SiCl4 or Si(OEt)4 to the fabrics.
Hydrophobicity of the fabrics is observed by observing the beading and non-wetting behavior of the fabric samples. The durability of the hydrophobicity is measured by washing in soapy water until non-wetting performance ends Four different commercial detergents, Ajax, Dawn, Tide, and Tide with 5% bleach are employed for the washing, which used the detergents in the amounts indicated by the suppliers. After each wash fabrics samples are dried at about 93° C. (about 200° F.) for 15 min
The data for each fabric sample's response to washing are presented in Table 27. Those data suggest that significant hydrophobicity, with resistance to washing, can be introduced into fabrics.
This application is a continuation of PCT/US2009/005512, filed Oct. 7, 2009, which claims the benefit of priority to U.S. Provisional Application No. 61/103,295, filed on Oct. 7, 2008, and U.S. Provisional Application No. 61/159,914, filed Mar. 13, 2009, the contents of each of which are hereby incorporated by reference in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 870439 | Kade | Nov 1907 | A |
| 2191701 | Wood | Feb 1940 | A |
| 2976386 | Salton | Mar 1961 | A |
| 3185426 | Bjerke | May 1965 | A |
| 3244541 | Fain et al. | Apr 1966 | A |
| 3354022 | Dettre et al. | Nov 1967 | A |
| 3579540 | Ohlhausen | May 1971 | A |
| 3716502 | Loew | Feb 1973 | A |
| 3931428 | Reick | Jan 1976 | A |
| 3963349 | Albright et al. | Jun 1976 | A |
| 3967030 | Johnson et al. | Jun 1976 | A |
| 3975197 | Mikelsons | Aug 1976 | A |
| 3976572 | Reick | Aug 1976 | A |
| 3980153 | Andrews | Sep 1976 | A |
| 4142724 | Reick | Mar 1979 | A |
| 4151327 | Lawton | Apr 1979 | A |
| 4199142 | Reick | Apr 1980 | A |
| 4301197 | Franz et al. | Nov 1981 | A |
| 4301213 | Davies | Nov 1981 | A |
| 4311755 | Rummel | Jan 1982 | A |
| 4415405 | Ruddle et al. | Nov 1983 | A |
| 4451619 | Heilmann et al. | May 1984 | A |
| 4453533 | Scheidler et al. | Jun 1984 | A |
| 4474852 | Craig | Oct 1984 | A |
| 4492217 | Scheidler | Jan 1985 | A |
| 4581149 | Horodysky et al. | Apr 1986 | A |
| 4591530 | Lui | May 1986 | A |
| 4614464 | Christensen | Sep 1986 | A |
| 4624900 | Fau | Nov 1986 | A |
| 4646948 | Jennings | Mar 1987 | A |
| 4680173 | Burger | Jul 1987 | A |
| 4687707 | Matsuo et al. | Aug 1987 | A |
| 4716183 | Gamarra et al. | Dec 1987 | A |
| 4733843 | Bessinger | Mar 1988 | A |
| 4738426 | Bessinger | Apr 1988 | A |
| D295950 | Johnston | May 1988 | S |
| 4749110 | Maeno et al. | Jun 1988 | A |
| 4753977 | Merrill | Jun 1988 | A |
| 4782112 | Kondo et al. | Nov 1988 | A |
| 4835014 | Roth et al. | May 1989 | A |
| 4855176 | Ohwaki et al. | Aug 1989 | A |
| 4870907 | McKee | Oct 1989 | A |
| 4923260 | Poulsen | May 1990 | A |
| 4971912 | Buhl et al. | Nov 1990 | A |
| 4983459 | Franz et al. | Jan 1991 | A |
| 5011727 | Kido et al. | Apr 1991 | A |
| 5011963 | Ogawa et al. | Apr 1991 | A |
| 5032641 | Nanishi et al. | Jul 1991 | A |
| 5041304 | Kusano et al. | Aug 1991 | A |
| 5057050 | Hill | Oct 1991 | A |
| 5084191 | Nagase et al. | Jan 1992 | A |
| 5104938 | Toyama et al. | Apr 1992 | A |
| 5121134 | Albinson et al. | Jun 1992 | A |
| 5156611 | Haynes et al. | Oct 1992 | A |
| 5202361 | Zimmerman et al. | Apr 1993 | A |
| 5212215 | Nanri et al. | May 1993 | A |
| 5225274 | Ogawa et al. | Jul 1993 | A |
| 5228764 | Cherry et al. | Jul 1993 | A |
| 5228905 | Grunewalder et al. | Jul 1993 | A |
| 5238746 | Soga et al. | Aug 1993 | A |
| 5240774 | Ogawa et al. | Aug 1993 | A |
| 5274159 | Pellerite et al. | Dec 1993 | A |
| 5284707 | Ogawa et al. | Feb 1994 | A |
| 5294252 | Gun | Mar 1994 | A |
| 5300239 | Ozaki et al. | Apr 1994 | A |
| 5308705 | Franz et al. | May 1994 | A |
| 5312573 | Rosenbaum et al. | May 1994 | A |
| 5316799 | Brunken et al. | May 1994 | A |
| 5317129 | Taplan et al. | May 1994 | A |
| 5324566 | Ogawa et al. | Jun 1994 | A |
| 5328768 | Goodwin | Jul 1994 | A |
| 5338345 | Scarborough et al. | Aug 1994 | A |
| 5348547 | Payne et al. | Sep 1994 | A |
| 5352733 | Hart | Oct 1994 | A |
| 5362145 | Bird et al. | Nov 1994 | A |
| 5364299 | Hill et al. | Nov 1994 | A |
| 5366810 | Merrifield et al. | Nov 1994 | A |
| 5368892 | Berquier | Nov 1994 | A |
| 5372888 | Ogawa et al. | Dec 1994 | A |
| 5380585 | Ogawa et al. | Jan 1995 | A |
| 5385966 | Hermansen et al. | Jan 1995 | A |
| 5395657 | Strepparola et al. | Mar 1995 | A |
| 5424130 | Nakanishi et al. | Jun 1995 | A |
| 5429433 | Bird et al. | Jul 1995 | A |
| 5435839 | Ogawa | Jul 1995 | A |
| 5437894 | Ogawa et al. | Aug 1995 | A |
| 5437900 | Kuzowski | Aug 1995 | A |
| 5441338 | Kane et al. | Aug 1995 | A |
| 5458976 | Horino et al. | Oct 1995 | A |
| 5466770 | Audenaert et al. | Nov 1995 | A |
| 5489328 | Ono et al. | Feb 1996 | A |
| 5500216 | Julian et al. | Mar 1996 | A |
| 5540493 | Kane et al. | Jul 1996 | A |
| 5556667 | Teranishi et al. | Sep 1996 | A |
| 5558940 | Michels et al. | Sep 1996 | A |
| 5564809 | Kane et al. | Oct 1996 | A |
| 5576096 | Ono et al. | Nov 1996 | A |
| 5578361 | Tsujioka et al. | Nov 1996 | A |
| 5584957 | Schultheis et al. | Dec 1996 | A |
| 5585896 | Yamazaki et al. | Dec 1996 | A |
| 5599893 | Asai et al. | Feb 1997 | A |
| 5612433 | Ono et al. | Mar 1997 | A |
| 5618627 | Merrifield et al. | Apr 1997 | A |
| 5651921 | Kaijou | Jul 1997 | A |
| 5658969 | Gerace | Aug 1997 | A |
| 5674967 | Goodwin | Oct 1997 | A |
| 5679460 | Schakenraad et al. | Oct 1997 | A |
| 5688864 | Goodwin | Nov 1997 | A |
| 5697991 | Frazer | Dec 1997 | A |
| 5707740 | Goodwin | Jan 1998 | A |
| 5725789 | Huber et al. | Mar 1998 | A |
| 5735589 | Herrmann et al. | Apr 1998 | A |
| 5747561 | Smirnov et al. | May 1998 | A |
| 5753734 | Maruyama | May 1998 | A |
| 5798144 | Varanasi et al. | Aug 1998 | A |
| 5800918 | Chartier et al. | Sep 1998 | A |
| 5813741 | Fish et al. | Sep 1998 | A |
| 5814411 | Merrifield et al. | Sep 1998 | A |
| 5824421 | Kobayashi et al. | Oct 1998 | A |
| 5830529 | Ross | Nov 1998 | A |
| 5840201 | Elledge | Nov 1998 | A |
| 5843338 | Inoue et al. | Dec 1998 | A |
| 5853690 | Hibino et al. | Dec 1998 | A |
| 5853800 | Dombrowski et al. | Dec 1998 | A |
| 5856378 | Ring et al. | Jan 1999 | A |
| 5858551 | Salsman | Jan 1999 | A |
| 5876806 | Ogawa | Mar 1999 | A |
| 5890907 | Minasian | Apr 1999 | A |
| 5910557 | Audenaert et al. | Jun 1999 | A |
| 5921411 | Merl | Jul 1999 | A |
| 5924359 | Watanabe | Jul 1999 | A |
| 5945482 | Fukuchi et al. | Aug 1999 | A |
| 5947574 | Avendano | Sep 1999 | A |
| 5948685 | Angros | Sep 1999 | A |
| 5952053 | Colby | Sep 1999 | A |
| 5958601 | Salsman | Sep 1999 | A |
| 5980990 | Goodwin | Nov 1999 | A |
| 6013724 | Mizutani et al. | Jan 2000 | A |
| 6017609 | Akamatsu et al. | Jan 2000 | A |
| 6017831 | Beardsley et al. | Jan 2000 | A |
| 6017997 | Snow et al. | Jan 2000 | A |
| 6024948 | Samain et al. | Feb 2000 | A |
| 6025025 | Bartrug et al. | Feb 2000 | A |
| 6033738 | Teranishi et al. | Mar 2000 | A |
| 6045650 | Mitchnick et al. | Apr 2000 | A |
| 6068911 | Shouji et al. | May 2000 | A |
| 6090447 | Suzuki et al. | Jul 2000 | A |
| 6093559 | Bookbinder et al. | Jul 2000 | A |
| 6096380 | Takebe et al. | Aug 2000 | A |
| 6105233 | Neal | Aug 2000 | A |
| 6114446 | Narisawa et al. | Sep 2000 | A |
| 6117555 | Fujimori et al. | Sep 2000 | A |
| 6119626 | Miyazawa et al. | Sep 2000 | A |
| 6120720 | Meier et al. | Sep 2000 | A |
| 6136210 | Biegelsen et al. | Oct 2000 | A |
| 6153304 | Smith et al. | Nov 2000 | A |
| 6187143 | Juppo et al. | Feb 2001 | B1 |
| 6191122 | Lux et al. | Feb 2001 | B1 |
| 6201058 | Mahr et al. | Mar 2001 | B1 |
| 6207236 | Araki et al. | Mar 2001 | B1 |
| 6221434 | Visca et al. | Apr 2001 | B1 |
| 6224974 | Wuu | May 2001 | B1 |
| 6228435 | Yoshikawa et al. | May 2001 | B1 |
| 6228972 | Hikita et al. | May 2001 | B1 |
| 6235383 | Hong et al. | May 2001 | B1 |
| 6235833 | Akamatsu et al. | May 2001 | B1 |
| 6245387 | Hayden | Jun 2001 | B1 |
| 6264751 | Kamura et al. | Jul 2001 | B1 |
| 6280834 | Veerasamy et al. | Aug 2001 | B1 |
| 6288149 | Kroll | Sep 2001 | B1 |
| 6291054 | Thomas et al. | Sep 2001 | B1 |
| 6333074 | Ogawa et al. | Dec 2001 | B1 |
| 6333558 | Hasegawa | Dec 2001 | B1 |
| 6337133 | Akamatsu et al. | Jan 2002 | B1 |
| 6340502 | Azzopardi et al. | Jan 2002 | B1 |
| 6342268 | Samain | Jan 2002 | B1 |
| 6352758 | Huang et al. | Mar 2002 | B1 |
| 6358569 | Badyal et al. | Mar 2002 | B1 |
| 6361868 | Bier et al. | Mar 2002 | B1 |
| 6376592 | Shimada et al. | Apr 2002 | B1 |
| 6379751 | Schafer et al. | Apr 2002 | B1 |
| 6383642 | Le Bellac et al. | May 2002 | B1 |
| 6403397 | Katz | Jun 2002 | B1 |
| 6419985 | Ishizuka | Jul 2002 | B1 |
| 6423372 | Genzer et al. | Jul 2002 | B1 |
| 6423381 | Colton et al. | Jul 2002 | B1 |
| 6432181 | Ludwig | Aug 2002 | B1 |
| 6451432 | Azzopardi et al. | Sep 2002 | B1 |
| 6458420 | Akamatsu et al. | Oct 2002 | B1 |
| 6461537 | Turcotte et al. | Oct 2002 | B1 |
| 6461670 | Akamatsu et al. | Oct 2002 | B2 |
| 6462115 | Takahashi et al. | Oct 2002 | B1 |
| 6471761 | Fan et al. | Oct 2002 | B2 |
| 6476095 | Simendinger, III | Nov 2002 | B2 |
| 6479612 | Del Pesco et al. | Nov 2002 | B1 |
| 6482524 | Yamamoto et al. | Nov 2002 | B1 |
| 6488347 | Bienick | Dec 2002 | B1 |
| 6564935 | Yamamoto et al. | May 2003 | B1 |
| 6579620 | Mizuno et al. | Jun 2003 | B2 |
| 6582825 | Amarasekera et al. | Jun 2003 | B2 |
| 6584744 | Schultheis et al. | Jul 2003 | B1 |
| 6596060 | Michaud | Jul 2003 | B1 |
| 6610363 | Arora et al. | Aug 2003 | B2 |
| 6613860 | Dams et al. | Sep 2003 | B1 |
| 6623863 | Kamitani et al. | Sep 2003 | B2 |
| 6641654 | Akamatsu et al. | Nov 2003 | B2 |
| 6649222 | D'Agostino et al. | Nov 2003 | B1 |
| 6652640 | Asai et al. | Nov 2003 | B2 |
| 6660339 | Datta et al. | Dec 2003 | B1 |
| 6660363 | Barthlott | Dec 2003 | B1 |
| 6660686 | Inagaki et al. | Dec 2003 | B2 |
| 6683126 | Keller et al. | Jan 2004 | B2 |
| 6685992 | Ogawa et al. | Feb 2004 | B1 |
| 6689200 | Scarborough et al. | Feb 2004 | B2 |
| 6692565 | Johansen, Jr. et al. | Feb 2004 | B2 |
| 6706798 | Kobayashi et al. | Mar 2004 | B2 |
| 6720371 | Furuta et al. | Apr 2004 | B2 |
| 6729704 | Ames | May 2004 | B2 |
| 6743467 | Jones et al. | Jun 2004 | B1 |
| 6767984 | Toui et al. | Jul 2004 | B2 |
| 6770323 | Genzer et al. | Aug 2004 | B2 |
| 6780497 | Walter | Aug 2004 | B1 |
| 6786562 | Obrock et al. | Sep 2004 | B2 |
| 6793821 | Lee et al. | Sep 2004 | B2 |
| 6800354 | Baumann et al. | Oct 2004 | B2 |
| 6806299 | Baumann et al. | Oct 2004 | B2 |
| 6808835 | Green et al. | Oct 2004 | B2 |
| 6811716 | Stengaard et al. | Nov 2004 | B1 |
| 6811844 | Trouilhet | Nov 2004 | B2 |
| 6845788 | Extrand | Jan 2005 | B2 |
| 6852389 | Nun et al. | Feb 2005 | B2 |
| 6852390 | Extrand | Feb 2005 | B2 |
| 6855375 | Nakagawa et al. | Feb 2005 | B2 |
| 6855759 | Kudo et al. | Feb 2005 | B2 |
| 6858284 | Nun et al. | Feb 2005 | B2 |
| 6871923 | Dietz et al. | Mar 2005 | B2 |
| 6872441 | Baumann et al. | Mar 2005 | B2 |
| 6890360 | Cote et al. | May 2005 | B2 |
| 6923216 | Extrand et al. | Aug 2005 | B2 |
| 6926946 | Ogawa et al. | Aug 2005 | B2 |
| 6931888 | Shekunov et al. | Aug 2005 | B2 |
| 6938774 | Extrand | Sep 2005 | B2 |
| 6942746 | Niejelow et al. | Sep 2005 | B2 |
| 6966990 | Chattopadhyay et al. | Nov 2005 | B2 |
| 6976585 | Extrand | Dec 2005 | B2 |
| 6976998 | Rizzo et al. | Dec 2005 | B2 |
| 6982242 | Liss et al. | Jan 2006 | B2 |
| 6994045 | Paszkowski | Feb 2006 | B2 |
| 6998051 | Chattopadhyay et al. | Feb 2006 | B2 |
| 7004184 | Handique et al. | Feb 2006 | B2 |
| 7019069 | Kobayashi et al. | Mar 2006 | B2 |
| 7022416 | Teranishi | Apr 2006 | B2 |
| 7026018 | Kranovich | Apr 2006 | B2 |
| 7037591 | Henze et al. | May 2006 | B2 |
| 7048889 | Arney et al. | May 2006 | B2 |
| 7052244 | Fouillet et al. | May 2006 | B2 |
| 7056409 | Dubrow | Jun 2006 | B2 |
| 7057832 | Wu et al. | Jun 2006 | B2 |
| 7057881 | Chow et al. | Jun 2006 | B2 |
| 7074273 | Shimomura et al. | Jul 2006 | B2 |
| 7074294 | Dubrow | Jul 2006 | B2 |
| 7083748 | Chattopadhyay et al. | Aug 2006 | B2 |
| 7083828 | Muller et al. | Aug 2006 | B2 |
| 7109256 | Amano et al. | Sep 2006 | B2 |
| 7112369 | Wang et al. | Sep 2006 | B2 |
| 7141276 | Lehmann et al. | Nov 2006 | B2 |
| 7148181 | Tanaka et al. | Dec 2006 | B2 |
| 7150904 | D'Urso et al. | Dec 2006 | B2 |
| 7153357 | Baumgart et al. | Dec 2006 | B2 |
| 7157018 | Scheidler | Jan 2007 | B2 |
| 7166235 | Majeti et al. | Jan 2007 | B2 |
| 7175723 | Jones et al. | Feb 2007 | B2 |
| 7179758 | Chakrapani et al. | Feb 2007 | B2 |
| 7179864 | Wang | Feb 2007 | B2 |
| 7188917 | Bienick | Mar 2007 | B2 |
| 7198855 | Liebmann-Vinson et al. | Apr 2007 | B2 |
| 7204298 | Hodes et al. | Apr 2007 | B2 |
| 7211223 | Fouillet et al. | May 2007 | B2 |
| 7211313 | Nun et al. | May 2007 | B2 |
| 7211329 | Metz et al | May 2007 | B2 |
| 7211605 | Coronado et al. | May 2007 | B2 |
| 7213309 | Wang et al. | May 2007 | B2 |
| D547640 | Remmers | Jul 2007 | S |
| 7238751 | Wang et al. | Jul 2007 | B2 |
| 7253130 | Chiang et al. | Aug 2007 | B2 |
| 7258731 | D'Urso et al. | Aug 2007 | B2 |
| 7264845 | Papadaki et al. | Sep 2007 | B2 |
| 7265468 | Mancl et al. | Sep 2007 | B1 |
| 7268179 | Brown | Sep 2007 | B2 |
| 7273658 | Banayoun et al. | Sep 2007 | B2 |
| 7285331 | Reihs et al. | Oct 2007 | B1 |
| 7288311 | Kawashima et al. | Oct 2007 | B2 |
| 7288592 | Stark et al. | Oct 2007 | B2 |
| 7291653 | Baumann et al. | Nov 2007 | B2 |
| 7306895 | Kano et al. | Dec 2007 | B2 |
| 7309278 | Shibata | Dec 2007 | B2 |
| 7312057 | Bookbinder et al. | Dec 2007 | B2 |
| 7323033 | Kroupenkine et al. | Jan 2008 | B2 |
| 7338835 | Bao | Mar 2008 | B2 |
| 7342551 | King | Mar 2008 | B2 |
| 7344619 | Helmeke | Mar 2008 | B2 |
| 7344758 | Franchina et al. | Mar 2008 | B2 |
| 7344783 | Shea | Mar 2008 | B2 |
| 7354328 | Lee | Apr 2008 | B2 |
| 7354624 | Millero et al. | Apr 2008 | B2 |
| 7354650 | Nakajima et al. | Apr 2008 | B2 |
| D568344 | Baacke et al. | May 2008 | S |
| 7368510 | Lee et al. | May 2008 | B2 |
| 7388211 | Chao et al. | Jun 2008 | B2 |
| 7393515 | Hoshino et al. | Jul 2008 | B2 |
| 7396395 | Chen et al. | Jul 2008 | B1 |
| 7419615 | Strauss | Sep 2008 | B2 |
| 7449233 | Arora | Nov 2008 | B2 |
| 7468333 | Kimbrell, Jr. et al. | Dec 2008 | B2 |
| 7524531 | Axtell, III et al. | Apr 2009 | B2 |
| 7527832 | Sakoske et al. | May 2009 | B2 |
| 7544411 | Baumann et al. | Jun 2009 | B2 |
| D596931 | Fernandez | Jul 2009 | S |
| D596932 | Kleinsasser | Jul 2009 | S |
| 7563505 | Reihs | Jul 2009 | B2 |
| 7568583 | Wing et al. | Aug 2009 | B2 |
| 7607744 | Casoli et al. | Oct 2009 | B2 |
| D607020 | Baacke et al. | Dec 2009 | S |
| D612404 | Picken et al. | Mar 2010 | S |
| D612405 | Eicher | Mar 2010 | S |
| D613316 | Schmidt | Apr 2010 | S |
| 7726615 | Rutz | Jun 2010 | B2 |
| 7731316 | Wing | Jun 2010 | B2 |
| 7748806 | Egan | Jul 2010 | B2 |
| 7919180 | Furukawa | Apr 2011 | B2 |
| 7989619 | Guire et al. | Aug 2011 | B2 |
| 8258206 | Kanagasabapathy et al. | Sep 2012 | B2 |
| 8286561 | Driver et al. | Oct 2012 | B2 |
| 8596205 | Driver et al. | Dec 2013 | B2 |
| 20010018130 | Hayden | Aug 2001 | A1 |
| 20010019773 | Akamatsu et al. | Sep 2001 | A1 |
| 20010024728 | Kamitani et al. | Sep 2001 | A1 |
| 20010030808 | Komatsu et al. | Oct 2001 | A1 |
| 20010055677 | Wuu | Dec 2001 | A1 |
| 20020001676 | Hayden | Jan 2002 | A1 |
| 20020034627 | Jacquiod et al. | Mar 2002 | A1 |
| 20020045007 | Arora et al. | Apr 2002 | A1 |
| 20020077412 | Kobayashi et al. | Jun 2002 | A1 |
| 20020111402 | Mizuno et al. | Aug 2002 | A1 |
| 20020115736 | Koshy | Aug 2002 | A1 |
| 20020177655 | Pratt et al. | Nov 2002 | A1 |
| 20020192472 | Metz et al. | Dec 2002 | A1 |
| 20020197490 | Amidaiji et al. | Dec 2002 | A1 |
| 20030009049 | Smith et al. | Jan 2003 | A1 |
| 20030021902 | Yamamoto et al. | Jan 2003 | A1 |
| 20030026972 | Reihs | Feb 2003 | A1 |
| 20030040243 | Ward | Feb 2003 | A1 |
| 20030040568 | Furuta et al. | Feb 2003 | A1 |
| 20030070677 | Handique et al. | Apr 2003 | A1 |
| 20030072723 | Gers-Barlag et al. | Apr 2003 | A1 |
| 20030073067 | Bookfinder et al. | Apr 2003 | A1 |
| 20030077533 | Murota et al. | Apr 2003 | A1 |
| 20030091809 | Scarborough et al. | May 2003 | A1 |
| 20030110976 | Abidh et al. | Jun 2003 | A1 |
| 20030117051 | Kweon | Jun 2003 | A1 |
| 20030119684 | Tsao | Jun 2003 | A1 |
| 20030125656 | Davankov et al. | Jul 2003 | A1 |
| 20030143339 | Kobayashi | Jul 2003 | A1 |
| 20030149218 | Cote′ et al. | Aug 2003 | A1 |
| 20030166840 | Urry et al. | Sep 2003 | A1 |
| 20030170401 | Shimomura et al. | Sep 2003 | A1 |
| 20030176572 | Maekawa et al. | Sep 2003 | A1 |
| 20030179494 | Kaneko | Sep 2003 | A1 |
| 20040005469 | Metz et al. | Jan 2004 | A1 |
| 20040020104 | Feldhege et al. | Feb 2004 | A1 |
| 20040025747 | Kamitani et al. | Feb 2004 | A1 |
| 20040050297 | Kobayashi et al. | Mar 2004 | A1 |
| 20040053058 | Kamitani et al. | Mar 2004 | A1 |
| 20040056575 | Dietz et al. | Mar 2004 | A1 |
| 20040097616 | Hoppler et al. | May 2004 | A1 |
| 20040102124 | Suzuki | May 2004 | A1 |
| 20040121168 | Goodwin et al. | Jun 2004 | A1 |
| 20040137814 | Kimbrell, Jr. et al. | Jul 2004 | A1 |
| 20040138083 | Kimbrell, Jr. et al. | Jul 2004 | A1 |
| 20040142557 | Levy et al. | Jul 2004 | A1 |
| 20040154106 | Oles et al. | Aug 2004 | A1 |
| 20040201048 | Seki et al. | Oct 2004 | A1 |
| 20040202872 | Fang et al. | Oct 2004 | A1 |
| 20040209203 | Kano et al. | Oct 2004 | A1 |
| 20040213904 | Muller et al. | Oct 2004 | A1 |
| 20040216227 | Papadaki et al. | Nov 2004 | A1 |
| 20050000463 | Mochizuki | Jan 2005 | A1 |
| 20050004264 | Tanabe | Jan 2005 | A1 |
| 20050008859 | Forgacs | Jan 2005 | A1 |
| 20050009953 | Shea | Jan 2005 | A1 |
| 20050020763 | Milic | Jan 2005 | A1 |
| 20050022313 | Scheidler | Feb 2005 | A1 |
| 20050053793 | Benay-Oun et al. | Mar 2005 | A1 |
| 20050075020 | Benayoun et al. | Apr 2005 | A1 |
| 20050106762 | Chakrapani et al. | May 2005 | A1 |
| 20050121782 | Nakamura et al. | Jun 2005 | A1 |
| 20050143547 | Stark et al. | Jun 2005 | A1 |
| 20050165194 | Benayoun et al. | Jul 2005 | A1 |
| 20050170098 | Baumann et al. | Aug 2005 | A1 |
| 20050221098 | Azzopardi et al. | Oct 2005 | A1 |
| 20050239211 | Uchihara et al. | Oct 2005 | A1 |
| 20050245395 | Tanaka et al. | Nov 2005 | A1 |
| 20060013983 | Sebastian et al. | Jan 2006 | A1 |
| 20060029808 | Zhai et al. | Feb 2006 | A1 |
| 20060040164 | Vyas et al. | Feb 2006 | A1 |
| 20060051561 | Badyal | Mar 2006 | A1 |
| 20060052556 | Franchina et al. | Mar 2006 | A1 |
| 20060057390 | Kittle et al. | Mar 2006 | A1 |
| 20060058458 | Hasskerl et al. | Mar 2006 | A1 |
| 20060062695 | Haab et al. | Mar 2006 | A1 |
| 20060062929 | Kittle et al. | Mar 2006 | A1 |
| 20060081394 | Li et al. | Apr 2006 | A1 |
| 20060089466 | Shimomura et al. | Apr 2006 | A1 |
| 20060110541 | Russell et al. | May 2006 | A1 |
| 20060110542 | Dietz et al. | May 2006 | A1 |
| 20060113443 | Remmers | Jun 2006 | A1 |
| 20060147634 | Strauss | Jul 2006 | A1 |
| 20060151739 | Sandner et al. | Jul 2006 | A1 |
| 20060154048 | Teranishi et al. | Jul 2006 | A1 |
| 20060172641 | Hennige et al. | Aug 2006 | A1 |
| 20060185555 | Giessler et al. | Aug 2006 | A1 |
| 20060207032 | Reiners et al. | Sep 2006 | A1 |
| 20060213849 | Bienick | Sep 2006 | A1 |
| 20060222865 | Hoshino et al. | Oct 2006 | A1 |
| 20060240218 | Parce | Oct 2006 | A1 |
| 20060263516 | Jones et al. | Nov 2006 | A1 |
| 20060266258 | Asakura et al. | Nov 2006 | A1 |
| 20060269758 | Helmeke | Nov 2006 | A1 |
| 20060281889 | Kobayashi et al. | Dec 2006 | A1 |
| 20060286305 | Thies et al. | Dec 2006 | A1 |
| 20060292345 | Dave et al. | Dec 2006 | A1 |
| 20070003705 | Strauss | Jan 2007 | A1 |
| 20070005024 | Weber et al. | Jan 2007 | A1 |
| 20070009657 | Zhang et al. | Jan 2007 | A1 |
| 20070014970 | Nun et al. | Jan 2007 | A1 |
| 20070026193 | Luzinov et al. | Feb 2007 | A1 |
| 20070036906 | Reeve | Feb 2007 | A1 |
| 20070046160 | Egan | Mar 2007 | A1 |
| 20070065668 | Idei | Mar 2007 | A1 |
| 20070075199 | Stewart et al. | Apr 2007 | A1 |
| 20070141114 | Muisener et al. | Jun 2007 | A1 |
| 20070141306 | Kasai et al. | Jun 2007 | A1 |
| 20070148407 | Chen et al. | Jun 2007 | A1 |
| 20070166513 | Sheng et al. | Jul 2007 | A1 |
| 20070172650 | O'Rear, III et al. | Jul 2007 | A1 |
| 20070172658 | Deruelle et al. | Jul 2007 | A1 |
| 20070172661 | Fechner et al. | Jul 2007 | A1 |
| 20070176379 | Sonnendorfer et al. | Aug 2007 | A1 |
| 20070196656 | Rowell | Aug 2007 | A1 |
| 20070202342 | Whiteford et al. | Aug 2007 | A1 |
| 20070213230 | Pfeiffer et al. | Sep 2007 | A1 |
| 20070215004 | Kuroda et al. | Sep 2007 | A1 |
| 20070218265 | Harris et al. | Sep 2007 | A1 |
| 20070224898 | Deangelis et al. | Sep 2007 | A1 |
| 20070231517 | Golownia | Oct 2007 | A1 |
| 20070238807 | Safir et al. | Oct 2007 | A1 |
| 20070259156 | Kempers et al. | Nov 2007 | A1 |
| 20070274871 | Jiang | Nov 2007 | A1 |
| 20070275245 | Persson et al. | Nov 2007 | A1 |
| 20070298216 | Jing et al. | Dec 2007 | A1 |
| 20080008838 | Arpac et al. | Jan 2008 | A1 |
| 20080012459 | Picken et al. | Jan 2008 | A1 |
| 20080018709 | Takenaka et al. | Jan 2008 | A1 |
| 20080020127 | Whiteford et al. | Jan 2008 | A1 |
| 20080021212 | Whiteford et al. | Jan 2008 | A1 |
| 20080032403 | Saito et al. | Feb 2008 | A1 |
| 20080039558 | Lazzari et al. | Feb 2008 | A1 |
| 20080044635 | O'Neill et al. | Feb 2008 | A1 |
| 20080050567 | Kawashima et al. | Feb 2008 | A1 |
| 20080063870 | O'Rear et al. | Mar 2008 | A1 |
| 20080066648 | Asakura et al. | Mar 2008 | A1 |
| 20080070146 | Fomitchev et al. | Mar 2008 | A1 |
| 20080081858 | Okazaki | Apr 2008 | A1 |
| 20080088192 | Hsu | Apr 2008 | A1 |
| 20080090004 | Zhang et al. | Apr 2008 | A1 |
| 20080101041 | Chang et al. | May 2008 | A1 |
| 20080102347 | Blunk | May 2008 | A1 |
| 20080107864 | Zhang et al. | May 2008 | A1 |
| 20080131653 | Lyons et al. | Jun 2008 | A1 |
| 20080160257 | Takada et al. | Jul 2008 | A1 |
| 20080166549 | Shieh et al. | Jul 2008 | A1 |
| 20080171805 | Mingarelli | Jul 2008 | A1 |
| 20080172937 | Palmer et al. | Jul 2008 | A1 |
| 20080176991 | Osawa et al. | Jul 2008 | A1 |
| 20080197760 | Leconte et al. | Aug 2008 | A1 |
| 20080199657 | Capron et al. | Aug 2008 | A1 |
| 20080199659 | Zhao | Aug 2008 | A1 |
| 20080205950 | Moorlag et al. | Aug 2008 | A1 |
| 20080206550 | Borlner | Aug 2008 | A1 |
| 20080207581 | Whiteford et al. | Aug 2008 | A1 |
| 20080213601 | Yamamoto et al. | Sep 2008 | A1 |
| 20080220170 | Van Der Flaas | Sep 2008 | A1 |
| 20080220676 | Marin et al. | Sep 2008 | A1 |
| 20080221009 | Kanagasabapathy et al. | Sep 2008 | A1 |
| 20080221263 | Kanagasabapathy et al. | Sep 2008 | A1 |
| 20080226694 | Gelbart et al. | Sep 2008 | A1 |
| 20080237126 | Hoek et al. | Oct 2008 | A1 |
| 20080241512 | Boris et al. | Oct 2008 | A1 |
| 20080241523 | Huignard et al. | Oct 2008 | A1 |
| 20080245273 | Vyorkka et al. | Oct 2008 | A1 |
| 20080246804 | Kawase et al. | Oct 2008 | A1 |
| 20080248263 | Kobrin | Oct 2008 | A1 |
| 20080250978 | Baumgart et al. | Oct 2008 | A1 |
| 20080261024 | Xenopoulos et al. | Oct 2008 | A1 |
| 20080268233 | Lawin et al. | Oct 2008 | A1 |
| 20080269358 | Inoue et al. | Oct 2008 | A1 |
| 20080280699 | Jarvholm | Nov 2008 | A1 |
| 20080286556 | D'Urso et al. | Nov 2008 | A1 |
| 20080295347 | Braham | Dec 2008 | A1 |
| 20080296252 | D'Urso et al. | Dec 2008 | A1 |
| 20080306202 | Lin et al. | Dec 2008 | A1 |
| 20080310660 | Lin | Dec 2008 | A1 |
| 20090010870 | Greiner et al. | Jan 2009 | A1 |
| 20090011222 | Xiu et al. | Jan 2009 | A1 |
| 20090011227 | Furukawa | Jan 2009 | A1 |
| 20090011960 | Ws | Jan 2009 | A1 |
| 20090018249 | Kanagasabapathy et al. | Jan 2009 | A1 |
| 20090025508 | Liao et al. | Jan 2009 | A1 |
| 20090025609 | Egami et al. | Jan 2009 | A1 |
| 20090032088 | Rabinowitz | Feb 2009 | A1 |
| 20090036978 | Kleiner et al. | Feb 2009 | A1 |
| 20090042469 | Simpson | Feb 2009 | A1 |
| 20090058247 | Collins et al. | Mar 2009 | A1 |
| 20090064894 | Baumgart et al. | Mar 2009 | A1 |
| 20090076430 | Simpson et al. | Mar 2009 | A1 |
| 20090084574 | Balfour et al. | Apr 2009 | A1 |
| 20090084914 | Picken et al. | Apr 2009 | A1 |
| 20090085453 | Daley et al. | Apr 2009 | A1 |
| 20090087670 | Peng et al. | Apr 2009 | A1 |
| 20090095941 | Nakata et al. | Apr 2009 | A1 |
| 20090099301 | Naraghi et al. | Apr 2009 | A1 |
| 20090105409 | Munzmay et al. | Apr 2009 | A1 |
| 20090105679 | Joubert et al. | Apr 2009 | A1 |
| 20090111344 | Murphy et al. | Apr 2009 | A1 |
| 20090115302 | Benz et al. | May 2009 | A1 |
| 20090123728 | Cheung et al. | May 2009 | A1 |
| 20090134758 | Vardon | May 2009 | A1 |
| 20090136737 | Ring et al. | May 2009 | A1 |
| 20090142604 | Imai et al. | Jun 2009 | A1 |
| 20090155566 | Gentleman et al. | Jun 2009 | A1 |
| 20090162592 | Baikerikar et al. | Jun 2009 | A1 |
| 20090163637 | Li et al. | Jun 2009 | A1 |
| 20090182085 | Escobar Barrios et al. | Jul 2009 | A1 |
| 20090186070 | Guire et al. | Jul 2009 | A1 |
| 20090188877 | Stewart | Jul 2009 | A1 |
| 20090195136 | Wing et al. | Aug 2009 | A1 |
| 20090212505 | McMillin et al. | Aug 2009 | A1 |
| 20090240004 | Maier et al. | Sep 2009 | A1 |
| 20090298369 | Koene et al. | Dec 2009 | A1 |
| 20100001625 | Eckartsberg et al. | Jan 2010 | A1 |
| 20100003493 | Cheng et al. | Jan 2010 | A1 |
| 20100026156 | Leconte et al. | Feb 2010 | A1 |
| 20100052491 | Vardon | Mar 2010 | A1 |
| 20100102693 | Driver et al. | Apr 2010 | A1 |
| 20100109498 | Ramm et al. | May 2010 | A1 |
| 20100117502 | Kang et al. | May 2010 | A1 |
| 20100133970 | Shin et al. | Jun 2010 | A1 |
| 20100176703 | Kim | Jul 2010 | A1 |
| 20100181884 | De La Garza et al. | Jul 2010 | A1 |
| 20100196702 | Furukawa | Aug 2010 | A9 |
| 20100213334 | Davenport | Aug 2010 | A1 |
| 20100272913 | Russell et al. | Oct 2010 | A1 |
| 20100314575 | Gao et al. | Dec 2010 | A1 |
| 20100330347 | Badyal et al. | Dec 2010 | A1 |
| 20110111656 | Gao et al. | May 2011 | A1 |
| 20110217544 | Young et al. | Sep 2011 | A1 |
| 20120009396 | Sikka et al. | Jan 2012 | A1 |
| 20120040577 | Kissel et al. | Feb 2012 | A1 |
| 20140087134 | Gesford et al. | Mar 2014 | A1 |
| 20140205804 | Jones et al. | Jul 2014 | A1 |
| 20140296409 | Sikka et al. | Oct 2014 | A1 |
| 20150005424 | Jones et al. | Jan 2015 | A1 |
| 20150030779 | Bleecher et al. | Jan 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 2175848 | Dec 1996 | CA |
| 10 2010 022 265 | May 2010 | DE |
| 0 166 363 | Jan 1986 | EP |
| 0 207 282 | Jul 1987 | EP |
| 0 307 915 | Mar 1989 | EP |
| 0 317 057 | May 1989 | EP |
| 0 332 141 | Sep 1989 | EP |
| 0 399 568 | Nov 1990 | EP |
| 0 446 391 | Sep 1991 | EP |
| 0 452 723 | Oct 1991 | EP |
| 0 472 215 | Feb 1992 | EP |
| 0 476 510 | Mar 1992 | EP |
| 0 493 270 | Jul 1992 | EP |
| 0 545 201 | Jun 1993 | EP |
| 0 623 656 | Nov 1994 | EP |
| 0 649 887 | Apr 1995 | EP |
| 0 657 393 | Jun 1995 | EP |
| 0 714 870 | Jun 1996 | EP |
| 0 714 921 | Jun 1996 | EP |
| 0 719 743 | Jul 1996 | EP |
| 0 719 821 | Jul 1996 | EP |
| 0 739 714 | Oct 1996 | EP |
| 0 745 567 | Dec 1996 | EP |
| 0 745 568 | Dec 1996 | EP |
| 0 752 459 | Jan 1997 | EP |
| 0 770 706 | May 1997 | EP |
| 0 904 343 | May 1997 | EP |
| 0 799 791 | Oct 1997 | EP |
| 0 811 430 | Dec 1997 | EP |
| 0 863 191 | Sep 1998 | EP |
| 0 969 718 | Sep 1998 | EP |
| 0 903 389 | Mar 1999 | EP |
| 0 914 873 | May 1999 | EP |
| 0 915 103 | May 1999 | EP |
| 0 930 351 | Jul 1999 | EP |
| 1 047 735 | Nov 2000 | EP |
| 1 048 696 | Nov 2000 | EP |
| 1 097 979 | May 2001 | EP |
| 1 108 735 | Jun 2001 | EP |
| 1 113 064 | Jul 2001 | EP |
| 1 136 539 | Sep 2001 | EP |
| 1 180 533 | Feb 2002 | EP |
| 1 187 872 | Mar 2002 | EP |
| 1 193 289 | Apr 2002 | EP |
| 1 215 252 | Jun 2002 | EP |
| 1 401 903 | Sep 2002 | EP |
| 1 261 559 | Dec 2002 | EP |
| 1 392 619 | Dec 2002 | EP |
| 1 392 772 | Dec 2002 | EP |
| 1 429 919 | Feb 2003 | EP |
| 1 492 837 | Oct 2003 | EP |
| 1 360 253 | Nov 2003 | EP |
| 1 362 904 | Nov 2003 | EP |
| 1 503 813 | Nov 2003 | EP |
| 1 387 011 | Feb 2004 | EP |
| 1 387 169 | Feb 2004 | EP |
| 1 407 792 | Apr 2004 | EP |
| 1 433 821 | Jun 2004 | EP |
| 1 583 615 | Jul 2004 | EP |
| 1 473 355 | Nov 2004 | EP |
| 1 475 234 | Nov 2004 | EP |
| 1 479 738 | Nov 2004 | EP |
| 1 524 290 | Apr 2005 | EP |
| 1 875 279 | Nov 2006 | EP |
| 1 883 669 | Nov 2006 | EP |
| 1 902 091 | Jan 2007 | EP |
| 1 752 284 | Feb 2007 | EP |
| 1 857 497 | Nov 2007 | EP |
| 1 873 218 | Jan 2008 | EP |
| 1 908 804 | Apr 2008 | EP |
| 1 988 129 | Nov 2008 | EP |
| 1 997 619 | Dec 2008 | EP |
| 2 346 678 | Jul 2011 | EP |
| 2 678 400 | Aug 2012 | EP |
| 2 791 255 | Jun 2013 | EP |
| 1 341 605 | Dec 1973 | GB |
| 2 484 751 | Apr 2012 | GB |
| 62-246960 | Oct 1987 | JP |
| H05-186738 | Jul 1993 | JP |
| H07-090691 | Apr 1995 | JP |
| H10-309768 | Nov 1998 | JP |
| 2004162133 | Jun 2004 | JP |
| 2004308984 | Nov 2004 | JP |
| 2005082616 | Mar 2005 | JP |
| 2006131938 | May 2006 | JP |
| 2007144917 | Jun 2007 | JP |
| 2007182491 | Jul 2007 | JP |
| 2008228958 | Oct 2008 | JP |
| 2009071672 | Apr 2009 | JP |
| 10-2003-0052853 | Jun 2003 | KR |
| 10-2009-90240 | Oct 2010 | KR |
| 175646 | Aug 1994 | MX |
| 183533 | Dec 1996 | MX |
| 192053 | May 1999 | MX |
| 195031 | Jan 2000 | MX |
| 199899 | Nov 2000 | MX |
| 201072 | Mar 2001 | MX |
| 203880 | Aug 2001 | MX |
| 205074 | Nov 2001 | MX |
| PA01011653 | Dec 2002 | MX |
| 215752 | Aug 2003 | MX |
| PA02006399 | Sep 2003 | MX |
| PA04010165 | Feb 2005 | MX |
| PA05006898 | Aug 2005 | MX |
| PA02012841 | Jan 2006 | MX |
| 234477 | Feb 2006 | MX |
| PA06003323 | Mar 2006 | MX |
| WO 91-04305 | Apr 1991 | WO |
| WO 93-16131 | Aug 1993 | WO |
| WO 94-13734 | Jun 1994 | WO |
| WO 96-04123 | Feb 1996 | WO |
| WO 96-07621 | Mar 1996 | WO |
| WO 97-07993 | Mar 1997 | WO |
| WO 98-20960 | May 1998 | WO |
| WO 99-23137 | May 1999 | WO |
| WO 99-23437 | May 1999 | WO |
| WO 99-40431 | Aug 1999 | WO |
| WO 99-47578 | Sep 1999 | WO |
| WO 99-48339 | Sep 1999 | WO |
| WO 99-57185 | Nov 1999 | WO |
| WO 99-64363 | Dec 1999 | WO |
| WO 00-05321 | Feb 2000 | WO |
| WO 00-14297 | Mar 2000 | WO |
| WO 00-25938 | May 2000 | WO |
| WO 00-34361 | Jun 2000 | WO |
| WO 00-39240 | Jul 2000 | WO |
| WO 00-46464 | Aug 2000 | WO |
| WO 00-66241 | Nov 2000 | WO |
| WO 01-19745 | Mar 2001 | WO |
| WO 01-62682 | Aug 2001 | WO |
| WO 01-74739 | Oct 2001 | WO |
| WO 01-79142 | Oct 2001 | WO |
| WO 01-79371 | Oct 2001 | WO |
| WO 01-98399 | Dec 2001 | WO |
| WO 02-14417 | Feb 2002 | WO |
| WO 02-28951 | Apr 2002 | WO |
| WO 02-062910 | Aug 2002 | WO |
| WO 02-074869 | Sep 2002 | WO |
| WO 02-098983 | Dec 2002 | WO |
| WO 03-010255 | Feb 2003 | WO |
| WO 03-012004 | Feb 2003 | WO |
| WO 03-030879 | Apr 2003 | WO |
| WO 03-037702 | May 2003 | WO |
| WO 03-045693 | Jun 2003 | WO |
| WO 03-063646 | Aug 2003 | WO |
| WO 03-080258 | Oct 2003 | WO |
| WO 03-082998 | Oct 2003 | WO |
| WO 03-093568 | Nov 2003 | WO |
| WO 2004-012625 | Feb 2004 | WO |
| WO 2004-043319 | May 2004 | WO |
| WO 2004-058418 | Jul 2004 | WO |
| WO 2004-104116 | Dec 2004 | WO |
| WO 2004-110132 | Dec 2004 | WO |
| WO 2005-021843 | Mar 2005 | WO |
| WO 2005-023935 | Mar 2005 | WO |
| WO 2005-028562 | Mar 2005 | WO |
| WO 2005-068399 | Jul 2005 | WO |
| WO 2005-077429 | Aug 2005 | WO |
| WO 2006044641 | Apr 2006 | WO |
| WO 2006-044642 | Apr 2006 | WO |
| WO 2006-081891 | Aug 2006 | WO |
| WO 2006-083600 | Aug 2006 | WO |
| WO 2006-101934 | Sep 2006 | WO |
| WO 2006-135755 | Dec 2006 | WO |
| WO 2007-011731 | Jan 2007 | WO |
| WO 2007-027276 | Mar 2007 | WO |
| WO 2007-052260 | May 2007 | WO |
| WO 2007-053266 | May 2007 | WO |
| WO 2007-056427 | May 2007 | WO |
| WO 2007-070801 | Jun 2007 | WO |
| WO 2007-075407 | Jul 2007 | WO |
| WO 2007-092746 | Aug 2007 | WO |
| WO 2007-102960 | Sep 2007 | WO |
| WO 2007-104494 | Sep 2007 | WO |
| WO 2007-126432 | Nov 2007 | WO |
| WO 2007-126743 | Nov 2007 | WO |
| WO 2007-130294 | Nov 2007 | WO |
| WO 2007-149617 | Dec 2007 | WO |
| WO 2008-004827 | Jan 2008 | WO |
| WO 2008-004828 | Jan 2008 | WO |
| WO 2008-006078 | Jan 2008 | WO |
| WO 2008-021791 | Feb 2008 | WO |
| WO 2008-035347 | Mar 2008 | WO |
| WO 2008-035917 | Mar 2008 | WO |
| WO 2008-050895 | May 2008 | WO |
| WO 2008-051221 | May 2008 | WO |
| WO 2008-066828 | Jun 2008 | WO |
| WO 2008-078346 | Jul 2008 | WO |
| WO 2008-106494 | Sep 2008 | WO |
| WO 2008-112158 | Sep 2008 | WO |
| WO 2008-123650 | Oct 2008 | WO |
| WO 2008-123955 | Oct 2008 | WO |
| WO 2008-123961 | Oct 2008 | WO |
| WO 2008-134243 | Nov 2008 | WO |
| WO 2008-137973 | Nov 2008 | WO |
| WO 2008-151991 | Dec 2008 | WO |
| WO 2008-153687 | Dec 2008 | WO |
| WO 2009-003847 | Jan 2009 | WO |
| WO 2009-005465 | Jan 2009 | WO |
| WO 2009-012116 | Jan 2009 | WO |
| WO 2009-018327 | Feb 2009 | WO |
| WO 2009-037717 | Mar 2009 | WO |
| WO 2009-041752 | Apr 2009 | WO |
| WO 2009-061199 | May 2009 | WO |
| WO 2009-148611 | Dec 2009 | WO |
| WO 2009-158567 | Dec 2009 | WO |
| WO 2010-033288 | Mar 2010 | WO |
| WO 20100042191 | Apr 2010 | WO |
| WO 2010-042191 | Apr 2010 | WO |
| WO 2010-042668 | Apr 2010 | WO |
| WO 2011-151151 | Dec 2011 | WO |
| WO 2012-115986 | Aug 2012 | WO |
| WO 2013-090939 | Jun 2013 | WO |
| WO 2014-003852 | Jan 2014 | WO |
| Entry |
|---|
| “Composition”, in Collins English Dictionary, (2000), viewed Aug. 26, 2013, <from http://www.credoreference.com/entry/hcengdict/composition>. |
| U.S. Appl. No. 60/699,200, filed Jul. 14, 2005, Guire et al. (Innovative Surface Technologies, Inc.) |
| U.S. Appl. No. 60/807,143, filed Jul. 12, 2006, Guire et al. (Innovative Surface Technologies, Inc.) |
| U.S. Appl. No. 60/891,876, filed Feb. 27, 2007, Lawin et al. (Innovative Surface Technologies, Inc.) |
| U.S. Appl. No. 61/058,902, filed Jun. 4, 2008, Driver et al. |
| U.S. Appl. No. 61/090,002, filed Aug. 19, 2008, Driver et al. |
| U.S. Appl. No. 61/133,273, filed Jun. 27, 2008, Driver et al. |
| U.S. Appl. No. 12/037,520, filed Feb. 26, 2008, Lawin et al. (issued in U.S. 7,943,234), file history. |
| EP App 06787306.7 Prosecution History, as of May 22, 2013, Guire (Innovative Surface Technologies) (published as WO2007/11731). |
| 2009 R&D 100 Award Entry Form (p. 5 excerpt from another document) showing Fig. 1 Schematic of NICE (“no ice nanocoating”) (2009). |
| Bayer Materials Science product information on Bayhydrol® 140AQ, polyurethane dispersion (Aug. 2002). |
| Bayer Materials Science product information on Bayhydrol® A145, aqueous hydroxyl-functional polyurethane dispersion (Jan. 2010). |
| Bayer Materials Science product information on Bayhydrol® 110 polyurethane dispersion (two first pages of this brochure) (Aug. 2002). |
| Bayer Materials Science product information on Bayhydrol® 122 polyurethane dispersion (Jan. 2004). |
| Bayer Materials Science product information on Bayhydrol® 124 polyurethane dispersion (Jan. 2004). |
| Clark, M.D.T. et al. “Paints and Pigments” available at nzic.org.nz/ChemProcesses/polymers/10D.pdf (copyright 2005-2008 at http://nzic.org.nz/ChemProcesses/polymers/). |
| EPO Communication dated Dec. 5, 2011, regarding third-party observations filed in European Application No. 09771098.2. |
| Extended European search report for European Application No. 09771098.2, dated Dec. 27, 2011. |
| International Preliminary Report on Patentability for International Application No. PCT/US2009/048775, dated Jan. 13, 2011. |
| International Preliminary Report on Patentability for International Application No. PCT/US2010/059909, dated Apr. 21, 2011. |
| International Search Report and Written Opinion for International Application No. PCT/US2009/048775, dated Nov. 19, 2009. |
| International Search Report and Written Opinion for International Application No. PCT/US2009/059909, dated Dec. 4, 2009. |
| International Search Report and Written Opinion for International Application No. PCT/US2010/048711, dated Mar. 17, 2011. |
| International Search Report and Written Opinion for International Application No. PCT/US2010/054936, dated Feb. 16, 2011. |
| International Search Report and Written Opinion for International Application No. PCT/US2009/005512, dated Dec. 8, 2009. |
| International Search Report and Written Opinion for International Application No. PCT/US2012/025982, dated Jun. 13, 2012. |
| Kobayashi et al., Surface Tension of Poly[(3,3,4,4,5,5,6,6,6-nonafluorohexyl)-methylsiloxane], Macromolecules, 23:4929-4933 (1990). |
| Sherwin Williams Chemical Coatings product information for CC-E14, POLANE® 700T, water reducible enamel (May 2010). |
| Two webpages re pigment particle size: http://www.specialchem4coatings.com/tc/color-handbook/index.aspx?id=size and http://www.specialchem4coatings.com/tc/tio2/index.aspx?id=whiteness, SpecialChem, S.A. (printed on Jul. 19, 2013). |
| Smith et al., “Modeling of PDMS—Silica Nanocomposites,” NSTI-Nanotech, 3:115-118 (2004). |
| U.S. Appl. No. 61/198,414, filed Jun. 16, 2009, Gao. |
| U.S. Appl. No. 61/216,540, filed May 18, 2009, Driver et al. |
| U.S. Appl. No. 61/252,229, filed Oct. 16, 2009, Gao. |
| “NeverWet—product characteristics,” found at http://www.neverwet.com/product-characteristics.php, NeverWet LLC (viewed Mar. 7, 2013). |
| “Yield strength, elastic limit, and ultimate strength,” found at http://inventor.grantadesign.com/en/notes/science/material/S04%20strength.htm, Granta Design Ltd. (viewed Feb. 10, 2015). |
| Bae et al., “Superhydrophobicity of cotton fabrics treated with silica nanoparticles and water-repellent agent,” J Colloid Interface Sci, abstract only (May 3, 2009; epublication ahead of print). |
| Beyler et al, “Thermal Decomposition of Polymers,” Chapter 7 of The SFPE Handbook of Fire Protection Engineering (3rd ed.), pp. 1-110-1-131 (2002). |
| Bliznakov et al., “Double-scale roughness and superhydrophobicity on metalized Toray carbon fiber paper,” Langmuir, 25(8):4760-4766, abstract only (Apr. 21, 2009). |
| Boinovich et al., “Principles of design of superhydrophobic coatings by deposition from dispersions,” Langmuir, 25(5):2907-2912, abstract only (Mar. 3, 2009). |
| Boinovich et al., “Principles of Design of Superhydrophobic Coatings by Deposition from Dispersions,” Langmuir, abstract only (Feb. 10, 2009; epublication ahead of print). |
| Bravo et al., “Transparent superhydrophobic films based on silica nanoparticles,” Langmuir, 23(13):7293-7298, abstract only (Jun. 19, 2007; epublished May 25, 2007). |
| Choi et al., “Large slip of aqueous liquid flow over a nanoengineered superhydrophobic surface,” Phys Rev Lett, 96(6):066001, abstract only (Feb. 17, 2006; epublished Feb. 16, 2006). |
| de Givenchy et al., “Fabrication of Superhydrophobic PDMS Surfaces by Combining Acidic Treatment and Perfluorinated Monolayers,” Langmuir, 25(11):6448-6453, abstract only (Jun. 2, 2009). |
| Du, “Surfactants, Dispersants, and Defoamers for the Coatings, Inks, and Adhesives Industries,” in Coatings Technology Handbook, Third Edition, Tracton (ed.), CRC Press (2005). |
| Expancel DE product list, “Product Specification for Expancel® Microspheres,” Issue 10.2010, AkzoNobel (Oct. 2010). |
| Extended European search report for European Application No. 920119918, dated Jul. 22, 1997. |
| Extended European search report for European Application No. 0981951.8, dated Jul. 22, 2014. |
| Fürstner et al., “Wetting and self-cleaning properties of artificial superhydrophobic surfaces,” Langmuir, 21(3):956-961, abstract only (Feb. 1, 2005). |
| García et al., “Use of p-toluenesulfonic acid for the controlled grafting of alkoxysilanes onto silanol containing surfaces; preparation of tunable hydrophilic, hydrophobic, and super-hydrophobic silica,” J Am Chem Soc, 129(16):5052-5060, abstract only (Apr. 25, 2007; epublished Mar. 31, 2007). |
| Gonçalves et al., “Superhydrophobic cellulose nanocomposites,” J. Colloid Interface Sci, 324(1-2):42-46, abstract only (Aug. 2008; epublished May 7, 2008). |
| Guo et al., “A novel approach to stable superhydrophobic surfaces,” Chemphyschem, 7(8):1674-1677, abstract only (Aug. 11, 2006; epublished Jul. 17, 2006). |
| In re Inter Partes Review of USP 8,286,561, Amended Petition for Inter Partes Review of U.S. Patent No. 8,286,561 Under 35 U.S.C. §§ 311-319 and 37 C.F.R. § 42.100 et seq., Trial No. IPR2013-00358 (Jun. 21, 2013). |
| In re Inter Partes Review of USP 8,286,561, Christopher B. Schechter Deposition, Trial No. IPR2013-00358 (Jan. 23, 2014). |
| In re Inter Partes Review of USP 8,286,561, Decision, Trial No. IPR2013-00358 (Nov. 14, 2013). |
| In re Inter Partes Review of USP 8,286,561, Declaration of Bradley M. Nall—Redacted Version, Trial No. IPR2013-00358 (Jan. 17, 2014). |
| In re Inter Partes Review of USP 8,286,561, Declaration of Chris B. Schechter, Trial No. IPR2014-00367 (Jan. 21, 2014). |
| In re Inter Partes Review of USP 8,286,561, Declaration of John Driver, Trial No. IPR2013-00358 (Feb. 7, 2014). |
| In re Inter Partes Review of USP 8,286,561, Patent Owner Preliminary Response Under 37 C.F.R. §§ 42.107, Trial No. IPR2013-00358 (Aug. 14, 2013). |
| In re Inter Partes Review of USP 8,286,561, Patent Owner Preliminary Response, Trial No. IPR2014-00367 (Apr. 29, 2014). |
| In re Inter Partes Review of USP 8,286,561, Patent Owner Response Under 37 C.F.R. §§ 42.120, Trial No. IPR2013-00358 (Feb. 7, 2014). |
| In re Inter Partes Review of USP 8,286,561, Patent Owner's Motion for Additional Discovery Pursuant to 37 C.F.R. §42.51(b)(2)—Redacted Version, Trial No. IPR2013-00358 (Aug. 14, 2013). |
| In re Inter Partes Review of USP 8,286,561, Paul Saunders Deposition, Trial No. IPR2013-00358 (Apr. 11, 2014). |
| In re Inter Partes Review of USP 8,286,561, Petition for Inter Partes Review of U.S. Patent No. 8,286,561 Under 35 U.S.C. §§ 311-319 and 37 C.F.R. § 42.100 et seq., Trial No. IPR2013-00358 (Jun. 14, 2013). |
| In re Inter Partes Review of USP 8,286,561, Petition for Inter Partes Review of U.S. Patent No. 8,286,561 Under 35 U.S.C. §§ 311-319 and 37 C.F.R. § 42.100 et seq., Trial No. IPR2014-00367 (Jan. 18, 2014). |
| In re Inter Partes Review of USP 8,286,561, Petitioner's Reply to Patent Owner's Response to Petition—Public Redacted Version, Trial No. IPR2013-00358 (Apr. 22, 2014). |
| In re Inter Partes Review of USP 8,286,561, Second Declaration of Bradley M. Nall, Trial No. IPR2013-00358 (Feb. 6, 2014). |
| In re Inter Partes Review of USP 8,286,561, Second Notice of Deposition of Paul Saunders Pursuant to 37 C.F.R. § 42.53, Trial No. IPR2013-00358 (Apr. 10, 2014). |
| International Search Report and Written Opinion for International Application No. PCT/US2012/070200 dated Feb. 27, 2013. |
| International Search Report and Written Opinion for International Application No. PCT/US2013/031751, dated Dec. 23, 2013. |
| International Search Report and Written Opinion for International Application No. PCT/US2014/057848, dated Dec. 29, 2014. |
| Jauregui-Beloqui et al., “Thermoplastic polyurethane-fumed silica composites: influence of the specific surface area of fumed silica on the viscoelastic and adhesion properties,” Journal of Adhesive Science and Technology, 13(6):695-711, abstract only (1999). |
| Kietzig et al., “Patterned superhydrophobic metallic surfaces,” Langmuir, 25(8):4821-4827, abstract only (Apr. 21, 2009). |
| Kim et al., “A simple fabrication route to a highly transparent super-hydrophobic surface with a poly(dimethylsiloxane) coated flexible mold,” Chem Commun (Camb), 22:2237-2239, abstract only (Jun. 14, 2007; epublished Mar. 6, 2007). |
| Le Marechal et al., “Textile Finishing Industry as an Important Source of Organic Pollutants,” in Organic Pollutants Ten Years After the Stockholm Convention—Environmental and Analytical Update, Puzyn (ed.), Chapter 2, pp. 29-54, InTech (2012). |
| Lee et al., “Impact of a superhydrophobic sphere onto water,” Langmuir, 24(1):142-145, abstract only (Jan. 1, 2008; epublished Nov. 14, 2007). |
| Li et al., “Conversion of a metastable superhydrophobic surface to an ultraphobic surface,” Langmuir, 24(15):8008-8012, abstract only (Aug. 5, 2008; epublished Jul. 8, 2008). |
| Ling et al., “Stable and transparent superhydrophobic nanoparticle films,” Langmuir, 25(5):3260-3263, abstract only (Mar. 3, 2009). |
| Litvinov et al., “Structure of a PDMS Layer Grafted onto a Silica Surface Studied by Means of DSC and Solid-State NMR,” Macromolecules, 35(11):4356-4364 (2002). |
| Manca et al., “Durable superhydrophobic and antireflective surfaces by trimethylsilanized silica nanoparticles-based sol-gel processing,” Langmuir, 25(11):6357-6362, abstract only (Jun. 2, 2009). |
| Marmur, “Super-hydrophobicity fundamentals: implications to biofouling prevention,” Biofouling, 22(1-2):107-115, abstract only (2006). |
| Ming et al., “Toward Superlyophobic Surfaces,” Contact Angle, Wettability and Adhesion (ed. Mittal), vol. 6, pp. 191-205, Koninklijke Brill NV, Leiden (2009). |
| Nosonovsky et al., “Patterned nonadhesive surfaces: superhydrophobicity and wetting regime transitions,” Langmuir, 24(4):1525-1533, abstract only (Feb. 19, 2008; epublished Dec. 12, 2007). |
| Park et al., “Wetting transition and optimal design for microstructured surfaces with hydrophobic and hydrophilic materials,” J. Colloid Interface Sci, 336(1):298-303, abstract only (Aug. 1, 2009; epublished Apr. 15, 2009). |
| Perez, Jr., et al., “Performance and Processing Enhancements of Aromatic Polyurea Elastomer Systems Prepared from High 2,4′—MDI Isocyanates,” in Polyurethanes Conference 2000: Defining the Future Through Technology, Boston, Massachusetts, pp. 219-232 (Oct. 8-11, 2000). |
| Piret et al., “Biomolecule and nanoparticle transfer on patterned and heterogeneously wetted superhydrophobic silicon nanowire surfaces,” Langmuir, 24(5):1670-1672, abstract only (Mar. 4, 2008; epublished Feb. 6, 2008). |
| Puukilainen et al., “Superhydrophobic polyolefin surfaces: controlled micro- and nanostructures,” Langmuir, 23(13):7263-7268, abstract only (Jun. 19, 2007; epublished May 23, 2007). |
| Sakai et al., “Direct observation of internal fluidity in a water droplet during sliding on hydrophobic surfaces,” Langmuir, 22(11):4906-4909, abstract only (May 23, 2006). |
| Sherwin Williams Chemical Coatings product information for CC-D14, POLANE® 2.8T, plus polyurethane enamel (Oct. 19, 2006). |
| Sherwin Williams Chemical Coatings product information for CC-D5, POLANE® T, polyurethane enamel (Sep. 2001). |
| Shirtcliffe et al., “Wetting and wetting transitions on copper-based super-hydrophobic surfaces,” Langmuir, 21(3):937-943, abstract only (Feb. 1, 2005). |
| SSW Holding Company, Inc. v. Schott Gemtron Corporation, Civil Docket, Civil Action No. 3:12-cv-00661-CRS (as of Dec. 6, 2013). |
| SSW Holding Company, Inc. v. Schott Gemtron Corporation, Complaint for Patent Infringement, Demand for Jury Trial, Civil Action No. 3:12-cv-00661-CRS (Oct. 16, 2012). |
| Su et al., “From Suerhydrophophilic to Superhydrophobic: Controlling Wettability of Hydroxide Zinc Carbonate Film on Zinc Plates,” Langmuir, abstract only (Feb. 10, 2009; epublication ahead of print). |
| Synytska et al., “Wetting on Fractal Superhydrophobic Surfaces from ‘Core-Shell’ Particles: A Comparison of Theory and Experiment,” Langmuir, abstract only (Feb. 10, 2009; epublication ahead of print). |
| Torró-Palau et al., “Characterization of polyurethanes containing different silicas,” International Journal of Adhesion and Adhesives, 21(1):1-9, abstract only (2001). |
| Venkateswara et al., “Preparation of MTMS based transparent superhydrophobic silica films by sol-gel method,” J Colloid Interface Sci, 332(2):484-490, abstract only (Apr. 15, 2009; epublished Jan. 14, 2009). |
| Wang et al., “One-step coating of fluoro-containing silica nanoparticles for universal generation of surface superhydrophobicity,” Chem Commun (Camb),7:877-879, abstract only (Feb. 21, 2008; epublished Dec. 18, 2007). |
| Yang et al., “Influence of surface roughness on superhydrophobicity,” Phys Rev Lett, 97(11):116103, abstract only (Sep. 15, 2006; epublished Sep. 14, 2006). |
| Zhang et al., “Application of superhydrophobic edge effects in solving the liquid outflow phenomena,” Langmuir, 23(6):3230-3235, abstract only (Mar. 13, 2007; epublished Jan. 25, 2007). |
| Zhou et al., “Study on the morphology and tribological properties of acrylic based polyurethane/fumed silica composite coatings,” Journal of Materials Science, 39:1593-1594, abstract only (2004). |
| Number | Date | Country | |
|---|---|---|---|
| 20120045954 A1 | Feb 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61103295 | Oct 2008 | US | |
| 61159914 | Mar 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2009/005512 | Oct 2009 | US |
| Child | 13082327 | US |
