text:
|Publication number
|Publication type
|Application number
|Publication date
|Mar 12, 2002
|Filing date
|Feb 18, 1999
|Priority date
|Aug 6, 1996
|Fee status
|Also published as
|Publication number
|James P. Bell, Nicole Baker
|Original Assignee
|The University Of Connecticut
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (21), Non-Patent Citations (2), Classifications (26), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation-in-part of U.S. application Ser. No. 09/092,212, filed on Jun. 5, 1998, which is incorporated herein in its entirety, which is a divisional of U.S. application Ser. No. 08/692,515, filed on Aug. 6, 1996, now U.S. Pat. No. 5,807,612.
1. Field of the Invention
This invention relates to compositions and methods for coating metal substrates. In particular, this invention relates to compositions and methods for forming a polymeric coating on a metal surface by dip autopolymerization. Importantly, the polymerization requires no application of external driving force, such as thermal or electrical energy. The coatings thus formed are uniform, conformal and pinhole-free. The method is suitable for forming coatings with a variety of desirable properties, such as corrosion and erosion resistance, abrasion resistance, and electrical and thermal insulation.
2. Brief Description of the Prior Art
Surface treatment, i.e., coating, of metals plays an important role in metal applications. Such coating processes may be applied for protective or decorative purposes. Conventional coating processes include, for example, spray painting, electrodeposition, electrophoresis, powder coating, anodization, and chromate conversion coatings. Metals ordinarily treated by these methods include iron, aluminum, copper, and their alloys. Each of these process technologies is currently used extensively in the metal finishing industry, and each has certain advantages and disadvantages.
For example, U.S. Pat. Nos. 5,232,560 and 5,466,357 to Bell et al. describe a method for electropolymerization in a substantially aqueous solution to form copolymer coatings onto electrically conductive substrates. Similarly, as described in U.S. Pat. No. 5,238,542 to Bell et al., cyclic N-substituted methacrylamide monomers may be electropolymerized onto electrically conductive filler. Electropolymerization is advantageous in that it allows the deposition of thick, thermally stable coatings. But while suitable for their intended purposes, electropolymerization requires the application of electrical energy as a driving force.
The practice of the other above-mentioned methods can be expensive, and result in undesirable waste products that must be subsequently disposed of. Spray painting may require a separate prepolymerization step prior to application of the coating. Electrodeposition and anodization require specialized equipment and thus capital investment. Many technologies require the input of heat or thermal energy as a driving force for the deposition processes. For these reasons, industry is in constant search of less expensive technologies to improve competitiveness in the world marketplace. In addition, increasing environmental concerns call for cleaner technologies to meet government regulations and reduce waste treatment and disposal cost.
In particular, aluminum is the most widely used metal today by volume. Areas of application for aluminum range from aerospace to marine to architectural. In almost all cases where aluminum is used, a surface treatment and finishing process are applied. The two most common surface treatments for aluminum are anodization and conversion coating. Anodization is an energy-intensive process, using phosphates. Conversion coating uses chromate and other heavy metal ions. Both of these treatments thus generate environmentally hazardous waste, which must be properly disposed of. Accordingly, there remains a need for efficient, inexpensive compositions and coating methods for aluminum and other metals that generate minimal waste.
The above-discussed and other problems and deficiencies of the prior art are overcome or alleviated by the composition and method of the present invention for coating metals by dip autopolymerization, wherein organic monomer in an acidic solution undergoes autopolymerization upon contact with a metal substrate at room temperature, thereby forming a polymeric coating on the metal substrate. Importantly, the polymerization requires no application of external driving force, such as thermal or electrical energy. The coatings thus formed may be up to 50 or more microns thick, and have molecular weights up to about 250,000 or more.
In one preferred embodiment of the present invention, the composition comprises an acidic solution of an organic electron acceptor monomer that undergoes autopolymerization in contact with a metal substrate, thereby forming a polymeric coating on the substrate. In another preferred embodiment of the present invention, the composition comprises an acidic solution of an organic electron acceptor monomer and an organic electron donor monomer that undergo autopolymerization in contact with a metal substrate, thereby forming a polymeric coating on the substrate. By electron acceptor monomer it is meant a monomer or small polymer having at least one electron withdrawing group, capable of further polymerization with the electron donor monomer. By electron donor monomer it is meant a monomer or small polymer having at least one electron donating group, capable of further polymerization with an electron acceptor monomer. Other metals suitable for use in the practice of the present invention include copper, iron, and zinc.
In another embodiment of the present invention, there is described metal-polymer composites comprising a metal such as copper, aluminum, iron, zinc, steel, or alloys thereof, and a polymeric coating.
In accordance with a method of the present invention, an acidic monomer solution is provided, and a clean metal substrate is submerged (dipped) into the monomer solution for a prescribed period of time. Polymerization occurs on the metal surface in the monomer solution spontaneously without application of any external driving force, such as thermal or electrical energy. Rather, polymerization is initiated at the metal-solution interface due to the interaction of the metal surface with the monomer in solution. The monomer converts directly to a polymer coating on the metal surface and thus obviates the need for the prepolymerization step required in conventional coating methods.
In another preferred embodiment of the present invention, an acidic monomer solution is applied onto a metal substrate by spraying, painting, roll coating, rod coating, blade coating, wire bar coating, extrusion coating, air knife coating, curtain coating, slide coating, doctor coating, gravure coating and the like. Polymerization occurs without application of external driving force, and converts directly to a polymer coating on the metal surface. The acidic monomer solution optionally comprises a viscosity modifier, usually a thickening agent, which facilitates application and which is optionally subsequently removed from the formed coating.
The present invention results in the formation of a uniform, conformal and pinhole free polymeric organic coating on metal surfaces. Physical and chemical properties such as corrosion and erosion resistance, electrical or thermal insulation, adhesion, printability, and scratch resistance of the coating may be varied simply by varying the composition of the monomer solution. The polymer coating formed may also be used as a primer for further surface finishing treatments or as a final coating.
The process can be very easily applied in various industrial settings. Relative to other polymerization techniques, the method is robust, being insensitive to moisture and other impurities. No special metal treatment is required other than cleaning of the metal surface. In the practice of the method, the low cost of operation relative to other coating processes will result in considerable energy savings. Sophisticated equipment is not required, so capital equipment cost is also minimal. Solvent use is minimal, and no heavy metals are required to be present. Also, water is frequently used as a co-solvent with a suitable solvent to dissolve the monomer, resulting in a more environmentally acceptable coating composition and method.
The above-discussed and other features and advantages of the present invention will be appreciated and understood by those skilled in the art from the following detailed description and drawings.
Referring now to the drawings wherein like elements are numbered alike in the several FIGURES:
FIG. 1 is a transmission IR spectrum of a typical poly(4-CPMI/styrene) coating on steel obtained according to the method of the present invention;
FIG. 2 is transmission IR spectra of (a) poly(4-CPMI), (b) polystyrene, and (c) a blend of the two hompolymers;
FIG. 3 is a plot showing the absorbance ratio of 1510 cm−1 to 1493 cm−1 vs. the ratio of 4-CPMI to styrene in a blend of polystyrene homopolymer and poly(4-CPMI);
FIG. 4 is a plot showing the effect of varying the 4-CPMI to styrene feed ratio on the 4-CPMI to styrene ratio in a poly(4-CPMI/styrene) according to the present invention;
FIG. 5 is a plot showing the effect of varying the 4-CPMI content in the feed on the yield of poly(4-CPMI/styrene) according to the present invention;
FIG. 6 is a plot showing the effect of varying concentrations on yield of poly(4-CPMI/styrene) according to the present invention;
FIG. 7 is a plot showing the effect of varying the pH of the monomer solution on the yield of poly(4-CPMI/styrene) according to the present invention;
FIG. 8 is a TGA thermogram of a poly(4-CPMI/styrene) coating obtained on steel by the method according to the present invention as measured under (a) nitrogen atmosphere and (b) oxygen atmosphere;
FIG. 9 is a plot showing the weight average molecular weight (MW) of a poly(NPMI/styrene) coating formed by the method according to the present invention as a function of total monomer concentration for solutions of varying pH;
FIG. 10 is an FTIR overlaid spectrum showing formation of poly(NPMI/styrene/MEA) polymer in accordance with the present invention;
FIG. 11 is a plot showing the effect of polymerization time on the coating thickness for various monomer feed compositions in the practice of the present invention;
FIG. 12 is a plot showing the effect of polymerization temperature over time on the measured coating thickness of poly(NPMI/styrene/MEA/BMI) aluminum composite according to the present invention;
FIG. 13 is a plot showing the effect of varying 4-CPMI content in the feed on the glass transition temperatures of poly(4-CPMI/MMA) coatings in accordance with the present invention; and
FIGS. 14(A)-(C) are photographs showing corrosion resistance of poly(NPMI/styrene/MEA) aluminum composites according to the present invention.
The present invention is directed to a composition and method for producing polymeric coatings on clean metal substrates, wherein organic monomers in an acidic solution undergo autopolymerization upon contact with a metal substrate at room temperature, thereby forming a polymeric coating on the metal substrate. The coating solution and method is environmentally benign. The method is particularly advantageous in that it requires no external application of thermal or electrical energy.
In accordance with one embodiment of the method, the metal substrate is dipped into one of the below-described compositions. In another embodiment, the substrate metal is painted or sprayed with one or more of the below-described compositions. The painting or spraying application process is particularly useful for substrates that do not lend themselves to the dipping method, for example, large volume applications such as aircraft, boats, and the like. The compositions of this embodiment preferably further comprise a viscosity-modifying agent and/or an adhesion promoter. The viscosity-modifying agent is usually a thickening agent which increases the viscosity of the composition, thus facilitating application of the solution by methods such as spraying, painting, roll coating, rod coating, blade coating, wire bar coating, extrusion coating, air knife coating, curtain coating, slide coating, doctor coating, gravure coating and the like, and preventing the solution from running off the substrate. Preferably, the thickening agent is sufficiently hydrophilic to enable its removal from the formed polymer-coated metal composite by rinsing with water or a water-solvent rinse. Thickening agents suitable for use in the present invention include, but are not limited to, poly(vinylpyrrolidone), poly(ethylene oxide), poly(acrylic acids) and derivatives thereof, ethylene-maleic anhydride copolymers, vegetable gums, such as guar gum, sodium alginate, and gum tragacanth, cellulose-based compounds, such as cellulose, methyl cellulose, carboxymethylcellulose, and sodium carboxymethyl cellulose, and ethylene-vinyl ether copolymer.
Preferably, an adhesion promoter is also added to the compositions wherein the application is by spraying, painting, roll coating, rod coating, blade coating, wire bar coating, extrusion coating, air knife coating, curtain coating, slide coating, doctor coating, gravure coating and the like. The adhesion promoter may be selected from those known in the art that function at or near room temperature. Preferably, the adhesion promoter is a silane monomer such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy) silane, γ-methacryloxypropyltimethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxy)silane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. A particularly preferred adhesion promoter is the silane monomer 3-(methoxysilyl) propyl methacrylate. The adhesion promoter may be used alone or in a combination of a plurality of the adhesion promoters. Most preferably, the compositions of this embodiment comprise both a thickening agent and an adhesion promoter.
The composition of the present invention comprises an acidic starting solution of organic monomer, capable of undergoing autopolymerization upon contact with a metal substrate, thereby forming a polymeric coating on the metal substrate. As used herein, and as is shown in the accompanying Examples 1-6, "autopolymerization" refers to a polymerization process whereby polymerization of monomers occurs upon exposure of the monomer solution to the metal substrate in the absence of other catalyst or catalysts. Water may be used as a co-solvent with a suitable solvent to dissolve the monomers, resulting in a more environmentally acceptable coating composition and method. Polymerization ordinarily proceeds at room temperature. However, heat may be applied to the solution in order to increase the rate of polymerization, or to effect a variation in the properties of the final coating.
Although the preferred embodiments of the present invention contemplate at least a two-component monomer solution, a one-component monomer solution is also with the scope of the present invention. A particularly preferred one-component monomer solution comprises N-phenylmaleimide as the monomer undergoing autopolymerization. Furthermore, the term "monomer" as used herein is intended to comprise both monomers and small polymers, e.g., small molecules with one or more repeating units. Such polymers must be soluble in the solvents suitable for use with the present invention, and capable of undergoing autopolymerization upon exposure to a metal substrate.
In one preferred embodiment of the present invention, the composition comprises an acidic starting solution of organic electron acceptor monomer that undergoes autopolymerization in contact with a metal substrate, thereby forming a polymeric coating on the substrate. Thus, one particularly preferred embodiment of the present invention comprises an acidic starting solution of methyl methacrylate (MMA) and 4-carboxyphenyl maleimide (4-CPMI). Introduction of a steel substrate into this solution induces autopolymerization of the MMA and 4-CPMI, thereby forming a poly(MMA/4-CPMI) coating onto the steel. Polymeric coatings thus formed may be up to about 50 microns or more thick. They are even, conformal, and pinhole-free. Other particularly preferred embodiments of this type comprise an acidic starting solution of 4-CPMI and acrylonitrile (AN). Preferably, these monomer solutions are used to coat steel, although other metals might also be used. Without being bound by theory, it is hypothesized that when used to coat steel, polymerization is initiated by a redox process on the surface of the steel substrate. It is unlikely that the process is Lewis-acid catalyzed, as the addition of Fe+3 to the acidic monomer solution failed to induce polymerization.
Another preferred embodiment of the present invention comprises an acidic starting solution of an electron acceptor monomer and an electron donor monomer. By electron acceptor monomer it is meant a monomer or small polymer having at least one electron withdrawing group, capable of further polymerization with the electron donor monomer. By electron donor monomer it is meant a monomer or small polymer having at least one electron donating group, capable of polymerization with an electron acceptor monomer. The molar ratio of the electron donor monomer to the electron acceptor monomer will generally range from about 5:95 to about 95:5. The preferred concentration of electron donor monomer in solution is generally between about 0.01-5 moles per mole of electron acceptor monomer, and preferably about 0.05-1 moles of electron donor monomer per mole of electron acceptor monomer.
Typical electron withdrawing groups for electron acceptor monomers include, but are not limited to, carbonyl, carboxyl, carboxylate, carboxamide, nitrite groups and the like. Thio analogues of the oxygen-containing functional groups are also effective groups for electron acceptor monomers.
Illustrative electron acceptor monomers include, but are not limited to, acrylic acid, acrylamide, acrylonitrile, and alkyl acrylates in which the alkyl moiety contains 1 to 40 carbon atoms. Preferably, the alkyl moieties have 1 to 22 carbon atoms, including methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, octadecyl acrylate and the like.
Other electron acceptor monomers include but are not limited to aryl and aralkyl acrylates such as phenyl acrylate and p-tolyl acrylate, cycloalkyl acrylates such as cyclohexyl acrylate, methacrylic acid, methacrylamide, methacrylonitrile, and alkyl methacrylates in which the alkyl moiety contains 1-40 carbon atoms. Preferably, the alkyl moieties contain 1 to 22 carbon atoms, including methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, and the like.
Other electron acceptor monomers contemplated for use with the present invention include, but are not limited to, aralkyl methacrylates such as benzyl methacrylate, aryl methacrylates such as phenyl methacrylate and p-tolyl methacrylate and cycloalkyl methacrylates such as cyclohexyl methacrylate, as well as various ketones, such as methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, acrolein, methacrolein and the like.
Sulphur-containing compounds which are effective electron acceptor monomers include thiocarboxylic acids such as thioacrylic acid and thiomethacrylic acid, thiocarboxamides such as thioacrylamide and thiomethacrylamide, as well as alkyl, aryl, aralkyl and cycloalkyl thiocarboxylates such as methyl thioacrylate, methyl thiomethacrylate, phenyl thioacrylate, benzyl thiomethacrylate, cyclohexyl thiomethacrylate and the like. Dithioacrylic acid, dithiomethacrylic acid and the esters of these dithiocarboxylic acids are also useful electron acceptor monomers.
Electron donor monomers are typically acyclic and cyclic monoolefins and conjugated dienes. The monoolefins may be alpha-olefins or internal olefins, including cycloolefins, and may be unsubstituted or may contain alkyl, aryl or aralkyl substituents. The effective alpha-olefins include, but are not limited to, 1-alkenes such as ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene and other 1-alkenes containing up to 40 carbon atoms.
1-Alkenes having substituents further removed from the double bond are also effective, including, but not being limited to, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 5-methyl-1-hexene and the like.
Aromatic substituted alpha-olefins are particularly effective electron donor monomers and include styrene, alpha-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-nonylstyrene, p-chlorostyrene, and other 1-alkenes containing alkyl substitute aromatic moieties. Similarly, alpha-olefins containing aromatic substituents further removed from the double bond such as 3-phenyl-1-butene, 4-p-methylphenyl-1-pentene and the like are effective electron donor monomers.
Internal olefins which are useful electron donor monomers in the present invention may be unsubstituted alkyl or aryl substituted acyclic or cyclic monoolefins, including 2-butene, 2-pentene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 4-octene, 2-nonene, 3-nonene, 4-nonene, 2-methyl-2-butene, 2-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-2-hexene, 4-methyl-2-hexene, 5-methyl-2-hexene, 2,5-dimethyl-3-hexene, 1-phenyl-3-pentene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1-methylcycloheptene, 5-methylcycloheptene and the like.
Illustrative conjugated dienes useful as electron donor monomers according to this invention include butadiene, isoprene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2,3-dimethylbutadiene, propylene, 2,4-hexadiene, 2-methyl-1,3-pentadiene, 2-ethyl-1,3-butadine, 2-propyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-pentadine, 2-methyl-1,3-hexadiene and the like. Cyclic conjugated dienes such as 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, 1,3-cyclononadine and the like are also effective electron donor monomers.
Preferred electron acceptor monomers are 4-carboxyphenyl maleimide (4-CPMI), N-phenyl maleimide (NPMI), bis-maleimide (BMI), and 2-(methacryloyloxy)ethyl acetoacetate (MEA), and acrylonitrile (AN). A preferred electron donor monomer is styrene.
A particularly preferred embodiment of the electron donor/electron acceptor monomer solution comprises styrene and N-phenyl maleimide. Without being bound by theory, it is hypothesized that in this system, the driving force for autopolymerization in the electron donor/electron acceptor systems on aluminum substrates is derived from the metal surface where Lewis acids such as Al3+ are generated when immersed in an acidic solution. The Al3+ ion is classified as a hard Lewis acid and therefore has a strong affinity for an electron pair. Lewis acids may increase the electrophilicity of the electron-poor monomer by complexing to its lone pair of electrons. This in turn increases the electron disparity between the reaction partners. It is proposed here that these transition metal Lewis acids interact with an electron acceptor monomer such as NPMI, thereby increasing the electrophilicity of the monomer and resulting in the spontaneous formation of an NPMI-styrene tetramethylene diradical. The polymerization may then proceed by alternate addition of the electron donor monomer, e.g., styrene, and the electron acceptor monomer, e.g., NPMI, to the growing radical. This kind of alternating addition of monomers is also known as cross-propagation.
Where two monomers are present in the monomer solution, the polymer formed therefrom may be an essentially alternating copolymer, that is, a copolymer in which the comonomer units are present in essentially equimolar quantities and are situated alternately along the copolymer chain. However, random polymers may also be formed by the autopolymerization method of the present invention. Furthermore, a third and even a fourth monomer (or more) may be introduced into the monomer solution. Variation in the number of monomers, the monomer ratios, and their composition allows for variation in the final properties of the formed coating. Other process parameters that may be used to affect the final properties of the coatings include monomer concentration, metal surface pretreatment, polymerization time, and drying temperature.
A single solvent may be used to dissolve the monomers, or a mixture of several hydrocarbon, halogenated, aromatic, or oxygen donating solvents. Appropriate solvents include, but are not limited to, benzene, toluene, chloroform, methylene chloride, hexane, acetone, tetrahydrofuran, acetonitrile, dimethyl formamide, dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. In many instances, water may be used as a co-solvent, especially where other polar solvents, such as acetone, tetrahydrofuran, acetonitrile, dimethyl formamide, dimethylacetamide, N-methyl-2-pyrrolidone, diglyme, cyclohexyl-2-pyrrolidone, pyridine, or dimethyl sulfoxide are used. Such aqueous systems are preferable because the process cost is lowered. Where polymerization proceeds via a free radical mechanism, aqueous systems would favor such a mechanism, thus allowing high molecular weight polymer coatings to be easily obtained.
The solvent or solvent mixture used in the method of the present invention must be compatible with the monomer(s) used. The solvent or solvent mixture should have reasonable solubility for the monomer(s) used in the process, i.e, able to dissolve each monomer to a concentration of about 0.01-5 molar, and preferably to a concentration of about 0.1-1 molar. Alternatively, the monomers may be present in solution as an aqueous emulsion. However, such solvent or solvent mixture preferably has significantly lower solubility for the formed polymer, as the polymer should be insoluble to prevent it from dissolving into the solution. Using the proper solvent or solvent mixture thus allows the formation of a uniform coating on the metal substrate.
Importantly, the pH of the monomer solution must be acidic, having a pH of preferably less than about 6.5. The optimal pH value is within the range of about 1 to about 6.5, and preferably from about 2.5 to about 5.5. Solutions having an essentially neutral pH failed to undergo autopolymerization, even in the presence of a metal substrate. When the monomer solution is itself acidic as prepared, pH adjustment may be unnecessary. Otherwise, the pH may be adjusted using acids such as dilute sulfuric acid, hydrochloric acid, dilute nitric acid, acetic acid, phosphoric acid, and citric acid.
While not required, an accelerator may be added to the monomer solution to increase the reaction rate. Preferably, the accelerator is a metal salt. The salt most likely interacts with the electron acceptor monomer to increase its reactivity. Possible salts may include, but are not limited to, halides of aluminum, zinc, nickel, magnesium, cerium, tin, zirconium, chromium, vanadium, titanium and molybdenum, and boron trifluoride, ethyl aluminum dichloride or ethyl aluminum sesquichloride. The amount of accelerator used may vary over a wide range. However, the preferred concentration is generally between about 0.01-5 mole of accelerator per mole of electron acceptor monomer, and most preferably, about 0.05-1 mole of accelerator per mole of electron acceptor monomer.
Metal substrates which may be coated by the method of the present invention include a number of economically important metals, including, but not limited to, aluminum, iron, copper, steel, zinc, and alloys thereof. Other metals may be possible, for example, other transition metals and their alloys, such as chromium, tin, indium, nickel, cobalt, and titanium and their alloys. Metals such as magnesium, or inert substances such as silica or glass are not coated by the autopolymerization method of the present invention.
In accordance with one method of the present invention, the above-described acidic monomer starting solution is provided and a clean metal substrate is submerged (dipped) into the monomer solution for a prescribed period of time. Polymerization occurs on the metal surface in the monomer solution spontaneously without application of any external driving force, such as thermal or electrical energy. Rather, polymerization is apparently initiated at the metal-solution interface due to the interaction of the metal surface with the monomers in solution, converting the monomers directly to polymer coatings on the metal surface and obviating the prepolymerization step in the conventional coating methods.
In accordance with another method of the present invention, the above-described acidic monomer solution is painted or sprayed onto the metal substrate, or applied by rod coating, roll coating, and the like. In this embodiment, the above-described monomer solution preferably additionally comprises a viscosity-modifying agent and/or an adhesion promoter, more preferably both.
The viscosity-modifying agent is preferably a thickening agent which increases the viscosity of the composition, thus facilitating application of the solution by methods such as roll coating, rod coating, painting and spraying, and preventing the solution from running off the substrate. Preferably, the thickening agent is sufficiently hydrophilic to enable its removal from the formed polymer-coated metal composite by rinsing with water or a water-solvent rinse. Thickening agents suitable for use in the present invention include, but are not limited to, poly(vinylpyrrolidone), poly(ethylene oxide), poly(acrylic acids) and derivatives thereof, ethylene-maleic anhydride copolymers, vegetable gums, such as guar gum, sodium alginate, and gum tragacanth, cellulose-based compounds, such as cellulose, methyl cellulose, carboxymethylcellulose, and sodium carboxymethyl cellulose, and ethylene-vinyl ether copolymer.
Preferably, an adhesion promoter is also added to the compositions wherein the application is by painting and spraying. The adhesion promoter may be selected from those known in the art that function at or near room temperature, for example silanes, titanates such as neopentyl(diallyl)trineodecanoyl titanate), neopentyl(diallyl)oxytri(dioctyl)phosphate titanate, and zirconates such as neopentyl(diallyl)oxytri(dioctyl) pyrophosphate zirconate, and neopentyl(diallyl)oxytri(N-ethylenediamine)ethyl zirconate. Preferably, the adhesion promoter is a silane such as vinyltrimethoxysilane, vinyltriethoxysilane, phenyl trimethoxy silane, phenyl triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxy)silane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropylmethyldimethoxysilane, and mixtures thereof. A particularly preferred adhesion promoter is 3-(methoxysilyl) propyl methacrylate. The adhesion promoter may be used alone or in a combination of a plurality of the adhesion promoters. Most preferably, the compositions of this embodiment comprise both a thickening agent and an adhesion promoter.
In the painting or spraying application method, the polymer coated metal composite is preferably treated after polymerization to remove the viscosity modifier. Treatment may be any treatment that removes the viscosity modifier. The preferred method is to rinse the polymer coated metal composite with a water or water-solvent rinse. Preferred solvents in the water-solvent rinse are water miscible, dissolve the viscosity modifier and excess monomer but not the formed coating. Suitable solvents include, but are not limited to, N-methyl-2-pyrrolidone, tetrahydrofuran, acetone, benzene, toluene, chloroform, methylene chloride, hexane, acetonitrile, dimethyl formamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, dimethyl formamide, dimethylacetamide, diglyme, cyclohexyl-2-pyrrolidone, pyridine, dimethyl sulfoxide, dioxane, N,N-dimethylformamide, and the like.
No special surface treatments are necessary for the autopolymerization methods. The only requirement is a clean, preferably dry, surface. Furthermore, simple cleaning processes such as detergent washing, grit blasting, and trichloroethylene degreasing are sufficient to remove dirt and organic contaminants on the metal surface.
The methods of the present invention may be used for various applications requiring coatings on metals, such as automobile bodies and parts, circuit board heat sinks, electric motor starters, air conditioner fins, and any other type of metal parts or fittings requiring an organic coating. The process can be scaled up to industrial requirements without apparent complications. Process scale-up involves simply larger solution volume formulations and use of larger polymerization tanks.
Thus, still another embodiment of the present invention is a polymer-metal composite comprising a metal substrate and a polymeric coating. In this embodiment, the metal substrate comprises aluminum, copper, steel, iron, or zinc, and alloys thereof. Preferably, the polymeric coating comprises a coating of poly(4-CPMI/styrene), poly(4-CPMI/MMA), poly(4-CPMI/AN), poly(NPMI/styrene), poly(NPMI/BMI/styrene), and poly(NPMI/BMI/MEA/styrene).
The composition and methods for autopolymerization on metals of the present invention allows polymer coatings to be synthesized directly onto the metal surface. The method may be conducted at room temperature, and no external driving force, i.e., thermal or electrical energy, is required. The key difference between this process and other conventional coating processes, such as dip coating or electrophoresis, is that here, the polymer chains "grow" at the metal surface, allowing formation of uniform coatings on objects with complex topographies. The composition and method also results in better adhesion of the metal substrate to the polymer coating, because wetting of the metal surface is easier by monomers, compared with polymers. Furthermore, it is not necessary to evaporate large quantities of solvent during the drying of the polymer coating, as is required by conventional coating methods.
The present invention is further illustrated by the following non-limiting examples.
Styrene and methyl methacrylate were obtained from Fisher Scientific Company. Inhibitor-free styrene was obtained by vacuum distillation at 40� C. Methyl methacrylate was also purified by vacuum distillation. N-Methyl-2-pyrrolidone (NMP) was used as received from Fisher Scientific Company. 4-Carboxyphenyl maleimide (4-CPMI) was prepared according to the method described by B. S. Rao, in Journal of Polymer Science: Part C: Polymer Letters, Vol. 26, p. 3 (1988). Monomer purity was confirmed by nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). The DSC thermogram showed only one sharp melting peak at 241� C. N-phenyl maleimide (NPMI) and bis-maleimide (BMI) were purchased from Mitsui Toatsuo Chemical Co., Japan. NPMI was recrystallized from cyclohexane and BMI was used as obtained. 2-(Methacryloyloxy)ethyl acetoacetate (MEA) from Aldrich Chemical Co. was purified by passing through DHR-4 inhibitor removal columns from Scientific Polymer Products. 3-(Methoxysilyl)propyl methacrylate was purchased from Fisher Scientific Company.
Metal substrates were SAE 1010 carbon steel coupons from Q-Panel Company, and aluminum 1100, 2024, 6061, or 7071 alloy. Metal substrates in the aluminum 3000 series may also be used. The steel surface was cleaned by washing with detergent, rinsing with an ample amount of distilled water, and oven-drying at 90� C. Aluminum was cleaned by one of two methods: (i) degreasing with 5% aqueous Micro� (an alkaline soap) solution in an ultrasonic bath for 5 min., rinsing with distilled water, treating with 5% hydrofluoric acid for 15 sec., and rinsing with distilled water; or (ii) grit blasting using 170 mesh silica, then rinsing with distilled water.
A Nicolet 60SX Fourier transform infrared spectrometer (FT-IR) was used to characterize the composition of the polymer coating at a resolution of 4 cm−1, by pressing KBr pellets from mixtures of about 150 mg KBr powder and 10 mg polymer. A differential scanning calorimeter (DSC) model 2920 and thermogravimetric analyzer (TGA) model 2950 from TA Instruments were used for thermal analyses, using a heating rate of 10� C./min for the DSC and 20� C./min for the TGA. The molecular weights of the polymers were obtained by GPC on a Waters 150C gel permeation chromatograph using polystyrene standards. The measurements were conducted at 35� C. in tetrahydrofuran. Dielectric constant measurements of the coating were obtained using a Time Domain Dielectric Spectrometer (TDDS) from IMASS, Inc. Corrosion protection properties of the polymer coatings were studied by exposing samples to a 5% NaCl salt fog, following the ASTM B-117 test method.
General Polymerization Procedure: A monomer solution was prepared by first dissolving the styrene and 4-CPMI in NMP on a 1:1 mole basis, then mixing with water to a final concentration of 0.2 M in each monomer. Polymerization was initiated by dipping a cleaned substrate in the solution. Simultaneous polymerization of the monomers and deposition of the formed polymers occurred at the metal surface. After a prescribed period of time, ranging from 1 minute to 1 hour, the metal substrate was withdrawn from the solution, thoroughly rinsed with distilled water, and dried in an oven at 50 to 150� C. for 1-24 hours. Further drying was carried out at 250� C. under vacuum to remove any trapped solvent.
Results and Discussion: The IR spectrum of a typical poly(4-CPMI/styrene) polymeric coating obtained by the above procedure is shown in FIG. 1. The symmetric and asymmetric C═O stretching of the carbonyl groups in the imide ring absorb at 1776 cm−1 and 1714 cm−1, respectively. The strong absorption at 1383 cm−1 is due to symmetric C—N—C stretching of the imide ring. The peak at 1512 cm−1 is attributed to the para-substituted phenyl ring in 4-CPMI, while the aromatic C—C stretching at 1608 cm−1 has contributions from both 4-CPMI and styrene. The characteristic absorption of polystyrene at 1493 and 1452 cm−1 is assigned as the semi-circle stretching and mixed C—H bending of a mono-substituted phenyl ring. The C—H bending of the vinyl group at 991 cm−1 and 908 cm−1 of styrene, and the C—C stretching of the imide ring at 949 cm−1 of 4-CPMI are absent in the spectrum, confirming that the polymerization reaction occurred via opening of the double bond.
To determine the composition of the coating, a calibration was obtained using homopolymers of 4-CPMI and styrene. FIGS. 2(a) and 2(b) are transmission IR spectra of polystyrene and poly(4-CPMI), respectively, obtained by solution polymerization in THF. The spectrum of the blend of the homopolymers agrees with that of the copolymer with no additional peaks appearing, as shown in FIG. 2(c).
A calibration plot was then constructed using blends of these two homopolymers at various ratios. The absorption peaks at 1510 cm−1 for styrene and at 1493 cm−1 for 4-CPMI were chosen as the characteristic peaks for styrene and 4-CPMI, respectively. When the absorbance ratio of these two peaks is plotted vs. the molar ratio of poly(4-CPMI) to polystyrene present in the blend, as shown in FIG. 3, very good linearity is obtained. The polymerization was controlled in such a way as to proceed at low monomer conversion levels, in which case the monomer concentrations can be assumed to be constant during the reaction course. Using the above calibration, the ratio of 4-CPMI and styrene incorporated into the polymer obtained were then determined to be 1:1. As shown in FIG. 4, as the ratio of 4-CPMI to styrene in the feed changes, the ratio of 4-CPMI to styrene in the polymer coating remains essentially constant.
The molecular weight of the polymer formed was determined to be fairly high, with the weight average molecular weight, MW, of 146,000 by GPC, and a polydispersity index, MW/MN, of 2.4. These results are typical for free radical polymerization, in that high molecular weight polymer can usually be obtained relatively easily.
The effects of various process parameters on yield of poly(4-CPMI/styrene) are shown in FIGS. 5, 6, and 7. FIG. 5 is a plot of yield based on mole percent of 4-CPMI in the feed at a polymerization time of five minutes. As shown in FIG. 6, yield generally increases both with increased reaction time and increased molar concentration of both monomers. Yield decreases with increasing pH (FIG. 7).
The incorporation of the rigid five-membered ring of 4-CPMI into the polymer backbone significantly hindered segmental rotation and stiffened the chain, resulting in much improved thermal stability as compared with polystyrene homopolymer. As shown in the TGA thermogram in FIG. 8, when measured under nitrogen atmosphere, the copolymer is stable up to 450� C., after which it undergoes a one-stage decomposition. The thermal stability is still excellent in an oxygen atmosphere, where the onset temperature for degradation is only lowered by about 50� C., to 400� C. It is likely that the significant improvement in thermal properties of the poly(4-CPMI/styrene) obtained by the method of the present invention, as compared to polystyrene, is due to the large proportion of 4-CPMI incorporated into the polymer chain.
A low dielectric constant is very critical for insulation applications. Dielectric constant measurements on the coating at selected frequencies are listed in Table 1 below. The poly(4-CPMI/styrene) coating has a dielectric constant of about 2.6 in the frequency range investigated, comparable to or slightly lower than that of one of the widely used commercial polyimides. Thus the coating of the present invention will be an attractive candidate for insulation applications.
Dielectric Constant of Poly(4-CPMI/styrene)
Frequency (Hz)
Dielectric Constant
General Polymerization Procedure :NMPI and styrene were dissolved in NMP in an equimolar ratio to obtain the final concentrations shown in FIG. 9. Dilute aqueous sulfuric acid (0.025 M) was then added to the solution while stirring, until a 57/43 volume ratio of NMP/water was obtained.
The monomer solution was then purged with nitrogen. Dissolved oxygen content was kept to less than 2 ppm. When the pretreated aluminum was immersed in the monomer bath, a white, swollen polymer coating began to form. Polymerization time for samples in the bath varied from 10 minutes to 120 minutes. The coated sample was then immersed in a gently stirred 10% NMP solution for 1 hour, to remove excess NMP, and was oven dried at 150� C. for 1 hour and then at 225 to 250� C. for 4-6 hours.
Results and Discussion: The solvent quantity of the 57/43 NMP/water solution is close to the solubility limit of the monomers. The polymer formed on the aluminum surface is insoluble in the solution but is in a swollen state. The swollen nature of the polymer coating permits the diffusion of monomers through the polymer to reach the aluminum surface and also to react with the propagating chain ends. Thus, coatings up to 50 μm thick can be obtained. Coating thickness can be controlled by varying the polymerization time, or the monomer concentration.
FIG. 9 shows the weight average molecular weight (MW) of the coatings formed by autopolymerization plotted as a function of total monomer concentration for solutions of varying pH as determined by GPC measurement. At low pH it is expected that a greater number of Lewis acid sites should be generated at the aluminum metal surface, resulting in a high rate of initiation. This would give a relatively low molecular weight polymer, in keeping with classical free radical polymerization equations. As the pH increases, the number of Lewis acid sites formed should be less, and thus the molecular weight of the polymer obtained should be higher. It was further found that the polymerization reaction was quenched by the addition of 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH), confirming the free radical nature of the reaction of NPMI and styrene autopolymerization on aluminum.
Furthermore, use of higher monomer concentration yielded higher molecular weight polymers. At any given concentration, molecular weight increased with solution pH. Polydispersity index (PDI) ranged from 2.5 to 3.5 in all cases.
The polymer coatings of poly(NPMI/styrene) formed on aluminum exhibited a tendency to crack while drying when the coating thickness was greater than 10 microns. To solve this problem, another monomer was incorporated into the polymer. The MEA monomer is an electron acceptor due to presence of electron withdrawing carbonyl groups next to the C═C bond, similar to NPMI, and has been previously used in adhesives and anti-corrosion primer compositions.
Thus, MEA was introduced in the feed solution and the NPMI/MEA ratio was varied while maintaining a constant styrene concentration. In this way, an equimolar ratio of acceptor and donor monomers was maintained in the solution. Coatings of poly(NPMI/MEA/styrene) were synthesized according to the general procedure of Example 2, wherein NPMI and styrene were dissolved in NMP. Dilute aqueous sulfuric acid (0.025 M) was then added slowly to the solution while stirring, until a 57/43 volume ratio of NMP/water was obtained. MEA was then added dropwise, yielding a clear, yellow-colored solution of pH 3.3.
Inclusion of MEA in the polymer resulted in crack free coatings and a significant improvement in the adhesion of the swollen coating to the aluminum substrate. Corrosion resistance of the coated samples was also improved by addition of MEA (see FIG. 14).
To detect the inclusion of MEA in the polymer coating, FTIR spectra were collected on a series of polymer coatings made by varying the NPMI/MEA ratio from 0.10M/0.00M to 0.00M/0.10M in increments of 0.01M. The total concentration of NPMI and MEA was kept at 0.10M. Styrene concentration was 0.10M. Spectra for the series are shown in FIG. 10. As the concentration of MEA in feed is increased, a carbonyl peak in the 1625-1635 cm−1 region appears, and increases in intensity, relative to the 1774 cm−1 imide peak from NPMI. The low wave number from the MEA peak is due to the hydrogen bonded enol form to the beta-diketone linkage. Also a general broadening of the carbonyl bands in the 1720 cm−1 region occurs, due to the overlapping from MEA and NPMI. The 1598 cm−1 peak is due to the phenyl ring from NPMI. It also decreases in intensity as MEA content relative to NPMI increases in the resulting polymer.
A series of poly(NPMI/MEA/BMI/styrene) coatings on aluminum were prepared by the method of Example 4, wherein the concentration of BMI was 0.0025 M. Similar FTIR results were obtained as those for Example 3. The addition of BMI to the comonomer solution also illustrates the versatility of the autopolymerization process, in that different monomers, or different monomer ratios may be used to adjust the properties of the final coating. After the metal substrate is coated with polymer, it is withdrawn from the bath, rinsed in another bath and then dried. During the drying process, water evaporates faster due to its lower boiling point (the boiling point of NMP is 210� C.), and the relative content of NMP in the polymer coating increases. Consequently, the swollen polymer coating is plasticized and some flow of the coating occurs before all of the solvent evaporates. This phenomenon occurs frequently when poly(NPMI/MEA/styrene) coatings are dried.
To arrest this flow, BMI was incorporated to cross-link the coating and increase the molecular weight of the coating. Addition of 0.0025M BMI in the NMP/water monomer feed solution arrested the flow of the coatings during drying and gave coatings with uniform thickness.
FIG. 11 shows a plot of coating thickness obtained as a function of polymerization time for various monomer compositions in feed. The ordinate axis is plotted as the square root of time, which results in linear fits of the measured coatings thickness. This indicates that such a polymerization process is limited by rate of diffusion of monomers to the propagating radicals. These observations are consistent with the equations obtained using a flat plate surface reaction model, where the rate limiting step is the process of diffusion of monomers in the swollen polymer coating being formed on the aluminum surface. According to this model, the thickness of the polymer coating is proportional to the square root of reaction time. As the ratio of MEA to NPMI in the feed was increased, the rate of polymerization decreased. This suggests a lower activity for MEA monomer compared to NPMI monomer. Sand-blasting and HF etching pretreatments gave similar kinetic results.
FIG. 12 shows the coating thickness obtained at different polymerization temperatures and times. The increase in the polymerization rate is due to the increase in diffusion coefficients of the monomers in the solution, consistent with the diffusion limited model. Regression fits show that the rate of polymerization increases with temperature. The effect, however, is not very dramatic. This also indicates that the polymerization process is limited by the monomer diffusion, rather than reaction rate limited.
Coatings comprising poly(4-CPMI/MMA) on steel were obtained using the same general procedure of Example 1. Thus, 4-CPMI and MMA were dissolved in NMP on a 1:1 mole basis, then mixed with water to form a solution of 0.2 M in each monomer. Polymerization was initiated by dipping a cleaned substrate in the solution. Simultaneous polymerization of the monomers and deposition of the formed polymers occurred at the metal surface. As shown in FIG. 13, the change in composition of the coatings (as indicated by change in Tg) with change in 4-CPMI content of the feed indicates that a random, rather than an alternating copolymer is formed. Poly(4-CPMI/acrylonitrile) may also be formed on steel by this method.
A viscous paint solution was prepared by mixing 57 mL of N-methyl-2-pyrrolidone (NMP) as a solvent with sufficient NPMI, BMI, and styrene to make the solution 0.3 M in N-phenyl maleimide, 0.3 M in styrene, and 0.075 M in bis-maleimide when the solution is mixed with 43 mL of deionized water as follows. The solution was placed in a cold water bath and 43 mL of deionized water containing enough H2SO4 to bring the solution pH to within a range of 2.5 to 3.5, was added with thorough mixing to make a solution that is 0.3M in N-phenyl maleimide, 0.3 M in styrene, and 0.075 M in bis-maleimide. Acidity may be adjusted by other acids, for example H3 PO4. The selection of acid is dependent upon the choice of metal substrate to be coated. The solution was then purged by bubbling with nitrogen gas to remove most of the dissolved oxygen from the system. Polyvinylpyrrolidone (1.3 million molecular weight) was added after purging as a thickening agent at a concentration of about 12.5 to 25 wt. % based on the total weight of solution, to form a viscous paint solution. Just prior to application of the solution to the metal substrate, 3-(methoxysilyl)propyl methacrylate was added as an adhesion promoter.
An aluminum substrate was pretreated to remove the weak oxide layer in an aqueous bath containing 5% hydrofluoric acid, rinsed with deionized water, and wiped dry with a laboratory paper towel just prior to the application of the paint solution. Other standard metal treatments such as grit blasting or alkaline treatments may be used.
The viscous paint solution was poured onto the surface of the aluminum metal substrate, spread with a doctor blade, and allowed to stand at room temperature for several hours. A skin of polyvinylpyrrolidone was observed as the monomers migrated to the metal surface. Eventually an opaque layer was observed underneath the polyvinylpyrrolidone. This is due to the insoluble nature of the polymer.
After polymerization, the coated aluminum substrate was rinsed several times with a water-solvent rinse bath containing approximately 15-20% N-methyl-2-pyrrolidone solvent by volume based on the total volume of the water and N-methyl-2-pyrrolidone solvent rinse, to remove the poly(vinylpyrrolidone), excess monomer, etc., but not the formed coating.
Thermal Properties: Glass transition temperatures were measured using differential scanning calorimetry (DSC). A single Tg was observed for all poly(NPMI/styrene) polymers and all other compositions of poly(NPMI/MEA/styrene) and poly(NPMI/MEA/BMI/styrene). A separate Tg of poly(MEA) (25� C.) was not observed. This indicates that MEA-styrene acceptor-donor monomers were included in the NPMI/styrene copolymer in random units. As shown in Table 2 below, the Tg decreased only slightly with increasing MEA content in the polymer coatings, both in presence and absence of BMI. All transition temperatures were greater than 200� C. Glass transition temperatures of the coating also increased with addition of BMI in feed. This very significant outcome demonstrates that the autopolymerization process is suitable for making high temperature resistant coatings by polymerization at room temperature. Thermal stability of the coatings was found to be very good. As shown in FIG. 14, onset of degradation for poly(NPMI/styrene) on aluminum occurred at more than 350� C. under nitrogen atmosphere and was not affected by incorporation of MEA.
Glass Transition Temperatures.
Monomer Feed
Monomer Feed
Tg (� C.)
Tg (� C.)
Electrical Resistance: The coatings exhibited good resistance to DC potential. Samples coated with 20 μm thick polymer, spontaneously polymerized from a feed solution of NPMI/MEA/BMI/styrene ratio of 0.05/0.05/0.0025/0.10 M, did not show any significant current leakage up to an applied potential of 1800V.
Corrosion Studies: FIG. 11A shows an unexposed 6061 aluminum sample coated with 20 μm thick poly(NPMI/MEA/styrene) polymer coating on the right half. FIG. 11B shows the sample after 1500 hours of exposure to salt fog as measured by ASTM B-117. The coated side is unaffected, while the uncoated side is corroded. No propagation of corrosion is seen occurring at the polymer-metal interface. No corrosion is seen around any of the edges of the sample, illustrating the uniformity of the polymer coating. Similar results are seen for the sample exposed for 3000 hours (FIG. 11C). This is an inherent property and advantage of the dip autopolymerization process. Since polymerization is initiated only at the surface, metal samples with complex surface topographies can be uniformly coated. Coating also forms inside holes and on edges.
In summary, the method of the present invention is easy, efficient and environmentally friendly. It requires minimal equipment, and has the advantage of being economical. Polymer coatings up to 50 microns in thickness may be formed, and very high molecular weights in the range of MW=250,000 and over may be obtained. The coatings are of uniform thickness and conformal, with excellent adhesion to the substrate. Coatings are readily formed even on complex surfaces. Furthermore, the coatings may be readily formulated to provide properties such as high temperature resistance and stability, good electrical breakdown resistance, low dielectric constant, and abrasion and corrosion protection by appropriate monomer selection and ratio. Such coatings may be used in a variety of applications, ranging from coating of circuit board components to automotive components.
While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation.
|Cited Patent
|Filing date
|Publication date
|May 14, 1963
|Aug 13, 1968
|Boller Ernest R
|Metal finishing process and composition therefor
|Jan 16, 1969
|Jul 13, 1971
|Amchem Prod
|Process and composition for coating metals
|Jul 17, 1972
|Feb 11, 1975
|Toyota Motor Co Ltd
|Method of coating by redox polymerization
|Oct 2, 1980
|Dec 28, 1982
|Amchem Products, Inc.
|Formation of polymeric coatings
|Jun 9, 1980
|Feb 8, 1983
|Amchem Products, Inc.
|Process and composition for coating metals
|Mar 14, 1989
|Apr 2, 1991
|The British Petroleum Company P.L.C.
|Process for treating metal surfaces
|Sep 24, 1990
|Oct 29, 1991
|Henkel Corporation
|Autodeposition process with low volatile organic chemical emissions
|Jun 12, 1992
|Aug 3, 1993
|Bell James P
|Electropolymerization method
|Sep 18, 1992
|Aug 24, 1993
|The University Of Connecticut
|Process for forming methacrylamide polymer prepreg composite by electropolymerization
|Jun 22, 1993
|Nov 14, 1995
|The University Of Connecticut
|Electropolymerization method and product
|Jun 2, 1995
|May 12, 1998
|The Dow Chemical Company
|Protective coating for metal surfaces
|Aug 6, 1996
|Sep 15, 1998
|The University Of Connecticut
|Method for coating metals by dip autopolymerization
|Mar 26, 1996
|Oct 6, 1998
|Minnesota Mining And Manufacturing Company
|Free-radically polymerizable compositions capable of being coated by electrostatic assistance
|Nov 29, 1978
|Jun 25, 1980
|Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America
|Process for forming a polymeric coating on a metallic surface, acidic aqueous coating compositions and coating systems employing such compositions
|Jul 24, 1984
|Feb 13, 1985
|HENKEL CORPORATION (a Delaware corp.)
|Vinylidene chloride latex in autodeposition and low temperature cure
|Title not available
|Title not available
|Title not available
|Title not available
|Dec 14, 1993
|Jul 21, 1994
|Henkel Corporation
|Method for applying autodeposition coating
|Aug 4, 1997
|Feb 12, 1998
|The University Of Connecticut
|Composition and method for coating metals by dip autopolymerization
|Liang et al., J. Applied Polymer Science, vol. 48, pp. 465-476, 1993.*
|Polymer Technology Dictionary by Whelan, Sep. 17, 1997, p. 363.
|U.S. Classification
|428/447, 428/461, 428/450, 428/463
|International Classification
|Cooperative Classification
|European Classification
|May 13, 1999
Owner name: UNIVERSITY OF CONNECTICUT, THE, CONNECTICUT
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BELL, JAMES P.;BAKER, NICOLE;REEL/FRAME:009969/0001
Effective date: 19990507
|Sep 12, 2005
|Fee payment
Year of fee payment: 4
|Oct 19, 2009
|Maintenance fee reminder mailed
|Mar 12, 2010
|Lapse for failure to pay maintenance fees
|May 4, 2010
|Expired due to failure to pay maintenance fee
Effective date: 20100312


text:
Expansive Poetry
From Wikipedia, the free encyclopedia
Expansive Poetry is a movement in United States poetry that began in the 1980s. It is an umbrella term coined by Wade Newman for the movements of New Formalism and New Narrative, and the term is controversial even among many of the writers it purports to describe. Although more New Formalism and New Narrative poets have gained prominence in recent years, as evidenced by the number of books and anthologies they have published and the rapid expansion of the West Chester University Poetry Conference, the term "Expansive Poetry" is increasingly rarely used.
Further reading[edit]
- Gwynn, R.S. (April 15, 1999). (Rev Sub ed.). Story Line Press. ISBN 978-1-885266-69-9. Missing or empty
- Feirstein, Frederick (October 1989). Expansive Poetry. Story Line Press. ISBN 978-0-934257-27-5.
- Walzer, Kevin (November 1, 1998). The Ghost of Tradition: Expansive Poetry and Postmodernism (First U.S. ed.). Story Line Press. ISBN 978-1-885266-66-8.
- Finch, Annie (May 1994). Formal Feeling Comes: Poems in Form by Contemporary Women. Story Line Press. ISBN 978-0-934257-98-5.
See also[edit]
External links[edit]
- Essay by Dick Allen
- EXPANSIVE MOMENT, Introduction to New Expansive Poetry
- Expansive Poetry & Music Online, In Defense of Meter by Annie Finch
IN AMERICAN POETRY, essay by Wade Newman
|This poetry-related article is a stub. You can help Wikipedia by expanding it.

subset: commoncrawl


text:
World Bulletin / News Desk
Egypt's Foreign Ministry on Friday denied recent speculation that a plan had been hatched to resettle Palestinians in the Sinai Peninsula with a view to establishing a Palestinian state in Sinai and Gaza.
"Sinai is Egyptian territory," ministry spokesman Ahmed Abu Zeid said in televised comments.
The notion of resettling Palestinians on the peninsula, he added, "has not at any stage been the subject of discussion between Egyptian and foreign officials".
Abu Zeid's assertion follows recent statements by Ayoob Kara, a Druze-Israeli politician, in which he said that Israeli Prime Minister Benjamin Netanyahu and U.S. President Donald Trump had discussed a plan -- allegedly proposed by Egyptian President Abdel Fattah al-Sisi -- to establish a Palestinian state in Sinai and the Gaza Strip.
"Egypt's stance on the Palestinian [national] cause is clear: Egypt supports a two-state solution [to the Israel-Palestine dispute]," the spokesman said.
He went on to stress that Palestinian aspirations for a state of their own could only be achieved through direct negotiations between Palestinians and Israelis.
At a Wednesday joint press conference with Netanyahu at the White House, Trump appeared to throw cold water on the notion of a two-state solution.
While the U.S. president did not reject a two-state solution outright, he broke with Washington's longstanding support for the idea by saying he could "live with" either a one- or two-state solution to the conflict.
Gunmen open fire on bus carrying Coptic Christians in Egypt's central Minya province
Cholera has recently killed more than 400 people in Yemen, prompting humanitarian agencies to step up aid deliveries
According to UNESCO, about 60 percent of the old city of Aleppo was badly damaged and, of this area, 30 percent was totally destroyed.
Blocked websites include those of Qatar's Al Jazeera and Muslim Brotherhood's Rassd news network
The announcement as US President Donald Trump makes a maiden foreign tour in which Saudi and Israeli concerns about Iran have loomed large is likely to stoke new tensions with Washington.
The UN envoy's convoy reportedly came under fire as he left the Sanaa airport
External powers influencing situation on ground should participate in Syrian crisis settlement, says Russian FM Lavrov
The UN envoy's convoy reportedly came under fire as he left the Sanaa airport
ISIL-linked militants in Sinai have previously claimed responsibility for rocket fire into Israel
OPEC heavyweights Saudi Arabia and Iraq agreed on Monday on the need to extend a global cut in oil supply by nine months
On Tuesday, Trump will meet Palestinian president Mahmud Abbas in Bethlehem in the West Bank, visit the Yad Vashem Holocaust memorial in Jerusalem and give a speech at the Israel Museum.
Envoy arrives in Yemeni capital in hopes of reviving stalled peace talks and concluding Ramadan cease-fire
The coalition now has control of the six largest Iranian cities, including Tehran, the holy city of Mashhad and tourist hotspot Isfahan -- and could capture more when final results are announced.
Sunday's protesters, who flooded Aden from several southern provinces, defended Zoubeidi's council, chanting "Independence is our objective" as they marched.
Gun battle erupted Saturday when Indian soldiers intercepted militants in Nowgam sector crossing over from Pakistan
Hamas says U.S. President Donald Trump's remarks at Riyadh summit mentioning it alongside terror groups are biased


text:
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Posted by: headm on: May 13, 2017
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Inside the car insurance in California non-government schemes, the claimant should not be otherwise engaged in occupation or employment for wages or profit. Area and Municipal have similar provisions with the additional restriction how the claimant must neither report regularly for, nor engage regularly in, employment at a place outside his / her residence. British Columbia doesn't need a restriction such as this. There is no need there because the benefit is similar if the body's claiming within this category or claiming being an employed person. The Area provision contemplates that the claimant is not otherwise utilized by allowing her to choose from the advantages payable to a unemployed victim or perhaps the limited reimbursement for replacement services. In the provinces in which the restriction applies, it isn't an issue. In each and every case, a target should be off by claiming being a one who was employed because the main benefit levels for that category are higher. The lowest rates on California car insurance can be found here at www.cheapinsurancecalifornia.net!
One serious auto insurance in California anomaly associated with benefits for homemakers is the fact that, in many jurisdictions, how much disability required is greater than that for employed persons. Area requires confinement, on health advice, to hospital, bed or wheel chair and total inability to perform all household duties. The Municipal provision requires that the claimant be rendered entirely not capable of performing every household duty. The non-government schemes require how the insured be completely incapacitated and struggling to perform some of his / her household duties. In California and Area, the disability requirements have become consistent with those relating to claims by employed people. Get valuable information about California car insurance here.
Posted by: headm on: May 13, 2017
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Posted by: headm on: May 13, 2017
How your nose looks matters a lot. It affects your overall facial appearance. That is why rhinoplasty at RpsInstitute is so popular among people looking to change their appearance. If you have breathing problems, this procedure will help rectify the problem too. The rhinoplasty cost is something that you need to deal with. The procedure is not just about the science of medicine. It requires a cosmetic surgeon who is an expert at ear, nose, and throat issues while displaying a highly artistic skill. Think of a surgeon of this nature as you would an expert sculptor. This cosmetic procedure should not go wrong. The nose job cost is something that will vary based on different factors. You need to be realistic about the associated costs because they will be significant. The average rhinoplasty cost is around $4500. Based on the varying factors, this number may go as high as $7000 or lower to $4000. Bear in mind that this value does not include other associated costs.
So, what factors affect the cost of nose jobs? The caliber of surgeon is one. The qualifications of your rhinoplasty surgeon will affect the cost of your nose job. Popular surgeons like RPSinstitute.com with excellent academic qualifications and more experience will provide the services you need at higher costs. The geographic region where do you intend to get your nose job done is plays a role. The location matters a lot when it comes to this procedure. In areas of high demand but low or medium supply of qualified surgeons, like Oklahoma, the procedure will cost more. In high demand and high supply areas like California, the prices are likely to be much higher among surgeons that are more popular. In low demand areas however, you will pay less for your rhinoplasty. If you have a limited budget, consider having a rhinoplasty procedure in a low demand area.
What kind of problem do you intend to address. The kind of procedure you intend to have done will affect your nose job cost. For example, if you need extensive work done because you have a severe breathing problem or your first procedure was botched completely you may be charged more. This is because it will take longer for the surgeon to correct the problem that you have. On the other hand, a minor rhinoplasty procedure to correct a bump will cost much less.
The basic nose job procedure may cost around $4500 but that is not the only cost you will deal with. The associated costs will drive the final costs much higher. One of the major costs is the anesthesiologist's fees. These fees vary based on the qualification and level of experience of the professional. They may range from $1000-$1500. You will also have to deal with the facility fees to pay for the services you will receive before and after surgery. This may include medical tests, post-surgery overnight stay, medication and garment costs. Facility fees cost upward of $500 and may even reach $2000.
If you can get your doctor's authorization for the rhinoplasty, then your health insurance would probably cover most or all of the rhinoplasty cost. You can also use your savings to pay for the procedure if you plan well ahead and saved money each month. You can also finance your nose job using a loan, which you can then pay off slowly. These are just some of the options you have to pay for the procedure.
Posted by: headm on: May 2, 2017
Shopping online is the simplest and best way to purchase items today. There are various advantages associated to shopping online. One can be able to get anything online from shoes to research chemicals. You can get research chemicals by simply visiting BuyResearchChemicalsUsaBiz. From the site you can be able to BUY diphenidine FOR SALE and several other research chemicals. There are several other sites that one can use. It is however not easy to find a site that has all the appropriate products and is easy to use.
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It might take a while before you get to find the perfect site but it will be worth the time spent. These steps will help you avoid scams and fake products. Once you get to find the perfect site do not get rid of the list since it might help you in future. You can BUY 1p-lsd FOR SALE when at home or even in the office once you opt to do it online.
Posted by: headm on: April 19, 2017
Weight loss shakes became a household word years ago. They were designed to help people lose weight. The shake itself is actually created from vitamins, minerals, proteins, and fibers. It is supposed to replace a normal meal. Lots of people were very skeptical about these shakes in terms of replacing a meal and their effectiveness for weight loss. Others, however, were quite satisfied. Here are some of the benefits of this type of shake –
They satisfy hunger quickly and contain fewer calories than a normal meal, which means they promote weight loss. The person simply grabs all the ingredients, puts them together, and blends them into a tasty shake. The drink gets absorbed into the bloodstream much faster than food that has to digest, and it also provides the energy they need while also lowering their calorie intake.
Aside from those benefits, these protein-rich shakes are high in fiber, which assists the body with detoxification. The fiber actually helps in removing fat metabolism residues, which improves the bowel movement within the colon. The end result is an increase in waste removal from the body.
One of the biggest benefits to weight loss shakes is they carry much-needed nutrients that are crucial for the body. So not only are you reducing how much food you eat, but you still get the benefit of necessary healthy nutrients by drinking this shake. You can supplement either 1 or 2 meals a day by and simply drink one of these healthy weight loss shakes instead.
The shakes are very easy to make and easy to drink. Many thought they were merely a fad that would pass away like so many before them. However, the weight loss shake is still going strong and more and more people are finding out how practical and effective they really are.
Posted by: headm on: April 7, 2017
For the absolute best price on auto insurance in Texas, you must get this offer. A recent case in British Columbia, however, has held how the word claim in mention of claim up against the tortfeasor, should be construed so as to mean separate claims for pecuniary damages to the date of trial, for non-pecuniary damages, for future care as well as for order from the court interest. Each one of these claims ought to be subject to another deduction. For each and every claim the amount being deducted will be the amount covered the identical Texas auto insurance group of loss in the no-fault scheme and the amount to be deducted for each claim cannot exceed the total amount allocated inside the damage award for your group of loss. Assuming the precision with the tort assessment, it is a logical approach which protects against under-compensation. It's got already been held in Bc that damages dependant on means of settlement cannot, without express agreement between the parties, be reduced to take into account no-fault benefits. This can often happen of amounts paid in advance of judgment.
At the time judgment is given the entire extent of the no-fault entitlement is probably not known. Disability or medical payments, as an example, could be continuing as well as in these cases it is usually unclear after they will cease. car insurance in Texas Nonetheless, future no-fault entitlements have to be considered once the final amount with the damage award is calculated. In British Columbia, Area and Municipal, a legal court is needed by legislation to estimate the present worth of future benefits. The problem of uncertainty which attends the assessment of damages for future losses applies because well. In the event the future entitlement to no-fault benefits is overestimated, the deduction will probably be too great as well as the damages lacking. When the entitlement is underestimated there will be double recovery. The regulations in British Columbia formerly allowed with this by giving for that adjustment (down or up in amount and duration) of no-fault benefits paid following your judgment if it ended up how the estimate done during the time of judgment was wrong. When the regulations were revised in 1983, this regulation was dropped. Get a great deal in less than 4 minutes with www.cheapcarinsuranceintexas.net!
located in trust, as well as the income created by that amount will be paid for the defendant by means of reimbursement on the periodic grounds for provided that the plaintiff is eligible for no-fault benefits. For more Texas information, read this!
Posted by: headm on: March 1, 2017
Find a salon that are more about quality rather than quantity. The service of qualified professionals and the use of high grade items can drive the prices up so be sure to prepare an adequate budget. Going to a good salon will give you the results you want.
It can be hard to look for good salons and stylists. For this, you will have to be on the lookout for people who have great locks. If one of your friends have decided to get an extension and it looks good on her, ask for a recommendation. Asking around will surely yield some names.
Familiarize yourself with the different brands of extension that wholesale human hair weave. You want to get strands that are lustrous looking and will remain so for an acceptable period. To make the addition look natural, you should also find something that is as close as possible to what your real strands look like.
One of the most common reasons why women get extensions is to add length to their hair. Another good reason would be to increase the volume of your locks. Before going to the salon, you should decide what you want to get out of this addition and then discuss your goals with the technician.
It is not a good thing to have these extensions woven in too tightly. This can cause adverse reactions and may even cause your strands to fall off. These extensions will also need care and maintenance if they are to last for months. You can ask your stylist for further tips on how to make your extension last.
As a general rule, it is not a good idea to use a lot of hairstyling products when you have extensions. These will only accumulate and can even make your strands smell. It is also best not to apply heat and just look for other alternatives when you have a hair weave brooklyn.
Posted by: headm on: March 1, 2017
In any action in another auto insurance quotes florida province or territory of The country against the licensed insurer, or its insured, arising out of an automobile accident in that province or territory, the insurer shall appear and shall not set up any defence to a claim under a contract evidenced by a motor vehicle liability policy issued in The state, including any defence as to the limit or limits of liability under the contract, that might not be set up if the contract were evidenced by a motor vehicle liability policy issued in the other province or territory.
Nova Scotia, the Northwest Territories florida car insurance rates and the Yukon Territory each have similar provisions including the reference in the first paragraph to no-fault benefits. ;The clear effect of this section is to make available to a victim who is injured in the province or territory whose statute contains the section, benefits to the levels normally paid under the scheme in that jurisdiction if her insurer is licensed there (and the action is brought there). Therefore a person from the Northwest Territories who is injured in The state and whose insurer is licensed to operate in The state, may claim The state benefits notwithstanding the fact that the policy was made in the Northwest Territories and included lower benefit levels. Save money on your car insurance with Floridacarinsurance.com!
It is not quite so clear, however, whether an insured florida car insurance quotes can sue her insurer in a jurisdiction other than one in which the insurer is licensed for a higher scale of benefits that might prevail in that jurisdiction. This is because paragraph 2 of the section quoted above makes no express reference to no-fault benefits. On one hand, the appearance of the reference in paragraph 1 only suggests that its omission from the second paragraph is deliberate. On the other hand, there is an argument that no-fault benefits are included by the mere reference to liability policies because of the requirement that every contract evidenced by a motor vehicle liability policy shall provide no-fault benefits. This argument has been adopted by a British Columbia court in Shea v. Shea. The court in that case, had to consider the reciprocity clause which applied to automobile insurance before the advent of the government-run scheme. That reciprocity section contained no express reference to no-fault benefits, merely to motor vehicle liability insurance. Nevertheless, the court stated. Florida info can be found here.


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iphone for dummiesDownload Book Iphone For Dummies in PDF format. You can Read Online Iphone For Dummies here in PDF, EPUB, Mobi or Docx formats.
Iphone 5 For DummiesAuthor : Edward C. Baig
Genre : Computers
File Size : 55. 74 MB
Format : PDF, ePub, Mobi
Download : 619
Read : 170
The full-color guide to getting the most out of your iPhone Completely updated and revised to include iOS 6, iCloud, and the latest iPhone 5 features, this full-color book is your guide to all things iPhone. Bestselling veteran authors Edward Baig and Bob "Dr. Mac" LeVitus introduce you to the capabilities of the iPhone for making phone calls, browsing the Internet, sending and receiving e-mails, working with the calendar, watching and recording HD videos, taking and editing great photos, and much more. You'll discover how to set up iTunes, buy music and videos, protect your information, troubleshoot, multitask, and download the hundreds of thousands of apps available from the App Store. Includes coverage of iPhone 5 and iPhone 4S as well as the older iPhone 4 model Gets you started with your iPhone, and introduces you to the multitouch interface, synching with iCloud, making phone and video calls, texting, working with the calendar, and more Explains setting up iTunes, watching your favorite movies and TV shows, taking stunning photos, and listening to your favorite music Helps you get organized with the calendar and Reminders features, keep on top of the latest news with Notification Center, and communicate with Siri, your voice-activated virtual assistant Walks you through connecting wirelessly, sending and receiving e-mails, making FaceTime video calls, getting directions from the all new Maps app, protecting your information, and troubleshooting Addresses the latest updates, iCloud, and new iOS 6 features that make your iPhone even more powerful and easy to use iPhone 5 For Dummies, 6th Edition is presented in the straightforward-but-fun style that defines the series. It's just the book you need to get acquainted with your brand-new iPhone.
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Genre : Computers
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Format : PDF, Mobi
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Get to know your iPhone with this colorful and easy-to-use guide So you just purchased your first iPhone? Although it seems like everyone has an iPhone these days, it's not a given that you'll instantly know how to use one. And that's where this handy book comes in. Written in the friendly For Dummies style and sporting senior-friendly larger type and full-color illustrations, this book clearly shows you how to use your iPhone, even if it's your first-ever smartphone. Make calls, send e-mail, download videos, read e-books, FaceTime video chat, and discover the wonderful world of apps. It's all here and much more! Covers the iPhone 5, iPhone 4S, and iPhone 4 Includes senior-friendly larger type and full-color illustrations Explains how to use the iPhone in the clear, friendly, easy-to-follow language that has defined the series for two decades Covers iPhone accessibility features, using maps, browsing the web, buying apps, playing music, shooting and sharing video and pictures, texting with iMessage, using Reminders and Newsstand, and of course, making calls iPhone 5 For Seniors For Dummies, 2nd Edition helps you discover the wonders of your smartphone and take advantage of all it has to offer!
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Genre : Computers
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Explains how to use the portable device to make and receive phone calls, set up iTunes and the iPod, take photographs, send and receive e-mail, browse the Internet, and play podcasts, music, video, and photograph slideshows.
Iphone For Seniors For DummiesAuthor : Nancy C. Muir
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iPhone For Seniors For Dummies, 5th Edition (9781119293484) was previously published as iPhone For Seniors For Dummies, 5th Edition (9781119137764). While this version features a new Dummies cover and design, the content is the same as the prior release and should not be considered a new or updated product. Learn to navigate the iPhone like a pro Learning to use new technology can be a bit of a challenge for seniors, especially now that smartphones are more like mobile computers. iPhone For Seniors For Dummies, 5th Edition is a full-color text that guides you through easy-to-understand lessons in iPhone features and functions. This step-by-step reference explains how to use the most basic of your phone's capabilities, such as making calls and sending text messages. Additionally, this newly revised book walks you through the most exciting features of your iPhone's hardware and software, from downloading new apps to keeping your data—and your phone—safe. With a larger font size and illustrations, this senior-friendly resource presents information in an accessible way. iPhones are among the most popular smartphones in the world, but learning how to use one can prove difficult if you're not up to date on the latest technology. To keep up with the cool kids and make sure to use a reference that fits your needs! Start from the very beginning by covering buying and getting started with your iPhone Explore your new phone's accessibility features, and dive into more complicated features as you build your understanding of the iPhone's technology Discover new forms of entertainment, such as surfing the web on mobile Safari, exploring new mobile apps, buying and reading iBooks, buying and listening to music on iTunes, and searching for interesting videos on YouTube Protect your new phone with key safety and maintenance best practices iPhone For Seniors For Dummies, 5th Edition guides you through the seemingly chaotic world of your new phone, helping you make sense of its features and functions.


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Bell tents: Motorhome campsites and campervan sites in RipleyView results on a map
2 bookable sites within 40 miles of Ripley
Bakewell, Derbyshire, England Show on mapLast booked
|Hillside non-electric grass tent or campervan pitch
|6 x
|From £12.50/€14.38/A$21.56/US$16.01/CA$21.59/CHF15.68/kr140.13/kr107.39/kr135.14/kr1,603/$258.26/$10,417/PEN52.72/NZ$22.73/R208.68/zł60.24/R$52.21/Kč382.26/RSD1,761 per night
|Medium electric grass tent or campervan pitch
|6 x
|From £15/€17.26/A$25.87/US$19.22/CA$25.90/CHF18.82/kr168.16/kr128.87/kr162.16/kr1,923/$309.92/$12,500/PEN63.26/NZ$27.27/R250.42/zł72.29/R$62.66/Kč458.72/RSD2,113 per night
|Large electric grass pitch
|8 x
|From £17.50/€20.13/A$30.18/US$22.42/CA$30.22/CHF21.95/kr196.19/kr150.34/kr189.19/kr2,244/$361.57/$14,583/PEN73.81/NZ$31.82/R292.15/zł84.34/R$73.10/Kč535.17/RSD2,465 per night
|Electric hardstanding pitch
|6 x
|From £17.50/€20.13/A$30.18/US$22.42/CA$30.22/CHF21.95/kr196.19/kr150.34/kr189.19/kr2,244/$361.57/$14,583/PEN73.81/NZ$31.82/R292.15/zł84.34/R$73.10/Kč535.17/RSD2,465 per night
Stoke-on-Trent, Staffordshire, England Show on mapLast booked
|Non-electric grass touring pitch
|unlimited x
|From £10/€11.50/A$17.24/US$12.81/CA$17.27/CHF12.54/kr112.11/kr85.91/kr108.11/kr1,282/$206.61/$8,333/PEN42.18/NZ$18.18/R166.94/zł48.19/R$41.77/Kč305.81/RSD1,408 per night
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Good value for money hotel. The rooms are big, nice view to the sea , very clean and quiet, liked the lobby alot. The food in the dining room was excellent, the stuff very helpful and quick in serving and the tables were clean. we...More
"Bungalows if you have kids , ocean view in first floor if just couple."
"If you book halfboard you can up grade to all inclusive for 10 euros pppd.& get a seaview room"


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Amirah Creations, a Brooklyn-based fashion and accessories line was created by designer Nailah Lymus in 2004. Inspired by her love for all things vintage and the whimsical power of femininity, the collection brings to life retro silhouettes with modern cuts. This line encompasses tapestry fabrics, genuine vintage embellishments, and bold prints.
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|Zumba Drop-in Exercise Class
Sat May 27 @10:00AM - 11:00AM