2009-06-24 Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUBNER, ANDREW D., BRIGHT, CLARK I., BUDD, KENTON D., INVIE, JUDITH M., LYONS, CHRISTOPHER S., MAKI, STEPHEN P., NACHTIGAL, ALAN K., PELLERITE, MARK J., WOOD, THOMAS E., ZELINSKY, MARIA L.
A method for forming an inorganic or hybrid organic/inorganic layer on a substrate, which method comprises vaporizing a metal alkoxide, condensing the metal alkoxide to form a layer atop the substrate, and contacting the condensed metal alkoxide layer with water to cure the layer is disclosed.
This application claims priority to Provisional Application Ser. No. 60/882,651, filed Dec. 29, 2006.
This invention relates to a process for manufacturing thin inorganic or hybrid inorganic/organic films.
Inorganic or hybrid inorganic/organic layers have been used in thin films for electrical, packaging and decorative applications. These layers can provide desired properties such as mechanical strength, thermal resistance, chemical resistance, abrasion resistance, moisture barriers, oxygen barriers, and surface functionality that can affect wetting, adhesion, slippage, etc.
Inorganic or hybrid films can be prepared by a variety of production methods. These methods include liquid coating techniques such as solution coating, roll coating, dip coating, spray coating, spin coating, and dry coating techniques such as Chemical Vapor Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), sputtering and vacuum processes for thermal evaporation of solid materials. Each of these methods has limitations.
Solution coating methods may require the use of solvents (organic or aqueous) to form the layer. Solvent usage can add cost to a process and can present environmental problems. Liquid phase methods may not be suitable for forming layers of immiscible materials or for mixtures of highly reactive materials because the materials can react immediately upon mixing in the liquid state.
Chemical vapor deposition methods (CVD and PECVD) form vaporized metal alkoxide precursors that undergo a reaction, when adsorbed on a substrate, to form inorganic coatings. These processes are limited to low deposition rates (and consequently low line speeds), and make inefficient use of the alkoxide precursor (much of the alkoxide vapor is not incorporated into the coating). The CVD process also requires high substrate temperatures, often in the range of 300-500° C., which may not be suitable for polymer substrates.
Sputtering has also been used to form metal oxide layers. This process is characterized by slow deposition rates allowing web speeds of just a few feet/min. Another characteristic of the sputtering process is its very low material utilization, because a major part of the solid sputtering target material does not become incorporated in the coating. The slow deposition rate, coupled with the high equipment cost, low utilization of materials, and very high energy consumption, makes it expensive to manufacture films by sputtering.
Vacuum processes such as thermal evaporation of solid materials (e.g., resistive heating or e-beam heating) also provide low metal oxide deposition rates. Thermal evaporation is difficult to scale up for roll wide web applications requiring very uniform coatings (e.g., optical coatings) and can require substrate heating to obtain quality coatings. Additionally, evaporation/sublimation processes can require ion-assist, which is generally limited to small areas, to improve the coating quality.
There remains a need for a method to prepare inorganic or hybrid inorganic/organic films on polymeric substrates that can be performed rapidly and at low cost.
The present invention provides, in one aspect, a method for forming an inorganic or hybrid organic/inorganic layer on a substrate, which method comprises vaporizing a metal alkoxide, condensing the metal alkoxide to form a layer atop the substrate, and contacting the condensed metal alkoxide layer with water to cure the layer.
In a second aspect, the invention provides a method for forming a hybrid organic/inorganic layer on a substrate, which method comprises vaporizing a metal alkoxide, vaporizing an organic compound, condensing the vaporized alkoxide and vaporized organic compound to form a layer atop the substrate, and curing the layer.
These and other aspects of the invention will be apparent from the accompanying drawing and this specification. In no event, however, should the above summaries be construed as limitations on the claimed subject matter, which subject matter is defined solely by the attached claims, as may be amended during prosecution.
FIG. 1 is a schematic representation of a roll-to-roll apparatus for carrying out the disclosed method.
FIG. 2 is a schematic representation of a static, step-and-repeat, in-line or conveyor coater suitable for use in the disclosed method.
FIG. 3 is a reflectance spectrum of the sample prepared in Example 1.
FIG. 4 is a reflectance spectrum of the sample prepared in Example 12.
FIG. 5 are reflectance spectra of the samples prepared in Examples 19-21.
FIG. 6 are reflectance spectra of the samples prepared in Examples 42-45.
FIG. 7 is a reflectance spectrum of the sample prepared in Example 46.
FIG. 8 are reflectance spectra of the samples prepared in Examples 47-53.
The words "a", "an", and "the" are used interchangeably with "at least one" to mean one or more of the elements being described. By using words of orientation such as "atop", "on", "covering", "uppermost", "underlying" and the like for the location of various elements in the disclosed coated articles, we refer to the relative position of an element with respect to a horizontally-disposed, upwardly-facing substrate. It is not intended that the substrate or articles should have any particular orientation in space during or after manufacture.
The term "polymer" includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed in a miscible blend, e.g., by coextrusion or by reaction, including, e.g., transesterification. The term "copolymer" includes both random and block copolymers.
The term "crosslinked" polymer refers to a polymer in which the polymer chains are joined together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. A crosslinked polymer is generally characterized by insolubility, but may be swellable in the presence of an appropriate solvent.
The term "water" refers to water vapor, liquid water or a plasma containing water vapor.
The term "cure" refers to a process that causes a chemical change, e.g., a reaction with water, to solidify a film layer or increase its viscosity.
The term "metal" includes a pure metal or a metal alloy.
The term "optically clear" refers to a laminated article in which there is no visibly noticeable distortion, haze or flaws as detected by the naked eye at a distance of about 1 meter, preferably about 0.5 meters.
The term "optical thickness" when used with respect to a layer refers to the physical thickness of the layer times its in-plane index of refraction. In some optical designs a preferred optical thickness is about ¼ the wavelength of the center of the desired waveband for transmitted or reflected light.
A variety of substrates can be employed. In one embodiment, the substrates are light-transmissive and can have a visible light transmission of at least about 50% at 550 nm. Exemplary substrates are flexible plastic materials including thermoplastics such as polyesters (e.g., poly(ethylene terephthalate) (PET) or poly(ethylene naphthalates)), polyacrylates (e.g., poly(methyl methacrylate)), polycarbonates, polypropylenes, high or low density polyethylenes, polysulfones, poly(ether sulfone)s, polyurethanes, polyamides, poly(vinyl butyral), poly(vinyl chloride), fluoropolymers (e.g., poly(vinylidene difluoride) and polytetrafluoroethylene), poly(ethylene sulfide), and thermoset materials such as epoxies, cellulose derivatives, polyimide, poly(imide benzoxazole) and polybenzoxazole. The substrate can also be a multilayer optical film ("MOF"), such as those described in U.S. Patent Application Publication No. 2004/0032658 A1.
In one embodiment, the disclosed films can be prepared on a substrate including PET. The substrate may have a variety of thicknesses, e.g., about 0.01 to about 1 mm. The substrate may however be considerably thicker, for example, when a self-supporting article is desired. Such articles can conveniently also be made by laminating or otherwise joining a disclosed film made using a flexible substrate to a thicker, inflexible or less flexible supplemental support.
Suitable metal alkoxides for forming a layer on a substrate are compounds that can be volatilized and condensed on the substrate. After condensation the alkoxides can be cured via reaction with water to form a layer having one or more desirable properties. Exemplary metal alkoxide compounds can have the general formula R1 xM-(OR2)y-x where each R1 is independently C1-C20alkyl, (C3-C8)cycloalkyl, (C2-C7)heterocycle, (C2-C7)heterocycle(C1-C8)alkylene-, (C6-C10)aryl, (C6-C10)aryl(C1-C8)alkylene-, (C5-C9)heteroaryl, or (C5-C9)heteroaryl(C1-C8)alkylene-, and each R2 is independently (C1-C6)alkyl, or (C2-C6)alkenyl, optionally substituted with hydroxyl or oxo, or two OR2 groups can form a ring together with the atom to which they are attached.
The R1 groups can be optionally substituted with one or more substituent groups, wherein each substituent is independently (C1-C4)alkyl, oxo, halo, —ORa, —SRa, cyano, nitro, trifluoromethyl, trifluoromethoxy, (C3-C8)cycloalkyl, (C2-C7)heterocycle or (C2-C7)heterocycle (C1-C8)alkylene-, (C6-C10)aryl, (C6-C10)aryl(C1-C8)alkylene-, (C5-C9)heteroaryl, (C5-C9)heteroaryl(C1-C8)alkylene-, —CO2Ra, RaC(═O)O—, RaC(═O)—, —OCO2Ra, RbRcNC(═O)O—, RaOC(═O)N(Rb)—, RbRcN—, RbRcNC(═O)—, RaC(═O)N(Rb)—, RbRcNC(═O)N(Rb)—, RbRcNC(═S)N(Rb)—, —OPO3Ra, RaOC(═S)—, RaC(═S)—, —SSRa, RaS(═O)—, —NNRb, —OPO2Ra, or two R1 groups can form a ring together with the atom to which they are attached. Each Ra, Rb and Rc is independently hydrogen, (C1-C8)alkyl, or substituted (C1-C8)alkyl wherein the substituents include 1, 2, or 3 (C1-C8)alkoxy, (C3-C8)cycloalkyl, (C1-C8)alkylthio, amino, aryl, or aryl(C1-C8)alkylene, or Rb and Rc, can form a ring together with the nitrogen atom to which they are attached. Exemplary rings include pyrrolidino, piperidino, morpholino, or thiomorpholino. Exemplary halo groups include fluoro, chloro, or bromo. The R1 and R2 alkyl groups can be straight or branched chains. M represents a metal, x is 0, 1, 2, 3, 4, or 5, and y is the valence number of the metal, e.g., y can be 3 for aluminum, 4 for titanium and zirconium, and may vary depending upon the oxidation state of the metal, provided that y−x≧1, e.g., there must be at least one alkoxy group bonded to the metal atom.
Exemplary metals include aluminum, antimony, arsenic, barium, bismuth, boron, cerium, gadolinium, gallium, germanium, hafnium, indium, iron, lanthanum, lithium, magnesium, molybdenum, neodymium, phosphorus, silicon, sodium, strontium, tantalum, thallium, tin, titanium, tungsten, vanadium, yttrium, zinc, and zirconium, or a mixture thereof. Several metal alkoxides, e.g., organic titanates and zirconates, are available from DuPont Co. under the Tyzor™ trademark. Non-limiting examples of specific metal alkoxides include tetra(methoxy) titanate, tetra(ethoxy) titanate, tetra(isopropoxy) titanate, tetra(n-propoxy)titanate, tetra(butoxy) titanate, 2-ethylhexyloxy titanate, octylene glycol titanate, poly(n-butoxy) titanate, triethanolamine titanate, n-butyl zirconate, n-propyl zirconate, titanium acetyl acetonate, ethyl acetoacetic ester titanate, isostearoyl titanate, titanium lactate, zirconium lactate, zirconium glycolate, methyltriacetoxy silane, fluorinated silanes (e.g., such as fluorinated polyether silanes disclosed in U.S. Pat. No. 6,991,826), tetra(n-propoxy) zirconate, and mixtures thereof. Additional examples include vaporizable prepolymerized forms of the above metal alkoxides including dimers, trimers, and longer oligomers including polydimethoxysiloxane and polybutyl titanate. Additional metal alkoxides include methoxy, ethoxy, n-propoxy, butoxy, acetoxy, and isopropoxy functionalized metal atoms, and prepolymerized forms of those metal alkoxides, e.g., poly(n-butoxy titanate). Other metal alkoxides that can be polymerized include tetra(ethoxy) titanate, tetra(n-propoxy) titanate, tetra(isopropoxy) titanate, methyltriacetoxy silane, fluorinated silanes, polydimethoxy silane, and tetra(n-propoxy) zirconate. Alkoxide mixtures may be selected to provide a preselected property, e.g., index of refraction or predetermined hardness, for the inorganic or hybrid organic/inorganic layer.
The metal alkoxides can be vaporized using a variety of methods known in the art. Exemplary methods include evaporation, e.g., flash evaporation, using techniques like those disclosed in U.S. Pat. Nos. 4,954,371 and 6,045,864, sublimation, and the like. The evaporation can be conducted under vacuum or at atmospheric pressure. Carrier gas flows (optionally heated) may be added to the evaporator to reduce the partial pressure of the metal alkoxide vapor or to increase the evaporation rate. The alkoxide may be condensed onto the substrate at a temperature below the condensation point of the vapor stream.
The condensed alkoxide layer is cured by contacting the layer with water. For example, the layer can be contacted with water vapor, liquid water or a plasma containing water vapor. Curing can be enhanced with heat. Heat can be provided using any suitable source, e.g., an infra red heater or a catalytic combustion burner. The catalytic combustion burner can also provide water vapor. Additional energy can be provided by UV or vacuum UV light input into the condensed alkoxide layer during the curing process.
The curing reactions may be accelerated with vaporizable catalysts. Exemplary catalysts include organic acids such as acetic acid and methane sulfonic acid, photoacid generators such as triphenyl sulfonium and diphenyl iodonium compounds, basic materials such as ammonia and photobase generators. Photoactive catalysts can be activated by exposure to UV light. The catalyst can condense into the coating layer or adsorb on the surface to promote the curing reactions.
In another embodiment, a metal alkoxide and an organic compound can be vaporized, condensed on the substrate, and cured. In one embodiment, the curing can include contacting the layer with water. Curing can involve reaction of the alkoxide with water to solidify the film layer or increase its viscosity together with polymerization of the organic compound to form an intermixed film layer. Curing can also be conducted in sequential steps. The components of the layer can be pre-reacted to form a volatilizable oligomer prior to deposition. Curing can also include reaction of the components of the layer (alkoxide and organic compound) together with or without water to form an organometallic copolymer. The films prepared having an organometallic copolymer may be designed to exhibit controlled properties such as viscosity, etc., or form films with a set of properties between the properties obtained when the films are prepared by separate deposition of the two components. The hybrid films thus prepared can provide a layer or surface having beneficial properties such as refractive index to affect optical transmission, reflection, or absorption, surface protection (hardness or lubrication) properties, low or high surface energy to affect wettability or interactions with other materials, low adhesion (release) or high adhesion to contacting materials, electrical conductivity or resistivity, anti-soiling and easy-clean, and surface functionalization.
The organic compounds can be vaporized using any methods like those described above for vaporizing the metal alkoxide. The alkoxide and the organic compound can be evaporated together to form a mixed vapor or they can be evaporated separately and mixed in the vapor phase. In applications where the alkoxide and the organic compound (or another metal alkoxide) are immiscible, it may be desirable to mix these materials in the vapor phase after separate evaporation. The alkoxide and organic compound may be condensed onto the substrate at a temperature below the condensation point of the vapor stream.
Exemplary organic compounds include esters, vinyl compounds, alcohols, carboxylic acids, acid anhydrides, acyl halides, thiols, amines and mixtures thereof. Non-limiting examples of esters include (meth)acrylates, which can be used alone or in combination with other multifunctional or monofunctional (meth)acrylates. Exemplary acrylates include hexanediol diacrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cyanoethyl (mono)acrylate, isobornyl acrylate, octadecyl acrylate, isodecyl acrylate, lauryl acrylate, beta-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, dinitrile acrylate, pentafluorophenyl acrylate, nitrophenyl acrylate, 2-phenoxyethyl acrylate, 2,2,2-trifluoromethyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A epoxy diacrylate, trimethylol propane triacrylate, ethoxylated trimethylol propane triacrylate, propylated trimethylol propane triacrylate, tris(2-hydroxyethyl)-isocyanurate triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, phenylthioethyl acrylate, naphthyloxyethyl acrylate, Ebecryl 130 cyclic diacrylate (from Cytec Industries Inc., New Jersey, U.S.A.), epoxy acrylate CN120E50 (from Sartomer Company, Exton, Pa., U.S.A.), the corresponding methacrylates of the acrylates listed above and mixtures thereof. Exemplary vinyl compounds include vinyl ethers, styrene, vinyl naphthylene and acrylonitrile. Exemplary alcohols include hexanediol, naphthalenediol, 2-hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and hydroxyethylmethacrylate. Exemplary vinyl compounds include vinyl ethers, styrene, vinyl naphthylene and acrylonitrile. Exemplary carboxylic acids include phthalic acid and terephthalic acid, (meth)acrylic acid). Exemplary acid anhydrides include phthalic anhydride and glutaric anhydride. Exemplary acyl halides include hexanedioyl dichloride, and succinyl dichloride. Exemplary thiols include ethyleneglycol-bisthioglycolate, and phenylthioethylacrylate. Exemplary amines include ethylene diamine and hexane 1,6-diamine.
Metal layers can be made from a variety of materials. Exemplary metals include elemental silver, gold, copper, nickel, titanium, aluminum, chromium, platinum, palladium, hafnium, indium, iron, lanthanum, magnesium, molybdenum, neodymium, silicon, germanium, strontium, tantalum, tin, titanium, tungsten, vanadium, yttrium, zinc, zirconium or alloys thereof. In one embodiment, silver can be coated on a cured alkoxide layer. When two or more metal layers are employed, each metal layer can be the same or different from another layer, and need not have the same thickness. In one embodiment, the metal layer or layers are sufficiently thick so as to be continuous, and sufficiently thin so as to ensure that the metal layer(s) and articles employing these layer(s) will have a desired degree of visible light transmission. For example, the physical thickness (as opposed to the optical thickness) of the visible-light-transmissive metal layer or layers may be from about 5 to about 20 nm, from about 7 to about 15 nm, or from about 10 nm to about 12 nm. The thickness range also will depend on the choice of metal. The metal layer(s) can be formed by deposition on the above-mentioned substrate or on the inorganic or hybrid layer using techniques employed in the metallizing art such as sputtering (e.g., rotary or planar magnetron sputtering), evaporation (e.g., resistive or electron beam evaporation), chemical vapor deposition (CVD), metalorganic CVD (MOCVD), plasma-enhanced, assisted, or activated CVD (PECVD), ion sputtering, plating and the like.
Polymeric layers can be formed from a variety of organic materials. The polymeric layer may be crosslinked in situ after it is applied. In one embodiment, the polymeric layer can be formed by flash evaporation, vapor deposition and polymerization of a monomer using, for example, heat, plasma, UV radiation or an electron beam. Exemplary monomers for use in such a method include volatilizable (meth)acrylate monomers. In a specific embodiment, volatilizable acrylate monomers are employed. Suitable (meth)acrylates will have a molecular weight that is sufficiently low to allow flash evaporation and sufficiently high to permit condensation on the substrate. If desired, the additional polymeric layer can also be applied using conventional methods such as plasma deposition, solution coating, extrusion coating, roll coating (e.g., gravure roll coating), spin coating, or spray coating (e.g., electrostatic spray coating), and if desired crosslinking or polymerizing, e.g., as described above. The desired chemical composition and thickness of the additional layer will depend in part on the nature of the substrate and the desired purpose for the article. Coating efficiency can be improved by cooling the substrate.
Films prepared using the disclosed method have a variety of uses including the fabrication of antireflective coatings for optical devices (e.g., such as displays, windows, instrument panels, and ophthalmic lenses), beam splitters, edge filters, subtraction filters, bandpass filters, Fabry-Perot tuned cavities, light-extracting-films, reflectors and other optical coating designs. The disclosed method enables the preparation of films having a wide range of refractive indices from less than 1.45 to greater than 2.0. Additional layers can be applied to the hybrid organic/inorganic layer to provide properties such as anti-reflective properties or to prepare a reflective stack having color shifting properties.
Films of the invention with color shifting properties can be used in security devices, for a variety of applications such as tamperproof images in value documents (e.g., currency, credit cards, stock certificates, etc.), driver's licenses, government documents, passports, ID badges, event passes, affinity cards, product identification formats and advertising promotions for verification or authenticity, e.g., tape cassettes, playing cards, beverage containers, brand enhancement images which can provide a floating or sinking or a floating and sinking image of the brand, information presentation images in graphics applications such as kiosks, night signs and automotive dashboard displays, and novelty enhancement through the use of composite images on products such as business cards, hang-tags, art, shoes and bottled products.
The security devices or other color shifting articles can include an image. Images can be formed by a variety of methods known in the art including etching, printing, or photographic techniques. Exemplary etching techniques include laser etching, abrasive and chemical etching. Exemplary printing techniques include screen printing, inkjet printing, thermal transfer printing, letterpress printing, offset printing, flexographic printing, stipple printing, laser printing, and so forth, using a variety of inks, including one and two component inks, oxidatively drying and UV-drying inks, dissolved inks, dispersed inks, and 100% solid ink systems. Exemplary photographic techniques include positive and negative photographic imaging and development. The image can be applied to the substrate or one or more of the layers in a reflective stack prior to the formation of any subsequent layer(s), or the image can be imprinted into the reflective stack using techniques like those disclosed in U.S. Pat. No. 6,288,842. The image should be formed such that it may be viewed or illuminated through the reflective stack. Images may be formed so as to have a restricted viewing angle. In other words, the image would only be seen if viewed from a particular direction, e.g., at normal incidence or at minor angular variations from the chosen direction. The image can be made to appear to be suspended, or float, above, in the plane of, or below the film.
Films prepared using the disclosed method can be used to provide low-surface energy anti-soil or anti-smudge properties for display devices, windows, and ophthalmic lenses. Films prepared using the disclosed method can be used to provide dielectric properties in electrical and electronic devices.
The smoothness and continuity of the film and the adhesion of subsequently applied layers to the substrate can be enhanced by appropriate pretreatment of the substrate or application of a priming or seed layer prior to forming the inorganic or hybrid layer. Modification of the surface to create hydroxyl or amine functional groups is particularly desirable. Methods for surface modification are known in the art. In one embodiment, a pretreatment regimen involves electrical discharge pretreatment of the substrate in the presence of a reactive or non-reactive atmosphere (e.g., plasma, glow discharge, corona discharge, dielectric barrier discharge or atmospheric pressure discharge), chemical pretreatment, or flame pretreatment. These pretreatments can help ensure that the surface of the substrate will be receptive to the subsequently applied layers. In one embodiment, the method can include plasma pretreatment. For organic surfaces, plasma pretreatments can include nitrogen or water vapor. Another pretreatment regimen involves coating the substrate with an inorganic or organic base coat layer optionally followed by further pretreatment using plasma or one of the other pretreatments described above. In another embodiment, organic base coat layers, and especially base coat layers based on crosslinked acrylate polymers are employed. The base coat layer can be formed by flash evaporation and vapor deposition of a radiation-crosslinkable monomer (e.g., an acrylate monomer), followed by crosslinking in situ (using, for example, an electron beam apparatus, UV light source, electrical discharge apparatus or other suitable device), as described in U.S. Pat. Nos. 4,696,719, 4,722,515, 4,842,893, 4,954,371, 5,018,048, 5,032,461, 5,097,800, 5,125,138, 5,440,446, 5,547,908, 6,045,864, 6,231,939 and 6,214,422; in published PCT Application No. WO 00/26973; in D. G. Shaw and M. G. Langlois, "A New Vapor Deposition Process for Coating Paper and Polymer Webs", 6th International Vacuum Coating Conference (1992); in D. G. Shaw and M. G. Langlois, "A New High Speed Process for Vapor Depositing Acrylate Thin Films: An Update", Society of Vacuum Coaters 36th Annual Technical Conference Proceedings (1993); in D. G. Shaw and M. G. Langlois, "Use of Vapor Deposited Acrylate Coatings to Improve the Barrier Properties of Metallized Film", Society of Vacuum Coaters 37th Annual Technical Conference Proceedings (1994); in D. G. Shaw, M. Roehrig, M. G. Langlois and C. Sheehan, "Use of Evaporated Acrylate Coatings to Smooth the Surface of Polyester and Polypropylene Film Substrates", RadTech (1996); in J. Affinito, P. Martin, M. Gross, C. Coronado and E. Greenwell, "Vacuum deposited polymer/metal multilayer films for optical application", Thin Solid Films 270, 43-48 (1995); and in J. D. Affinito, M. E. Gross, C. A. Coronado, G. L. Graff, E. N. Greenwell and P. M. Martin, "Polymer-Oxide Transparent Barrier Layers", Society of Vacuum Coaters 39th Annual Technical Conference Proceedings (1996). If desired, the base coat can also be applied using conventional coating methods such as roll coating (e.g., gravure roll coating) or spray coating (e.g., electrostatic spray coating), then crosslinked using, for example, heat, UV radiation or an electron beam. The desired chemical composition and thickness of the base coat layer will depend in part on the nature of the substrate. For example, for a PET substrate, the base coat layer can be formed from an acrylate monomer and may for example have a thickness of only a few nm up to about 20 micrometers.
The films can be subjected to post-treatments such as heat treatment, UV or vacuum UV (VUV) treatment, or plasma treatment. Heat treatment can be conducted by passing the film through an oven or directly heating the film in the coating apparatus, e.g., using infrared heaters or heating directly on a drum. Heat treatment may for example be performed at temperatures from about 30° C. to about 200° C., about 35° C. to about 150° C., or about 40° C. to about 70° C.
An example of an apparatus 100 that can conveniently be used to perform the disclosed method is shown in FIG. 1. Powered reels 102 a and 102 b move substrate 104 back and forth through apparatus 100. Temperature-controlled rotating drum 106 and idlers 108 a and 108 b carry substrate 104 past plasma source 110, sputtering applicator 112, evaporator 114, and UV lamps 116. Liquid alkoxide 118 is supplied to evaporator 114 from reservoir 120. Optionally, liquid 118 can be discharged into the evaporator through an atomizer (not shown). Optionally, gas flows (e.g., nitrogen, argon, helium) can be introduced into the atomizer or into the evaporator (not shown in FIG. 1). Water can be supplied through the gas manifold in plasma source 110 after the alkoxide layer is condensed. Infrared lamp 124 can be used to heat the substrate prior to or after application of one or more layers. Successive layers can be applied to the substrate 104 using multiple passes (in either direction) through apparatus 100. Optional liquid monomer can be applied through evaporator 114 or a separate evaporator (not shown) supplied from reservoir 120 or a separate reservoir (not shown). UV lamps 116 can be used to produce a crosslinked polymer layer from the monomer. Apparatus 100 can be enclosed in a suitable chamber (not shown in FIG. 1) and maintained under vacuum or supplied with a suitable inert atmosphere in order to discourage oxygen, dust and other atmospheric contaminants from interfering with the various pretreatment, alkoxide coating, crosslinking and sputtering steps.
Another example of an apparatus 200 that can conveniently be used to perform the disclosed method is shown in FIG. 2. Liquid alkoxide in syringe pump 201 is mixed with nitrogen from heater 202 in atomizer 203 which atomizes the alkoxide. The resulting droplets can be delivered to vaporizer 204 where the droplets are vaporized. The vapor passes through diffuser 205 and condenses on substrate 206. The substrate 206 with condensed alkoxide is treated in-place or removed and treated with water, to cure the alkoxide in a subsequent step. A catalytic burner (not shown) can be used to supply heat and water vapor. Apparatus 200 can be used to apply optional liquid monomer through syringe pump 201 or a separate syringe pump (not shown). The condensed monomer on substrate 206 is crosslinked in a subsequent step.
For some applications, it may be desirable to alter the appearance or performance of the film, such as by laminating a dye containing layer to the inorganic or hybrid film, applying a pigmented coating to the surface of the inorganic or hybrid film, or including a dye or pigment in one or more of the materials used to make the inorganic or hybrid film. The dye or pigment can absorb in one or more selected regions of the spectrum, including portions of the infrared, ultraviolet or visible spectrum. The dye or pigment can be used to complement the properties of the inorganic or hybrid film. A particularly useful pigmented layer that can be employed in the films is described in published PCT Application No. WO 2001/58989. This layer can be laminated, extrusion coated or coextruded as a skin layer on the disclosed film. The pigment loading level can be varied, e.g., between about 0.01 and about 2% by weight, to vary the visible light transmission as desired. The addition of a UV absorptive cover layer can also be desirable in order to protect any inner layers of the article that may be unstable when exposed to UV radiation. Other functional layers or coatings that can be added to the inorganic or hybrid film include an optional layer or layers to make the article more rigid.
The uppermost layer of the article is optionally a suitable protective layer. If desired, the protective layer can be applied using conventional coating methods such as roll coating (e.g., gravure roll coating), spin coating, or spray coating (e.g., electrostatic spray coating), then crosslinked using, for example, UV radiation. The protective layer can also be formed by flash evaporation, vapor deposition and crosslinking of a monomer as described above. Volatilizable (meth)acrylate monomers are suitable for use in such a protective layer. In a specific embodiment, volatilizable acrylate monomers are employed.
The invention is further illustrated in the following examples, in which all parts, percentages and ratios are by weight unless otherwise indicated.
A thin film was formed from tetra(ethoxy) titanate (DuPont Tyzor ET) using a vapor coater similar to the coater illustrated schematically in FIG. 1. The substrate was a 4-mil thick, 18-inch wide polyester (DuPont 454). In the first pass through the coater, the substrate was plasma treated with water vapor plasma at 0.3 Torr, operating at 400 kHz, a net power of 400 W and a line speed of 40 fpm.
Tetra(ethoxy) titanate was dispensed into a glass jar and placed into a vacuum bell jar for degassing. The bell jar was evacuated to 0.012 Torr for a period of 20 minutes. After degassing, the bell jar was vented to atmosphere and the liquid loaded into a syringe. The syringe was mounted on a syringe pump and connected to an atomizer/evaporator system as described in "METHOD FOR ATOMIZING MATERIAL FOR COATING PROCESSES" (PCT/US2006/049432, filed Dec. 28, 2006). For the second pass through the coater, the tetra(ethoxy) titanate was pumped to the atomizer at a flow rate of 1.0 ml/min. The flow rate of nitrogen gas to the atomizer was 15 sccm. The tetra(ethoxy) titanate was atomized into fine droplets and flash evaporated when the droplets contacted the hot evaporator wall surface (150° C.). The vapor flow exited a 16-inch-wide coating die and condensed on the substrate moving at a line speed of 16 fpm. The process drum temperature was 158° F. The condensed layer of tetra(ethoxy) titanate was immediately exposed to water vapor in the vacuum chamber to cure the coating. A continuous flow of distilled water vapor was introduced into the chamber from a temperature controlled flask of liquid water held at 80° F. The chamber throttle valve kept the chamber pressure (mostly water vapor) at 0.95 Torr.
The reflectance spectrum of Sample 1 is shown in FIG. 3. The cured organotitanate film has higher reflectance than the uncoated PET substrate, indicating a higher refractive index than that of the PET (n=1.65). From the reflectance data, the thickness and refractive index of the film were calculated to be about 82 nm and 1.82, respectively at a wavelength of 600 nm.
A polyester substrate (DuPont 454) was coated using the procedure of Example 1, with the following changes: The coating material, tetra(ethoxy) titanate, was handled in a nitrogen-purged glove box with vacuum capability to degas the liquid and was not exposed to atmospheric moisture during the degas and syringe loading process. The water vapor was continuously flowing into the coater chamber via a mass flow controller (MKS VODM) at a flow rate of 1000 sccm. The process drum temperature was 60° F. The evaporator temperature was 200° C. Nitrogen gas was introduced as a carrier gas in the evaporator at a flow rate of 67 sccm. The substrate speed was 18.7 fpm. The throttle valve kept the chamber pressure at 2.0 Torr. From the reflectance data, the thickness and refractive index of the film were calculated to be about 79 nm and 1.80, respectively, at a wavelength of 570 nm.
A polyester substrate (DuPont 454) was coated using the procedure of Example 1, with the following changes: The coating material was tetra(isopropoxy) titanate (DuPont Tyzor TPT). The process drum temperature was 63° F. The evaporator temperature was 100° C. The substrate speed was 15 fpm. The throttle valve kept the chamber pressure at 1.0 Torr. The first pass plasma pretreatment gas was nitrogen. From the reflectance data, the thickness and refractive index of the film were calculated to be about 59 nm and 1.89, respectively.
A polyester substrate (DuPont 453, 2-mil) was coated using the procedure of Example 1, with the following changes: Two monomer syringes and syringe pumps were used, one containing tetra(n-propoxy) titanate (DuPont Tyzor NPT) and the other containing tetra(n-butoxy) zirconate (DuPont Tyzor NBZ). The syringes containing the alkoxides were connected in parallel to enable either syringe separately or both together (mixed as liquids) to pump material to the atomizer. The evaporator temperature was 275° C. The remaining process conditions, coating thickness and refractive index for Examples 4-6 are described in Table 1, below.
A polyester substrate (DuPont 454, 4-mil) was coated using the procedure of Example 2, with the following changes: The coating material was tetra(n-propoxy) zirconate (Tyzor NPZ). The evaporator temperature was 275° C. The substrate line speed was 9.5 fpm. The liquid Tyzor NPZ flow rate was 1.05 ml/min. The throttle valve kept the chamber pressure at 3 Torr. The nitrogen flow into the atomizer was 10 sccm. From the reflectance data, the thickness and refractive index of the film were calculated to be about 82 nm and 1.72, respectively, at a wavelength of 565 nm.
A polyester substrate (DuPont 454, 4-mil) was coated using the procedure of Example 2, with the following changes: Two monomer syringes and syringe pumps were used, one containing tetra(n-propoxy) zirconate (DuPont Tyzor NPZ) and the other containing tetra(ethoxy) titanate (DuPont Tyzor ET). The syringes containing the alkoxides were connected in parallel to enable either syringe separately or both together to pump material to the atomizer. The evaporator temperature was 275° C. The coating die was 12-inches wide. The substrate line speed was 12 fpm. The nitrogen flow into the atomizer was 10 sccm. The remaining process conditions, coating thickness and refractive index for Examples 8-10 are described in Table 2, below.
A polyester substrate (DuPont 454, 4-mil) was coated using the procedure of Example 2, with the following changes: Two monomer syringes and syringe pumps were used, one containing Polydimethoxysiloxane (Gelest PS-012) and the other containing tetra(ethoxy) titanate (DuPont Tyzor ET). The polydimethoxysiloxane syringe was connected to the atomizer via a capillary tube. The tetra(ethoxy) titanate was delivered from the syringe directly to the interior wall of the hot evaporator via a capillary. In this way, the two reactive liquids were delivered separately into the evaporator, evaporated, and mixed as low pressure vapors prior to exiting the coating die, co-condensing and curing on the substrate. The evaporator temperature was 275° C. The coating die was 12-inches wide. The liquid polydimethoxysiloxane flow rate to the atomizer was 0.938 ml/min and the tetra(ethoxy) titanate flow rate to the evaporator wall was 0.1 ml/min. The substrate line speed was 12 fpm. The nitrogen flow into the atomizer was 10 sccm. From the reflectance data, the thickness and refractive index of the film were calculated to be about 175 nm and 1.50, respectively, at a wavelength of 1050 nm.
A polyester substrate (DuPont 454) was coated using the procedure of Example 2, with the following changes: The coating material was methyltriacetoxy silane (a solid at room temperature). The material was melted at 50° C. and loaded into a heated syringe (50° C.) after degassing. The water vapor pressure in the chamber was 3.0 Torr. The water vapor flow rate was 2000 sccm. The nitrogen carrier gas flow rate into the evaporator was 200 sccm. The substrate speed was 10.9 fpm.
The reflectance spectrum of PET and the film formed in Example 12 are shown in FIG. 4. The cured methyltriacetoxy silane film has lower reflectance than the uncoated PET substrate, indicating a lower refractive index than that of the PET (n=1.65). The thickness and refractive index of the coating, calculated from the reflectance data, were about 131 nm and 1.45, respectively, at a wavelength of 760 nm.
A polyester substrate (DuPont 453, 4-mil) was coated using the procedure of Example 2, with the following changes: Two monomer syringes and syringe pumps were used, one containing tetra(ethoxy) titanate (DuPont Tyzor ET) and the other containing ethyleneglycol-bisthioglycolate (Sigma-Aldrich). The syringes containing the alkoxides were connected in parallel to enable either syringe separately or both together to pump material to the atomizer. The evaporator temperature was 275° C. The coating die was 12-inches wide. The liquid tetra(ethoxy) titanate flow rate was 0.9 ml/min and the liquid ethyleneglycol-bisthioglycolate flow rate was 0.1 ml/min. The substrate line speed was 16 fpm. The water vapor flow rate into the chamber was 2000 sccm. The nitrogen flow into the atomizer was 10 sccm. The nitrogen carrier gas flow into the evaporator was 200 sccm. The thickness and refractive index of the coating, calculated from the reflectance data, were about 87 nm and 1.82, respectively, at a wavelength of 635 nm.
A polyester substrate (DuPont 454, 4-mil) was coated, as in Example 2, with the following changes: Two monomer syringes and syringe pumps were used, one containing tetra(ethoxy) titanate (DuPont Tyzor ET) and the other containing a mixture of 97% tripropyleneglycol diacrylate (Sartomer SR-306) and 3% photoinitiator Darocur 1173 (Ciba). In example 14, the liquid streams from both syringes were joined together just before entering the atomizer, enabling the metal alkoxide and acrylate materials to mix inline as liquids prior to atomization and evaporation. In example 15, the liquid streams from the two syringes were kept separate. Each liquid stream was directed to a separate atomizer mounted in separate evaporators. The evaporated metal alkoxide and acrylate materials were mixed as vapors and exited one coating die prior to condensation onto the substrate. The coating die was 12-inches wide. The nitrogen flow into each atomizer was 10 sccm.
The remaining process conditions, coating thickness and refractive index for Examples 14 and 15 are described in Table 3. Note that the coating of sample 14 was thick enough to have two reflection maxima in the spectral range 350-1250 nm. Thus, two separate calculations to estimate refractive index and thickness were performed on these data and both calculations are recorded in Table 3.
Process Conditions and Coating Characterization.
A polyester substrate (DuPont 454, 4-mil) was coated using the procedure of Example 2, with the following changes: Two monomer syringes and syringe pumps were used, one containing tetra(ethoxy) titanate (DuPont Tyzor ET) and the other containing a mixture of 82.5% phenylthioethylacrylate (Bimax PTEA), 14.5% pentaerythritol triacrylate (San Ester Viscoat 300 PETA) and 3% photoinitiator Darocur 1173 (Ciba). The syringes were connected in parallel to enable either syringe separately or both together to pump material to the atomizer. The evaporator temperature was 275° C. The coating die was 12-inches wide. The liquid Tyzor ET flow rate was 0.675 ml/min and the liquid acrylate mixture flow rate was 0.075 ml/min. The substrate line speed was 8 fpm. The nitrogen flow into the atomizer was 10 sccm. The thickness and refractive index of the coating, calculated from the reflectance data, were about 161 nm and 1.96, respectively, at a wavelength of 420 nm.
A polyester substrate (DuPont 454, 4-mil) was coated using the procedure of Example 2, with the following changes: The substrate was attached to the process drum. Tyzor ET (8.5 g) was mixed with 1.5 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173 from Ciba) in the nitrogen-purged glove box, prior to vacuum degassing and loading into the syringe. The substrate (PET) was plasma-treated with a water-vapor plasma at a pressure of 300 mtorr, water vapor flowrate of 500 sccm, net plasma power of 600 W at a frequency of 400 kHz, with the process drum rotating for 1 drum revolution with the sample passing the plasma source at 40 fpm. After the plasma treatment, the evaporator was heated to 200° C. and the process drum temperature was set to 61° F. The chamber was filled with water vapor and nitrogen to a pressure of 2.0 Torr with a water vapor flow of 1000 sccm and a nitrogen flow of 77 sccm (into the atomizer and evaporator). The coating die was 12-inches wide. The liquid (Tyzor ET and Darocur 1173) flow rate was 1.0 ml/min. The sample was rotated past the vapor coating die at a speed of 15 fpm for 1 revolution to condense the liquid layer of Tyzor ET and Darocur 1173. Then the process drum was heated to 150° F. and the chamber pressure increased to 8 Torr (with a flow of 3000 sccm water vapor and 210 sccm nitrogen). The sample was exposed to this continuous flow of water vapor for 30 minutes. The thickness and refractive index of the coating, calculated from the reflectance data, were about 79 nm and 1.90, respectively, at a wavelength of 600 nm.
A polyester substrate (DuPont 454) was coated using the procedure of Example 1, with the following changes: The substrate surface was sputter-coated with a thin layer of chromium (˜5 nm) prior to (in a previous coater pass) the application of the tetra(ethoxy) titanate. No surface plasma treatment was applied before the titanate coating. The process drum temperature was 25° F. The pressure of the water vapor in the chamber was controlled to 1.5 Torr by the throttle valve. The substrate line speed was varied between 13 and 30 fpm.
A polyester substrate (DuPont 454) was coated, as described in Example 2, with the following changes: The substrate was a 5-mil thick clear PET substrate with a surface coating (hard-coat formulation containing acrylate materials and SiO2 particles). The gas/vapor used in the first-pass plasma pretreatment was varied: in Example 19 the gas was nitrogen, in Example 20 the gas was oxygen, and in Example 21 the gas was water vapor. The substrate speed for the tetra(ethoxy) titanate deposition was 14 fpm. The liquid Tyzor ET flow rate was 0.75 ml/min. The nitrogen flow into the atomizer was 7.5 sccm. The coating die was 12-inches wide. The reflectance spectra of the samples from Examples 19-21 and the PET support are shown in FIG. 5.
A polyester substrate (DuPont 453 2-mil) was coated using the procedure of Example 1, with the following changes: The first pass plasma pretreatment gas was nitrogen. In the second pass, the throttle valve kept the chamber pressure (H2O vapor) at 0.3 Torr. In the second pass through the coater the plasma-treated substrate was exposed to UV light for about 4 seconds (in the presence of 0.3 Torr water vapor) immediately before the tetra(ethoxy) titanate deposition. Two low-pressure-mercury-arc lamps were used, generating UV light with primary emission lines at 185 nm and 254 nm wavelengths. Also in the second pass, the coated substrate was exposed to 0.3 Torr water vapor plasma (650 W, 400 kHz) for about 12 seconds immediately after deposition of the titanate. The thickness and refractive index of the coating, calculated from the reflectance data, were about 85 nm and 1.78, respectively.
The acrylate material was a mixture of Ebecryl 130 (Cytec-73.5%) and Lauryl Acrylate (Sartomer Chemicals-24.5%) with Photoinitiator (Darocur 1173-Ciba Specialty Chemicals-2%).
The flow of acrylate mixture was 1.0 ml/minute.
The evaporator temperature was 275° C.
The drum temperature was 25° F.
The substrate speed was 34 fpm.
The acrylate layer was cured by exposure to UV lamps (2 low-pressure-mercury-arc lamps emitting 185 and 254 nm wavelengths as described in Example 22 and 3 low-pressure-mercury-arc lamps emitting the 254 nm wavelength only).
Same pass plasma pretreatment of surface was with N2 plasma at 0.3 Torr, power set to 340 W, and 400 kHz.
Coater pass 2 was UV lamps post-cure at 10 fpm of selected substrate regions.
Coater pass 3 was sputter deposition of a CrOx (˜1-2 nm) layer in selected substrate regions (see Table 4, below).
Coater pass 4 was a substrate rewind pass.
Coater pass 5 was an H2O plasma treatment pass of selected substrate regions at 0.3 Torr, 40 fpm and 400 W at 400 kHz (see Table 4, below).
Coater pass 6 was tetra(ethoxy) titanate deposition using the procedure of Example 1, except at 9 fpm, and with the inclusion of IR lamp post-heating of the surface immediately following the deposition zone.
A polyester substrate (DuPont 454 4 mil) was coated using the procedure of Example 1, with the following changes: Two monomer syringes and syringe pumps were used, each containing tetra(ethoxy) titanate (DuPont Tyzor ET). The syringes containing the alkoxide were in parallel and each operated at 0.5 ml/min, generating a total liquid flow rate of 1.0 ml/min to the atomizer. The temperature-controlled flask contained 3% acetic acid in water. The pressure of the water and acetic acid vapor in the chamber was controlled to 2 Torr by the throttle valve. The thickness and refractive index of the coating, calculated from the reflectance data, were about 49 nm and 1.92, respectively.
A polyester substrate (DuPont 454 4-mil) was coated using the procedure of Example 1, with the following change: The pressure of the water vapor in the chamber was controlled to 0.2 Torr by the throttle valve. The thickness and refractive index of the coating, calculated from the reflectance data, were about 87 nm and 1.79, respectively.
A polyester substrate (DuPont 454) was coated using the procedure of Example 3, with the following change: During the second pass (tetra(isopropoxy) titanate deposition) the coated substrate was heated to ˜140° F. in the presence of 1.0 Torr H2O vapor by 5 second exposure to two IR lamps just prior to substrate windup. The thickness and refractive index of the coating, calculated from the reflectance data, were about 67 nm and 1.85, respectively.
A polyester substrate (DuPont 454) was coated, as in Example 3, with the following change: The coated substrate was exposed to 1.0 Torr water vapor plasma (500 W, 400 kHz) for about 12 seconds immediately after deposition of the titanate. The thickness and refractive index of the coating, calculated from the reflectance data, were about 69 nm and 1.78, respectively.
The coated substrate prepared using the procedure of Example 33 was placed in an oven at 70° C. for 60 minutes. After heating, the optical reflectance spectrum was obtained. The thickness and refractive index of the coating, calculated from the reflectance data, were about 61 nm and 1.95, respectively.
A polyester substrate (DuPont 454) was coated using the procedure of Example 1, with the following changes: The process drum temperature was about 30° F. After coating, the substrate was post-treated in the process chamber in a 0.3 Torr nitrogen environment, at a substrate speed of 10 fpm. The post-treatment involved heating the film coated substrate on the process drum at 158° F. the second sample (Example 37) was exposed for 18 seconds to the UV lamps described in Examples 23-26. The post-process conditions, coating thickness and refractive index for Examples 36-37 are described in Table 6, below.
A polyester substrate (DuPont 454) was coated using the procedure of Example 33, with the following changes: The web speed during the second pass (titanate layer deposition) was 15 fpm. In a third pass through the chamber, the titanate coating was heated to a temperature above 150° F. in the presence of 0.3 Torr water vapor by 12 seconds exposure to two IR lamps. The thickness and refractive index of the coating, calculated from the reflectance data, were about 71 nm and 1.86, respectively.
A polyester substrate (DuPont 454) was coated using the procedure of Example 3, with the following changes: In a third pass through the coater, the tetra(isopropoxy) titanate coating was exposed to 0.3 Torr water vapor plasma post-treatment (500 W, 400 kHz) for 12 seconds (15 fpm), with the drum temperature during the plasma post-treatment controlled at 63° F. There was no heating by IR lamps during the third pass. The thickness and refractive index of the coating, calculated from the reflectance data, were about 70 nm and 1.85, respectively.
A polyester substrate (DuPont 454) was coated using the procedure of Example 1, with the following changes: In a third pass through the chamber, the tetra(ethoxy) titanate coating was exposed to a plasma post-treatment (500 W, 400 kHz, 0.3 Torr) for 4 minutes (substrate stopped), with the drum temperature during the plasma post-treatment controlled to 60° F. The plasma gas was either oxygen or argon, as indicated for Examples 40 and 41 in Table 7, below.
The first coater pass was an H2O plasma treatment at 0.3 Torr chamber pressure, 400 watts net power, 400 kHz, and at 40 fpm.
The second coater pass was deposition of tetra(ethoxy) titanate using the procedure of Example 1, except that substrate speed was varied, in discrete intervals, over the course of the coater pass (see Table 8, below).
The acrylate material was a mixture of Ebecryl 130 (Cytec-73.5%) and Lauryl Acrylate (Sartomer Chemicals-24.5%) with Photoinitiator (Darocur 1173 Ciba Specialty Chemicals-2%).
The liquid acrylate formulation flow rate was 1.0 ml/minute.
The substrate speed was varied, in discrete intervals, over the course of the coater pass (see Table 8, below).
The acrylate layer was cured by exposure to UV lamps as described in Examples 23-26.
Same pass plasma pretreatment of surface was with N2 plasma at 0.3 Torr, 400 kHz, and power (W) varied as 10× that of substrate speed (fpm).
The reflectance spectra of coated sections of the films prepared in Examples 42-45 are included in FIG. 6. Removal of back surface reflection from the polyester substrate was accomplished by lightly abrading the back surface and applying black tape (Yamato Co., Japan).
the substrate speed was 16 fpm.
The substrate speed was 22.7 fpm.
After deposition of the two-layer construction, the coated substrate was treated in an oven for 24 hrs at 70° C.
The reflectance spectrum of the coated substrate is shown in FIG. 7. Removal of back surface reflection from the polyester substrate was accomplished by lightly abrading the back surface and applying black tape (Yamato Co., Japan).
A polyester substrate (DuPont 454) was coated using the procedure of Example 18, with the following changes: In a third pass through the coater a layer of silver (˜40 nm) was sputter-coated atop the titanate layer, completing a three layer chromium-titanate-silver optical stack which, when viewed from the uncoated side of the polyester substrate, exhibits reflected color. Table 9 summarizes the line speeds used during the titanate deposition passes for Examples 47-53.
Reflectance spectra of Examples 47-53 are included in FIG. 8. The spectral appearance ("color") of the sections is primarily determined by the varied thickness of the titanate layer (controlled by substrate speed changes during titanate deposition).
where X═CONHCH2CH2CH2Si(OCH3)3, m is about 10, n is about 10, and having an average molecular weight of about 2000 was used for coating a glass plate.
The fluorinated trialkoxysilane polyether oligomer was coated onto anti-reflectance coated (AR) glass (TDAR) from Viracon in a system shown schematically in FIG. 2. The oligomer was atomized and evaporated by the methods such as those described in U.S. Pat. No. 6,045,864. The liquid flow rate into the atomizer was 0.075 ml/min. The hot nitrogen flow into the atomizer was 44 lpm at a temperature of 186° C. The evaporator zone temperature was 162° C. The substrate was exposed to the vapor flow exiting the diffuser for 5 seconds to form a very thin, condensed liquid coating on the AR glass. The liquid film was cured by exposure to atmospheric water vapor in an oven at 110° C. for 5 minutes.
After curing, the coating had ink repellency (Sharpie® pen ink beaded up) and the ink was easily removed with a dry wipe. The durability of the coating was tested by mechanically rubbing the coating with 24 layers of cheese cloth (grade 90) under a weight of 1 kg for 2500 rub cycles. The coating maintained the ink repellency (Sharpie® pen ink beaded up) and the ink was easily removed with a dry wipe after the cheese cloth rubbing.
A polycarbonate plate 12 inches×9 inches was coated with the fluorinated trialkoxysilane polyether oligomer, using the procedure of Example 54, with the following changes: the diffuser was replaced with a slot coating die 10 inches wide, the liquid monomer flow rate was 0.10 ml/min, the nitrogen flow to the atomizer was 50 lpm at 300° C., the evaporation zone temperature was 300° C., and the substrate was moved past the coating die slot at 1 inch/second. The liquid coating was cured by exposure to a hot flux of water vapor from a catalytic combustion source. The 12×4 inch catalytic burner (Flynn Burner Corp.) was supported by combustible mixture consisting of 385 ft3/hr of dried, dust-filtered air and 40 ft3/hr of natural gas, which provided a flame power of 40,000 Btu/hr-in. The flame equivalence ratio was 1.00. The gap between the catalytic burner and the coated substrate was about 2 inches. The exposure time was less than 2 seconds. After curing, the coating was repellent to solvent-based ink.
Illustrative embodiments of this disclosure are discussed and reference has been made to possible variations within the scope of this disclosure. These and other variations and modifications in the disclosure will be apparent to those skilled in the art without departing from the scope of the disclosure, and it should be understood that this disclosure and the claims shown below are not limited to the illustrative embodiments set forth herein.
contacting the condensed metal alkoxide layer with water to cure the layer.
3. The method of claim 1, further comprising exposing the inorganic or hybrid organic/inorganic layer to a heat treatment.
7. The method of claim 1, comprising contacting the metal alkoxide layer with liquid water.
8. The method of claim 1, comprising contacting the metal alkoxide layer with water vapor.
9. The method of claim 8, comprising contacting the metal alkoxide layer with a plasma containing water vapor.
10. The method of claim 1, wherein the metal alkoxide comprises an alkoxide of aluminum, antimony, arsenic, barium, bismuth, boron, cerium, gadolinium, gallium, germanium, hafnium, indium, iron, lanthanum, lithium, magnesium, molybdenum, neodymium, phosphorus, silicon, sodium, strontium, tantalum, thallium, tin, titanium, tungsten, vanadium, yttrium, zinc, zirconium, or a mixture thereof.
11. The method of claim 10, wherein the metal alkoxide comprises an alkoxide of titanium, zirconium, silicon, aluminum, tantalum, barium, tin, indium, zinc, gallium, bismuth, magnesium, strontium, boron, cerium, hafnium, neodymium, lanthanum, tungsten, or a mixture thereof.
12. The method of claim 11, wherein the metal alkoxide comprises tetra(ethoxy) titanate, tetra(isopropoxy) titanate, tetra(n-propoxy)titanate, polydimethoxysiloxane, methyltriacetoxy silane, tetra(n-propoxy) zirconate, tetra(n-butoxy) zirconate, or a mixture thereof.
13. The method of claim 10, wherein the metal alkoxide comprises a trialkoxysilane.
18. The method of claim 16, wherein the vaporized alkoxide and vaporized compound are vaporized separately and mixed in the vapor phase before condensing atop the substrate.
19. The method of claim 16 wherein the alkoxide and the organic compound are vaporized together.
21. The method of claim 16, wherein the organic compound comprises an alcohol, carboxylic acid, ester, acid anhydride, acetyl halogen, thiol, or amine.
22. The method of claim 21, wherein the ester comprises an acrylate.
23. The method of claim 22, wherein the acrylate is cured simultaneously with the metal alkoxide curing.
24. The method of claim 22, wherein the acrylate and metal alkoxide are cured separately.
25. A film comprising at least one inorganic or hybrid organic/inorganic layer formed by the method of claim 1.
26. The film of claim 25, wherein the inorganic or hybrid organic/inorganic layer provides an article with antireflection properties.
27. The film of claim 25, further comprising at least one additional layer that in combination with the hybrid organic/inorganic layer provides an article with anti-reflective properties.
28. The film of claim 25, further comprising at least one additional layer that in combination with the hybrid organic/inorganic layer provides an article with color-shifting properties.
30. An ophthalmic lens comprising the film of claim 27.
31. A security device comprising the color shifting article of claim 28.
32. The device of claim 31 comprising an image.
33. A film comprising at least one hybrid organic/inorganic layer formed by the method of claim 16.
34. The film of claim 33, wherein the hybrid layer comprises an acrylate polymer.
35. The film of claim 33, further comprising at least one additional layer that in combination with the hybrid organic/inorganic layer provides an article with anti-reflective properties.
36. The film of claim 33, further comprising at least one additional layer that in combination with the hybrid organic/inorganic layer provides an article with color-shifting properties.
37. An ophthalmic lens comprising the antireflection film of claim 35.
38. A security device comprising the color shifting article of claim 36.


GitHub - dyve/jquery-autocomplete: The original jQuery autocompleter. Does not need any other plugins. Supports local and remote data sets, plain text and JSON data, various options and callback hooks.
Want to be notified of new releases in dyve/jquery-autocomplete?
The time has come to retire this project. The code is not up to my current programming standards, and I don't feel motivated enought to go through another rewrite. There is also not much need, because of excellent alternatives like Select2 (http://ivaynberg.github.io/select2/) and the various jQuery autocomplete efforts that have evolved from or parrallel to my original (just google jquery autocomplete).
This means that current and future bugs probably won't be fixed, unless the project finds a new caretaker. Contact me if you are interested in that role.
I'm immensely proud that this autocompleter has served the web as long as it has. It's found is way into all kinds of projects and web sites (including Barack Obama's campaign and several Mozilla projects). Thank you all!
Transforms an INPUT element into an autocompleter. The autocompleter helps the user pick a value value from a list by showing available values based on keyboard input.
Works out of the box, but highly configurable using options and callback hooks.
For more info refer to the docs (doc/jquery.autocomplete.txt).
The only requirement for jquery-autocomplete is jQuery. No other plugins are required.
Keep up to date on announcements and more by following jquery-autocomplete on Twitter, @jqautocomplete.


text:
2020 Marks the Arrival of 'The Eternals' in the Marvel Cinematic Universe
In theaters November 6!
by Christine Dinh
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Marvel Studios' The Eternals was previously announced at San Diego Comic-Con, and the casting fully revealed along with concept art designs at D23 Expo last summer.
The Walt Disney Studios released details about their 2020 film slate, and we now have more details about the upcoming The Eternals movie arriving in theaters on November 6.
What could draw out and unite the celestial beings known as the Eternals out from hiding? The global...universal scale of the events of Avengers: Endgame!
Marvel Studios' The Eternals features an exciting new team of Super Heroes in the Marvel Cinematic Universe, ancient aliens who have been living on Earth in secret for thousands of years. Following the events of Avengers: Endgame, an unexpected tragedy forces them out of the shadows to reunite against mankind's most ancient enemy, The Deviants.
The outstanding ensemble cast include Richard Madden as the all-powerful Ikaris, Gemma Chan as humankind-loving Sersi, Kumail Nanjiani as the cosmic-powered Kingo, Lauren Ridloff as the super-fast Makkari, Brian Tyree Henry as the intelligent inventor Phastos, Salma Hayek as the wise and spiritual leader Ajak, Lia McHugh as the eternally young, old-soul Sprite, Don Lee as the powerful Gilgamesh, Barry Keoghan as the aloof loner Druig, and Angelina Jolie as the fierce warrior Thena. Kit Harrington was cast as Dane Whitman.
Directed by Chloe Zhaé, who helmed the critically acclaimed Sundance film The Rider, and produced by Kevin Feige, The Eternals opens in U.S. theaters on November 6, 2020.
The Eternals will make their Marvel Cinematic Universe debut in theaters on November 6, 2020.
The countdown is on! Get up to the second updates on The Eternals movie page!
Stay tuned to Marvel.com for more details!
Marvel Studios' The Eternals and More Coming in 2020!
The Hype Box
Can't-miss news and updates from across the Marvel Universe!
Artboard 1 Earn Points, Get RewardsJoin NOW!
Iconic Moments from Phase 3 of the MCU!
The Avengers Join the Battle Against the King in Black
'WandaVision': Explore New Images from Episode 1
In this article: Eternals, Eternals, Deviants, Ikaris, Sersi, Kingo, Makkari, Phastos, Sprite, Gilgamesh, Druig, Thena, Black Knight (Dane Whitman)
Evil Rises Again in 'Eternals' #1
The Eternals have returned from the grave – and they're not alone.
ETERNALS #1 On Sale Now! | Marvel Comics
NEVER DIE. NEVER WIN. ETERNALS. From the minds of Kieron Gillen and Esad Ribić comes an iconic new vision of the classic Marvel mythology! ETERNALS #1 is on sale now!
7 Things We Learned About the Eternals
Who are the Eternals? Find out in their 1985 series, now on Marvel Unlimited.
The Black Knight Rides Again in a New Comic Series This March
Writer Simon Spurrier and artist Sergio Dávila team up for BLACK KNIGHT: CURSE OF THE EBONY BLADE!

redpajama_set_name: RedPajamaCommonCrawl


text:
Bluths
Jessica Walter Delivers a Major Arrested Development Season 5 Scoop
Looks like the Bluth family could be in for the trial of the century.
By Joe Reid
Courtesy of Netflix.
Jessica Walter is at San Diego Comic-Con promoting the upcoming season of animated spycraft on Archer, but she showed up armed with a story-line spoiler for Arrested Development fans thirsty for any talk of a fifth season. In an interview with TVLine's Michael Ausiello, Walter was practically bubbling over with excitement that she had the chance to unveil her big scoop: "Now that Buster has been arrested for the murder of Liza Minnelli, we're very anxious to get the show started."
Of course, Buster, played by Tony Hale, was the on-screen paramour of Minelli's Lucille Austero, whose fate at the end of Season 4 (the show's first on Netflix) appeared to be in doubt. Seems like a high-profile murder case could be the engine that drives the show when it returns next year. One can only hope that Liza gets plenty of flashbacks so we don't have to do without her.
Season 5 of Arrested Development has been a hot topic in the last several weeks. Executive producer Brian Grazer said last month that the [new season would air some time in 2016] (http://deadline.com/2015/06/arrested-development-season-5-debut-brian-grazer-1201436698/).


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Online ExclusivesMilitary Maneuvers in the Water Industry
Military Maneuvers in the Water Industry
A focus on hiring veterans could help ease the industry's skilled-labor shortage
By Ken Wysocky
Hiring Employee Shortage Employee
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Jose Martinez firmly believes that military veterans are great candidates for jobs in the water and sewer industries, which sometimes struggle to attract employees. And the general manager of the Otay Water District should know — he's a United States Navy veteran himself.
Granted, Martinez had an easier path than many veterans when he transitioned from the Navy into the water and sewer industry. After leaving the Navy, he worked as a consultant and project manager for power and water utilities for five years before the OWD — based in Spring Valley, less than 10 miles east of downtown San Diego — hired him.
Nonetheless, Martinez realizes that obstacles exist to what otherwise should be a perfect marriage between well-qualified veterans with high-level, skilled-trade experience and an industry facing a shortfall of skilled laborers, especially as baby boomers prepare to retire in the coming years.
After all, a machinist that can fix a broken pump while cruising underwater on a nuclear submarine can surely apply those same skills at utilities.
"This is a big passion of mine," says Martinez, who serves as the vice chairman of the California-Nevada Section of the American Water Works Association's Veterans Engagement and Transition committee. He also works on veterans' issues with other like-minded personnel at the 24 regional water agencies that belong to the San Diego County Water Authority, one of the primary agencies from which OWD buys water.
The OWD provides water, recycled water and sewer service to a population of about 226,000 people in a 125-square-mile area. It owns and operates about 723 miles of potable waterlines, 104 miles of recycled waterlines and 84 miles of sewer lines.
Large labor pool
Military veterans represent a huge labor pool. By some estimates, 30,000 veterans leave the military each year in just California alone. And most of them prefer to stay in the state, which means there's an available labor pool that would be the envy of many employers, says Martinez.
Furthermore, veterans typically have the aptitude and mindset to be great utility employees.
"It sounds corny, but the military culture centers on discipline and accomplishing a mission — figuring out how to get things done," he notes. "In addition, employees at utilities serve the public, doing something that's bigger than themselves — making sure the water supply is safe, reliable and cost effective. And this is a culture to which veterans, with their can-do attitudes, can relate."
The OWD employs roughly 140 people, including nine veterans. While the district certainly would like to hire more, utility agencies tend to have lower turnover rates, which limits hiring opportunities. However, Martinez points out that's expected to change with the coming wave of retirements.
Furthermore, until very recently, there hasn't been a clear career path for veterans to join the water and wastewater industries without starting at the bottom, then earning certification, even though they have experience that's equivalent to a more advanced certification.
In addition, the industry only started focusing more heavily on the veteran employment issue a few years ago. And to use a Navy metaphor, it takes a while to turn around an aircraft carrier.
Martinez speaks from experience. He graduated from the U.S. Naval Academy in Annapolis, Maryland, in 2001 with a degree in mechanical engineering. After serving on a Los Angeles-class, fast-attack nuclear submarine, Martinez left the Navy in 2007.
The OWD hired him as a utility services manager in 2012, then promoted him to assistant chief of water operations. He became general manager in early 2020.
So why is there such a disconnect between veterans with skilled-trade experience and water and sewer utilities that need them? Martinez says that it's a multipronged issue.
For starters, there's a language barrier, so to speak. Too many human resources departments at utilities look at veterans' resumes and don't understand that their job skills, often spelled out in hard-to-decipher military jargon, are well suited for jobs at utilities.
"Too many hiring managers think they need employees with specific [water sector] experience," he says. "So when I talk to them about hiring, say, an Air Force water and fuel systems specialist, they say no — even though there are strong similarities between that job and a position like a utility maintenance worker responsible for the installation and maintenance of water and wastewater distribution systems."
By the same token, many veterans simply aren't aware of the solid career opportunities that exist at water and sewer utilities. "We need to educate them more, get them excited about these great careers," Martinez says.
Another obstacle is the job certifications required to be, say, a water plant operator, for example. Some veterans might be highly qualified for such positions. But without the required certifications, they're forced to start at lower-paying, entry-level positions for which they're overqualified.
Unfortunately, that can be a disappointing non-starter for many vets.
"An experienced petty officer might be eligible for a job that pays $70,000 or $80,000 a year at a power utility but starts out at ground zero in the water industry," Martinez explains. "It's a shame."
Establish best practices
To better connect with veterans, Martinez says the OWD is focused on implementing best hiring practices to make it easier for veterans to find jobs.
For example, the district now is more intentional about where it posts job advertisements. Military-oriented Facebook groups and other social media offer good examples of oft-overlooked fertile ground, Martinez says.
Furthermore, utilities need to carefully craft job descriptions in those advertisements so that veterans can easily see how their skillsets match up.
"They need to use language that's more general — that talks more toward veterans' skill sets than just a position title," he says. "If you use water industry terminology, veterans are likely to feel they're unqualified."
At OWD, job applications include a box that candidates can check if they served in the military. If the box is checked, human resources personnel know they need to assess and scrutinize the application more carefully to be sure they're not overlooking a qualified candidate. Sometimes another veteran will assist with the review.
"We have to get hiring managers more comfortable with and understand exactly what those military qualifications really mean," Martinez adds. "Human resources is a critical component in this process."
The agency also taps into programs such as SkillBridge, a U.S. Department of Defense program that allows military personnel to work at internships during the last six months of their service.
"A couple agencies in our region just brought on board a couple of veterans as interns in the instrumentation field and the feedback after a few months was, 'Wow, these people are amazing,'" Martinez says.
No quick fix
In 2019, Martinez and leaders at San Diego County also spearheaded the passage of a California bill that allows any education and experience earned during military service to count toward state certification requirements for jobs such as water and wastewater operator.
"So if they have, say, 20 years of experience and can check off a certain number of boxes, they can apply for these higher-level jobs instead of being forced to start at the bottom," Martinez explains. "That was a huge development."
Looking ahead, Martinez urges utilities nationwide to get their human resources departments to make water industry careers more accessible to veterans. Many of the best practices they can implement, such as translating job descriptions into more understandable language, don't require a lot of time and effort.
"There's no doubt it's a tough problem with no easy solutions, but as long as we're mindful and intentional about it in the long term, these best practices can make a big difference in solving the nationwide shortage of skilled labor — provide water and sewer utilities with the technical and administrative skills they need," he says.


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government will challenge low bids
Contractors face "intense scrutiny" if they submit unrealistically low bids for public sector contracts, according to a senior official at the Department for Business, Energy, and Industrial Strategy (BEIS).
Fergus Harradence, deputy director for infrastructure and construction, told a webinar hosted by the Building Engineering Services Association (BESA) that any bids which appear unrealistically low will be rejected unless the bidder has a plausible explanation.
He told BESA chief executive David Frise that the new procurement rules contained in the government's 'Construction Playbook' were designed to "reset the government's relationship with the industry because at the moment it is not working for either party".
Unrealistic bidding means the government does not get the quality projects it wants, and the industry suffers from low margins and lack of investment. It also leads to poor payment practices and unfair contract conditions that pass on too much risk to suppliers, added Harradence.
"We need to get away from a situation where people are only able to make a profit by putting pressure on their supply chains…that is what led to Carillion," he said. "We need the industry to behave responsibly and embed the rigorous comprehensive approach to quality that has been so successful in manufacturing."
He said the playbook depended on everyone being more "open and honest with each other" and that government would prefer that projects appeared to cost more from the outset to avoid problems further down the line.
The Playbook was developed by the Cabinet Office in partnership with the construction industry and sets out how the government aims to achieve project delivery that is "faster, better and greener". It includes advice to make wider use of digital and offsite methods and engage with suppliers earlier in the procurement process.
Social value also makes up 10% of awarding criteria according to the Playbook, which became mandatory for all projects procured by central government in England last December. The Cabinet Office is working with the industry to develop a clear definition of whole-life value, which is due to be published later this year.
"The fundamental principle is that contracts should be profitable," said Harradence. He also warned clients against issuing incomplete tender documents with poorly defined specifications, which increase the risk for bidders.
"We are starting from the basis that we want to do things differently. This persistent under-bidding for projects leads to ministers having to stand up in parliament and apologise for projects running over time and budget," he told the BESA webinar.
He said too many clients were being given totally unrealistic expectations about how much a project would cost, which led to disputes and project over-runs. "There has to be a greater level of trust between the industry and its clients – this is absolutely pivotal. Without that trust, the process will run into the mud."
Harradence confirmed that anyone who underbid would face a detailed interrogation. "If they have a good explanation that's fine, but it is better for projects to appear to cost more – than us having to go cap in hand to the Treasury for more money further down the line.
"We need to spend more time and money at the start of the process to get the design right. That will give clients greater reassurance that they will get the quality asset they need – and BIM can support that by giving a realistic production schedule and more transparency."
Frise said all BESA members would welcome the intention behind the Playbook and the move towards fully designed projects but would be watching carefully to make sure the rules were properly enforced and payment practices improved.
The government believes that greater use of digital systems and BIM models can improve transparency, according to Harradence. "We want suppliers competing on the right basis – not on lowest price, but whole life cost, efficiency and social value."
He added that as much as £35bn of the £50bn worth of projects currently in the central government pipeline could be delivered through offsite fabrication, improving productivity and quality.
Harradence said the process of putting the Playbook together was the most open and productive exercise he had experienced in 20 years in government because the pandemic had made sure officials engaged online with representatives from the entire construction supply chain.
He also explained that the government was keen to see more people directly employed in the construction sector and that was behind recent policy changes like the revised IR35 scheme.
"We would prefer the industry directly employed a smaller number of highly skilled individuals rather than pulling in large numbers of unskilled people from overseas. That model is not viable," he told the BESA webinar. This should also help to raise the profile of vocational training, he added.
"The vocational side has been the poor relation in our Higher Education system. It is often seen as something you fall into rather than aspire to. There's more of a commitment now to change that…and it will be crucial if we are going to be able to do things like the effective retrofitting of buildings."


1. Why were Parables given?
4: We will not hide them from their children, shewing to the generation to come the praises of the LORD, and his strength, and his wonderful works that he hath done.
7: That they might set their hope in God, and not forget the works of God, but keep his commandments.
Parables are illustrative stories which explain spiritual concepts and truths about Yahweh's law. They were used extensively by the Saviour to unveil "...things which have been kept secret from the foundation of the world." (Matt 13:35) Their main purpose is to explain the Almighty's involvement in human affairs. To those who understand parables they impart a wealth of information: but to those who don't, they are a mystery. The parables of Jesus teach faith and obedience. The parable of the dragnet adds some awesome truths. Here is the parable.
48: Which, when it was full, they drew to shore, and sat down, and gathered the good into vessels, but cast the bad away.
50: And shall cast them into the furnace of fire: there shall be wailing and gnashing of teeth.
Prayer Meetings ... calling upon Yahweh's assistance to guide the fish to the net. Prayer is the most successful form of fishing for souls. Sad to say few Christians realise this fact. Prayer harnesses Yahweh's power when fishing for souls.
Gospel Sermons ... throwing out the net. Evangelical radio and TV broadcasts, Bible study, Youth activities etc. This is man's part in fishing for souls.
Gospel Literature ... The written word is still one of the most powerful tools in winning souls. The Protestant Reformation owes much of its success to the Bible which began to be printed in large numbers in the 16th century.
Who knows, the Internet may catch more souls than the printing press. We'll have to wait and see.
The chief fisherman in this expedition is the Saviour himself. He is far more interested in catching 'fish' (human souls) than we ever will be. His understanding of the human mind is all important, and his success in bringing fish to the net is unparalleled. When a fish is caught, it normally brings other fish with it. One could conclude from this fact that a "captured fish could well become a fisherman."
In this parable the fish represent human beings. You will find every type of individual in the church. Rich and poor, educated and ignorant, black and white, young and old. Yahweh nets every type of fish, some turn out to be good fish, others bad. As in the parable of the wheat and the tares every type is found in the church of the Most High - both bad and good alike.
But there is coming the Day of Judgement, a time of sifting and sorting when the fish will be closely examined. In Bible terms that sort program is called the Day of Judgement. Let no-one forget that the Day of Judgement is near. The Saviour's return is very near, 'even at the doors.' When he comes the great 'sort program' will take effect. Unclean fish, those unfit for spiritual consumption (see Leviticus 11:9-12) will be cast out. They are an abomination to God.
Romans 14:10 "... for we shall all stand before the judgment seat of Christ.
For some people the Day of Judgement will be a day of eternal bliss. For others it will be a day of terrifying anguish. Multiplied millions of souls will then realise that they are spiritually unfit for the kingdom. They have been weighed in the balances and found wanting: they are unclean fish! They will be thrown to utter destruction. Oh what a frightening prospect is here displayed! Make sure you are saved.
In the parable of the wheat and the tares (weeds) the Saviour voices the same truth: that the unbeliever will perish at the coming Judgement. Not that unbelievers are worse than believers. Oh no! Many unbelievers are apparently good people: often better than believers. But unbelievers are sinners. They have rejected pardon for the sins they have committed. Their greatest sin is unbelief, a sin of the mind which is infinitely more weighty than that of the flesh. And for those sins - particularly their unbelief - they will die. The believer on the other hand has accepted pardon for all his/her sins. He/she will live because of his/her faith.
42: And shall cast them into a furnace of fire: there shall be wailing and gnashing of teeth.
All are invited to the Kingdom of God and all kinds of 'fish' enter the net, the church.
But before anyone is permitted to enter the Kingdom of Heaven there will be a time of sorting, evaluation and judgement. 'Unclean fish' will be thrown out.
On that Day of Judgement millions will realise that they are not only excluded from the Kingdom of Heaven but are consigned to the fires of hell.
Every believer should ensure that he/she is living a good life. Only then can they be sure of being sorted with the clean fish: those who have been cleansed by living faith in the Yeshua the Saviour, the Son of the living God.


CCS joins international outcry at measures instituted in Turkey against doctors who set up emergency medical facilities to treat protesters injured during demonstrations last summer. Criminal prosecutions started in May, 2014, call for long jail sentences. Legislation and administrative measures punish emergency care taken without government oversight last summer, putting professionals in conflict with their ethical obligations.
We are writing in concern with punitive action against Turkish physicians who provided emergency care to persons injured during protests in May of 2013.
According to press reports, doctors following their ethical duty to treat injuries are being prosecuted among other defendants in criminal trials that started on May 6, 2014 in Istanbul's Criminal Court of First Instance. The doctors are being prosecuted for their actions in a makeshift medical center in the Bezmi Alem Valide Sultan Mosque on June 1, 2013, for allegedly establishing unauthorized emergency medical centers and for using the mosque for this purpose. Doctors Selcan Yuksel and Erenc Ysemin Dokudag face criminal charges calling for up to 11 years in jail.
These charges are taking place in the context of legislation signed by Turkish President Abdullah Guhl on January 17, 2014, criminalizing emergency care for protester and fining medical professionals for certain related actions. Physicians for Human Rights (PHR) called the law as "part of the Turkish government's continuing effort to harass the medical community for treating those in need, including demonstrators injured during last summer's anti-government protests." We understand that leading medical associations and the UN Special Rapporteur on the Right to Health Care have criticized the law, which puts professionals in conflict with their internationally recognized ethical obligations, as well as with Turkish law.
Finally, we are also concerned with the Ministry of Health's lawsuit against the Turkish Medical Association. According to PHR, that action would remove from office the governors of the Association because of the establishment of urgently needed emergency healthcare units during the protests at Gezi Park and in other cities in 2013.
We join the numerous medical associations around the world that have protested the trials, the law, and the actions of the Ministry of Health. These include the World Medical Association, British and German medical associations, and the American Academy of Emergency Medicine. We urge you to order the immediate dropping of criminal and civil actions against medical personnel acting under their ethical obligations to treat the injured, including protesters injured during demonstrations. We recommend that the law authorizing these trials be repealed and that administrative actions pursuing the same punitive goals be ceased immediately.


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Childhood Trauma written by Alexandra Madureira MBPsS, resident psychologist at the medical and psychological clinic, Cortijo Care, based in San Pedro with the assistance of Claire Puttock.
A trauma can happen to most people during their lives, dealing with the death of a loved one or coping with a serious illness in a family for example, and the aftermath can be extremely difficult to cope with. However childhood trauma can have an even more profound impact and can influence our character, behaviour and the way we perceive ourselves throughout our lives. It can cause us to be abusive to ourselves or to others. Dealing with the fallout can be difficult, but recovery is possible.
Low self-esteem, depression, anxiety, addictions and other mental health conditions, such as eating or personality disorders, can be caused or exacerbated by what we experience in our childhood.
Take Michael for example; he bullies other children at his school, calling them names and physically hurting them; he is disruptive in class and disrespectful to his teachers. Or little Sarah who seems nervous, isolates herself and is often in tears at the most insignificant thing. Both Michael and Sarah may be reacting to trauma experienced at the hands of parents, relatives or other caregivers from birth and / or throughout their childhood years. Sometimes it's much harder to spot.
This type of abuse could be physical, mental or the result of exposure to aggression or addiction at home. The way we are treated as children influences the way our brain develops and creates a long lasting 'blueprint' that can shape the way we live our lives. This can manifest itself by unconsciously repeating the patterns of childhood trauma in the form of abusing others or ourselves, forming unhealthy addictions, or living with unmanageable emotions.
Psychiatrists and psychologists often refer to the impact of childhood trauma as 'dysregulation'. In short this means we can find it hard to regulate our thoughts, feelings and behaviour because of what happened to us as children. In our early years our brains are delicate so if a parent or caregiver abuses us and inflicts stress, our brains develop differently to those who grow up in more stable and loving environments.
Trauma in our early years will alert the brain to scan for threats and respond to them instinctively. Continuous activation of these responses can create a permanent susceptibility to perceive the world as a hostile place in which we have to protect ourselves. For some there may be a genetic vulnerability that is aggravated by trauma; for others this is not the case. Regardless of this we are born with an instinctive predisposition to form a strong bond with our mother. If she fails us in any way it can affect the health of our connection to her, or others as we grow.
The brain however, does have the ability to recover from childhood trauma and we can stop the cycle of abuse. A transformation can occur by which we make the transition from feeling neglected to feeling secure, from feeling unloved to feeling cherished. Psychotherapy is an effective way of helping people to make the changes in their lives that can restore their ability to stop destructive patterns and enhance a state of well-being.
Therapists will encourage clients, in a healthy and manageable way, to talk about themselves, their feelings, behaviours and life experiences. This helps the therapist to establish trust with the client. Through this the client can start to experience a more accurate sense of self-awareness and an understanding of how childhood traumas have impacted their lives within a safe environment. Through this process of realisation, the client can begin to understand why they may endure or inflict abusive behaviours on themselves, others, or indeed both. It then becomes possible, with the ongoing support of the therapist, to influence their brains to think and act in a more positive way, using coping strategies, better communication skills and thought processing.
Mental illnesses, addictions, eating and anxiety disorders are problems that are surmountable when we can get the right help from highly trained therapists and doctors. The impact of this treatment can be far reaching, improving our relationships with partners, children and loved ones and, most importantly, ourselves.
If your feelings and behaviour have become unmanageable and damaging, or if you know someone who in this position, help is at hand and recovery is possible. Moving from an emotionally dark place into one of light takes courage, effort and time, but the improvement in the quality of our lives and those of the people around us is more than worth the effort.
Cortijo Care specialises in Trauma Resolution Therapies including EMDR (Eye Movement Desensitisation and Reprogramming). Call us now for a confidential chat or to book an appointment on 952 780 181.
To find out more information about Cortijo Care Marbella and for their full contact details please click here and visit their listing page in our directory.
Cortijo Care Marbella is an Addiction Clinic / Psychological Wellbeing Centre based in San Pedro de Alcantara, Marbella on the Costa del Sol in Spain. To find out more information about Cortijo Care Marbella and for their full contact details please click here and visit their listing page in our directory.