Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/001—General methods for coating; Devices therefor
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
  • C03C17/23—Oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2201/00—Polymeric substrate or laminate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
  • B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2350/00—Pretreatment of the substrate
  • B05D2350/60—Adding a layer before coating
  • B05D2350/63—Adding a layer before coating ceramic layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking

Definitions

• the present application relates to the provision of an adherent, self- assembled, phosphorous acid-based coating on an oxide surface, both as a coating layer for the surface and as an interface between the oxide surface and overlaying layers.
• an interface in improving the bond of an overlaying adhesive layer and in the provision of a patterned osteoconductive layer
• the method of the present invention and the adherent, phosphorous acid-based coating layers provided thereby have much broader applicability.
• BACKGROUND The provision of an organic layer which is bonded to the surface of a substrate having insulating, metallic, conductive, or electronic properties is essential in building up devices for use as an interface between inorganic materials and organic or biological materials.
• Examples of interfaces using a biological/inorganic material interface are materials for in vivo implant, for example, bone ingrowth-promoting orthopedic implants and implantable biosensors that utilize a bioactive layer to detect a chemical or biological species.
• a biologically active layer also referred to herein as an bioactive layer
• a semi-conductor layer to generate an electronic or optical signal proportional to the amount or concentration of the species detected.
• Devices utilizing an organic/inorganic material interface are, for example, organic-based transistors (OT's) and light emitting diodes (OLED's).
• the mechanical, chemical, and electronic properties of the interface between an organic or bioactive layer and an inorganic substrate depend upon many factors, not the least of which are: (a) the organization of the molecular moieties comprising the layer, for example, their alignment and attachment to the substrate's surface; and (b) the area specific density of bonds between the surface of the substrate and the organic layer.
• the interface must display chemically stability and be robust under the conditions of use or it will deteriorate in use.
• U.S. Application Numbers 10/701 ,591 filed November 4, 2003, 10/405,557, filed April 1 , 2003, and 10/179,743, filed June 24, 2002, each of which is incorporated herein by reference in their entirety, and as described in U.S. Patent No. 6,433,359 to Kelley et al., it is known that a phosphorous acid can be used to provide a layer which adheres to an oxide surface.
• one aspect of the present invention is the provision of a method for forming an adherent phosphorous acid-based coating layer bonded to an oxide surface, said method comprising contacting said oxide surface with a carrier conveying a coating composition comprising an acid selected from the group consisting of phosphoric acids, organo- phosphoric acids, and phosphonic acids, and mixtures thereof, said contact being carried out at a sufficient temperature and for a sufficient time to bond at least a portion of said acid to said oxide surface.
• the carrier conveys the coating composition to the oxide surface by a process comprising: (a) contacting said carrier with a solution comprising one or more of said acids in a solvent; (b) removing said carrier from said contact; and (c) placing at least a portion of said carrier in contact with said oxide surface.
• the carrier conveys the coating composition to the oxide surface in the form of a pattern, thereby providing a phosphorous acid-based coating layer on said oxide surface in substantially similar pattern.
• the coating solution comprises at least one acid having an omega carbon substituent selected independently for each occurrence from the group consisting of carboxylic acid, phosphonic acid, hydroxyl, amino, and thiol
• the method of providing a phosphorous acid-based coating layer further comprises: (a) contacting at least a portion of said coating layer with a reagent capable of a bond-forming reaction with said omega-substituents; and (b) forming a bond between at least a portion of said contacting reagent and at least a portion of said omega- carbon substituents.
• the reagent which is capable of a bond-forming reaction with said omega-carbon substituents is contacted to the coating layer in a printing medium, more preferably, is patterned on the coating layer using a printing technique.
• the acid in the coating composition is selected from phosphoric acid and phosphonic acids.
• the coating composition comprises a phosphonic acid having an organic ligand selected independently for each occurrence from the group consisting of: (a) linear or branched, saturated or unsaturated hydrocarbon moieties having from about 2 to about 40 carbon atoms which optionally includes an aromatic segment are optionally substituted on any carbon thereof with one or more functional groups; (b)oligoarene and polyarene moieties which are optionally substituted on any carbon thereof with one or more functional groups; and (c) substituted and unsubstituted TCNQ and TTF derivatives.
• the carrier comprises a hydrophilic material.
• the carrier is a porous or reticulated material, more preferably, a woven material, and even more preferably, comprises cotton fiber.
• the oxide surface is selected from the group consisting of hative oxides on metals, ceramics, semiconductors, and insulators, more preferably the oxide surface is selected from: (a) native oxides on titanium, steels, iron, silicon, aluminum, and the alloys of each of these, ceramics, and semiconductors; (b) an insulating oxide deposited on a substrate, more preferably a dielectric layer in an electronic device; and (c) a conducting oxide deposited on a substrate, more preferably indium tin oxide on glass.
• Another aspect of the invention is a method for providing improved adhesion between an adhesive coating applied to an oxide surface and the oxide surface comprising providing a phosphorous acid-based layer in at least a portion of the interface between the oxide layer and the adhesive coating.
• the phosphorous acid-based layer is formed on the oxide surface by contacting a carrier conveying at least one phosphorous acid to the oxide surface under temperature conditions sufficient to form on at least a portion of said contacted oxide surface an adherent, phosphorous acid-based coating layer.
• the phosphorous acid species from which said coating layer is formed is an omega-functionalized phosphoric acid species and the adhesive layer applied comprises a polymer layer formed from a reactive polymerizing organic species which reacts with at least a portion of the omega functional groups of said phosphorous acid-based coating layer, thereby bonding at least a portion of said coating layer to at least a portion of said adhesive polymer layer.
• Another aspect of the invention is the provision of an adherent phosphorous acid-based coating layer on the surface of an oxide using any of the above-described coating methods.
• the methods of the present invention provide an adherent, phosphorous acid-based coating layer bonded to an oxide surface of a material.
• These coating layers have utility in derivitizing the oxide surface to alter the properties of the surface.
• the chemical properties of the surface for example, the affinity of the surface for hydrophilic or lipophilic substances may be altered in this manner.
• the electrical properties for example, the ability of the surface to carry out charge carrier injection processes can be altered in this manner.
• the methods and coating layer of the present invention have broad utility in providing a chemically derivatizated coating layer on oxide surfaces, it is anticipated that the present invention will be most useful in the provision of phosphorous acid- based coatings which act as interface between the oxide surface and overlayer adhered thereto, thereby improving or facilitating the adherence of said overlayer to the oxide surface.
• Examples of such uses include improvement in the adhesion of an adhesive for a metal oxide surface, for example, an epoxy adhesive layer bonded to the native oxide surface of a titanium alloy, and the provision of a osteoadhesive layer in a medical implant in living bone tissue.
• the method of the present invention has broad applicability in providing a phosphorous acid-based adherent coating layer to an oxide surface
• the method of the present invention will be most useful in the provision of an adherent phosphorous acid-based coating layer on the oxide surface of metals, semi-conductors, and insulators.
• oxide surfaces include, but are not limited to, oxide surfaces which form spontaneously (native oxides) as well as those applied to a surface, for example by sputtering.
• the method will find greatest utility in the provision of a phosphorous-based coating layer on oxides of traditionally low reactivity, for example, the native oxide surface of titanium alloys.
• the method and coating layer of the present invention has broad applicability in providing an adherent phosphorous acid-based coating layer on oxide surfaces on a wide scale of sizes, it is anticipated that the present invention will find its greatest utility in the provision of coating layers in operations wherein coating is done in a continuous operation, for example, by lamination of a carrier furnished with a phosphorous acid and a carrier of material comprising the oxide surface to which the coating layer is applied.
• THE METHOD Without wanting to be bound by or to any particular theory, as described in copending U.S.
• the method of the present invention provides a coating layer with improved order and improved bonding of multi-layer character over methods utilizing "dip" coating, as described for example in the above-mentioned copending U.S. Application No. 10/179,743.
• This improvement in layer organization and bonding provides improved coverage of the surface, improved adhesion of the coating layer, and increases the chemical and electronic communication between the coating layer and the surface.
• the method of the present invention is believed to provide improvement in the efficiency of applying a coating of the invention to a large surface area in comparison to dip-on or paint-on methods.
• the method of the present invention is readily adaptable to a continuous coating operation using a web or belt system to provide a coating of the invention to a continuous supply of oxide surface.
• the method of the present invention also provides a convenient method of placing a coating on an oxide surface in a pattern which has here-to-fore only been possible by masking portions of the surface to be coated prior to providing the coating. Accordingly the method of the present invention provides for a reduction in the unit operations necessary required to prepare a patterned phosphorous acid- based coating layer on an oxide surface.
• the method of the present invention comprises contacting a carrier conveying a coating composition comprising a phosphorous acid to an oxide surface for a sufficient duration and under temperature conditions sufficient to form bonds between at least a portion of the furnished phosphorous acid and the contacted oxide surface.
• No particular environmental conditions are required to provide a coating layer on an oxide surface by the present invention method, although if it is desired the present invention can be carried out within environmental chambers or under inert atmospheres.
• the carrier may be in many different forms, for example, a roller, pad, sheet, roll, web, or belt. Other forms will be apparent. It will also be appreciated that the method of contacting the carrier to the oxide surface will vary depending upon the phosphorous acid(s) comprising the coating solution, the concentration, the temperature conditions, and the nature and character of the oxide surface to be coated.
• examples of the various methods which may be used to contact the carrier to the oxide surface include fashioning the carrier into a roller which is rolled across the oxide surface, fashioning it into a stamp or plate which is contacted to the oxide surface either manually or by mechanical means, furnishing a roll of the carrier with the coating solution which is unrolled onto the oxide surface, laminating a web or belt of carrier material which has been furnished with the coating solution to a supply of the oxide surface.
• the oxide surface permits it to be presented as a web, belt, or sheet, for example, acrylic and polyethylene oxide terphthalate PET which has been coated with silicon dioxide, a continuous lamination process can be used.
• the oxide surface is in a more or less rigid form, for example, an indium tin oxide coating on glass
• a feeding mechanism accompanying a belt, chain, or web-feed type of lamination equipment can be adapted to laminate sections of the oxide surface with a continuous belt or web of the carrier.
• many other modifications exist in the coating, printing and laminating arts which can be adapted to contact both flexible and rigid carrier materials with oxide surfaces residing on either flexible or rigid substrates. The duration of the contact between the carrier and the oxide surface will depend upon the coating solution selected, the oxide surface, and the temperature conditions obtaining during contact.
• the coating layer will form spontaneously at any ambient temperatures, for example about 20 °C, and above.
• ambient temperatures for example about 20 °C, and above.
• contact is made under temperature conditions of from at least about 100 °C up to about 200 °C. If lower temperatures are employed, or for different oxide surfaces and phosphorous acids, longer contact times, for example several hours, may be required.
• contact times employed in the method of the present invention are from about 1 minute to about 20 minutes at temperatures from ambient, about 20 °C to about 200 °C. More preferably, contact times from about 5 minutes to about 20 minutes are employed at temperatures from about 50 °C to about 200 °C.
• the oxide surface and carrier can be in the form of a sheet which is transported through an oven or furnace on a belt or in a batch conveyance.
• the oxide surface and carrier can be in the form of a two webs which are contacted and passed in contact through a heated zone, as for example, will be familiar to those of skill in the laminating arts.
• heat to drive the coating reaction can be provided by heating the oxide surface separately and bringing the carrier into contact with the heated oxide surface thereafter.
• the process of conveying the coating composition to the oxide surface requires furnishing the coating composition to the carrier. This can be accomplished by contacting the carrier with a coating solution, removing the carrier from contact with the coating solution, and contacting the carrier with the oxide surface.
• the coating solution comprises the phosphorous acid to be used in forming the coating and a solvent, for example, an alcohol.
• an evaporation step is conducted during which a portion, preferably a substantial portion, of the solvent conveyed by the carrier from the coating solution is evaporated.
• the carrier appears to be "dry" when visually inspected, and can be handled, transported, and packaged without exuding any solvent.
• the carrier provided with the coating composition in this manner will be employed to provide a coating on an oxide surface remote in time and/or location from the time and place in which the coating composition was provided to the carrier. It will be appreciated that other methods of providing the coating composition to the carrier can be employed. Without wanting to be bound by or to any particular theory, it is thought that the evaporation step improves the organization of the coating composition on the carrier prior to contacting the carrier to the oxide surface.
• the carrier of the present invention can comprise numerous flexible and rigid materials.
• the carrier is selected to have some affinity, for example, hydrogen bonding or Van-der-waals interaction, for the phosphorous acid(s) comprising the coating solution, but not to react with them.
• affinity for example, hydrogen bonding or Van-der-waals interaction
• the carrier imposes some order on the acid moieties therein prior to contacting the surface, and thereby presents the phosphorous acid from which the coating is derived to the oxide surface as a collection of moieties having at least short range ordering, and thereby providing a coating layer which has imparted to it at least localized ordering of the coating moieties.
• preferred carriers are those which have non-reactive surface hydroxyl groups with which the phosphorous acid(s) comprising the coating solution can form hydrogen bonding.
• examples of this include cellulose materials, for example, cotton fiber.
• materials having surfaces which have been derivatized to have greater or lesser hydrophilic nature can also be employed. It will be appreciated that this includes surfaces comprising materials which, for example, fibers have regions comprising various alcohol, ether, ester, amino, amido and like moieties.
• this includes both materials in which this type of functionality is either naturally occurring or in which the functionality has been introduced by chemical derivatization of the materials.
• An example of one such naturally occurring material is cotton fiber and materials made therefrom.
• suitable carriers for the present method include those which have absorbent properties for the coating solution, adsorbent properties for the coating solution, or both.
• the carrier material can have, for example, the form of a reticulated or porous material which provides interstices into which a coating solution can be take up by absorption.
• the carrier can also be non-porous, utilizing adsorptive properties, for example, a material which has an affinity for the coating solution such that it is readily "wetted" by the coating solution.
• Suitable carrier materials will generally have a mixture of both types of properties. Accordingly, it will be appreciated that for some applications, a non-porous, smooth carrier will be employed which relies on adsorption of the phosphorous acid comprising the coating solution to convey it to the oxide surface to be coated. In other applications, the carrier will be porous or reticulate and have absorptive properties for the coating solution.
• Preferred carriers include cellulose materials having a hydrophilic surface, for example woven and non-woven cotton and woven and non-woven polymers which have hydrophilic surfaces. Rigid materials having hydrophilic materials which are non-reactive toward phosphorous acids are also preferred. It will be appreciated that surfaces which have been derivatized with a phosphorous acid which contains hydrophilic functional groups may also be employed.
• the coating composition comprises the acid used in forming the coating layer of the invention organized on the carrier, some amount of the solvent retained from the coating solution, and optionally other constituents which may be added to improve the stability or handling characteristics of the coating solution, as are known in the art.
• coating compositions suitable for use in the present invention method comprise an acid selected from the group consisting of phosphoric, organo-phosphoric, and phosphonic acids and a solvent.
• the solvent is water or an alcohol. Particularly preferred are phosphonic acids and alcohol solvents, particularly ethanol.
• coating compositions employ dilute solutions of the acid, typically in the millimolar (mM) concentration range.
• the coating compositions are prepared from solutions having an acid concentration of from about 0.01 mM to about 5.0 mM, more preferably from about 0.1 mM to about 3.0 mM.
• concentration of the solution may be adjusted to higher or lower values.
• phosphorous acid refers to phosphoric acid (H3 PO4), organo-phosphoric (R 1 -0-PO 3 H 2 ), wherein R 1 is an organic moiety bonded to the phosphorous atom through an oxygen atom, and phosphonic acid compounds having the formula R-PO 3 H 2 , wherein R is an organic ligand, that is, wherein a carbon atom is directly bonded to phosphorus.
• organo-phosphoric acids can be selected from the same organic moieties described below for the phosphonic acid organic ligand, guided by general chemical principles regarding the stability of the phosphorate species after bonding to an oxide surface.
• any of the acid species which are disclosed for preparing coatings in any of copending U.S. Application Numbers 10/701,591, filed November 4, 2003, 10/405,557, filed April 1, 2003, and 10/179,743, filed June 24, 2002, each of which is incorporated herein by reference in their entirety, may be employed in the methods of the present invention to prepare the coatings of the present invention.
• the preferred acids for use in the present invention are phosphonic acids.
• Preferred phosphonic acids have an organic ligand selected from the group of organic moieties consisting of aliphatic and aromatic hydrocarbon moieties having from about 2 to about 40 carbon atoms, and more preferably from about 2 to about 20 carbon atoms.
• Suitable aliphatic organic moieties may be linear or branched, saturated or unsaturated, and may be optionally substituted with one or more functional groups, including aromatic substituents.
• Aromatic organic moieties may comprise arene structures, for example a monomeric, oligiomeric, or polymeric arene structure, for example anthracene and pentacene, which are directly bonded to a phosphate moiety. Alternatively, aromatic moieties may be bonded to a phosphate moiety through an intervening aliphatic moiety.
• Aromatic moieties may optionally be substituted on any carbon with one or more functional groups.
• the ligands are selected from organic moieties which are based on organic compounds having electron donor and acceptor properties, for example, moieties which are based on derivatives of the art recognized electron acceptor and donor molecules TCNQ and TTF, the structures of which are well known.
• TCNQ and TTF are typically used as building blocks in the provision of organic conductors.
• substituted molecular derivatives of TCNQ with altered electron acceptor properties are also known and have been described, for example, by Yamashita et al.
• TCNQ derivatives are also preferred as liganads in phosphorous acids employed in coating solutions for the present development.
• TTF derivative compounds with altered electron donating properties. Such molecules have been described, for example, by Hasegawa et al. in Synthetic Metals (1997), 86, pages 1801-1802, which is incorporated herein in its entirety also by reference.
• TTF can be substituted, with electron donating groups to enhance its electron-donor properties.
• Moieties based on these TTF derivatives are also preferred as ligands for phosphorous acids used in coating solutions for the present invention.
• Substituents on the hydrocarbon ligand of phosphonic acids useful in, the present invention may be appended to any carbon atom of the hydrocarbon ligand.
• Useful substituents are, for example, those which may influence the hydrophilicity and/or lipophilicity of a coating prepared therefrom, for example, alkyl groups, and reactive functional groups, for example those selected from the group consisting of hydroxyl, carboxylic acid group, amino, a thiol, a sulfonic acid group, a phosphonic acid group and chemical derivatives thereof. It will be appreciated that any functional group which can participate in a further derivatization reaction can be employed.
• suitable hydrocarbon ligands may contain within their structure or appended to their structure, reactive moieties, for example sites of unsaturation, which may be further reacted in a polymerization reaction with reactive substituents on the hydrocarbon ligands appended to other phosphonate sites bound to the surface of the oxide during a phosphonate derivatizing reaction.
• reactive functional groups may be included on one or more carbon atoms of the organic ligand of the acid used to form the coating. These functional groups may be employed to further derivatize the coating layer formed, as explained in detail below and in each of copending U.S.
• coatings are formed from phosphonic acids having an organic ligand functionalized at the omega- carbon of the ligand.
• omega-functionalized phosphonic acids when omega-functionalized phosphonic acids are used to form the coating layers of the invention, after reaction of the acid to oxide surface resultant phosphonic acid film generally comprises phosphonate moieties bonded to the oxide surface with the omega-carbon directed away from the surface and available for covalent bonding or further chemical modification.
• Preferred omega-functional groups include hydroxyl, amino, carboxylate and thiol groups.
• Another class of substituents which may advantageously be bonded to a phosphonic acid organic ligand are pi-electron delocalized moieties.
• Particularly useful compounds are pi-electron delocalized aromatic ring compounds (oligo- and polyarene ligands).
• Five-membered heteroaromatic ring compounds having phosphonic acid ring substituents are also desirable because of their high degree of pi-electron delocalization. Examples of such rings include furan, thiophene and pyrrole.
• THE OXIDE SURFACE As explained in detail in each of copending U.S.
• a coating layer comprising a phosphorous acid in accordance with the present invention can be formed on both native oxide surfaces and oxide surfaces which are deposited on a substrate or formed on an existing oxide surface.
• native oxide surfaces upon which a phosphorous acid-based film can be formed include materials which have metallic, conducting, semiconducting, and insulating properties, as those terms are defined, for example, by A. West in Basic Solid State Chemistry, second edition, John Wiley & Sons, New York, pp.
• substrates suitable for use in the process of the invention include, but are not limited to materials which possess a native oxide surface, that is, they comprise an oxide or form a native oxide upon exposure to the ambient environment.
• Non-limiting examples of oxide materials include bulk metal oxides, for example silica and alumina, oxides deposited on a substrate, for example, conducting oxides, for example, indium doped tin oxide and zinc/indium doped tin oxide each deposited on a glass substrate, and oxide insulators, for example, low dielectric constant glass in gate insulator material of integrated circuits and metal oxide deposid on plastic substrates, for example "stacked" metal oxide on PET plastic (which has a top layer of silicon dioxide), for example anti reflective plastic obtained commercially from Berkaert Specialty Films.
• bulk metal oxides for example silica and alumina
• oxides deposited on a substrate for example, conducting oxides, for example, indium doped tin oxide and zinc/indium doped tin oxide each deposited on a glass substrate
• oxide insulators for example, low dielectric constant glass in gate insulator material of integrated circuits and metal oxide deposid on plastic substrates, for example "stacked" metal oxide on PET plastic (which
• Non-limiting examples of materials which form native metal oxide surfaces upon exposure to the ambient include steels, including stainless steels, iron, and metals which acquire a non-ablating oxide coating upon exposure to the ambient environment, for example, titanium, titanium alloys, aluminum, and aluminium alloys. Additional examples of materials which acquire a native oxide layer upon exposure to the ambient are ceramic materials, for example, silicon nitride and semiconductors, for example silicon. Also suitable for application of a coating of the present invention are materials which have an oxide coating imparted to them intentionally, for example, thick film oxide insulators in semiconducting devices, and those which can be derivatized to have an oxide surface, for example, gallium arsenide, gallium nitride, and silicon carbide.
• a coating layer of the present invention are naked surfaces which can undergo hydrolysis and which have an adsorption affinity for phosphonic acid functional groups, for example, silicon nitride.
• Particularly preferred substrates are those which are useful in preparing electronic devices and those useful for mechanical devices for contact with biological tissue or fluids.
• An example of those useful for the preparation of electronic devices are thick oxide insulating layers on gate junctions for use in bio-electronic sensors which are suitable for in vivo and in vitro diagnosis and monitoring of conditions.
• An additional example is indium tin oxide conducting oxide deposited on glass.
• An example of a surface useful in the preparation of mechanical devices is an implantable material, for example, a titanium reinforcing member useful for in vivo implant in the repair
• suitable surfaces include the surfaces of semiconductor substrates, for example silicon single crystal surfaces. They include also the surfaces of polycrystalline substrates, for example, metals, for example titanium and its alloys, aluminium and its alloys, and silicon. Also included are the surfaces of amorphous substrates, for example, the surface of an oxide conductor or oxide insulator.
• conductive oxides include Fe 3 ⁇ 4 , tin oxide doped to conduction with indium and/or zinc, zinc oxide doped to conduction with aluminium, zinc oxide, and sub-stoichiometric oxides, for example, TiO and V.
• Ceramic substrates for example, silicon nitride and silicon carbide
• semiconductors for example germanium and semiconducting germanium-based compounds.
• an oxide surface is prepared prior to contact with the carrier by cleaning the surface to remove residual metals and organics, generally by an oxidation treatment followed by a water rinse.
• Oxide surfaces that are stable toward such treatment for example, a single crystal or polycrystalline silicon wafer surface, the surface may be treated with the standard hydrogen peroxide/sulfuric acid "piranha" solution followed by a water rinse and a second treatement with a standard hydrogen peroxide/hydrochloric acid "buzzard" solution, in the manner typically followed for cleaning silicon wafers prior to fabricating integrated circuits on the wafer.
• the process of the invention affords best results on oxide surfaces which are devoid of free base species, zero-valent metals, and residual hydrocarbon species.
• the process of the invention will still provide a coating layer which has good adhesion to the oxide surface upon which the coating layer is formed.
• Other cleaning methods applicable to particular surfaces for the removal of the unwanted species typical of those surfaces will be apparent to those of skill in the art.
• a phosphorous acid- based coating layer of the invention is prepared from a coating composition comprising a di- or polyfunctional phosphorous acid, for example, an omega- functionalized phosphonic acid, the coating layer formed can be further derivatized with additional reagents.
• Nonlimiting examples of such reagents include derivatizing the omega hydroxyl groups of a coating layer formed from an omega-hydroxy phosphonic acid with a protein coupling reagent and incorporating the hydroxyl groups of such a coating layer into an epoxy adhesive layer applied on top of the coating layer.
• protein coupling reagents include maleimido and succinimidoyl coupling reagents.
• Such reactions can be employed to provide a pattern of the derivatized species on the surface of a coating layer provided by the present invention.
• the above-described protein coupling reagent incorporated into a printing medium can be applied in a pattern to a coating layer prepared by the process of the invention utilizing a printing technique.
• Non-limiting examples of this include providing the coupling reagent in a medium suitable for delivery from an ink-jet printing device.
• patterns of derivatizing reagents When such patterns of derivatizing reagents are applied they can find utility in biosensor devices and in providing engineered biological structures for example, which can be utilized in implantable devices.
• other non-impact and impact printing techniques for example, lithography, screen printing, stamping, and gravure printing can be adapted to provide patterns of derivatizing reagents on coating layers of the invention.
• the coating process of the present invention can be used to provide a coating layer which is in a pattern on the oxide surface.
• a coating composition can be provided to the carrier in a pattern which will be transferred to the oxide surface when the carrier is contacted to an oxide surface under temperature conditions suitable to form a bond between the oxide surface and the coating composition.
• numerous means can be used to provide a pattern of coating composition on the carrier. Non-limiting examples include spraying a coating solution onto the carrier in only predetermined areas, for example, by ink-jet printing and stencilling. Other methods may be found by adapting printing techniques, including stamping, lithographing, and gravure printing a coating solution onto the carrier in a pattern.
• the carrier itself can be provided in the form of a pattern, for example, a stencil or a stamp.
• the pattern of the carrier will transfer the coating composition to an oxide surface in a like pattern.
• the carrier conveying a coating composition is in a form suitable for mechanical manipulation, for example, in the form of a roller or ball, it can be mechanically directed in a pattern across an oxide surface to provide a coating layer having a pattern reflecting the path along which it was directed on the surface.
• 11-Hydroxyundecylphosphonic acid (a linear, 11 carbon atom difunctional phosphonic acid having an omega hydroxyl functional group to the phosphonic acid) was synthesized according to published procedures. Disks were cut from titanium Ti-6AI-4V rod (1" in diameter, obtained from Goodfellow, Inc.) and prepared for use by sanding, followed by cleaning with methanol. The disks were dried for at least an hour before use, and stored in an oven at 200°C. Samples were analyzed using either a Nicolet 730 FT-IR equipped with a Spectra Tech diffuse reflectance (DRIFT) attachment or a MIDAC Illuminator equipped with a Surface Optics specular reflectance head.
• DRIFT Spectra Tech diffuse reflectance
• Example I Application Of A Coating Layer
• a white cotton swatch of commercial textile measuring 2" square was prepared as a carrier by rinsing in distilled water and drying in air.
• a 1.0 millimolar coating solution of 11-Hydroxyundecylphosphonic acid was prepared by dissolving 0.1 mM of the acid in 100 ml of ethanol. About 50 ml of the solution was placed in a shallow dish and the carrier was placed into the solution and saturated with it. The carrier was then removed from the solution and permitted to remain in air until it was visibly dry (overnight).
• the carrier with containing a coating composition comprising 11- Hydroxyundecylphosphonic acid was placed over a titanium disk prepared as described above.
• a consumer cloth iron with a Teflon ® coated heating platen (Black & Decker) set for cotton cloth (no steam) was placed on top of the assembly for a period of 5 minutes. At the end of the heating period the iron was removed and the oxide substrate (titanium disk) was allowed to cool in the ambient air. The disks were sonicated in ethanol and rinsed with copious amounts of ethanol and dried in air. Infrared examination of the area covered by the carrier by the procedure described above showed the presence of a coating layer comprising bound 11-Hydroxyundecylphosphonate. Integration of the signal strength indicated that the films comprised about 10 times the amount of material typically observed by treating similar surfaces directly with a similar coating solution. Repeated rinising and sonication did not result in a diminution of the signal, indicating that the coating layer was well bound to the surface. Visual inspection of the coupon shows that a coating layer is applied to the coupon only where contact was made with the carrier.
• Example 2 Deposition Of a Coating Layer on A Metal Oxide Coated Plastic.
• a sheet of antireflective coated polyethylene oxide terphthalate(PET) which has a top layer of silicon dioxide will be obtained from Bekaert Specialty
• Example 3 Derivatization of the Surface With An Adhesive Layer It will be found that the coating layer prepared in Example 1 above (a phosphonate coating derived from 11-Hydroxyundecyl phosphonic acid) can be further derivatized with an epoxy linking group by applying a film of Cytec Fiberite FM 1000® epoxy adhesive to the surface. Before the adhesive cured, a second titanium coupon prepared according to Example 1 can be placed in contact with the epoxy such that a lap joint is formed. When the epoxy is cured under ambient conditions, it will be found that the strength of the lap joint, when compared with substantially similar assemblies prepared from equivalent titanium coupons which have not received a coating layer by the process of the invention, is considerably lower. It will be found if these samples are compared according to to ASTM testing standard F1044-99, that on average, the joint between the uncoated coupons failed at 2/3 the pressure which must be applied to fail the joint between the coated coupons.

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