CN101193744A

CN101193744A - Aluminum phosphate compounds, coatings, related composites and applications

Info

Publication number: CN101193744A
Application number: CNA2005800339096A
Authority: CN
Inventors: S·桑巴斯万; K·K·兰根
Original assignee: Applied Thin Films Inc
Current assignee: Applied Thin Films Inc
Priority date: 2004-10-05
Filing date: 2005-10-05
Publication date: 2008-06-04

Abstract

Composites comprising an aluminum phosphate-based coating component and methods for sealing porous substrate surfaces.

Description

Aluminophosphate composition, coating and relevant composite

The application is the application of submitting on December 23rd, 2,003 10/745 of awaiting the reply, the part continuation application and the application of 955 (its full content is included into this paper as a reference) require its priority, await the reply and apply for 10/745,955 require the application 60/615 of while in submission on December 23rd, 2002, the priority of 920 and 60/615,986 (these two pieces of patents are also included in this paper as a reference in full).

Technical field

The present invention relates to be deposited on the aluminum phosphate coatings on the base material, to give required electrical property, chemical property, engineering properties and physical property.The present invention has also disclosed the method for sealing porous material, and has disclosed the new compositions and the improvement of aluminum phosphate material.

Background technology

Have many prior art patent to relate to the synthetic of aluminum phosphate material, this material is mainly as the catalyst carrier that comprises crystal form and amorphous form.Most of synthetic methods adopt sol-gel techniques, raw materials usedly comprise the aluminium salt that can extensively buy on market, and comprise phosphoric acid, the various phosphorus source of ammonium hydrogen phosphate, phosphorous acid etc.Many described methods obtain crystal form and the thermally-stabilised amorphous compositions of minute quantity (United States Patent (USP) the 4th, 289, No. 863, Hill etc.; United States Patent (USP) the 5th, 698, No. 758, Rieser etc.; United States Patent (USP) the 6th, 022, No. 513, Pecaro etc.).The material of prior art, for instance, at elevated temperatures can't be as preventing base material corrosion or oxide coating.

Need to use heat-resisting and stable amorphous dense coating to protect used various base materials in industry and consumer applications.The coating that prior art obtains makes material be subjected to heat treatment or is being exposed to the harsh industry of corrosive atmosphere or the durability deficiency under the applied environment under some environmental condition or at some.Developed the amorphous coating of silicon-dioxide-substrate, a nearest patent has been described a kind of peculiar methods (United States Patent (USP) the 6th, 162, No. 498) that deposits this coating.Yet this coating is durable inadequately under some rigor condition, and heat endurance deficiency at elevated temperatures can not be fully as clear coat on glass.Also developed the glassy or vitreous coating of high-temperature stable, in the method, at first the slurries of coating glass dust on base material are handled the material that applies then under sufficiently high temperature, make the glass dust fusion form glassy coating.Have many different vitreous enamel coatings of forming and had many decades.Yet they are usually thick and can deform at elevated temperatures.The required high-temperature process of melten glass powder may make the base material degraded, if select the low-melting glass composition, they may be durable inadequately.

What use at present in a lot of the application is the inorganic coating of vapor deposition, yet they need expensive equipment and are not suitable for non-sight line (non-line of sight), and (for example United States Patent (USP) the 3rd for the base material geometric configuration, 442, No. 686, United States Patent (USP) the 4th, 702, No. 963, United States Patent (USP) the 5th, 434, No. 008, United States Patent (USP) the 5th, 792, No. 550).The inorganic coating cost that is made by solution is low and coated substrate had the conformal ability.

The inorganic coating that prior art obtains neither be fully transparent, can not be used on glassly, otherwise its transmission property can be affected, and can not be used for other base materials that needs keep its aesthetic properties (metal appearance).

At the widely-used iron and steel of brushing such as the front of building, shopping mall, elevator, desk lamp, bathroom fittings (bath fixture), cabinet door, wall plate etc. or other the relevant surface of solids.These required character in surface comprise easy cleaning and anti-fingerprint and thermal stress or heat, light, all kinds of solvents and common cleaning agent, UV radiation have enough tolerances and food can not be stained with and other relevant nature contacting.

When being used for purposes such as storage, porous surface is polluted easily.Cooking equipment, baking box inner panel, meal tray, cooktop surface and other ceramic surface relevant in the stoneware of enamel, granite, marble, floor tile, glass, porcelain, baking box and the kitchen have big and little hole and defective, and this is undesirable in its terminal applies.On granite, for example on kitchen countertops, closed hole will help to give antifouling property.The sealing in these holes will help to reduce gas permeation, and this is very important in some applications.Known with polymer surfaces in this area and handled the sealed ceramic surface, yet their tolerance is limited when heat, contact cleaning solvent or cleaning agent, and relatively low.Need chemical inertness and heat-staple suitable thin inorganic coating.Many these classes are used a large amount of sale of representative, consider that the dip-coating of solution-based or spraying are most preferred method of application, and technology is very important cheaply.Such processing also make the surface can self-cleaning, easy to clean, have biological safety, have aesthetic value, hardness and wearability, antibiotic property and solvent resistance.In addition, this class sealant should have good thermal shock (for example, the heat pot on the granite desk) and heat endurance; Even described sealant is worn, the effect of filling lip-deep hole will help obviously to prolong the durability of coating.Can improved performance, durability by the material of the present invention on the aluminium part of anodization or other associated materials, and protection environment, energy-conservation.Material of the present invention can be used as sealed ceramic and adhesion promotor (monolithic integrated circuit, composite and glass-ceramic) in various application, to improve durability and to reduce gas permeation, described application comprises ceramic tile, is used for the base material of Electronic Packaging and refrigerator.

For space flight and aviation platform optical material, carborundum has outstanding character, but its frangible character and material hardness height make its inaccessible required tolerance.The size and the shape that depend on base material want catoptrical wavelength to need several thoughtful some months to sub-fraction surface grinding.

Present low-dielectric material does not have required dielectric constant values and heat endurance and mechanical stability.Need new low-k materials to improve the current state of semiconductor applications.

Researchers just polymer and metallic foil substrates and printable TFT base plate are being combined so that flexible display near commercial needs.In the past few years, " Holy grail " (although also being unrealized) of display industry has been thin, limpid, the flexible base material with the protective properties the same with sheet glass (barrier property).In addition, some shortcoming of indented material.

Photomask is the pinpoint accuracy plate that contains the microimage of circuit.Should keep structure to reach flawless photomask.When the chromium layer is influenced by the reaction of environment or interlayer, can go wrong.Have open defect, comprise glass fragment on the edge of the scratch above the chromium of array outside, AR coating damage or that part is removed, the pollution on the chromium, mask etc., these defectives all need to avoid.Coating should very thin (in the scope of about 10 nanometers) and zero defect.

Generally speaking, plastic basis material is easily because wearing and tearing, moisture invasion and attack, UV radiation, elemental oxygen, solvent contact, chemical substance and a lot of other materials and degrading.At present, in a lot of the application, use the inorganic coating of vapor deposition on plastics, yet, their need expensive equipment and are not suitable for the base material geometric configuration of non-sight line, and (for example United States Patent (USP) the 3rd, 442, No. 686, United States Patent (USP) the 4th, 702, No. 963, United States Patent (USP) the 5th, 434, No. 008, United States Patent (USP) the 5th, 792, No. 550).Therefore, need be used for the protective finish (inorganic and organic-organic composite material) that the solution cheaply of plastic basis material is derived, this coating has suitable processing scheme and carries out the continuous processing of spool to spool or roller to roller, and can apply complex-shaped base material.

Yet different with glass and metal, all polymer demonstrate the permeability of measuring to gas and steam.Developed the permeability that many technology reduce polymer, thereby increased its scope of application the F﹠B packing.In the time must transporting the material of impregnability, the infiltration barrier layer is just very important.Except that existing performance, the pipe and the flexible pipe that are used for (important at automobile and appliance applications) such as gasoline, fluorocarbon steam need barrier property.Similarly, for these display application, need thin zero defect and the moisture-barrier of atresia and the inorganic coating of oxygen.

Summary of the invention

According to foregoing description, the purpose of this invention is to provide aluminophosphate-based compound, composition, coating and/or relevant composite or goods, and their use and preparation method, thereby overcome the various shortcoming and defect of prior art, comprise those shortcoming and defect of listing above.It will be understood by those skilled in the art that one or more aspect of the present invention can satisfy some other purpose.Each purpose may not be to be equal to aspect all at it to be applicable to various aspects of the present invention.Therefore, according to of the present invention any one treat following purpose.

For purposes of the present invention, phrase " material of the present invention " and mention the phrase of this phrase or will be understood that to refer to any of the present invention with reference to the phrase of this phrase: aluminophosphate-based compound or composition in the P stoichiometric proportion scope at whole available Al, its can with method of the present invention, composite or goods, and/or film, associated layer or coating are used together, or as other place hereinafter mentioning, this compound or preparation of compositions or characterize as described herein, this compound and composition also can be distinguished otherwise statement, as aluminum phosphate compound and composition, and as below being prepared described in the reference of including in mentioned and/or the United States Patent (USP), characterize and/or use: United States Patent (USP) 6,036,762 and 6,461, the patent application serial numbers 10/362 that awaits the reply jointly that on July 15th, 415 and 2003 submitted to, 869, and respectively in 10/627 of on July 24th, 2003 and submission on November 19th, 2003,194 and PCT/US03/36976, and 10/642, the PCT/US03/25542 that on August 14th, 069 and 2003 submitted to, these patents are included this paper in as a reference separately in full.Unrestricted, as described herein and/or by one or more above-mentioned patent of including in or applications, material of the present invention can comprise aluminophosphate-based compound and contain adulterant, particle and/or comprise the composition of organic molecule, polymer, carbon, silicon, metal, metal oxide and/or other metal ion/salt (bag non-oxidized substance), no matter aluminium is stoichiometric with respect to the molar content of P, still be less than stoichiometry or more than stoichiometric.The embodiment of material of the present invention is can be available from Applied Thin Films, the product of the Cerablak trade mark of Inc..

" material of the present invention " also comprises aluminophosphate-based material and can use the custom-designed precursor solution that produces unique unbodied aluminum phosphate to be deposited as film on base material.Authorize people's such as Sambasivan United States Patent (USP) 6,036,762 and 6,461,415 and above-cited patent application the details of synthetic and chemistry, character is provided about precursor, and provide the details of other processing.Also think embodiments of the present invention for various interpolations or the improvement that carry out on the surface of using material of the present invention to apply, the embodiment of embodiments of the present invention is provided below.

Similarly, term " base material " or phrase " solid substrate " comprise any solid material, include but not limited to polymer, plastics, pottery, metal, alloy, carborundum, silicon, oxide, chalcogenide, pnictide, quartz, glass etc.

One or more following purposes can be coated on the various base materials in conjunction with material of the present invention and realize, lay special stress on to the roller of base material to roller continuously coated with protecting base material to avoid suffering various environmental factors, comprise moisture, oxygen, ultraviolet ray etc.Therefore, material coating of the present invention can be used as protective coating and functional coat.

The objective of the invention is to use material coating of the present invention as insulating barrier with effective dielectric strength, to be used in the various application that need electric insulation, the photovoltaic device on the conductor base material for example.

Another object of the present invention provides coating or the film with above-mentioned character, and this coating or film can remain on the moisture of given content in the packaging volume.

The objective of the invention is to use material of the present invention as anti-iridescence (anti-iridescent) and fade-proof (anti-tarnishing) coating.

The present invention relates on the metal surface, form material layer of the present invention, the method that promotes the fusible interface between metal surface and the organic compound coating is provided for the oxide skin(coating) coated metal surface that obtains.Described method also comprises apply material of the present invention on the metal surface.The coating that obtains can be used as the fusible interface that promotes between metal surface and the organic compound coating.

The objective of the invention is material coating of the present invention is used in the shell to the device of moisture-sensitive, for example to the optics of moisture-sensitive, described device to moisture-sensitive comprise many in the welding of its edge to limit the metallic plate of described shell, wherein organic polymer paint is applied on the outer surface of the shell that is positioned at the junction at least, prevents the moisture barrier of corroding to provide in the junction.

An object of the present invention is to provide a kind of method of using simple dip-coating, spin coating, spraying, brushing or flow coat method material coating of the present invention to be deposited as thin, sealing, dense micro-structure, uniform clear coat.

The objective of the invention is to use material coating of the present invention to protect solid substrate to exempt from moisture, light, gas, chemical substance and other ambient influnence.

The objective of the invention is under room temperature and high temperature to handle and use in protect the surface of solid substrate.

The objective of the invention is to improve the mechanical performance of solid substrate, the damage that includes but not limited to resistance to marring, resistance to soiling, wearability, corrosion resistance, takes place owing to the impact of high velocity particle, rain, water, liquid and other object.

The objective of the invention is to protect the solid space material to exempt from the LEO environment, for example high-throughout atom and molecule, for example influence of oxygen, hydrogen, nitrogen etc.

The objective of the invention is material of the present invention as subbing or cohesive promoting layer on the polymer surfaces.

The objective of the invention is material of the present invention as subbing or cohesive promoting layer on the metal surface.

The objective of the invention is material of the present invention as subbing or cohesive promoting layer on the ceramic surface.

The objective of the invention is material of the present invention as lip-deep subbing of metal chalcogenide element thing or cohesive promoting layer.

The objective of the invention is material of the present invention as lip-deep subbing of solid substrate or cohesive promoting layer.

The objective of the invention is material of the present invention as adhesive or bonding two kinds of similar dissimilar materials.

The objective of the invention is material of the present invention as adhesive or bonding two kinds of similar different optical materials.

The objective of the invention is to use material of the present invention to come hole on covering surfaces defective and the sealing solid substrate surface.

The objective of the invention is to make the solid substrate surface planeization of coating.

The frictional force that the objective of the invention is the solid substrate surface that reduces to apply.

The objective of the invention is material of the present invention as the antistatic coating on the solid substrate.

The objective of the invention is material coating of the present invention as the low dielectric layer on the solid substrate.

The objective of the invention is the material of the present invention of material of the present invention and modification as the anti-reflection layer on polymer and the similar base material.

The objective of the invention is material coating of the present invention as moisture and oxygen barrier layer in the flexible display structure.

The objective of the invention is material coating of the present invention as the barrier layer that prevents the solid substrate mechanical failure.

The objective of the invention is material coating of the present invention is used to customize the optical property of solid material.

The objective of the invention is to use material coating protection polymer of the present invention, thermoplastic and similar material to avoid being subjected to light degradation.

The objective of the invention is to use material coating protection solid substrate of the present invention to exempt from the influence of the microorganism of being damaged property.

The objective of the invention is on Medical Devices and the part that makes by solid material, to use material coating of the present invention to make it exempt from chemistry and physical damnification.

The objective of the invention is on Medical Devices and the part that makes by solid material, to use material coating of the present invention to make it exempt from the body fluid corrosion.

The objective of the invention is on Medical Devices, implant and other part, to use the material of the present invention of material coating of the present invention and modification to give its biocompatibility.

The objective of the invention is to use exploitation to mix material of the present invention and on solid substrate, mix the biocompatible material of material coating of the present invention.

The purpose of this invention is to provide a kind of barrier film and preparation method thereof with high water white transparency degree.

It is the film of about 10-500 nanometer that another object of the present invention provides the thickness with above-mentioned character.

Another object of the present invention provides the coating or the film of the low-frictional force with above-mentioned character.

Another object of the present invention provides the coating or the film of the cost that can the reduce production with above-mentioned character.

Another object of the present invention provides coating or the film that has above-mentioned character and can reduce solid material total amount required in the device.

Another object of the present invention provides to be had above-mentioned character and can reduce coating or the film that reclaims degree of difficulty.

Another object of the present invention provides the coating or the film of the packaging for foodstuff that has above-mentioned character and can be used for using in micro-wave oven.

Another object of the present invention provides to be had above-mentioned character and can be used for using in micro-wave oven and the coating or the film of still transparent packaging for foodstuff in very long shelf-life.

Another object of the present invention provides coating or the film that has above-mentioned character and can keep the moisture of given content for the content of packaging in barrier film.

The method that another object of the present invention provides coating or film and can produce Obstruct membrane with high speed of production.

Another object of the present invention provides the coating that can make the polymer surfaces complanation and help to reduce light scattering.

The objective of the invention is provides functional coat by additive being dispersed in the material precursor solution of the present invention on solid substrate, preferred conductive coating or magnetic coating.

The objective of the invention is provides transparent substance on the improved machine (aircrafttransparency) by using material coating of the present invention on the solid substrate with on the conducting metal oxide coating that is deposited on the described solid substrate.

The objective of the invention is provides protective layer and cohesive promoting layer for transparent substance on the machine.

The objective of the invention is the material of the present invention that exploitation is mixed with inorganic polymer and molecule (material that for example contains P and B, phosphorus nitrence (phosphazene) for example, borazine or borozole).

The material of the present invention that the objective of the invention is to develop material of the present invention and be dispersed with boron nitride, molybdenum silicide, molybdenum sulfide or other lubricant material is to form the high-temperature lubricant coating.

The objective of the invention is by suitably regulating the microstructure of material of the present invention, the vesicularity exploitation that increases material coating of the present invention specifically has the material of the present invention of low-k.

The present invention relates on plastics or polymeric substrate, use based on the inorganic of aluminophosphate composition and inorganic-organic composite material coating,, and protect it to avoid the environment invasion and attack with the protection of raising to wearing and tearing or grinding away.

Particularly, the present invention relates to the curable coating composition that precursor solution chemistry or be used to obtains being deposited on the structure and the character of the protective coating on plastics or the polymeric substrate.

The objective of the invention is to customize the precursor chemistry that contains Al, P and O and other material, have good fusible coating and inorganic coating roughly under the condition of cure of lower temperature, to form.

Another object of the present invention is to comprise captive water or hydroxyl, organic matter and have some nitrate or other salt in inorganic coating roughly, to strengthen the flexible and toughness of coating.

Generally speaking, another object of the present invention is to add some organic and inorganic additive in the curable coating composition that contains aluminum phosphate compound, is used to make the condition of cure of minimise stress with customization advantageously, and increases other function for coating.

Another object of the present invention is to use multilayer, this multilayer comprises adhesion promotion bottom and cover layer (overlayer), this bottom is the basic inorganic or organic and inorganic mixture that is in essence, described cover layer a) seals the microcrack of described bottom, improve barrier property, this layer is basic for being inorganic or organic and inorganic mixture and b in essence) comprise solvent resistance or wearability that some organic or inorganic additive improves coating system, the gross thickness of multilayer system can be above about 15 microns like this, more preferably from about 10 microns, most preferably from about 5 microns.

Another object of the present invention is the stable preparation that sprays that exploitation can be solidified under heat or ultraviolet or infra-red radiation or microwave treatment.Available a kind of processing method or the combination that surpasses a kind of processing method are cured.

Another object of the present invention is the aluminophosphate-based coating that the visible spectrum of exploitation electromagnetic radiation can see through substantially.

Another object of the present invention is deposition top organic layer or specific organic additive is incorporated in the curable preparation to improve durable hydrophobic or hydrophily.

Another object of the present invention is to use aluminophosphate-based coating composition as adhesive plastic basis material to be attached on other metal, pottery, glass and other plastic material.

An object of the present invention is to provide a kind of simple dip-coating, spin coating, spraying, brushing or flow coat method used material coating of the present invention is deposited as thin, sealing, dense micro-structure, even and transparent coating.

The objective of the invention is to use material coating of the present invention to protect materials such as plastics, polymer to avoid moisture, light, gas and other ambient influnence.

The objective of the invention is to use the Obstruct membrane of material of the present invention, as Obstruct membrane to chemically reactive gas (for example water, carbon dioxide) and liquid or steam (for example fragrance, fine chemicals, gasoline) as opposing inert gas (for example oxygen, nitrogen and hydrogen).

The objective of the invention is under room temperature and high temperature to handle and use in protect the surface of polymer.

The objective of the invention is to improve mechanical performance, the damage that includes but not limited to resistance to marring, wearability, takes place owing to the impact of high velocity particle and other object.

The objective of the invention is to protect polymer to exempt from the LEO environment, for example high-throughout atom and molecule, for example influence of oxygen, hydrogen, nitrogen etc.

The objective of the invention is to use material of the present invention to come covering surfaces defective and the lip-deep hole of sealed polymer.

The objective of the invention is to make the polymer surfaces complanation of coating.

The frictional force that the objective of the invention is the polymer surfaces that reduces to apply.

The objective of the invention is material of the present invention as the antistatic coating on polymer and the relevant base material.

The objective of the invention is material coating of the present invention as dielectric layer.The objective of the invention is the material coating of the present invention of material of the present invention and modification as the anti-reflection layer on polymer and the similar base material.

The objective of the invention is material coating of the present invention as the barrier layer that prevents mechanical failure.

The objective of the invention is material coating of the present invention is used to customize the optical property of polymer and similar material.

The objective of the invention is to use material coating protection of the present invention to avoid the influence of the microorganism of being damaged property.

The objective of the invention is on Medical Devices and the part that makes by polymer and similar material, to use material coating of the present invention to make it exempt from chemistry and physical damage.

The purpose of this invention is to provide a kind of barrier film with high grade of transparency of above-mentioned character.

Another object of the present invention provides coating or the film that gross thickness with above-mentioned character reduces.

Another object of the present invention provides curling coating or the film of the polymer flexibility base material that can not make described coating with above-mentioned character.

Another object of the present invention provides coating or the film that has above-mentioned character and can reduce plastics required in the device or polymer total amount.

Another object of the present invention provides coating or the film that has above-mentioned character and can reduce to reclaim degree of difficulty.

The objective of the invention is to be provided for by material coating of the present invention the improved polymeric substrate of electronics or opto-electronic device, material coating of the present invention can be avoided or reduce prior art problems at least.

The objective of the invention is provides functional coat by additive being dispersed in the material precursor solution of the present invention on polymeric substrate, preferred conductive coating or magnetic coating.

The objective of the invention is provides transparent substance on the improved machine by using material coating of the present invention on the plastic basis material with on the conducting metal oxide coating that is deposited on the described plastic basis material.

Therefore, the present invention relates to the exploitation of material, described material can be inorganic, composite organic-inorganic material or be mainly inorganic material on forming.In some embodiments, can be used on aluminophosphate-based material in a lot of application can be used with powder, bulk, fiber with as coating in these are used.The invention still further relates to and apply aluminophosphate-based coating on multiple solid substrate, described solid substrate includes but not limited to plastics, polymer, metal, alloy, pottery, silicon, carborundum, quartz, sapphire, glass and other substrate material.The invention still further relates under multiple exposure condition by the aluminophosphate-based material coating retention surface character reflectivity of metal or other reflective surface will for example, described exposure condition includes but not limited to high-temperature process, ultra-violet radiation, moisture etc.The invention still further relates to and apply the barrier coat of aluminophosphate-based coating as opposing gas, water and the diffusion of other liquid on multiple base material.The invention still further relates to and in the system with the structure that constitutes by narrow ditch and uneven surfaces (for example semiconductor devices and optical layers), use aluminophosphate-based precursor solution as being spin-coated on (spin-on-glass) on glass material (SOG).The present invention relates generally to aluminophosphate-based material compositions.The invention still further relates to the fusible method between the material that improves polymer and other type.

Partly, the invention still further relates to the composite (configured composite) with structure, described composite comprises base material and the coating composition on it.Described coating composition can comprise aluminum phosphate compound, the aluminium that described aluminum phosphate compound contains to the scope of the ratio of phosphorus for less than about 0.5 than about 1, to about 10 than about 1, to about 20 than about 1, perhaps, to about 25 than about 1.This composite can be arranged in vertical with the structure that is provided (configuration) basically axle around.

In some embodiments, described base material can be the profile flexibility, and the composite that has the described base material of this coating composition like this can twine around bobbin and/or not twine, then being made into goods.Therefore, just as road known in the art, this base material can be selected from metal, metal alloy and plastics.In some this class embodiment, (brushed) stainless steel that this metal base can be selected from stainless steel and brush.In any case, such as other of this paper local description, coating composition of the present invention can be in visible spectrum substantially transparent and/or can provide composite and the iridescence outward appearance.Perhaps, this coating composition can contain one or more additive components or reagent so that described composite and antimicrobial function to be provided, and described reagent should be to be understood known to those skilled in the art of the present invention.Can be by between base material and described coating composition, inserting one or more interlayers derive other function or effect, such as interlayer component as herein described.

In some embodiments, described base material can comprise plastic material, and described plastic material contains one or more Merlon and/or its copolymer, polyimides and/or its copolymer and polyester and/or its copolymer.Unrestricted, other this base polymer material also is described in other place of this paper, and it should be understands known to those skilled in the art of the present invention.No matter the characteristic of base material, its coating composition that has can provide the penetration barrier layer to moisture, gas and/or other penetrant.Perhaps, for plastic basis material, this component can provide the defencive function at the destructive effects of organic solvent.No matter offer the functional benefits of base material, in order further to give the composite functional benefits, the cover layer component can be positioned at the top or top of described coating composition.Depend on the characteristic of base material and the multiple composition aspect of described coating composition, as described in other place of this paper, described coating composition is accredited as to contain to absorb and is positioned at about 1230cm ^-1The structure division of INFRARED SPECTRUM.

In some other embodiment, the base material component can contain metal forming.Unrestricted, depend on terminal applies, this base material can be to be controlled as less than about 100 mils.This paper tinsel base material can be selected from aluminium, stainless steel, titanium, magnesium, nickel-base alloy and superalloy.As mentioned above, this composite also can comprise multiple interlayer component and cover layer component.For example but unrestricted, the metal cladding component on this coating composition can provide the reflecting surface as mirror, helps composite to be used in the various light application.

Partly, the present invention also provides the method for using the sealing porous substrate surface of aluminophosphate composition.This method comprises: the base material that comprises surface portion is provided; Described surface portion is contacted with the composition that contains aluminum phosphate compound, and described aluminum phosphate compound contains at least one phosphonate moiety; Heat described composition at a certain temperature, continue for some time, be enough to remove at least in part and/or the oxide ester part in one.Unrestricted, in this embodiment, described base material can be selected from granite, marble, engineered stone or the stone material of handling, porcelain and a lot of ceramic material.In any case this method can provide basic surface portion with the composition complanation that contacts, described composition is stable up to about 1000 ℃ temperature elementary heat.

In some embodiments, said composition can be sprayed on the surface portion.Depend on concrete application or processing requirements, said composition can contain at least a in the following at least component: aqueous carrier component, non-aqueous carrier component and aerosol propellant, these components are understood known to those skilled in the art of the present invention.Expect as wideer aspect of the present invention, this method can be used with multiple kitchen utensils and sales counter, bathroom platform and permanent plant and floor and walltile component, above in the manufacture process of these goods or after making said composition being applied in.

Description of drawings

Fig. 1 is the FTIR figure of the sample of preparation among the embodiment 4, has demonstrated the absworption peak corresponding to the group of phosphate in the coating and water.

Fig. 2 is the FTIR figure of the sample of preparation among the embodiment 6, has demonstrated the absworption peak corresponding to the group of phosphate in the coating and water.

Fig. 3 is the cross section TEM figure of the material coating of the present invention on sapphire, shows sealing, densification and uniformity.Electron diffraction diagram corresponding to material layer of the present invention demonstrates amorphous state character.

Fig. 4 is the photo of the enamel sample (enamelcoupon) that partly applies with material of the present invention in the bonding test back of food.

Fig. 5 has the uncoated silicon carbide of 1 micron polishing (left side) and the SiC (right side) that the material of the present invention after the heat treatment applies, and shows reflecting surface.

Fig. 6 shows AFM (AFM) photo with material of the present invention carborundum that apply, heat treated.

Fig. 7 shows the AFM photo with material of the present invention metal alloy that apply, heat treated.

Fig. 8 is the photo of the copper coin that partly applies with material of the present invention.

Fig. 9 shows uncoated glass (rms～1-2 nanometer) (left side) and applies the AFM photo of the glass on (rms～0.1-0.2 nanometer) (right side) with material of the present invention.

Figure 10 shows the FTIR spectrum of the material coating of the present invention on stainless steel to the function at 200 ℃ of heat treated temperature persistence lengths (temperature length).

Figure 11 is the FTIR spectrum of the material coating of the present invention on stainless steel foil of quick curing (flash-cured).

Figure 12 is the SEM microphoto on the Kapton surface of material coating of the present invention.

Figure 13 is unadulterated material of the present invention and the uv-visible absorption spectrum that is dispersed with the material coating of the present invention of Zinc oxide particles.

Figure 14 is the photo that partly is coated with the vitreous silica sample of material of the present invention, shows the iris action of coating for the environment invasion and attack.

Figure 15 be sapphire/ZnS in conjunction with right transmitted spectrum, be because sapphire in the transmission that weakens more than 6 microns.

Figure 16 is the transmitted spectrum of the material of the present invention on ZnS.

Figure 17 and Figure 18 illustrative roller are handled and are constructed according to the composite that the present invention obtains to roller.

The detailed description of some embodiment

Be used in for example enamel surface and the multiple alkalization complexing that is mixed with alumina silicate boron in the baking box etc. of kitchen appliance, and easy and multiple food chemistry material generation chemical reaction.Described product sticks on the described surface securely and is not easy to remove, and needs poisonous strong clean solution (causticity processing) itself.In addition, described surface has the hole of certain level, causes the mutual mechanical snap of particle, and this also is difficult to remove.Owing to lack the low-cost solution that sealing effectiveness can be provided, do not attempt surface processing solution with stable, inertia and low-surface-energy.Use material film of the present invention to represent this key in application innovation as gasket coating.

Use for furnace chamber, need material coating of the present invention that the surface pore is reduced by at least 50%,, make to be difficult to cleaning to prevent just mechanical snap to take place at barbi and enamel surface.In addition, the surface energy that reduces enamel is with easy to clean, and is similar with the non-stick pan that uses teflon to apply.For the surface energy of such application need less than 35 dynes per centimeter.

The processing that enamel sample and ceramic tile are carried out shows that material coating of the present invention has can be with the abundant coated ceramic of coating of sub-micron thick or the ability of metal surface.Because the coarse relatively configuration of surface in enamel surface, mechanical snap are considered to the main problem of paying close attention in this application.When interacting with various foods under the high temperature of baking box, the surface chemical property of the relative inertness of expection material of the present invention is stable.

Food-handling equipment is the source that bacterium/biomembrane (biofilm) adheres to and grows, and this becomes a serious health problem conversely.One of reason of bacterial adhesion is a rough surface, though rough surface helps to form biomembrane by mechanical snap.Another is to have moisture.The bacterium that can use material coating of the present invention and use material coating of the present invention to eliminate these two kinds of reasons with organic hydrophobic layer is bonding.Therefore antimicrobial coating can the factor 5 forms by reducing metal surface polishing (finish) for example, and the described factor 5 is lower than the electropolishing level of using material coating of the present invention to be reached.Material coating of the present invention also can be used to (cryomachined) surface (spraying and infrared lamp solidify in the lathe) of low temperature process.Material of the present invention also can be used as the wear-resistant coating on camera lens or the glass mirror.

Material of the present invention can be used as the non-sticking lining on polyester and other food Package plastic basis material.As following discussion, can use roller to cover and handle and solidify the coated product of realizing format high throughput fast to roller coat.

Another embodiment of the invention is to use the layer of low-surface-energy, for example organosilan, silicon fluoride, organic molecule or polymer on material coating of the present invention.This top layer can several modes work, and includes but not limited to reduce or eliminate at cooking temp form lacquer sample residue by food.Can easily apply these cover layers again by spraying technology.

Another embodiment of the invention is to use material of the present invention as the spray product that is used for commercial application or family expenses.

Described technology barriers (technical barrier) are to use paint formulation to produce the even cover layer of aimed thin film thickness (50-500 nanometer), and this is very important.Most of thicker (a few mil) of commercial sprayed coating and described method are not easy to develop high-quality film.Degree of difficulty in the aqueous formulation (for safety and environment reason, aqueous formulation is more preferred) that exploitation is fit to bigger than in the pure homologue of exploitation.Can alleviate a lot of danger relevant, toxicity, inflammability, refuse etc. with using pure based precursor.It is poor that aqueous formulation does not have the storage-stable of suitable wetability and aqueous formulation.

Another embodiment of the invention is that the precursor modification is to develop suitable spray agent.Aerosol technology all is amenable to for various environment and user.The film that deposits continuous submicron thickness will be our maximum in the prior art challenge.In addition, atomization parameter, surface coverage and the wetability that changes along with solvent and additive will be different because of base material.

Another embodiment of the invention is to develop the material solution of the present invention of water base or water-alcohol mixture base.Can increase the chain length of polymer by refluxing and improve the polymer property of precursor solution, thereby improve wettability.In order further to improve wetability, can add a spot of (＜2 weight %) commercially available surfactant and/or water/alcohol mixture solvent.Useful surfactant has reduced the surface tension of water, but also compatible with the precursor chemistry in solidification process (be easy to remove and desolvate).Can use the known aerosol technology that is used for alcoholic solution with the measured coating paint of matter solid substrate, commercially available solid substrate includes but not limited to enamel, stainless steel, glass, pottery and polymer.

The present invention also provides the cheaply method fast of polishing carborundum optical surface.This new method is suitable for polytype SiC, and can be used for the SiC surface planeization of aviation and land based optical systems and do not rely on manufacturing technology.Because the eutectic between aluminum phosphate and the silica, material of the present invention can make the SiC surface planeization by the reaction with base material.

Use material film of the present invention, separately or to make the complanation of SiC reflecting surface by reaction mechanism be to reduce cost and shortening aspect the required time one of present sufacing important improvement.By dropping into about 0.5 man-hour, the surface roughness of the SiC of a slice sintering has reduced above 100 times (1 micron rhombus abradant surface being polished to the roughness of 2.7 nanometer rms).In addition, the shallow layer of material of the present invention can be used for complanation aluminium mirror or silver mirror and other non-optical substrate surface, and does not rely on reaction mechanism.

Advantage based on the surfacing method of material of the present invention comprises:

● reduced the cost that obtains smooth (＜10 nanometer rms roughness) surface basically

● shortened manufacturing optical quality polishing (finish) required time

● be applicable to a lot of ceramic base materials and optics of metals system, do not consider final task

● do not need to drop into the polishing effect that important treatment facility obtains optical quality

● the method for deposition material of the present invention is extremely simple and general.The precursor solution viscosity that is used to develop described coating is low, and clear and stable (storage period is super in a few years), and suitable dip-coating and spin coating method.

● the surface that obtains is glassy and conventional in essence or MRF-base dressing technique can be used for further reducing surface roughness.

Therefore the invention provides by heat treatment or directly deposit material film of the present invention on ceramic surface, to obtain the chance of glassy layer, described film can be with polishing with the used similar step of step of glass-mirror, simultaneously the first-class mechanical performance and the hot property of exploitation pottery (such as but not limited to carborundum and silicon nitride).

Do not wish to be bound by any theory, promote the formation of phosphorus alumina silicate (aluminophosphosilicate) glass when as if the material of the present invention on the carborundum show high annealing.Known in the state of the art at SiO ₂Be the AlPO of 70 moles of % ₄-SiO ₂Eutectic 1400 ℃ of fusings (eutectic) is arranged in the system.As if the coating that is applied in the material of the present invention on the SiC of sintering form glassy phase after 1400 ℃ of annealing.Do not wish to be bound by any theory, it is believed that SiC is oxidized to SiO ₂, obtain forming the silica of reacting phase.Described lip-deep phase is seemingly glass, lacks the crystal outward appearance.Estimate the surface with SEM under light microscope, original base material or the sample uncoated, annealing of surface ratio is obviously smooth obviously.

With 1 micron diamond slurries (diamond slurry) polishing Hexoloy SiC, make surface smoothness on the rank of 1-3 micron.Hexoloy SA is the SiC of 99% pure sintering.Hexoloy is some porous (comparing with CVD SiC), seals these holes effectively with material coating of the present invention.This base material is applied and heat treatment, also have a uncoated sample.After the heat treatment, the reflectivity of the sample of coating is very high, shows smooth surface.Measure as AFM, the rms roughness of the sample of described coating is reduced to about 2.7 nanometers.Described (as-finished) surface with polishing uncoated, annealing is obviously more coarse, and keeps the configuration of surface than porous.Do not comprise initial polishing, coating and heat treatment step spend the time of about 0.5 man-hour.(in this case, the silicon carbide base material ultrasonic clean of described polishing (1 micron rhombus abrasive material) is used the solution dip-coating of material of the present invention, heat treatment in laboratory furnace then then.) do not wish to be bound by any theory, it is believed that the aluminum phosphate that exists in the material of the present invention with by the formed silica reaction of carborundum oxidation.In addition, when cooling, do not observe and break, show glass and SiC base material CTE coupling preferably.

In addition, material of the present invention can prevent well that SiC is at high temperature oxidized.With contact surpass 100 hours up to 1400 after resulting carborundum compare, for the material that applies, observed weight increase obviously reduces.Silicon is mixed material of the present invention be can be used as the silicon source and forms silicic acid aluminum phosphate (aluminosilicate-phosphate) glass composition.Behind high annealing, observe and lost some phosphorus, yet as if the surface is good seal, so that environmental protection to be provided.In an improved method, can also be suitable for other base material, by at first using any known method (comprising CVD) deposition SiC coating, use described material processed of the present invention surface then.C/C and C/SiC composite during high temperature is used need be prevented oxidation.Such processing can be considered to improve the protection to these and other non-oxidized substance and oxide composite system.

Also can use the present invention to improve organic polymer coating and have or do not have the cohesive of the metal surface of oxide skin(coating), described metal surface has or does not have oxide skin(coating).Described phosphate radical and aluminate can be covalently bound in metal surface and metallic atom.Organic matter or organosilan or organophosphorus ester cover layer that coating composition of the present invention also contains other at least are used to improve bonding with organic matter and polymer.Perhaps, can apply separately with the organic matter of the bonding reactive part of organic resin or organosilan or organophosphorus ester cover layer and be another cover layer having at least one.The present invention specifically is used to provide the interface of the fusible material of the present invention between the metal surface that can improve than inertia (for example precious metal surface, as gold, silver, platinum, palladium, iridium, rhenium, ruthenium and osmium) and the organic polymer coating.The adhesion promotion effect of material of the present invention is not limited to the metal-polymer material.This also comprises metal-ceramic, pottery-polymer, glass-polymer, glass-ceramic, ceramics-glass, ceramic to ceramic and other system.

The invention still further relates to the iridescence (iridescent) on stainless steel and the similar surfaces, non-iridescence, fade-proof and high reflection (high reflectance) coating.Because the difference of the refractive index of base material and coat, the thickness on the stainless steel demonstrates the iridescence look less than 1 micron protective oxide coatings.Stainless material of the present invention does not have the aluminum phosphate of deciding shallow layer and effectively prevents high-temperature oxydation, thereby fade-proof.They also keep or improve the reflectivity of coated metal surface.This coating also demonstrates the iridescence look, and this can be developed as the decorative coating on the goods.Do not wish to be bound by any theory, the inventor thinks that on coating observed iridescence look depends on chemical property, thickness and the uniformity of coating.

Coating material of the present invention can be suitable for other optical effect that improves reflectivity, improves iridescence look, gloss and shallow layer with priming coat and cover layer.Any phosphate material that contains the phosphorus atoms of 3 valencys or 4 valencys can be used as priming coat.Described phosphorus compound can be an organic or inorganic.Organic phosphate (ester) can be, such as but not limited to organic phosphite, phosphate, phosphonate (ester), phosphorous acid hydrogen salt, hydrophosphate, polyphosphate, polyphosphate, phosphate, phosphite ester, phosphine, alkyl chloride for phosphine (alkyl chlorophosphine), chlorine phosphonate ester (chlorophosphate) and their mixture.Inorganic phosphate is such as but not limited to metal phosphate, the phosphoric acid that is mixed with appropriate solvent, five phosphorous oxide solution, phosphorus Halides, phosphorus and their mixture.Cover layer can be organic or inorganic coating or mixed coating.Organic coating layer is such as but not limited to the self-assembled monolayer of grease molecule or polymer.Coating based on silane also can be used as cover layer.Itself also can be used as priming coat and cover layer material of the present invention.Material coating of the present invention also can have the organic or inorganic additive.Inorganic additive can be a metal ion, such as but not limited to silicon, iron, zinc and manganese and composition thereof.Nanocrystal oxide, for example zinc oxide, titanium oxide mixture extremely.

Can use organic formwork, for example polymer and big organic molecule are made material coating of the present invention the massive material of porous.Material of the present invention with designed porosity can be used as low k dielectric and as silicon, GaAs and other semi-conductive coating, especially also needs the coating of the carborundum of heat-staple low k dielectric layer as high temperature semiconductors.According to employed method, the spin glass deposition can be used as the material layer of the present invention of effective diffusion impervious layer.Hole in the material of the present invention can be designed at Nano grade, so that described coating can keep the favorable mechanical performance.Can adjust content of organics in the coating composition with the roughness that improves described layer and be to handle breaking of causing to minimize.

Can use material coating of the present invention to realize seal glass, polymer effectively and be used in semiconductor in other relevant base material, solar cell, flexible display on blemish.And material coating of the present invention can be used as the barrier layer that prevents oxygen, moisture, sodium and the diffusion of other envirment factor.

Defective on other base material that material of the present invention also can be used for sealing quartz, glass and be used as light-passing board (photoblank) in semi-conductor industry.Material of the present invention can also the sub-micron rank carry out etching, if necessary, uses chemistry or physical method.

Steel or other lip-deep iridescence glass can improve the aesthetic value on surface.When applying from the teeth outwards, material of the present invention demonstrates the iridescence look.Can art form, mark, parts tag and other form apply this coating.

Using solution based processes to obtain continuous and non-cracked coating in micron level is a very difficult task.Use contains jagged structure and the uneven surfaces structure is just more difficult.In the prior art, can in semiconductor devices, obtain such coating by spin glass (spin-on-glass) silicon-coating hydrochlorate, borosilicate and phosphosilicate.Yet they have such as breaking and shortcomings such as sodium diffusion and other problem.Semi-conductor industry is being sought can replace prior art, reduce manufacturing cost, have and equate or higher performance and multiple character is combined in low-cost technologies in a kind of material.

Coating should be enough thick and fine and close to stop or restriction sodium diffusion and should be non-cracked.Use sol-gel paint-on technique difficulty or ease to realize this two kinds of combinations.By suitably improving the composition of paint-on technique and use coating material of the present invention, can satisfy these conditions.Described coating should be able to make coated substrate planeization, to make up multilayer on coating.Described coating material should be stable, has high dielectric breakdown strength.The precursor of material of the present invention that can be by using proper additive, composition, viscosity and concentration of material of the present invention and modification is eliminated the surface tension of liquid effect or it is minimized, and described surface tension of liquid effect can have problems obtaining continuous cover layer or the coating on the edge.

Material of the present invention can be used as such as the spin glass coating on the base material of quartz, silicon, carborundum, GaAs and other base material.Material of the present invention has following characteristic, and such as but not limited to (planarizing) of insulation, low-k, complanation and ion barrier layer etc., these are necessary for the coating on the semiconductor devices.Because material of the present invention has strong bond property, for the heterogeneous surface of any kind, no matter its chemical property how, can form similar coating.Depend on coating layer thickness and method, the precursor of material of the present invention and modification thereof can be used as conformal coating and complanation coating.If desired, material coating of the present invention also can with other planarization technique, resemble MRF or CMP and make up the surface that obtains better quality.Described coating can prevent that the problem that is caused by the sodium diffusion from appearring in semiconductor, and prevents that it from influencing environment.The precursor of material of the present invention and modification thereof can be used as the flowable gap filling material that uses spin-on glass technology.Therefore, material of the present invention can be used for developing flowable spin coating insulator.Based on spin-on glass technology, little and have a product of complex geometric shapes, such as but not limited to fastener (fastener), available material of the present invention applies, to prevent electrolytic corrosion (for example, the steel fastener is received in the aluminum chassis) and to prevent to be subjected to solvent, chemical substance and other environment invasion and attack and degrading.

Metal and polymer foil base material can be used in the multiple application, include but not limited to display, photovoltage device, heat shielding etc.Can on these base materials, deposit the thermally-stabilised coating of material of the present invention to give required character.The multi-functional character of material of the present invention can provide important benefit with low processing cost and high-throughput with respect to prior art.For example, can deposit material of the present invention to give electrical insulating property and smooth surface is provided.This has been avoided depositing the aluminium lamination with other coating that need give enough complanation character with the PVD of normally used costliness or CVD method.For food packaging industry, the character that roller that can be continuous deposits material of the present invention and cannot not give stickingly food on plastic basis material to the mode of roller.Material of the present invention also will provide suitable barrier properties to the gas that diffuses into or diffuse out packaging material for food.

Because processing method, vacuum-based coating itself contain pin hole and other defective.The shallow layer of the material of the present invention on the vacuum-based coating can be eliminated these defectives and improve the barrier property of coating effectively.And material coating of the present invention can be used as the complanation template, is used to form the coating of other type.

Device, especially micron and nanoscale-liquid device (micro-and nano-fluidic device) are just used the mould that is prepared in the following manner by plastic material: blowing (below molding), press down molding (dipmolding), insertion film molding (film insert molding, FIM), the molding that gas is auxiliary, the reactive spray molding, the resin transfer molding, rotational molding, structural foam molding (structural foam molding), thermoplastic injection molded, the resin transfer molding (VARTM) of vacuum aided, vacuum-bag technique, vacuum forming, injection-molded, pressure forming, the extrusion blow molding, hot forming, UV reaction molding or embossing molding or other molding methods.These equipment find application in a plurality of fields, such as but not limited to biological medicine device, optical communication system (wherein accessory size is lower than 1 millimeter, and tolerance (tolerance) is lower than 1 micron) etc.Have the micro-optics part of nanostructured surface and have perfect definition and the long-term large-area automotive window of wearability is in the forefront of process in plastics technology.For a lot of laboratory applications, comprise clinical diagnosis and life science, the micro-fluid experiment chamber on chip system has very big potentiality.Develop a large amount of being fit to and satisfying the device that real clinical sample (for example whole blood and other body fluid) requires.Described device can be used in the independent utility as the passive disposable product (self-contained passive disposable) that comprises self, be used for quantitatively and semi-quantitative analysis with separate application, or they can be used as the assembly based on the system of equipment of precision.

Good part is the key of any effective molding methods fast and effeciently to discharge molding from instrument.In processing procedure, the high heat resin, for example PEI can reach the temperature above 700, causes the demoulding additives decompose of a lot of standards.Need the new high temperature demoulding to start a kind of like this processing window (processing window), this processing window can reappear piece surface preferably and realize reducing the quick mold cycle of the residue (scarp) in the part.Described die surface comprises metal, silicon etc.

The release coating that process in plastics need be used in the mould is a permanent coating.Other target comprises good coating wear-resisting, against corrosion and the improvement Resin Flow.Successful coating produces improved part release property and part quality, prevents that part is subjected to abrasive wear and reduces sedimental gathering, allows mould cleaning faster.By eliminating since the downtime that part is bonded in the mould, ejector pin damages and operation undeservedly and part (valve for example flows backwards) thereof are caused obtained the remarkable economical interests.Net effect can be circulation timei and the long maintenance intervals that shortens.

For example, hardness is that 40 Rockwell C and cavity periphery are that 12 * 18 inches P-20 mould is to be difficult for the mould parts that discharges, although it has teflon-nickel coating, grinding agent (lapping compound) and wire brush are handled (wire-brush treatment) and are used in the preceding demoulding of per injection (shot).In addition, the final step of circulation in 72 of part seconds comprises that the workman takes out part carefully with hand and do not cause any distortion or warpage simultaneously as far as possible from mould.Glass part proof is consuming time and cost is high.Percent defective (scrap rate) is 30-40%.Using (speaker grille application) for speaker grille need to have determined 6 microns fineness (finish) on the tool surfaces to come automatic demoulding.Use conventional EDM technology, behind 150 hours finishing process, may only reach 12 to 14 microns fineness.After 150 hours, can reach than this better sake fineness.

Material technology of the present invention can be used as permanent release coating.Material of the present invention following this be useful on the one hand: with the required work of the polishing technology of routine and the part of cost surface roughness is reduced to below 6 microns.When reducing surface roughness, go back the surface energy on the organic coating layer of available energy self assembly or layer surface that reduces to apply on itself.For plastics and microfluid industry, on 12 microns surface, improve energy and fineness is very useful with material coating of the present invention.Depend on application demand, can in molding, use various types of materials, for example polymer of polymer, metal, alloy, high-temperature stable etc.

The window of military aircraft, no matter be canopy on the fighter jet or the covering on the infrared sensor, all must be firm especially to keep out knocking of high speed fragment, keep transparent simultaneously so that the pilot can see the outside, or make infrared signal to enter.The window that is made by the yittrium oxide of routine breaks under flying condition easily.Material of the present invention can be used as medium and disperses this type nano granular with high capacity amount (high load) and apply as coating.This can be used as the cost effective method of the coating that is used on the infrared memory scanning instrument (infrared store scanner) and other application.Also help to prolong the life-span of the canopy of fighter jet.

Various other purposes of the present invention and application comprise following content:

Material coating of the present invention can be used on thermal spraying industry.For example, material of the present invention can be used as the infiltration sealant (infiltrating sealer) of the turbo blade spraying that is used for the MCrAlY class and is used for the feed that cold spraying is used.

Have or do not have hydrophobic tectal material coating of the present invention and can be used as the low windshield coatings of wettability.

Unbodied material coating/the Al of the present invention of low temperature ₂O ₃Coating can be used on multiple field, includes but not limited to electronics, weaving and polymer.

Material of the present invention can be used as the anti-catalyst coatings of the rich Ni element in the hot gas treatment system.

Material of the present invention can be used as the impregnating agent (infiltrant) of powder-metallurgical element (sintering-hardenable).

Material of the present invention can be used in fuel cell and the gas conversion elements (component) (hot surface) as coating composition.

Material coating of the present invention on the metal can be used as boundary layer, is used to improve cohesive, prevents to corrode and improve the cohesive of coating with lacquer.Consider the dielectric property that it is low, material coating of the present invention also can be used for photoelectric sensor and other sensor.For the solar cell of design on metal forming, the material of the present invention of electric insulation needs.Material coating of the present invention is as the electric back contact (electrical back contact) of solar cell and the protective layer between the conductive base.

The thickness demand of material coating of the present invention becomes along with application.

Some application and useful, required nonrestrictive bed thickness have been listed in the following table.

Use Bed thickness

Optical layers lamination (optical layer 10 nanometers-200 nanometer that is used for high reflectance and anti-reflection coating

stack)

Transparent gas barrier coat 30 nanometers-100 nanometer on the coiled plastic material (web)

Wear-resistant coating 4-6 micron on the POLYCARBONATE SHEET

Be used to improve fusible boundary layer (several base material) 5-20 nanometer

Conversion coating on the steel (anticorrosion, lacquer cohesive) 0.3-0.4 micron

Dielectric coat (back-protective of sensor, solar cell) 2-5 micron

Material coating of the present invention can be advantageously used in the character of regulating multiple substrate surface.For example, the slide of different company's manufacturing may not have identical composition.Even the slide of the different batches of same manufacturer manufacturing may be also not quite identical.For example, the processing that is subjected to these samples of surface roughness and different.In some applications, it is very crucial to have surface nature about the same in sample, for example, and the situation that microcosmic is arranged.Material coating of the present invention can provide the surface nature of homogeneous, for example surface roughness of the surface chemical property of homogeneous and homogeneous etc.

Since its favorable mechanical performance and avirulence, metal and alloy, for example titanium, Ti ₆Al ₄V, CoCr are widely used as the material of orthopaedic implants.Metal implantation field (implantology) play an important role owing to its intensity height, antifatigue degree high and handle easily, cost is low.Emphasis is pointed out titanium and alloy and CoCr alloy, because these metals can become one with on every side tissue (particularly sclerous tissues) and alloy and demonstrate chemistry and mechanical connection, demonstrate excellent biological compatibility/histocompatbility and Biofunctional (biofunctionality).Corrosion different and two-forty has influenced the selection of implant material, because fretting corrosion wherein (fretting corrosion) seriously causes the generation of wear particle, it can cause particle disease (particle disease) and implant to unclamp continuously.The metal surface also is a subject matter to microorgranic contaminant and biomembranous affinity.Implant infect (forcing riskful implant transposing) even ratio in good clinical effectiveness, also can reach 2%-3%.The design implant first time and replacement implant must be faced stress shielding (stress shielding) and bone storage (bone stock) loss problem carefully.The coating of most of prior art is crannied and has poor glass-metal interface reliability.Therefore, protective finish that cohesive is strong and biocompatible coating will be very favorable.

Develop several different methods in the prior art and come the surface of other used in polymer-modified, metal and alloy or device industry biomaterial.Example comprises conventional painting method, for example spraying or dip-coating; Evaporating deposition technique; With such as diffusion, laser and plasma method, chemical plating, grafting or bonding, hydrogel encapsulation with the process for modifying surface of high-energy particle bombardment.Traditionally, target is the improved physical and mechanical property that obtains element or device, for example adds non-sticking lining by conductive pipe, to be easy to insertion.Yet surface modification also is devoted to introduce concrete required biological response or suppress potential adverse effect day by day.Use invasive device, product and accessory for the invasive device that is used for the treatment of arteria carotis and bile duct occlusion and peripheral vascular disease, product and accessory and with carotid stents, lead, conduit etc., also need low-frictional force, hydrophilic, hydrophobic or other functional coating.

The present invention relates to the protectiveness based on material of the present invention, the exploitation of functional and biocompatible coating.The composition of customizable material of the present invention is to adapt to the needs of the coating on medical device and the implant.Material coating of the present invention on metal or the polymeric substrate can reduce coefficient of friction on suitable degree.After applying and solidifying material of the present invention, it is hydrophilic or hydrophobic that the surface can become.Use is used for the self assembly of the coating of the organic layer on organic layer or the material coating of the present invention, can give appropriate functional.Hydroxyapatite (hydroxylapatite) or other biologically active nanometer particle can be incorporated in the material coating of the present invention to improve biocompatibility.Can use vacuum, plasma or sol-gel base paint-on technique sedimentary organism active layer, for example hydroxyapatite.In this case, material coating of the present invention can be used as adhesive layer, improves the cohesive between metal or polymer medical device base material and the bioactive materials.

Material coating of the present invention can stop or reduce fused silica or quartzy and other amorphous materials that is used in for example surgical probe, luminous product etc. effectively because the crystallization (devitrification) that causes with alkali or other substance reaction.

Known boundaries is lubricated the lubricity that improves a lot of systems.The present invention relates on material coating of the present invention surface, deposit the stability of alkyl fluoride for monosilane and this organic layer.For low frictional properties matter, be starved of smooth surface, but need a large amount of surfaces to prepare, the existence of alloy surface upper surface defective (for example hole) has limited the quality of surface smoothness.Can make the good wear-resistant coating of the adhesion of surface planeization of great use for Tribological Applications.Material film of the present invention can prevent lubricated dose of base material and atmospheric corrosion.The material coating of the present invention of sealing can protect base material can not be subjected to the influence of the corrosive substance that exists in lubricant and the atmosphere.

The embodiment of the material coating of the present invention on materials such as polymer has the following advantages: a) prevent to be subjected to light radiation (for example ultra-violet radiation) well, b) prevent destructive acid well, alkali, organosol and other chemical substance c) abundant seal defect (for example hole) and the lip-deep particle of overlie polymer, the surface that makes described coating complanation coating, and reduce surface roughness (d) for inert gas (oxygen for example, nitrogen and hydrogen) and chemically reactive gas (water for example, carbon dioxide) fabulous stopping, (e) for find in the LEO or the laboratory in the elemental oxygen developed, nitrogen, oxygen, fabulous the stopping of hydrogen and other element, (f) (for example prevent multiple source admirably, the conventional treatment of material, with high speed material impacts etc.) mechanical failure of the polymer surfaces that causes, (g) prevent well oxidized, (h) prevent from well to be corroded, (i) prevent to be subjected to influence of moisture well, (j) prevent that well the biologic medical polymer that uses in the medical application is subjected to body fluid, the influence of chemical substance and microorganism, (k) reduce the coefficient of friction of polymer surfaces by complanation, (l) improve the wearability of the polymer surfaces that applies.In the middle of these advantages, not wish to be bound by any theory, feature relevant and innovation is that material of the present invention can promote fine and close, continuous, smooth and inorganic coating that adhesiveness is strong or be mainly inorganic coating or the formation of inorganic-organic composite material coating.

Example about the polymer that forms plastic sheeting or base material; comprise cellulose esters (tri acetyl cellulose for example; diacetyl cellulose; the propiono cellulose; the bytyry cellulose; acetyl group propiono cellulose; NC Nitroncellulose); polyamide; Merlon; polyester (for example poly-(PETP); poly-(naphthalenedicarboxylic acid second diester); poly-(1; 4-cyclohexanedimethyleterephthalate terephthalate); polyethylene-1; 2-biphenoxyl ethane-4,4 '-dicarboxylic ester; poly-(butylene terephthalate); polystyrene (for example syndiotactic polystyrene); polyolefin (polypropylene for example; polyethylene; polymethylpentene); polysulfones; poly-(ether sulfone); poly-arylide; poly-(ether acid imide); poly-(methyl methacrylate) and poly-(ether ketone).Preferred tri acetyl cellulose, Merlon, poly-(PETP) and poly-(naphthalenedicarboxylic acid second diester).Packaging material comprise polymer, for example polypropylene PP, polythene PE, polyamide PA, PET and by the multiple polymers material, for example PP/PE, PET/PP, PET/PE, PE/PA, the laminated film of making.

The plastic layer that is used in the display can be made by following material: polyester for example, Merlon, poly-vinyl butyrate, the polyethylene of polyethylene and replacement, poly butyric ester, poly-hydroxyl vinyl butyrate, PEI, polyamide, poly-(naphthalenedicarboxylic acid second diester), polyamide, polyethers, polysulfones, polyvinyl acetylene, transparent thermoplastic, transparent polybutadiene, polybutylcyanoacrylate, the polymer of cellulose-Ji, polyacrylate and polymethacrylates, polyvinyl alcohol, polysulfide and polysiloxanes.

Described base material can also be a laminate form, is coated on the glassy layer with the plastic layer of any suitable method with composite.That is to say, can consider different situation (i) when plastics be that film and tegillum press when on glass and be not the form of film when plastics (ii) but be coated on glass by dip-coating, spraying or other method.For example, prepolymer above-mentioned is applicable to that situation (ii).Yet, for situation (ii), can apply several other plastics above-mentioned.In this case, described polymer can be applied on glass, and main passing through applies, applies or apply as prepolymer from melt from solution,

Described base material can also be any organic matter, the organic polymer that preferably has high-temperature stability.Described polymer can be a thermoplasticity or heat cured, preferred high temperature thermoplasticity, for example polyimides, polyamide-imides, PEI, span come acid amides (bismalemide), fluoroplastics (for example polytetrafluoroethylene (PTFE)), the resin based on ketone, polyphenylene sulfide, polybenzimidazoles, aromatic polyester and liquid crystal polymer.In addition, can use polyolefin, especially the crystal of HMW type.

The available any condensation of Al-O-Al, P-O-Al group and method of formation of causing is cured.For example, heat treatment, be exposed to corresponding frequencies ultraviolet light, the pH of solution is brought up to more than 3, is exposed to infra-red radiation, is exposed to the microwave radiation, the chemical substance of contact meeting hydrolysis P-OR group, adds suitable meeting and improve the chemical substance of condensation speed or the combination of any said method.

Inorganic coating is the subject matter that limits the purposes of the coating of being reported in the prior art to the bonding of polymer.With adhesive tape test measure cohesive be coated with carry out on the polyimides sample of material of the present invention (with ASTM D-3359 test class like).With 3M ^TMScotch ^TMAdhesive tape is applied on the coating and removes fast then, and the cohesive of the material of the present invention on Kapton is not removed or loss.The Kapton that applies with optics observation by microscope material of the present invention after crooked 180 ° does not demonstrate coating and breaks.These results show Cerablak ^TMCoating is to the strong adhesiveness of polymer.Known have strong adhesiveness based on phosphatic coating to polymer.For example, calcium phosphate is respectively 6.4 and 5.8MPa to the adhesion strength of polyethylene and poly-(tetrafluoroethene).Without wishing to be bound to any theory, we think strong adhesiveness, and the chances are owing to formed the C-O key between phosphate radical and polymer interface in the process that coating is solidified.Also can be by improving adhesiveness with Ar ion pretreating substrates.Material precursor solution of the present invention is weakly acidic and can not destroys the surface of polymer substrates of acid labile in coating procedure.

Can reduce or remove the organic group that links to each other with phosphorus in the precursor solution fully by replace the P-OR group with the P-OG group.Yet any chemical change in the precursor solution may influence the condensation and the formation of film.Some embodiments of precursor solution of the present invention can keep the aluminum phosphate complex compound to combine with distinctive [O=P-O-Al-O-Al].Do not wish to be bound by any theory, we think and can reduce organic content by the relative amount that increases " P-OH " material.Except making water or the chemical material of other non-alcohol as the solvent, can be by using the big alcohol of steric hindrance, for example isobutanol reduces the content of organic substance as the solvent of aluminum nitrate.The reaction rate of (P-O-P) group of isobutanol and condensation is low.Even form the P-O-isobutyl group in solution, they are removed when refluxing easily, form the 2-methylpropane, and it is gas (6.6 ℃ of boiling points) when room temperature.

Polymer with the wetting low-surface-energy of alcohol is a challenge.Because need this high solidification temperature to improve adhesiveness, adhesiveness is very important.In the situation of Kapton, the adhesiveness of material coating of the present invention is fabulous, need not any surface treatment.With the situation of the coating poor adhesion of some polymer in, take the surface modification of polymer.Can use several technology, for example priming paint deposition, the individual layer SAM that uses surface-assembled, oxygen plasma etching and sulphur chromium (sulfochromic) are bathed to handle and are improved wetability.Material coating of the present invention can be used as the priming paint or the adhesiveness promoting layer of other metal, polymer and inorganic coating.

Bottom and cover layer are optional from organic polymer coating, inorganic-organic mixed coating or metal coating.These layers also can form by forming identical or different material of the present invention.These layers can also be formed by the precursor with the material of the present invention of any inorganic or organic functions agent modification.For example, the UV absorbent, be used for the scattering diluent of UV anti-radiation protection, for example ZnO, CeO ₂Or TiO ₂Oxide, be used for antibacterial activity the Ag ion, be used for the transparent metal oxide of electrical property, resemble ITO, or the photocatalysis material, as TiO ₂, to give hydrophilic nmature.As required, but in these bottoms of structure and the cover layer which floor.But material coating complanation polymer surfaces of the present invention and suitable improved refractive index help to reduce the light scattering of the polymeric substrate of coating.

The embodiment of the invention

Following non-restrictive example with data description various aspects and the feature relevant with composite of the present invention, goods and/or method, comprise the purposes of various aluminum phosphate compounds and associated composition, described compound and composition can obtain with synthetic method described herein.Compared with prior art, composition of the present invention, composite, goods and/or correlation technique provide wonderful, beyond thought and opposite result and data.Although the purposes by the employed coating composition based on aluminum phosphate of several composite/goods and its has been set forth purposes of the present invention, it will be understood by those skilled in the art that available as with the scope of the invention complementary various other composite/goods and/or coating composition obtain comparable result.

Embodiment 1

A kind of preferable methods that deposits amorphous phosphoric acid aluminized coating is that described solution preferably contains aluminium salt and the phosphate in organic solvent with limpid precursor solution.Aluminium is that 2: 1 the solution that is used to deposit amorphous phosphoric acid aluminized coating is by with 264 gram Al (NO to the ratio of phosphorus ₃) ₃9H ₂O is dissolved in and prepares in the 300mL ethanol.In other container, with 25 gram P ₂O ₅Be dissolved in the 100mL ethanol.These solution are mixed.Resultant solution is diluted to the solution of 0.2 mole of Al/L with ethanol.This solution is used for the amorphous phosphoric acid aluminized coating of deposition on base material.

Embodiment 2

Aluminium is that 4: 1 the solution that is used to deposit amorphous phosphoric acid aluminized coating is by with 528 gram Al (NO to the ratio of phosphorus ₃) ₃9H ₂O is dissolved in and prepares in the 300mL ethanol.In other container, with 25 gram P ₂O ₅Be dissolved in the 100mL ethanol.These solution are mixed.Resultant solution is diluted to the solution of 0.2 mole of Al/L with ethanol.

Embodiment 3

With cleaning agent and water cleaning corrosion resistant plate, then ultrasonic processing in methyl alcohol.Be immersed in the solution of embodiment 1 preparation.Use fan heater drying.Dried sample was 400 ℃ of heating 1 minute and be cooled to room temperature.The corrosion resistant plate surface of solidifying demonstrates strong iridescence look.Material coating of the present invention such as this type can be applied on the goods as decorative coating.

Embodiment 4

With cleaning agent and water cleaning corrosion resistant plate, then ultrasonic processing in methyl alcohol.Be immersed in the alcoholic solution of forming by phosphate and aluminium compound.Use the fan heater drying then.Dried sample was 400 ℃ of heating 1 minute and be cooled to room temperature.

Embodiment 5

Use the infrared reflection-absorption spectroscopy of sample of glancing angle part (Fig. 1) record embodiment 4 preparations of Perkin Elmer Spectrum One spectrometer and 80 ℃.

Embodiment 6

Be applied on the sample prepared among the embodiment 2 by the cover layer of dip-coating the precursor solution of embodiment 1 preparation.Then, 500 ℃ of heat treated sample 15 minutes and be cooled to room temperature.Uncoated part is because oxidative decoloration on the plate.The part that applies is glossy and keep silver color.The concentration of described precursor solution, composition and coated conditions depend on the configuration of surface on coated surface.Therefore, can remove the iridescence effect of material coating of the present invention by suitably regulating precursor and painting method.

Embodiment 7

Use the infrared reflection-absorption spectroscopy of the sample that glancing angle part (figure) the record embodiment 6 of Perkin Elmer Spectrum One spectrometer and 80 ℃ prepares.

Embodiment 8

Be coated with on the stainless surface of material of the present invention, by with thumb by producing finger-marks from the teeth outwards.Wipe finger-marks with clean cloth then.Wipe thumbprint from the surface of described coating at an easy rate, remaining very artistic clean surface.Use similar clean method not remove finger-marks from uncoated surface.

Embodiment 9

Demonstrated the in this embodiment anti-soil effect of the material coating of the present invention on solid substrate.With various materials, for example Ketch-up, H2O+NaCl, tomato, lemon, coffee, milk, acetate, citric acid 20%, lard+oleic acid, jam, butter, olive oil and other thing are done on the sample that material of the present invention applies and are made it in room temperature and 90 ℃ of dryings.Wash with water then, then the lip-deep stain of perusal coating.The surface that material of the present invention applies is without any stain.

Embodiment 10

The pencil hardness (pencilhardness) of the stainless steel sample that the material of the present invention of test implementation example 5 preparations applies.Described pencil hardness is greater than 6H.

Embodiment 11

Before up to 700 ℃ heat treatment and afterwards, measure the reflectivity on the surface that material of the present invention applies.Compare with uncoated control sample, the reflectivity on the surface of coating keeps.

Embodiment 12

With the little crystal aluminium oxide (sapphire) of deionized water, acetone and clean methanol.Use the precursor solution (4: 1 Al/P ratios) of embodiment 2 preparations.It is 2 cels that rate (withdraw rate) is withdrawed from dip-coating.Solidified 10 minutes at 800 ℃ then.Obtain clear coat.

Embodiment 13

The TEM photo of the material coating of the present invention on sapphire shows sealing, fine and close and uniform coating of the present invention (Fig. 3).The electron diffraction diagram of material coating of the present invention shows the amorphous property of coating.Material film of the present invention is that thickness is about 140nm uniformly.High-resolution TEM shows the amorphous contrast (contrast) in the typical film.Between material of the present invention and sapphire, have boundary layer (～5nm).

Embodiment 14

The test of the enamel sample that applies with material of the present invention shows to be compared with uncoated zone, and only water and soft cloth (Fig. 4) are removed the relatively easy evidence of tomato juice that solidifies 15 minutes at 300 ℃ from regions coated.As if when observing under light microscope, this residue combines well with base material.

Embodiment 15

Have the uncoated SiC surface of 1 micron polishing degree and the SiC that the material of the present invention after the heat treatment applies,, demonstrate reflective surface will (Fig. 5) with uncoated comparing.

Embodiment 16

The AFM figure of the heat treated SiC that material of the present invention applies shows very smooth surface.

Embodiment 17

Based on the sealed nature of material film of the present invention, a lot of metals, alloy and glass baseplate have been observed.Expect the material of the present invention blemish of micron order (microscale) on the sealed polymer well.Fig. 7 shows the AFM figure of the metal alloy surface that applies with material of the present invention, demonstrates the tangible planarization application of being induced by film.When having film, see reducing of surface roughness above 4X.

Micron-sized defective on the metal surface (even being polished to the fineness of sub-micron) causes the position as oxidation.Along with metal base is oxidized gradually in high-temperature oxidation process, these little blemish are as the initiation point of oxidation.These little defectives become big hole.Yet the material film of the present invention that deposition is thin is enough to cover these defectives makes pit foundation originally be removed.These results show the potentiality of the lip-deep micron order defective (cut, hole etc.) that material seal of the present invention is coated.

Embodiment 18

In acetone and methyl alcohol, carry out ultrasonic processing and clean the copper billet of 1 " * 3 " size.Dip-coating in material precursor solution of the present invention then.Air drying and in 200 ℃ heat treated 15 minutes in the stove.Photo shows the effect (Fig. 8) of material coating of the present invention after this heat treatment.The part that material of the present invention applies is still bright and glossy.On the other hand, uncoated face tarnishes fully.Similarly, also available material coated copper of the present invention, brass and other metal wire protect it not oxidized or be subjected to environmental damage.

Embodiment 19

The AFM of slide that applies with material of the present invention and uncoated glass is illustrated in Fig. 9.The very smooth and glass that the rms roughness ratio is uncoated in the surface that material of the present invention applies has reduced an order of magnitude.

Embodiment 20

Because thermal coefficient of expansion does not match and the temperature-sensitive character of polymeric substrate, on polymeric substrate, form the very challenging technically property of fissureless ceramic coating.Remaining thermal stress causes film rupture, especially when coating is at high temperature solidified.If coating layer thickness is remained on a minimum of a value and improves the adhesion energy of film to base material, this phenomenon is minimized.Because viscosity is low, the pyrolysis decomposition under lower temperature easily of phosphate base precursor solution can reach this two conditions with material of the present invention.The optical photograph of the material coating of the present invention on the composite polyimide material shows the lip-deep complanation effect that applies.Material of the present invention has also covered defective and sealing surfaces and has not formed this class and broken.

Embodiment 21

With polyvinylpyrrolidone, PVP (molecular weight 630,000) is dissolved in the precursor solution of material of the present invention of embodiment 2 preparation.The amount of PVP can change to 100 weight % from 0 weight % in the solution.The viscosity of described solution increases along with the increase of PVP content.Also can pass through directly with PVP and Al (NO ₃) ₃And P ₂O ₅Solution mixes and prepares described solution.Can also use PVP with other molecular weight.

Embodiment 22

With Merlon sample (1 " * 1 ") be immersed in sulphur chromium bathe in 30 seconds.Then with a large amount of deionized water washings.The material precursor dip-coating of the present invention for preparing with embodiment 2 then.Sample with the dry described coating of fan heater.Heat treatment in 130 ℃ baking oven then.After solidifying a period of time, form transparent coating.

Embodiment 23

With Merlon sample (1 " * 1 ") be immersed in sulphur chromium bathe in 30 seconds.Then with a large amount of deionized water washings.Use the material precursor dip-coating of the present invention of the modification of embodiment 3 preparations then.Sample with the dry described coating of fan heater.Heat treatment in 130 ℃ baking oven then.After solidifying a period of time, form transparent coating.

Embodiment 24

With the methyl ethyl ketone drips of solution on the polycarbonate film that the material of the present invention of embodiment 5 preparation applies.Do not observe reaction with Merlon.This hint material of the present invention prevents its ability that is subjected to chemical affect and its good barrier properties.

Embodiment 25

The Zinc oxide particles that is dispersed in the nanometer size in the medium mixes with the material precursor solution of the present invention of embodiment 2 preparations.The amount of zinc oxide can change.Can also pass through directly with zinc oxide and Al (NO ₃) ₃And P ₂O ₅Solution mixes and prepares described solution.

Embodiment 26

In order to measure the solid state of material coating of the present invention, the FTIR reflectance spectrum of the stainless steel foil that minute book invention material applies is to temperature and the function of heat treatment duration (Figure 10).Along with the increase of solidification temperature and time, organic absworption peak of phosphate (1370,1432,1,473 1720,2987cm ^-1) intensity reduces, at 1200cm ^-1Occurred one owing to the PO that connects fully ₄The strong absorption of group.Along with solidification temperature increases, can handle the required duration by shortening heat.Based on the FTIR data, the solidification temperature that needs are 325 ℃ obtains to contain the inorganic coating completely of some water.By being up to 340 ℃ of a kind of Kaptons that solidify material coating of the present invention, obtain fissureless coating.Described solidification temperature and coating stability change along with base material character, thickness and pretreatment condition.Solidification temperature also can change along with the composition of material precursor solution of the present invention.Notice very enjoyably in the FTIR of 200 ℃ of long-term samples of heat treatment data to show that the content of residual water in the coating is almost constant, even show also enough fine and close and sealing at 200 ℃ of solidified coatings.According to this research, 200 ℃ solidification temperature is enough to form protective coating on polymer.But high temperature can provide better adhesiveness, and airtight quality can be better.

Embodiment 27

Apply the stainless steel foil of cleaning with the precursor solution of embodiment 1 preparation.Heat treated sample is several seconds in being higher than 800 ℃ smelting furnace.The glancing angle (Figure 11) of the infrared external reflection of quick-setting material coating of the present invention spectrum shows and does not have organic matter and water, forms completely crued inorganic metal phosphate layer.In this quick solidification process, show that coating reaches the temperature more than 500 ℃, and base material is below 250 ℃.For the painting method of some type, for example roller is to roller and heat-sensitive substrate material, for example polymer, preferably this quick curing technology.

Embodiment 28

Polyimides is classified as organic resin, and uses owing to its good heat-resisting and chemical resistance is used for engineering.In semi-conductor industry, these materials mainly are used as the base material of flexible printed circuit board, the base material that the integrated circuit in wireless, numeral and the computer industry is used.The surface smoothness of these materials has direct influence for their performance, and it is very crucial therefore to optimize these conditions.Material of the present invention is coated on the Kapton of cleaning and and solidified 1 hour at 300 ℃.The SEM figure (Figure 12) of the Kapton that material of the present invention applies has shown the free from flaw character of coating.And the particle on the polyimide surface is also covered by material coating of the present invention.

Embodiment 29

When joining nano level ZnO (＜10 moles of %) in the material coating of the present invention, UV absorbs and has reduced by 40%.This embodiment shows the effect that adds the UV absorbent in material of the present invention.Be coated in material of the present invention and the ultraviolet-visible transmission spectrum (Figure 13) that is dispersed with the material of the present invention of ZnO on the sapphire plate.

Embodiment 30

Contain the silica glass product of material coating of the present invention or surface treatment can stop silicate in the course of the work with environment reaction.The result of this embodiment shows this effect of the material coating of the present invention on fusion heat release silica sample.Partly apply the quartz specimen of fusion and use sodium sulphate to handle 15 hours with material of the present invention at 900 ℃.Under these treatment conditions, uncoated vitreous silica is owing to becoming opaque with the sodium ion reaction.And the part that material of the present invention applies remains transparent, shows the barrier effect of material coating of the present invention to the sodium ion diffusion.

Embodiment 31

Material of the present invention specifically also can be used as chemistry and heat-staple adhesive or adhesive.In these experiments, the precursor solution of modification is applied on the surface of wanting bonding, other surface is pressed onto on the described first surface, guarantee that precursor solution has covered fully to want two bonding surfaces.Clamp two surfaces and heat treatment to form inorganic material.In view of the less effort of cost in these preliminary experiments, the attachment that obtains demonstrates bonding strength preferably.Phosphorus content can influence transmittance and bonding strength.Higher by phosphorus content, the rich phosphorus composition of material of the present invention has some absorptions in the IR scope, can be stronger but bonding.On glass and stainless steel sample, carry out bonding experiment.Glass has very smooth surface, and stainless steel has #3 fineness.These experiments show the substrate material that can bondingly have different surfaces fineness based on the adhesive of material of the present invention.

In order to obtain the further evidence directly related with this application, sapphire plate (rectangle) is adhered on the ZnS sheet sample.Described sample was annealed one hour in air at 450 ℃, with the heat endurance of test attachment.Described material still connects well, shows the bond property that material of the present invention is very strong.The transmission spectrum mensuration of bonding sample shows at 3-4 micrometer range iuuminting good, and makes light transmission weaken (Figure 15) owing to sapphire opaqueness more than 6 microns.

Embodiment 32

Can synthesize material of the present invention (for example 0.5/1 to 10/1 and to 25/1) in very big Al/P ratio ranges, comprise adding or other element that mixes, silicon for example may these yuan produces usually that some is functional.As seen from Figure 16, on ZnS two kinds transmission properties of forming different material films of the present invention have relatively disclosed with the higher composition of the phosphate content that adds silicon (silica also has absorption around the same area) and have compared, and the Al/P ratio is to demonstrate insignificant phosphate radical at 6/1 o'clock to absorb.Yet,, need find the balance between transmissivity and the high bonding strength because phosphate radical has good cohesive.Therefore, material system of the present invention allows to form flexibly variation to customize specific character.

Embodiment 33

Applying coating on polymer

Industry	Be coated with layer function	Example
Industry	Be coated with layer function	Example	Aviation	Diffusion barrier, antistatic coating, prevent to be subjected to space environment influence	Bathroom mirror, lampshade, hot forming part plate and desk, window
Utensil	The diffusion barrier of opposing moisture and oxygen	The container of console and thin film switch, instrument board, storage food, prints labels and nameplate	Aviation
Utensil	The diffusion barrier of opposing moisture and oxygen		Automobile	Prevent to be subjected to hydrophobic coating, antireflection coatings, the anti-static coating of mechanical failure (corrosion), easy to clean and windshield	Buffer component, windowpane
Building and building	Hydrophobic coating antireflection coatings easy to clean prevents to be corroded	General windowpane, illuminated diagram switch board windowpane (Lighting PanelGlazing), office inside, private savings room window (Privacy Glazing), public building, roof lamp, the wall that separates, skylight, soundproof wall (Soundwall), wallboard, window	Automobile		Buffer component, windowpane
Building and building			Electrical and Electronic	Electric insulation, diffusion barrier	Shell (Enclosure), insulation barrier, printed circuit
Machine (Machinables)	Prevent to be subjected to mechanical failure (grind away, corrode)	Bearing and bearing, gear	Electrical and Electronic	Electric insulation, diffusion barrier	Shell (Enclosure), insulation barrier, printed circuit
Machine (Machinables)		Bearing and bearing, gear	Maintenance and material processed	Prevent to be ground away and corrode	Chute liner, conveying rubstrip (Conveyor Wear Strip), fabricated parts, machine guards, hot formed plate
Sea-freight	Prevent to be subjected to the mechanical failure hydrophobic coating	Diving tower, outside, inside, furniture decoration parts	Maintenance and material processed	Prevent to be ground away and corrode
Sea-freight		Diving tower, outside, inside, furniture decoration parts	Optical medium	Moisture barrier	Display-LCD, OLED

Industry	Be coated with layer function	Example
Industry	Be coated with layer function	Example	Printing	Prevent to be subjected to mechanical failure	Decorative laminate, thin film switch, nameplate, profile paper
Safety means	Prevent to be subjected to mechanical failure	Goggles, machine guards	Printing	Prevent to be subjected to mechanical failure
Safety means	Prevent to be subjected to mechanical failure	Goggles, machine guards	Signal and demonstration	Prevent to be subjected to mechanical failure	Rear cockpit beacon light, building signboard (Building Fascia), awning, channel letter (Channel Letter), fixing industrial nameplate, LED cover plate, menu homepage, built on stilts installed device (Pole Mount), POP display, hot formed mark, retail kiosk (Tradeshow Booth), vending machine overcover (VendingCover), the wall-mounted equipment (WallMounted) in ground
Telecommunications and computer equipment	Prevent to be subjected to mechanical failure optical element easy to clean	Phone cover, die-cut insulator, keyboard and keypad, camera lens and lid, monitor ﹠ display	Signal and demonstration	Prevent to be subjected to mechanical failure
Telecommunications and computer equipment			Traffic	Prevent to be subjected to mechanical failure	Tapping device shelter (Bug Shield), windowpane, inside, hot forming part

Embodiment 34

Referring to the one or more embodiment or the description of front, use known in the art and understand that the roller that people of the present invention will be appreciated for preparing various composites and/or product component to roller or method for continuous production.Therefore, above-mentioned aluminophosphate composition coating and the coating that is incorporated herein by reference are (for example available from Applied Thin Films, Inc., Evanston, IL Cerablak ^TMCompound, composition and product) can be applied on a variety of substrate materials.At United States Patent (USP) 6,951, in 770 and 6,878,871 (these two pieces of full patent texts are included this paper in as a reference) this equipment and material and structure have been described more fully.

Randomly, can prepare base material by following steps: at first remove unstable surface patches, use one or more sprayers or dip-coating device with suitable organic or aqueous solution (for example acetone or cleaning agent/water) de-oiling then, water and/or alcohol clean.Use baker (temperature is 50-500 ℃) to remove all solvents,, use flow air, dry air, oxygen, nitrogen or any other inert gas for base material to the atmosphere sensitivity.

As mentioned above or in conjunction with the reference introduced, the precursor solution of aluminophosphate composition is sprayed on the base material.Perhaps, described base material being immersed in one or more precursor solutions bathes or stores in the pond.If two or more of this base material or all faces all will apply, can correspondingly dispose one or more nozzles.Perhaps, apply all substrate surfaces with dip-coating.Precursor composition can change in the following areas, such as but not limited to the additive (organic or inorganic) of Al/P stoichiometric proportion, viscosity, carrier (for example water-based or non-aqueous) and existence.For example, favourable for the coating possibility of high emissivity, prepare slurries with solvent (water-based or non-aqueous) carrier component.

Do not consider the demand of various volumes and output, coating composition can be solidificated in up to 100 feet or on the longer length with one or more baking ovens or heating/curing source.For example, can make length be enough to overlap flow process drying and the baking oven that solidifies or the temperature of smelting furnace according to one is 50-1000 ℃, and the time of staying is depended on the length of speed and effective heating/consolidation zone.This zone can be different because of one or more heating or curing source (for example air of UV/IR, the heating of flowing, other or inert gas or resistance heated source).Can clean cured coating with appropriate solvent.Dry then, apply next coating then.Perhaps, as contain in the composite of thermally sensitive base material (for example some plastics) used, available suitable thermal source is cured by this way, with higher temperature heating coating part, and keep base material lower temperature (for example about 250 ℃ or following), continuing for some time (for example less than about 1 hour) is enough to make coating to be solidified, and can adverse effect or effect not arranged to base material.

For the various considerations relevant with method, wish along or through rolling up base material with suitable angle before the heating/curing source.If base material is that suitably wet or uncured, because the crooked coating damage that causes will be minimum.Depend on initial surface roughness, can be before cleaning and applying coating, road as known in the art, electropolishing or machine glazed finish base material.In any case referring to signal Figure 17 and 18, it further illustrates the structure of roller to the composite of roller/continuous coating process and nonrestrictive winding that obtains thus or volume.

Claims

1. composite with structure, it comprises base material and the coating composition on base material, described coating composition contains aluminum phosphate compound, the aluminium that described compound contains is about 0.5: 1 to about 25: 1 to the ratio ranges of phosphorus, described composite be arranged in described structure vertical substantially the axle around.

2. composite as claimed in claim 1 is characterized in that described base material is selected from metal, metal alloy and plastics.

3. composite as claimed in claim 2 is characterized in that, the stainless steel that described base material is selected from stainless steel and brushed.

4. composite as claimed in claim 3 is characterized in that, described coating composition substantially transparent in visible spectrum.

5. composite as claimed in claim 3 is characterized in that, described coating composition provides the iridescence outward appearance for described composite.

6. composite as claimed in claim 3 is characterized in that described coating composition contains antibacterial components.

7. composite as claimed in claim 2, it comprises at least one interlayer component between described base material and described coating composition.

8. composite as claimed in claim 2 is characterized in that described base material comprises plastics, and described plastics contain a kind of in Merlon, Copolycarbonate, polyimides, polyimide copolymer, polyester and the polyester copolymer.

9. composite as claimed in claim 8 is characterized in that described coating composition comprises the infiltration barrier layer.

10. composite as claimed in claim 8 is characterized in that described coating composition to small part is insoluble to organic solvent.

11. composite as claimed in claim 8 comprises at least a cover layer component on described coating composition, described coating composition adheres on the described cover layer component.

12. composite as claimed in claim 11 is characterized in that, described coating composition contains the about 1230cm that is absorbed in the INFRARED SPECTRUM ^-1The structure division of radiation.

13. composite as claimed in claim 2 is characterized in that, described base material comprises the metal forming of gauge less than about 100 mils.

14. composite as claimed in claim 13 is characterized in that, described paper tinsel is selected from aluminium, stainless steel, titanium, manganese, nickel-base alloy and superalloy.

15. composite as claimed in claim 14 is included in the reflective metal cover layer on the described coating composition.

16. composite as claimed in claim 2 is characterized in that, described base material comprises wire rod.

17. the described composite of claim 1, it is on bobbin.

18. the described composite of claim 1, it makes goods.

19. use the method for the sealing porous substrate surface of aluminophosphate composition, described method comprises:

The base material that contains surface portion is provided;

Described surface portion is contacted with the composition that contains aluminum phosphate compound, and described compound contains at least one phosphonate moiety; With

Be enough to remove the described composition of heating under the temperature and time condition of described ester moiety to small part.

20. method as claimed in claim 19 is characterized in that, described base material is selected from granite, marble, engineered stone, porcelain and pottery.

21. method as claimed in claim 19 is characterized in that, described surface portion is complanation substantially.

22. method as claimed in claim 19 is characterized in that, the described composition that is touched elementary heat under up to about 1000 ℃ temperature is stable.

23. method as claimed in claim 19 is characterized in that, described composition is sprayed on described surface portion.

24. method as claimed in claim 23 is characterized in that, described composition contains at least a in aqueous carrier component, non-aqueous carrier component and the aerosol propellant.

25. method as claimed in claim 24 is characterized in that, described composition contains aerosol spray.

26. method as claimed in claim 19 is characterized in that, described base material is selected from kitchen utensils and sales counter, bathroom fixtures, floor tile and walltile part.