CN103044976A - Manufacturing method of composite sol and application method thereof in material design - Google Patents
Manufacturing method of composite sol and application method thereof in material design Download PDFInfo
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- CN103044976A CN103044976A CN2012101796298A CN201210179629A CN103044976A CN 103044976 A CN103044976 A CN 103044976A CN 2012101796298 A CN2012101796298 A CN 2012101796298A CN 201210179629 A CN201210179629 A CN 201210179629A CN 103044976 A CN103044976 A CN 103044976A
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Abstract
The invention discloses a manufacturing method of a series of composite sols, wherein the manufacturing method of the composite sols is applied to surface modification of materials, so that, a work system for implementing a material design scheme is constructed. The system is applied to surface modification of various base materials such as plastic, metals, ceramic, glass and woods. Nano thin films with special performance is designed and manufactured. In description, a series of novel method of designing and manufacturing novel materials is specified in detail, comprising process technologies such as manufacture of composite sols and coating and curing of thin films.
Description
Technical field
This design of material is one of most important branch of Materials science, also is the core technology of novel material research and development.Design of material at first is to sum up by various Theoretical Calculation and rule of thumb data, seeks that material property and material form, the relation between the structure, and with the mathematical model of existing data structure material property and material composition, relationship between structure; Use this mathematical model, can be according to the Nomenclature Composition and Structure of Complexes of material, the performance of forecast material also can be according to the performance requriements of material, the Nomenclature Composition and Structure of Complexes of designing material.
A series of complex sol manufacture method disclosed by the invention is implemented the selection of the good system of design of material scheme just, use this series methods, build seriatim the crystalline structure of material according to the microstructure of material from the molecule angle, can distributed, parallelly carry out the synthetic of material intermediate, and then obtain expediently the material of desired properties.
Disclosed serial of methods, core is to use sol-gel method, according to the Nomenclature Composition and Structure of Complexes of the pre-designed material of design of material, prepares easily nanometer or micro-nano colloidal sol, and by film-forming process manufacturing nano thin-film, this is a very practical utilisation technology of field of nanometer material technology.
Complex sol disclosed by the invention and film thereof are mainly used in material surface modifying, and various materials have advantage separately, defective is separately also arranged, by the nano thin-film that surface coverage has design performance, can improve the various performances of material surface, remedy the defective of material surface.
Background technology
Collosol and gel: colloidal sol refers to by hydrolysis and polymerization, nanometer or the micron-sized particle of the organic or inorganic that forms, these particles are usually with electric charge, and because charge effect, absorption one deck solvent molecule forms the nanometer or the micron particle that are coated by solvent, it is colloidal particle, these colloidal particles are owing to mutually repel with electric charge, thereby can be present in the solvent with suspended state, namely form colloidal sol; Colloidal particle is owing to lose electric charge, and the solvent layer that perhaps is coated on the outer ring is destroyed, colloidal particle generation polymerization, and colloidal sol occurs to solidify and namely forms gel.
Organometallic compound (metallo-organic compound), the alkyl that refers to alkyl (comprising methyl, ethyl, propyl group, butyl etc.) and aromatic base (phenyl etc.) is combined the compound that forms with atoms metal, and the general name of the material of carbon and the direct combination of atoms metal, can form more stable organometallic compound with metals such as lithium, sodium, magnesium, calcium, zinc, cadmium, mercury, beryllium, aluminium, tin, lead, be the compound that a class contains a metal-carbon (σ or π) key at least; Can be divided into alkyl metal cpd (alkylmetalic compounds) and arylide compound (arymetalic compounds) two classes.。
Metal alkoxide is the metal-organic part of the broad sense between mineral compound and organic compound, metal alkoxide can think simply that metal and pure condensation produce metal alkoxide and water, often some metal alkoxide is not like this preparation, and metal alkoxide can be used following formulate: M-O-R or M-(O-R usually) n represents.(wherein M represents metal ion, and R represents alkyl).
Organic molecule, or title organic monomer, referring to can be by the organic chemical reactionses such as addition reaction, polyreaction, crosslinking reaction occurs, generate the organic molecule of high molecular polymer, include but are not limited to the precursor of the polymkeric substance such as fluorocarbon resin, aminoresin, urethane resin, Plastic resin, engineering plastics resinoid.
Inorganic salt include but are not limited to the water-soluble metal strong acid salts such as hydrochloride, nitrate, vitriol, also comprise water miscible metal salt of weak acid.
Summary of the invention
A kind of manufacturing inorganic salt---the method for organic monomer complex sol may further comprise the steps:
1) water dissolve inorganic salts (such as muriate, vitriol, nitrate etc.); Inorganic salt and organic acid (such as oxalic acid, acetic acid etc.) reaction with dissolving form organic acid salt colloidal sol; Multiple organic acid salt colloidal sol is mixed, form the organic acid salt mixed sols; Or
2) plurality of inorganic salt is dissolved in the water jointly, forms mixture; With this mixture and organic acid reaction, form the organic acid salt complex sol;
3) in complex sol, add hydrolyzable organic monomer and initiator, by the organic monomer of initiator initiation and the polyreaction of organic acid salt, form inorganic salt---organic monomer complex sol.
A kind of manufacturing organometallic compound (metallo-organic compound)---the method for organic monomer complex sol comprises following steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) organic functional base R and hydrolyzable organic monomer (under the effect of initiator) are reacted, form organic---inorganic hybrid;
3) making this organic---the inorganic hybrid polymerization generates organometallic compound---organic monomer complex sol.
A kind of manufacturing metal alkoxide---the method for organic monomer complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is M (OR)
zMetal alkoxide form colloidal sol, M is for forming the metal of hydrolyzable alkoxide in the formula, R is low molecular weight alkyl, z is the valency of M;
2) in above-mentioned colloidal sol, add organic monomer and initiator, by the organic monomer of initiator initiation and the polyreaction of metal alkoxide, form metal alkoxide---organic monomer complex sol.
A kind of manufacturing organometallic compound---the method for metal alkoxide complex sol comprises following steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) according to reaction formula:
Be hydrolyzed a kind of general formula and be M ' (OR ' ')
Z 'Metal alkoxide, M ' is for forming the metal of hydrolyzable alkoxide in the formula, R ' ' is low molecular weight alkyl, z ' is the valency of M ', y ' is at least 1 and less than z ';
3) above-mentioned metal alkoxide colloidal sol and above-mentioned organometallic compound colloidal sol are mixed, press following reaction formula:
Reaction, until all metal alkoxides and organometallic compound reaction, and generate till the oxide network, organometallic compound---metal alkoxide complex sol formed.
A kind of method of making inorganic salt-organometallic compound complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
3) inorganic salt colloidal sol is mixed with organometallic compound colloidal sol, and polymerization reaction take place, inorganic salt-organometallic compound complex sol formed.
A kind of method of making inorganic salt-metal alkoxide complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is M (OR)
zMetal alkoxide form colloidal sol, M is for forming the metal of hydrolyzable alkoxide in the formula, R is low molecular weight alkyl, z is the valency of M, y is at least 1 and less than z;
2) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
3) inorganic salt colloidal sol is mixed with metal alkoxide colloidal sol, and polymerization reaction take place, inorganic salt-metal alkoxide complex sol formed.
The method of a kind of manufacturing inorganic salt---metal alkoxide---organic monomer complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is M (OR)
zMetal alkoxide form colloidal sol, M is for forming the metal of hydrolyzable alkoxide in the formula, R is low molecular weight alkyl, z is the valency of M, y is at least 1 and less than z;
2) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
3) inorganic salt colloidal sol is mixed with metal alkoxide colloidal sol, and add organic monomer and initiator, the organic monomer that is caused by initiator and the polyreaction of inorganic salt, metal alkoxide, formation inorganic salt---metal alkoxide---organic monomer complex sol.
The method of a kind of manufacturing inorganic salt---organometallic compound---organic monomer complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
3) inorganic salt colloidal sol is mixed with organometallic compound colloidal sol, and adding organic monomer and initiator, the organic monomer that is caused by initiator and the polyreaction of inorganic salt, organometallic compound, formation inorganic salt---organometallic compound---organic monomer complex sol.
The method of a kind of manufacturing inorganic salt---metal alkoxide---organometallic compound complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) according to reaction formula:
Be hydrolyzed a kind of general formula and be M ' (OR ' ')
Z 'Metal alkoxide, form metal alkoxide colloidal sol, M ' is for forming the metal of hydrolyzable alkoxide in the formula, R ' ' is low molecular weight alkyl, z ' is the valency of M ', y ' is at least 1 and less than z ';
3) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
4) inorganic salt colloidal sol is fully mixed with organometallic compound colloidal sol with metal alkoxide colloidal sol, and polymerization reaction take place, inorganic salt---metal alkoxide---organometallic compound complex sol formed.
The method of a kind of manufacturing metal alkoxide---organometallic compound---organic monomer complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) according to reaction formula:
Be hydrolyzed a kind of general formula and be M ' (OR ' ')
Z 'Metal alkoxide, form metal alkoxide colloidal sol, M ' is for forming the metal of hydrolyzable alkoxide in the formula, R ' ' is low molecular weight alkyl, z ' is the valency of M ', y ' is at least 1 and less than z ';
3) metal alkoxide colloidal sol is mixed with organometallic compound colloidal sol, and adding organic monomer and initiator, the organic monomer that is caused by initiator and the polyreaction of metal alkoxide, organometallic compound, formation metal alkoxide---organometallic compound---organic monomer complex sol.
A kind of method of making the controlled high stability colloidal sol of reaction process may further comprise the steps:
1) make in the process of complex sol, add strong acid (example hydrochloric acid, nitric acid, sulfuric acid etc.) or highly basic (such as sodium hydroxide), ammoniacal liquor or weak acid (such as acetic acid, oxalic acid etc.) maybe may provide the salt of potential of hydrogen;
2) regulate the pH value, control H
+And OH
-Concentration, the speed of response of the hydrolytic process of metal alkoxide and organometallic compound is promoted or suppresses, control size, distribution and the shape of nano particle in the colloidal sol, control collosol and gel speed; With
3) regulate the pH value, control H
+And OH
-Concentration, the molecular balance of the hydrolytic process of metal alkoxide and organometallic compound is controlled, control the equilibrium process of gel, realize simultaneously the long-term stability of colloidal sol.
A kind of method of making colored complex sol may further comprise the steps:
1) prepares complex sol with preceding method; With
2) according to the kind of solvent in the colloidal sol, select to add pure dissolubility or water-soluble organic toner.
The organic film of a kind of complex sol low temperature may further comprise the steps:
1) makes complex sol with preceding method;
2) complex sol is lifted, spares glue by infiltration and get rid of the surface that the methods such as film, pressure roller, spray or atomizing spraying are coated to plastics, timber, textiles, leather, metal, pottery or glasswork;
3) dry 5 minutes to 10 minutes, the solvent in the complex sol is volatilized, the particle of complex sol is able to ordered arrangement;
4) low-temperature bake in 60 degrees centigrade to 120 degrees centigrade scope forms cancellated inorganic---organic compound film.
The inorganic film of a kind of complex sol high temperature may further comprise the steps:
1) makes complex sol with preceding method;
2) complex sol is lifted, spares glue by infiltration and get rid of the surface that the methods such as film, pressure roller, spray or atomizing spraying are coated to metal, pottery or glasswork;
3) dry 5 minutes to 10 minutes, the solvent in the complex sol is volatilized, the particle of complex sol is able to ordered arrangement;
4) slowly intensification baking in 200 degrees centigrade to 500 degrees centigrade scopes is progressively burnt the organism in the complex sol;
5) continue to be warmed up to 550 degrees centigrade to 600 degrees centigrade, and be incubated 1 hour to 3 hours, make the inorganics in the complex sol form cancellated laminated film.
A kind of film of high transmission rate nano thin-film may further comprise the steps:
1) selects silicon and aluminium as main film forming element, namely select organometallic compound or the metal alkoxide of silicon and aluminium, prepare complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method, transmittance can reach more than 90.
A kind of high hardness nanocomposite thin film technology method may further comprise the steps:
1) selects titanium, aluminium and zirconium etc. as main film forming element, namely select organometallic compound or the metal alkoxide of titanium, aluminium and zirconium, make complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method, the Mohs' hardness of base material can be promoted 5 to 6 grades.
A kind of preparation method of damage resistant nano thin-film may further comprise the steps:
1) selects silicon and titanium as main film forming element, namely select the organometallic compound of silicon and titanium, select to add aminoresin or fluorocarbon resin, prepare complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method, can be with scratch resistance strength enhancing 2 to 3 newton of base material.
A kind of preparation method of super-hydrophobic, anti-dirty micro/nano film may further comprise the steps:
1) by regulating the pH value, the speed of response of control complex sol preparation, the particle size of the gel of a kind of colloidal sol in the aforementioned complex sol preparation process is controlled at 200 nanometers to 600 nanometers, and the particle size of the gel of another kind of colloidal sol is controlled at below 10 nanometers, prepares complex sol with preceding method; With
2) with the high temperature inorganic composite film of preceding method preparation, contact angle can reach 110 ° to more than 120 °; Or
3) add organic fluorine in complex sol, with the low temperature organic compound film of preceding method preparation, contact angle can reach more than 150 ° again, has ultra-hydrophobicity and anti-dirty performance.
A kind of preparation method of high abrasion nano thin-film may further comprise the steps:
1) selects titanium, aluminium and zirconium etc. as main film forming element, namely select organometallic compound or the metal alkoxide of titanium, aluminium and zirconium, select the salt of the high rigidity elements such as tungsten, copper, nickel, chromium, cadmium as inorganic salt, prepare complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method.
A kind of preparation method of long-term weatherability nano thin-film may further comprise the steps:
1) salt of selection rare earth element such as cerium oxide, hafnia etc., as inorganic salt, prepares complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method.
A kind of film post-treating method; Passing through colloidal sol---gelation process (comprises that hydrolysis or dissolving form colloidal sol, hydrolytic condensation product, and drying forms gel), prepare in the method for low temperature organic compound film or high temperature inorganic composite film, processing in gel with aqueous fluid is film, and remove residual organism, salt or solution by the solid water solution, to improve the follow-up stability of film.
A kind of method for preparing and use complex sol drafting multi color pattern may further comprise the steps:
1) select the inorganic coloring elements such as iron, cobalt, nickel, copper, manganese, chromium as inorganic salt, mix according to certain ratio, the prescription of design red, green, blue, Huang, the basic colour system such as black, white prepares the complex sol of each basic look with preceding method;
2) with this colloidal sol as printing ink, use computer control to match colors, with spraying process, at the surface rendering pattern of plastics, timber, textiles, metal, pottery or glasswork;
3) by baking or high temperature sintering pattern is cured processing.
A kind ofly use the method that complex sol prepares signature, may further comprise the steps:
1) prepares complex sol with preceding method;
2) in colloidal sol, add the fluorescence nano quantum dot;
3) prepare laminated film with preceding method.
A kind of fluorescence nano thin film technology method may further comprise the steps:
1) select silicon or titanium etc. as main film forming element, namely select the organometallic compound of silicon, the inorganic salt such as selection molysite prepare fluorescent nano particle as inorganic salt, prepare complex sol with preceding method;
2) prepare the low temperature organic compound film with preceding method, film can be kept 2 to 3 hours fluorescence after illumination.
A kind of preparation method who inhales the ripple nano thin-film for preparing may further comprise the steps:
1) selects silicon or titanium etc. as main film forming element, namely select the organometallic compound of silicon and titanium, select the inorganic salt such as molysite and manganese salt, prepare complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method, can make base material possess the suction wave energy.
A kind of preparation method of heat loss through radiation nano thin-film may further comprise the steps:
1) selects silicon or aluminium etc. as main film forming element, namely select the organometallic compound of silicon and aluminium, select the inorganic salt such as molysite, cobalt salt and manganese salt, prepare complex sol with preceding method;
2) prepare low temperature organic compound film or high temperature inorganic composite film with preceding method, can make base material possess absorb light or heat and with the mode distribute heat of ir radiation.
A kind of multifunctional nano thin film technology method may further comprise the steps:
1) needs the kind of design and selection organic molecule, inorganic salt, organometallic compound and metal alkoxide according to function;
2) prepare complex sol with preceding method;
3) prepare laminated film with preceding method.
Embodiment:
The invention provides a kind of manufacture method of transparent nano film, a preferred version is, the element of the high transmission rates such as silicon-oxygen, aluminium-oxygen is introduced sol system, namely select organometallic compound or the metal alkoxides such as silicon and aluminium, prepare sol gel process and film-forming process according to the present invention, make transmittance and be not less than 90 nano thin-film; Especially can utilize the difference of the different nano thin-film transmittances that form, make antireflective coating, be used for the numerous areas such as vehicle glass.
The invention provides a kind of manufacture method of high hardness nanocomposite film, a preferred version is, the element of the high rigidity such as titanium and zirconium is introduced sol system, namely select organometallic compound or the alkoxide of titanium, select the inorganic salt of zirconium, prepare sol gel process and film-forming process according to the present invention, make the nano thin-film of high rigidity; For example, be applied in wood surface, the surface hardness of timber can be reached the H rank from the lifting of 6B rank.
The invention provides a kind of manufacture method of damage resistant nano thin-film, a preferred version is, select organometallic compound or the hydrolysis of alkoxide of silicon or titanium to form silicon sol or titanium colloidal sol, add therein aminoresin or fluorocarbon resin, the preparation complex sol, prepare sol gel process and film-forming process according to the present invention, make organic and inorganic superposes, composite nano film; For example, be applied to the surface of the trolley part that ABS resin makes, can make ABS resin product surface adhesion strength reach 3-4 newton.
The invention provides a kind of manufacture method of rub resistance nano thin-film, a preferred version is, copper is introduced sol system in the mode of mixing, namely select organometallic compound or the hydrolysis of alkoxide of silicon or titanium to form silicon sol or titanium colloidal sol, select the inorganic salt of copper, prepare sol gel process and film-forming process according to the present invention, make the nano thin-film of low-friction coefficient, high rub resistance; For example, be applied to the surface treatment of high-grade leather, can make the crocking resistance of leather reach 300 circulations of testing standard.
The invention provides a kind of manufacture method of weatherability nano film, a preferred scheme is, Ce elements is introduced sol system in the mode of mixing, namely select organometallic compound or the hydrolysis of alkoxide of silicon or titanium to form silicon sol or titanium colloidal sol, select the inorganic salt of cerium, prepare sol gel process and film-forming process according to the present invention, make the weatherability nano film; For example, on the polyvinyl resin surface, the manufacturing plastic sheeting for farm use is under strong illumination, than the work-ing life of one times of ordinary agricultural membrane prolongation with this weatherability nano thin film cladding.
The invention provides a kind of manufacture method of super-hydrophobic, anti-dirty nano thin-film, a preferred version is, select the organometallic compound hydrolysis preparation silicon sol of silicon and control the sol particle degree less than 10 nanometers, select organometallic compound or the hydrolysis of alkoxide of titanium to prepare titanium colloidal sol and control the sol particle degree in 200 to 300 nanometers, select organic fluorine as organic molecule, mixing two kinds of colloidal sols prepares complex sol and adds organic fluorine, prepare sol gel process and film-forming process according to the present invention, make the super-hydrophobic nano film, contact angle can be above 150 °; For example, be applied to stainless steel surface, in the time of replacing electroplating technique, make Stainless Steel Products possess super-hydrophobic and the oil-stain-preventing performance.
The invention provides a kind of color nano film, a preferred scheme is to select the organometallic compound of silicon, the inorganic salt of selection iron, cobalt, nickel, chromium, vanadium, manganese, prepare sol gel process and film-forming process according to the present invention, make the nano thin-film that presents various colours; For example, be applied to the ceramic surface decoration, can for automatically controlling ink jet printing device as printing ink, draw coloury pattern.
The invention provides a kind of can fluorescigenic nano thin-film, a preferred scheme is to select molysite to prepare in advance fluorescence nano colloidal sol, the organometallic compound of selection silicon, prepare sol gel process and film-forming process according to the present invention, be manufactured on the nano thin-film that can send fluorescence after the illumination; For example, be applied to the cement matrix surface, can be used as the road traffic cue mark.
The invention provides a kind of luminous nano thin-film, a preferred scheme is, selects nickel salt to prepare in advance self luminous quantum dot, selects the organometallic compound of silicon, prepares sol gel process and film-forming process according to the present invention, and manufacturing can self luminous nano thin-film; For example, be applied to the polycarbonate resin base material, can be used as special anti-fake mark.
The invention provides a kind of nano thin-film of inhaling wave energy that has, a preferred scheme is that the organometallic compound of selection titanium is selected zirconates and lead salt, prepares sol gel process and film-forming process according to the present invention, makes to have the nano thin-film of inhaling wave energy; For example, be applied in the engineering plastics such as modification of nylon resin, can be for the manufacture of the parts as stealthy aircraft.
The invention provides a kind of nano thin-film of resistance to chemical corrosion, a preferred version is that the organometallic compound of selection silicon prepares sol gel process and film-forming process according to the present invention, makes the nano thin-film of resistance to chemical attack; For example, be applied to metallic aluminium base material surface, can make the soda acid chemical corrosion of the anti-pH value of metallic aluminium between 4-10.
The invention provides a kind of nano thin-film with ir radiation heat sinking function, a preferred version is, select the organometallic compound of silicon, select molysite and manganese salt, prepare sol gel process and film-forming process according to the present invention, make the nano thin-film that has absorb light or heat energy and distribute heat energy in the ir radiation mode; For example, be applied to cotton, can be used as the extremely frigid zones insulation garment.
In the various function nano thin-film process constructed in accordance, usually can give simultaneously material multiple premium properties, this also is that various novel materials are desired; So according to method of the present invention, at first carry out the design of the Nomenclature Composition and Structure of Complexes for the performance requriements of material, then according to the design of material scheme, select to be fit to organometallic compound, metal alkoxide, organic monomer or inorganic salt, prepare sol gel process and film-forming process according to the present invention, make nano thin-film; For example, for improving the surface hardness of polycarbonate resin material, in polycarbonate resin surface-coated high hardness nanocomposite film, can give polycarbonate resin surface rub resistance, damage resistant and prevent the over-all propertieies such as dirty.
For the realization of design of material scheme, complex sol system provided by the invention is a kind of flexible system, and for example the solvent of system can be selected water, also can the selective solvent type; Coating processes can be selected as required to infiltrate and lifts, even glue gets rid of film, roll-in is filmed, atomizing spraying or spray; Gel solidification can be selected from the high bake film-forming more than the room temperature to 1000 °, for timber, paper and the base materials such as leather, textiles, can select 45 ° to 80 ° low-temperature curing, for base materials such as various plastics, engineering plastics, can select 80 ° to 120 ° temperature-curable, for metallic aluminium or stainless steel substrate, can select 150 ° to 180 ° solidification value, for glass and cement matrix, can select 550 ° to 600 ° temperature-curable, for ceramic colored drawing, can select 900 ° to 1100 ° temperature baking-curing.
Application example:
Example 1: a kind of antireflective nano thin film technology:
1) butyl (tetra) titanate to 1-2, adds the distilled water hydrolysis of two volumes with the nitre acid for adjusting pH value, preparation titanium colloidal sol with the dehydrated alcohol dilution of two volumes;
2) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, the preparation silicon sol;
3) silicon sol is coated in the glass baseplate surface to infiltrate crystal pulling method, dry 30 minutes, with spraying process titanium colloidal sol is applied again, dry 30 minutes, treat solvent evaporates, through 550 ° of bakings 30 minutes, form the antireflective nano film on the glass baseplate surface;
4) because the specific refractory power of titanium and silicon differs larger, by the control nano particle diameter, can obtain the antireflection film of various effects.
Example 2: a kind of high hardness nanocomposite thin film technology:
1) butyl (tetra) titanate uses the nitre acid for adjusting pH value to 1-2 with the dehydrated alcohol dilution of two volumes;
2) the dissolved in distilled water zirconates of butyl (tetra) titanate two volumes;
3) aqueous solution with zirconium adds the butyl (tetra) titanate diluent, fully stirs, and forms complex sol;
2) complex sol is coated in surface of wooden substrate to infiltrate crystal pulling method, dry 30 minutes, through 100 ° of bakings 30 minutes, form the high hardness nanocomposite film at surface of wooden substrate, the pencil hardness of timber can be risen to more than the 2H from 6B.
Example 3: a kind of preparation of damage resistant nano thin-film:
1) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, the preparation silicon sol;
2) in silicon sol, add a small amount of fluorocarbon resin, form complex sol;
3) complex sol is coated in the ABS resin substrate surface in the atomizing spraying mode, dry 30 minutes, through 100 ° of bakings 30 minutes, form the damage resistant nano thin-film at the ABS resin substrate surface, can be used for making automotive upholstery.
Example 4: a kind of preparation of rub resistance nano thin-film:
1) butyl (tetra) titanate uses the nitre acid for adjusting pH value to 1-2 with the dehydrated alcohol dilution of two volumes;
2) mantoquita of the dissolved in distilled water 2%mol of butyl (tetra) titanate two volumes;
3) aqueous solution with copper adds the butyl (tetra) titanate diluent, fully stirs, and forms complex sol;
2) complex sol is coated in the leather substrate surface to infiltrate crystal pulling method, dry 30 minutes, through 70 ° of bakings 30 minutes, form the rub resistance nano thin-film on the leather substrate surface, can be used for making the high-grade car seat.
Example 5: a kind of weatherability nano thin film technology:
1) tetraethyl silicate is regulated the pH value to 4-5 with the dehydrated alcohol dilution of two volumes with Glacial acetic acid;
2) the lanthanum salt of the long-pending dissolved in distilled water 1%mol of tetraethyl silicate tetraploid;
3) the lanthanum salt brine solution is added the tetraethyl silicate diluent, fully stir, form complex sol;
2) complex sol is coated in acrylic resin base material surface to infiltrate crystal pulling method, dry 30 minutes, through 100 ° of bakings 30 minutes, form the weatherability nano film on acrylic resin base material surface, with the plastic sheeting for farm use life-span significant prolongation of this acrylic resin making more than one times.
Example 6: a kind of preparation of super-hydrophobic, anti-dirty nano thin-film:
1) butyl (tetra) titanate to 1-2, adds the distilled water hydrolysis of two volumes with the nitre acid for adjusting pH value with the dehydrated alcohol dilution of two volumes, and preparation titanium colloidal sol is also controlled sol particle in 200 to 300 nanometers;
2) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, and the preparation silicon sol is also controlled sol particle less than 10 nanometers;
3) titanium colloidal sol is mixed with silicon sol, add the organic fluorine of cumulative volume 0.1%, make complex sol;
4) complex sol is coated to the stainless steel substrate surface with the atomizing spraying method, dry 30 minutes, through 180 ° of bakings, form super-hydrophobic, anti-dirty nano thin-film on the stainless steel substrate surface, contact angle is above 150 °.
Example 7: a kind of color nano thin film technology:
1) tetraethyl silicate is regulated the pH value to 4-5 with the dehydrated alcohol dilution of two volumes with Glacial acetic acid;
2) the long-pending dissolved in distilled water of tetraethyl silicate tetraploid designs zinc salt and the chromic salts of proportioning;
3) inorganic salt solution is added the tetraethyl silicate diluent, fully stir, form complex sol;
2) with complex sol, under the control of computer, be coated in the ceramic base material surface with spraying process, dry 30 minutes, burn till through 1100 °, form the Preen nono film of layout on the ceramic base material surface.
Example 8: a kind of fluorescence nano thin film technology:
1) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, the preparation silicon sol;
2) select in advance vanadic salts to prepare fluorescence nano colloidal sol;
3) fluorescence nano colloidal sol is added silicon sol, fully stir, form complex sol;
2) complex sol is coated in the cement matrix surface with spraying process, dry 30 minutes, through 550 ° of bakings, form on the cement matrix surface through the sustainable nano thin-film of radiofluorescence more than two hours of illumination, can be used for the road traffic cue mark.
Example 9: a kind of quantum dot light emitting thin film technology:
1) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, the preparation silicon sol;
2) select in advance inorganic salt of rare earth to prepare quantum dot;
3) quantum dot is added silicon sol, fully stir, form complex sol;
4) complex sol is coated in transparent polycarbonate resin substrate surface with spraying process, dry 30 minutes, through 80 ° of bakings, form self luminous nano thin-film at the polycarbonate resin substrate surface, can be used for special anti-fake mark.
Example 10: a kind of preparation of inhaling the ripple nano thin-film:
1) butyl (tetra) titanate uses the nitre acid for adjusting pH value to 1-2 with the dehydrated alcohol dilution of two volumes;
2) dissolved in distilled water zirconates and the lead salt of butyl (tetra) titanate two volumes;
3) aqueous solution with inorganic salt adds the butyl (tetra) titanate diluent, fully stirs, and forms complex sol in the time of the Hydrolysis of Titanium acid butyl ester;
2) complex sol is coated in the modification of nylon substrate surface with the atomizing spraying method, dry 30 minutes, through 100 ° of bakings 30 minutes, form suction ripple nano thin-film at the modification of nylon substrate surface, can be used for making the parts of stealthy aircraft.
Example 11: a kind of resistance to chemical attack thin film technology:
1) the dehydrated alcohol dilution of tetraethyl silicate with volume regulated the pH value to 4-5 with Glacial acetic acid, adds the long-pending distilled water hydrolysis of tetraploid, the preparation silicon sol;
2) silicon sol is coated in metallic aluminium base material surface with spraying process, dry 30 minutes, through 150 ° of bakings, form the nano thin-film of resistance to chemical attack on metallic aluminium base material surface, can be used for various soda acid particular surroundingss.
Example 12: a kind of ir radiation heat radiation film:
1) butyl (tetra) titanate uses the nitre acid for adjusting pH value to 1-2 with the dehydrated alcohol dilution of two volumes;
2) the dissolved in distilled water molysite of butyl (tetra) titanate two volumes and manganese salt;
3) aqueous solution with inorganic salt adds the butyl (tetra) titanate diluent, fully stirs, and forms complex sol in the time of the Hydrolysis of Titanium acid butyl ester;
2) complex sol is coated in the fiber base material surface to infiltrate crystal pulling method, dry 30 minutes, through 70 ° of bakings 30 minutes, inhale the ripple nano thin-film in the fiber surface formation of modification cotton base material, can be used for making warming clothes etc.
In sum, according to the various technology and methods that the present invention announces, special requisition is protected related right item.
Claims (3)
1. make inorganic salt for one kind---method of metal alkoxide---organometallic compound---organic monomer complex sol may further comprise the steps:
1) according to reaction formula:
The hydrolysis general formula is R
xM (OR)
Z-xOrganometallic compound, form colloidal sol, R is the organic functional base in the formula, M is selected from silicon, aluminium, titanium, zirconium etc. or their mixture, R ' is hydrolyzable low molecular weight alkyl, z is the valency of M, and x is at least 1 less than z, y is at least 1 and less than z-x;
2) according to reaction formula:
Be hydrolyzed a kind of general formula and be M ' (OR ' ')
Z 'Metal alkoxide, form metal alkoxide colloidal sol, M ' is for forming the metal of hydrolyzable alkoxide in the formula, R ' ' is low molecular weight alkyl, z ' is the valency of M ', y ' is at least 1 and less than z ';
3) inorganic salt are dissolved in water or dehydrated alcohol, form inorganic salt colloidal sol;
4) inorganic salt colloidal sol is mixed with organometallic compound colloidal sol with metal alkoxide colloidal sol, and adding organic monomer and initiator, the organic monomer that is caused by initiator and the polyreaction of inorganic salt, metal alkoxide, organometallic compound, formation inorganic salt---metal alkoxide---organometallic compound---organic monomer complex sol.
2. the organic film forming of complex sol low temperature and the inorganic film of high temperature may further comprise the steps:
1) makes complex sol with preceding method;
2) complex sol is lifted, spares glue by infiltration and get rid of the surface that the methods such as film, pressure roller, spray or atomizing spraying are coated to plastics, timber, textiles, leather, metal, pottery or glasswork;
3) dry 5 minutes to 10 minutes, the solvent in the complex sol is volatilized, the particle of complex sol is able to ordered arrangement;
4) low-temperature bake in 60 degrees centigrade to 120 degrees centigrade scope forms cancellated inorganic---organic compound film; Perhaps
5) make complex sol with preceding method;
6) complex sol is lifted, spares glue by infiltration and get rid of the surface that the methods such as film, pressure roller, spray or atomizing spraying are coated to metal, pottery or glasswork;
7) dry 5 minutes to 10 minutes, the solvent in the complex sol is volatilized, the particle of complex sol is able to ordered arrangement;
8) slowly intensification baking in 200 degrees centigrade to 500 degrees centigrade scopes is progressively burnt the organism in the complex sol;
9) continue to be warmed up to 550 degrees centigrade to 600 degrees centigrade, and be incubated 1 hour to 3 hours, make the inorganics in the complex sol form cancellated laminated film.
3. the implementation method of a design of material may further comprise the steps:
1)---structure---performance is made on the basis of research at the composition to material, makes up the mathematical model of the relation of material property and composition, structure;
2) use above-mentioned model, according to material performance requirement, composition and the structure of design novel material;
3) according to the design of material scheme, the stoichiometry ratio of each component of Calculating material;
4) selection provides the raw material of each component, includes but are not limited to organic molecule (or claiming organic monomer), inorganic salt, organometallic compound and metal alkoxide;
5) prepare complex sol with preceding method;
6) prepare laminated film with preceding method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108504215A (en) * | 2018-03-29 | 2018-09-07 | 河南美罗希森新材料科技有限公司 | Glass infrared resistant ultraviolet light heat-proof coating material and preparation method thereof |
| CN109321050A (en) * | 2018-09-19 | 2019-02-12 | 福耀玻璃工业集团股份有限公司 | A kind of weather-proof masking liquid, weatherability vehicle glass and its manufacturing method |
| CN115948115A (en) * | 2022-12-26 | 2023-04-11 | 慧智科技湖北有限公司 | Glaze-like high-temperature-resistant glass coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108504215A (en) * | 2018-03-29 | 2018-09-07 | 河南美罗希森新材料科技有限公司 | Glass infrared resistant ultraviolet light heat-proof coating material and preparation method thereof |
| CN109321050A (en) * | 2018-09-19 | 2019-02-12 | 福耀玻璃工业集团股份有限公司 | A kind of weather-proof masking liquid, weatherability vehicle glass and its manufacturing method |
| CN109321050B (en) * | 2018-09-19 | 2020-05-19 | 福耀玻璃工业集团股份有限公司 | Weather-resistant coating liquid, weather-resistant automobile glass and manufacturing method thereof |
| CN115948115A (en) * | 2022-12-26 | 2023-04-11 | 慧智科技湖北有限公司 | Glaze-like high-temperature-resistant glass coating and preparation method thereof |
| CN115948115B (en) * | 2022-12-26 | 2024-01-30 | 慧智科技湖北有限公司 | Glaze-like high-temperature-resistant glass paint and preparation method thereof |
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Application publication date: 20130417 |