CN106047154A - Aluminum sol film coating and method for preparing same - Google Patents
Aluminum sol film coating and method for preparing same Download PDFInfo
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- CN106047154A CN106047154A CN201610515835.XA CN201610515835A CN106047154A CN 106047154 A CN106047154 A CN 106047154A CN 201610515835 A CN201610515835 A CN 201610515835A CN 106047154 A CN106047154 A CN 106047154A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0887—Tungsten
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention discloses aluminum sol film coating. The aluminum sol film coating comprises, by weight, 2-3 parts of aluminum isopropoxide, 4-5 parts of ammonium bicarbonate, 1-1.5 parts of vanadyl sulfate hydrate, 6-7 parts of sodium tungstate dihydrate, 20-30 parts of silane coupling agents KH570, 5-7 parts of methyl triethoxysilane, 60-70 parts of 2-3% ammonia aqueous solution, 0.3-0.4 part of aminopropyl triethoxysilane, 0.1-0.3 part of bisphenol A phosphite, 0.2-0.4 part of stannous mono-sulphate, 0.1-0.2 part of ricinoleic acid, 0.5-1 part of benzyltriethylammonium bromide, 0.2-0.3 part of hexafluoroacetylacetone, 0.7-1 part of ammonium molybdate and 0.1-0.2 part of citric acid. The aluminum sol film coating has the advantages that the silane coupling agents KH570 are subjected to modification treatment, molecules of the silane coupling agents KH570 are grafted onto tungsten-doped vanadium dioxide powder particles, accordingly, the hydrophobic property of modified particles can be effectively improved, and the surface strength of films further can be improved.
Description
Technical field
The present invention relates to film coating technical field, particularly relate to a kind of Alumina gel film coating and preparation method thereof.
Background technology
Inorganic nano-particle can play mechanics in coating to be strengthened or gives the effect of coating New function and be subject to extensively
Pay close attention to.The dispersion of nanoparticle is even more important for the realization of its function, special high transparent organic-inorganic hybrid nanocomposite coating
Preparation.
Vanadium dioxide has huge application prospect in terms of intelligence heat-insulating and energy-saving coating, but due to its preparation method and work
The restriction of skill, and the strong absorption that vanadium dioxide metal phase and quasiconductor are in short wave ranges, vanadium dioxide film is usual
There is relatively low optical clear, significantly limit its actual application.Therefore, the anti-reflection of vanadium dioxide film is increasingly becoming research
One of focus.
Due to the peculiar property of inorganic nano-particle, it is frequently used to join organic as enhancing phase or functional stuffing
In coating, improve coating tradition performance, give coating specific function characteristic.The nanoparticle being presently used for coating mainly has gold
Belong to oxide (such as TiCh, Si02, Sn02, ZnO etc.), nano metal powder (such as nanometer A1, Co, Ti, Cr, Nd, Mo etc.) and
Nano metal salt (such as CaCO), BaS04) etc..The function of inorganic particulate in hybrid coating to be given full play to, needs the uniform of particle
Fine dispersion, the when that particularly the transparency to composite coating having higher requirements;
, due to its manufacturing process, usually there is reunion stronger between particle in commercially available inorganic particle, is difficult to directly application
In preparing composite coating.In organic coating field, usually the various physics of integrated application and chemical dispersion techniques, enter nano-powder
Row is modified and dispersion, and carries out compound preparing nanocomposite coating with organic resin.Very difficult preparation is provided simultaneously with the visible transparency
The composite membrane strong with infrared barrier;
Vanadium dioxide has thermochromic function, reduces phase transition temperature by doping and makes it possess the potentiality of actual application.To the greatest extent
Pipe it has been reported the preparation method of a lot of vanadium dioxide and doped vanadium dioxide powder and thin film at present, but actual apart from it
Application, still has a segment distance.First, conventional the preparation technology such as apparatus expensive such as magnetron sputtering, vapour deposition, cost is high, relatively
Difficulty realizes large area and covers with paint, lacquer, colour wash, etc.;Secondly, traditional preparation method is due to the limitation of itself, the vanadium dioxide of preparation or dioxy
The visible region transparency changing vanadium (W) thin film is poor, does not substantially have the possibility of actual application.Although having done much at anti-reflection aspect
Attempt, such as doping, coat anti-reflection film, but the raising of the transparency still ratio is relatively limited;Again, the report that oneself has at present is substantially
Concentrate on vanadium dioxide or the preparation of vanadium dioxide (W) pure film, and seldom dabble organic coating route to prepare vanadium dioxide heat
Cause discoloration coating.4th, the research about hypovanadic oxide powder or the stability of thin film (including composite membrane) is reported very at present
Few.Therefore, preparation has the vanadium dioxide film of the relatively high visible district transparency or compound with vanadium dioxide as functional stuffing
Film, and investigate its stability, there is important practical significance;
On the other hand, the dispersion of nanoparticle and stabilization technique are more used for the preparation of organic-inorganic nanocomposite materials the sixth of the twelve Earthly Branches,
Disperse uniformly reaching it, fully realize its function as implant.Common step is to first pass through physical chemistry dispersion
Technology prepares the nano dispersion fluid of inorganic particulate, then dispersion liquid and organic resin is being combined.In organic coating field, first
Step often utilizes the scattered method of ball milling (having under dispersant existence condition) that inorganic particle particle is carried out de-agglomerated.At said process
In the middle of, the compatibility between the compatibility and nanoparticle and organic resin between nanoparticle and disperse medium may be produced
Raw contradiction, if the organic molecule of grafting and resin compatible are the best, during resin solidification is dried, it is possible that receive
Being separated between rice corpuscles and organic facies, causes the decline of the nano-composite coating transparency.Therefore, the purpose of the present invention is exactly
Prepare the nanoparticle that dispersibility is higher, join in organic coating, play the effect of enhancing.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of Alumina gel film coating and preparation side thereof
Method.
The present invention is achieved by the following technical solutions:
A kind of Alumina gel film coating, it is made up of the raw material of following weight parts:
Aluminum isopropylate. 2-3, ammonium hydrogen carbonate 4-5, hydrated sulfuric acid vanadyl 1-1.5, Disodium tungstate (Na2WO4) dihydrate 6-7, silane coupler
KH57020-30, the ammonia spirit 60-70 of MTES 5-7,2-3%, aminopropyl triethoxysilane 0.3-0.4,
Phosphorous acid bisphenol-A ester 0.1-0.3, stannous sulfate 0.2-0.4, ricinoleic acid 0.1-0.2, benzyl triethyl ammonium bromide 0.5-1, hexafluoro
Acetylacetone,2,4-pentanedione 0.2-0.3, ammonium molybdate 0.7-1, citric acid 0.1-0.2.
The preparation method of a kind of described Alumina gel film coating, comprises the following steps:
(1) above-mentioned ammonium hydrogen carbonate is joined in the deionized water of its weight 20-34 times, stir, add two tungstic acid hydrate
Sodium, magnetic force disperses 2-3 minute, obtains dispersion liquid;
(2) take above-mentioned hydrated sulfuric acid vanadyl, join in the deionized water of its weight 10-14 times, drip above-mentioned under stirring condition
Dispersion liquid, magnetic agitation 40-50 minute after dropping, filters, precipitate with deionized water and dehydrated alcohol is washed 2-3 successively
Secondary, it is vacuum dried 100-120 minute at 40-50 DEG C, sends in heating furnace, in a nitrogen atmosphere with the liter of 10-12 DEG C/min
Temperature speed liter high-temperature is to 800-860 DEG C, and Heat preservation 2.7-3 hour, discharging cools down, must mix tungsten hypovanadic oxide powder;
(3) above-mentioned aluminum isopropylate. is joined in its weight 14-20 times, 60-65% ethanol solution, stir, in addition
State citric acid, rise high-temperature and be 60-70 DEG C, insulated and stirred 20-30 minute, add above-mentioned benzyl triethyl ammonium bromide, stirring is all
Even, obtain Alumina gel;
(4) joining in Alumina gel by above-mentioned tungsten hypovanadic oxide powder of mixing, 100-200 rev/min is stirred 10-13 minute, rises high temperature
Degree is 80-90 DEG C, and insulated and stirred 30-40 minute adds above-mentioned ammonium molybdate, stirs, and filters, by precipitation washing 2-3 time, often
Temperature is dried, and obtains Alumina gel modification and mixes tungsten hypovanadic oxide powder;
(5) take the 70-80% of above-mentioned silane coupler KH570 weight, join in the butyl acetate of its weight 40-50 times, stirring
Uniformly, add above-mentioned Alumina gel modification and mix tungsten hypovanadic oxide powder, stannous sulfate, ultrasonic 18-20 minute, ball milling 6-8 hour, take out
Filter, washs filter cake 2-3 time with normal octane, is vacuum dried 100-120 minute at 40-45 DEG C, and cooling joins its weight 6-8
In butyl acetate again, stir, obtain nano dispersion fluid;
(6) take the ammonia spirit of above-mentioned 2-3%, mix with the dehydrated alcohol of its weight 1-1.2 times, stir;
(7) by remaining silane coupler KH570, MTES mixing, magnetic agitation 3-5 minute, drip above-mentioned
Ammonia, the mixed liquor of ethanol, insulated and stirred 4-4.5 hour at 86-90 DEG C, add above-mentioned hexafluoroacetylacetone, stir,
Obtain siloxane prepolymer;
(8) above-mentioned nano dispersion fluid is joined in siloxane prepolymer, ultrasonic 17-20 minute, add and remain each raw material, stirring
Uniformly, to obtain final product.
The invention have the advantage that using method:
By coating bar film on diaphragm of the present invention, cold curing is dried 7-8 days,.
The present invention, with hydrated sulfuric acid vanadyl and ammonium hydrogen carbonate as raw material, prepares presoma, calcining by solution reaction, it is thus achieved that
Vanadium dioxide and mix the hypovanadic oxide powder of W, by vanadium dioxide (W) powder body ball milling modification, centrifugal preparation nano-dispersed
Liquid, joins in polysiloxane prepolymers, with aminopropyl triethoxysilane as firming agent, be prepared under room temperature polysiloxanes/
Vanadium dioxide (W) nanocomposite coating, the phase transition temperature of this nanocomposite coating is close to room temperature, and hardness is high, and the transparency is good, the reddest
External modulation ability is preferable, is highly suitable for the preparation of in-service film surface intelligence heat insulating coat;
The hypovanadic oxide powder of prepared by the present invention mix tungsten has the near-infrared that reversible metal-semiconductor phase-change characteristic causes and intercepts
Performance, and the doping of tungsten can reduce the phase transition temperature of vanadium dioxide, improves the heat phase transition performance processed of film, then passes through
Butyl acetate disperses efficiently so that its film formed has the good transparency, and the present invention uses silane coupler
KH570 modification, is grafted to mix on tungsten hypovanadic oxide powder granule by silane coupler KH570 molecule, effectively raises
The hydrophobicity of modified particle, simultaneously because the hypovanadic oxide powder mixing tungsten has good mechanical property and this particle and poly-silicon
The crosslinked action of oxygen alkane, also further increases the surface strength of film.The present invention uses Alumina gel to process, and effectively raises
Nanoparticle dispersibility in coating, improves the stability of finished product coating surface.
Detailed description of the invention
A kind of Alumina gel film coating, it is made up of the raw material of following weight parts:
Aluminum isopropylate. 2, ammonium hydrogen carbonate 4, hydrated sulfuric acid vanadyl 1, Disodium tungstate (Na2WO4) dihydrate 6, silane coupler KH57020, methyl three
The ammonia spirit 60 of Ethoxysilane 5,2%, aminopropyl triethoxysilane 0.3, phosphorous acid bisphenol-A ester 0.1, stannous sulfate
0.2, ricinoleic acid 0.1, benzyl triethyl ammonium bromide 0.5, hexafluoroacetylacetone 0.2, ammonium molybdate 0.7, citric acid 0.1.
The preparation method of a kind of described Alumina gel film coating, comprises the following steps:
(1) above-mentioned ammonium hydrogen carbonate is joined in the deionized water of its weight 20 times, stirs, add Disodium tungstate (Na2WO4) dihydrate,
Magnetic force disperses 2 minutes, obtains dispersion liquid;
(2) take above-mentioned hydrated sulfuric acid vanadyl, join in the deionized water of its weight 10 times, under stirring condition, drip above-mentioned dispersion
Liquid, magnetic agitation 40 minutes after dropping, filter, precipitate with deionized water and dehydrated alcohol are washed 2 times successively, at 40 DEG C
Lower vacuum drying 100 minutes, sends in heating furnace, rises high-temperature to 800 with the programming rate of 10 DEG C/min in a nitrogen atmosphere
DEG C, Heat preservation 2.7 hours, discharging cools down, must mix tungsten hypovanadic oxide powder;
(3) above-mentioned aluminum isopropylate. is joined in its weight 14 times, the ethanol solution of 60%, stir, add above-mentioned Fructus Citri Limoniae
Acid, rising high-temperature is 60 DEG C, and insulated and stirred 20 minutes adds above-mentioned benzyl triethyl ammonium bromide, stirs, obtains Alumina gel;
(4) joining in Alumina gel by above-mentioned tungsten hypovanadic oxide powder of mixing, 100 revs/min are stirred 10 minutes, and rising high-temperature is 80
DEG C, insulated and stirred 30 minutes, add above-mentioned ammonium molybdate, stir, filter, precipitation is washed 2 times, normal temperature drying, obtain aluminum molten
Tungsten hypovanadic oxide powder is mixed in glue modification;
(5) take the 70% of above-mentioned silane coupler KH570 weight, join in the butyl acetate of its weight 40 times, stir,
Adding above-mentioned Alumina gel modification and mix tungsten hypovanadic oxide powder, stannous sulfate, ultrasonic 18 minutes, ball milling 6 hours, sucking filtration, with the most pungent
Alkane washing filter cake 2 times, is vacuum dried 100 minutes at 40 DEG C, cooling, joins in the butyl acetate of its weight 6 times, and stirring is all
Even, obtain nano dispersion fluid;
(6) take the ammonia spirit of above-mentioned 2%, mix with the dehydrated alcohol of its weight 1 times, stir;
(7) by remaining silane coupler KH570, MTES mixing, magnetic agitation 3 minutes, above-mentioned ammonia is dripped
Water, the mixed liquor of ethanol, insulated and stirred 4 hours at 86 DEG C, add above-mentioned hexafluoroacetylacetone, stir, obtain siloxanes
Prepolymer;
(8) joining in siloxane prepolymer by above-mentioned nano dispersion fluid, ultrasonic 17 minutes, add and remain each raw material, stirring is all
Even, to obtain final product.
The transparency: the transmitance at 550 nm still reaches more than 60%;
Mechanical property: hardness >=900MPa;
Heat phase transition performance processed: 2500nm infrared modulated amplitude: 23.2%.
Claims (2)
1. an Alumina gel film coating, it is characterised in that it is made up of the raw material of following weight parts:
Aluminum isopropylate. 2-3, ammonium hydrogen carbonate 4-5, hydrated sulfuric acid vanadyl 1-1.5, Disodium tungstate (Na2WO4) dihydrate 6-7, silane coupler
KH57020-30, the ammonia spirit 60-70 of MTES 5-7,2-3%, aminopropyl triethoxysilane 0.3-0.4,
Phosphorous acid bisphenol-A ester 0.1-0.3, stannous sulfate 0.2-0.4, ricinoleic acid 0.1-0.2, benzyl triethyl ammonium bromide 0.5-1, hexafluoro
Acetylacetone,2,4-pentanedione 0.2-0.3, ammonium molybdate 0.7-1, citric acid 0.1-0.2.
2. the preparation method of an Alumina gel film coating as claimed in claim 1, it is characterised in that comprise the following steps:
(1) above-mentioned ammonium hydrogen carbonate is joined in the deionized water of its weight 20-34 times, stir, add two tungstic acid hydrate
Sodium, magnetic force disperses 2-3 minute, obtains dispersion liquid;
(2) take above-mentioned hydrated sulfuric acid vanadyl, join in the deionized water of its weight 10-14 times, drip above-mentioned under stirring condition
Dispersion liquid, magnetic agitation 40-50 minute after dropping, filters, precipitate with deionized water and dehydrated alcohol is washed 2-3 successively
Secondary, it is vacuum dried 100-120 minute at 40-50 DEG C, sends in heating furnace, in a nitrogen atmosphere with the liter of 10-12 DEG C/min
Temperature speed liter high-temperature is to 800-860 DEG C, and Heat preservation 2.7-3 hour, discharging cools down, must mix tungsten hypovanadic oxide powder;
(3) above-mentioned aluminum isopropylate. is joined in its weight 14-20 times, 60-65% ethanol solution, stir, in addition
State citric acid, rise high-temperature and be 60-70 DEG C, insulated and stirred 20-30 minute, add above-mentioned benzyl triethyl ammonium bromide, stirring is all
Even, obtain Alumina gel;
(4) joining in Alumina gel by above-mentioned tungsten hypovanadic oxide powder of mixing, 100-200 rev/min is stirred 10-13 minute, rises high temperature
Degree is 80-90 DEG C, and insulated and stirred 30-40 minute adds above-mentioned ammonium molybdate, stirs, and filters, by precipitation washing 2-3 time, often
Temperature is dried, and obtains Alumina gel modification and mixes tungsten hypovanadic oxide powder;
(5) take the 70-80% of above-mentioned silane coupler KH570 weight, join in the butyl acetate of its weight 40-50 times, stirring
Uniformly, add above-mentioned Alumina gel modification and mix tungsten hypovanadic oxide powder, stannous sulfate, ultrasonic 18-20 minute, ball milling 6-8 hour, take out
Filter, washs filter cake 2-3 time with normal octane, is vacuum dried 100-120 minute at 40-45 DEG C, and cooling joins its weight 6-8
In butyl acetate again, stir, obtain nano dispersion fluid;
(6) take the ammonia spirit of above-mentioned 2-3%, mix with the dehydrated alcohol of its weight 1-1.2 times, stir;
(7) by remaining silane coupler KH570, MTES mixing, magnetic agitation 3-5 minute, drip above-mentioned
Ammonia, the mixed liquor of ethanol, insulated and stirred 4-4.5 hour at 86-90 DEG C, add above-mentioned hexafluoroacetylacetone, stir,
Obtain siloxane prepolymer;
(8) above-mentioned nano dispersion fluid is joined in siloxane prepolymer, ultrasonic 17-20 minute, add and remain each raw material, stirring
Uniformly, to obtain final product.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106566353A (en) * | 2016-11-08 | 2017-04-19 | 芜湖市鸿坤汽车零部件有限公司 | Aluminum sol modified antibacterial leather coating and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101265374A (en) * | 2008-01-24 | 2008-09-17 | 复旦大学 | Intelligent heat-insulating film and its preparing process |
CN103073942A (en) * | 2012-01-19 | 2013-05-01 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide composite powder and preparation method thereof |
CN103897437A (en) * | 2012-12-30 | 2014-07-02 | 比亚迪股份有限公司 | Titanium dioxide enveloping method, titanium dioxide with envelop, and coating |
-
2016
- 2016-07-04 CN CN201610515835.XA patent/CN106047154A/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101265374A (en) * | 2008-01-24 | 2008-09-17 | 复旦大学 | Intelligent heat-insulating film and its preparing process |
CN103073942A (en) * | 2012-01-19 | 2013-05-01 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide composite powder and preparation method thereof |
CN103897437A (en) * | 2012-12-30 | 2014-07-02 | 比亚迪股份有限公司 | Titanium dioxide enveloping method, titanium dioxide with envelop, and coating |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106566353A (en) * | 2016-11-08 | 2017-04-19 | 芜湖市鸿坤汽车零部件有限公司 | Aluminum sol modified antibacterial leather coating and preparation method thereof |
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Application publication date: 20161026 |