CN103274446A - Nano copper sulphide/barium sulphide-containing isolated membrane and preparation method thereof - Google Patents
Nano copper sulphide/barium sulphide-containing isolated membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano copper sulphide/barium sulphide-containing isolated membrane and a preparation method thereof. A base stock of the isolated membrane is an m(CH3SiO3/2)-n(TiO2)-based organic-inorganic isolated composite material formed by hydrolyzing and polymerizing organic modified silicon alkoxide methyl triethoxysilane(MTES) and butyl titanate through a sol-gel technology, and the nano powder for near-infrared absorption has a copper pyrite structure BaCu2S2. The powder is prepared through an ultrasonic atomization method. A copper sulphide/barium sulphide mixed solution and a sodium sulphide solution are subjected to a contact reaction to generate the BaCu2S2. The powder is treated by powder treatments, such as wet grinding and dry grinding, then dispersed in a cetyl methyl ammonium bromide solution and further compounded with the MTES/butyl titanate, and then, the compound material is coated on the surface of a clean terylene substrate membrane, thus, the nano BaCu2S2 unbraced thick membrane is prepared. The preparation method is simple in process, low in cost, convenient to operate and high in synthetic efficiency, and the refractive index of the prepared thin membrane material is high, thus, the preparation method can be expected to be used for infrared absorption materials for solar heat shielding and the infrared absorption materials in special fields.
Description
Technical field
The present invention relates to the sun power lagging material, be specifically related to contain isolated film and the preparation method of nano-copper sulfide barium.
Background technology
The sun power lagging material mainly contains heat-reflecting glass and low emissivity glass, and it has isolates near infrared light effectively, has high visible light transmissive performance simultaneously.Heat-reflecting glass is to form metal or metal oxide film at glass surface, and its height reflection to the near infrared sunlight reaches heat insulation purpose, but the height reflection of visible light is easily caused light pollution.Low emissivity glass is at glass surface dielectric layer deposition, blocking layer and nano metal layer etc., mid and far infrared line by the radiation of the anti-indoor hot object of height institute reaches heat insulation effect, being the application for a patent for invention of CN102092960 as publication number, then is medium layer-blocking layer-silver layer-transition layer-blocking layer-medium layer-glass; The expensive main equipment of multilayer deposition, manufacturing process complexity, manufacturing cost height.Notification number is the patent of invention of CN100588737C, then disclosing with cupric sulfide aluminium is target, with silicon chip or glass be substrate, pass through pulsed laser deposition, obtain the transparent film of cupric sulphur, but cupric sulfide aluminium be by copper, aluminium, sulphur simple substance or cupric sulfide, aluminium with solid state reaction after sintering obtain, react inhomogeneous, it is substrate that cupric sulfide aluminium needs silicon chip or glass again, can not independent film forming.
Summary of the invention
Technical problem to be solved by this invention provides a kind of stable performance, has the isolated film that contains nano-copper sulfide barium of strong near infrared absorption characteristic;
The invention also discloses the preparation method of the isolated film that contains nano-copper sulfide barium, it is simple that this preparation method has equipment, the advantage that production cost is lower, easy to operate, combined coefficient is high.
The present invention solves the problems of the technologies described above the technical scheme that adopts: contain the isolated film of nano-copper sulfide barium, this infrared absorption major ingredient that contains the isolated film of nano-copper sulfide barium is the nano-copper sulfide barium (BaCu that granularity is not more than 100 nanometers
2S
2), this isolated film base material that contains nano-copper sulfide barium is the m (CH that Union carbide A-162 (MTES) and butyl (tetra) titanate form after hydrolysis and polymerization
3SiO
3/2)-n (TiO
2) (m, n is molar content) base organic-inorganic composite material, described nano-copper sulfide barium is scattered in n-Hexadecane methyl bromination ammonium solution earlier, form nano-copper sulfide barium viscous fluid with the polyvinyl alcohol viscous fluid again, described nano-copper sulfide barium viscous fluid mixes with the organic and inorganic gel, evenly be coated on the dacron membrane substrate, dry, separation obtains.
The preparation method who contains the isolated film of nano-copper sulfide barium, its step is as follows:
A, all be 0.1 mol with cupric nitrate and nitrate of baryta concentration, the pH value is that cupric nitrate/nitrate of baryta mixed solution of 6～8 is packed in the automiser spray of ultrasonic atomizing device, be 0.2 mol with concentration, the pH value is that 6～8 sodium sulfide solution is packed in the reaction container of ultrasonic atomizing device, the volume ratio of described cupric nitrate/nitrate of baryta mixed solution and described sodium sulfide solution is 1: 1, the surface-area of sodium sulfide solution is greater than 15 square centimeters in the described reaction container, be 20W at ultrasonic power, frequency is 50KHz, flow rate of liquid is under 100 milliliters/hour in the ullrasonic spraying head, described cupric nitrate/nitrate of baryta mixing solutions spraying is atomized to described sodium sulfide solution, be to stir contact reacts under 50 rev/mins in stir speed (S.S.), reaction finished still aging 8 hours, obtained reaction soln; Spray atomization method copper, barium and reaction of Salmon-Saxl are more abundant, and reaction efficiency is higher, and the bigger reaction of the liquid surface area of reaction container is very fast, react more abundant;
B, reaction soln is filtered, obtain solid materials, the washed with de-ionized water solid materials of 3 times of volumes of first usefulness solid materials 3 minutes, raw spirit with 4 times of volumes of solid materials cleaned solid materials 3 minutes again, solid materials after cleaning is put into baking oven, drying is 5 hours under drying temperature is 80 ℃, obtains dried material;
C, in every gram dried material, add 20 milliliters of raw spirits, with Ceramic Balls wet-milling 2h, solid-liquid separation after the wet-milling, solid is put into baking oven, drying is 5 hours under drying temperature is 90 ℃, and drying finishes, and material is used the zirconia ball dry grinding 2h of Φ 25mm earlier, with the zirconia ball dry grinding 1h of Φ 5mm, obtain the nano-copper sulfide barium powder that granularity is not more than 100 nanometers again;
D, in 1: 2 the ratio of mass ratio of nano-copper sulfide barium powder and n-Hexadecane methyl brometo de amonio, nano-copper sulfide barium powder is poured in the n-Hexadecane methyl bromination ammonium solution of mass percentage concentration 30%, stir, again in 1: 10 the ratio of mass ratio of nano-copper sulfide barium powder and polyvinyl alcohol, the polyvinyl alcohol viscous fluid that adds mass percentage concentration 30%, stirred 7 hours under 90 ℃ of temperature, it is stand-by to obtain nano-copper sulfide barium viscous fluid;
E, 1: 1.5 in molar ratio ratio, butyl (tetra) titanate and ethanol are mixed, be 1: 1 ratio in butyl (tetra) titanate and Glacial acetic acid-methyl ethyl diketone aluminum chelating agent mol ratio then, add Glacial acetic acid-methyl ethyl diketone aluminum chelating agent that Glacial acetic acid and methyl ethyl diketone al mole ratio are preparation in 1: 1, under the magnetic agitation, be 1: 0.5 ratio in the mol ratio of butyl (tetra) titanate and hydrochloric acid, dropwise added the dilute hydrochloric acid hydrolysis reaction 4 hours, obtain the butyl (tetra) titanate hydrolyzed solution; In silicon alkoxide Union carbide A-162, ethanol and 1: 1.5: 0.5 ratio of hydrochloric acid mol ratio, silicon alkoxide Union carbide A-162, ethanol and dilute hydrochloric acid are mixed, under the magnetic agitation, it is 1: 0.5 ratio in the mol ratio of silicon alkoxide Union carbide A-162 and hydrochloric acid, dropwise added the dilute hydrochloric acid hydrolysis reaction 48 hours, be 1: 0.25 ratio again in the mol ratio of silicon alkoxide Union carbide A-162 and hydrochloric acid, dropwise add the dilute hydrochloric acid hydrolysis reaction 4 hours, and obtained silicon alkoxide Union carbide A-162 hydrolyzed solution; Press butyl (tetra) titanate and silicon alkoxide Union carbide A-162 mol ratio 1: 4～19, the butyl (tetra) titanate hydrolyzed solution is mixed with silicon alkoxide Union carbide A-162 hydrolyzed solution, stir reaction down 0.5 hour, the reaction knot finishes, be put in the baking oven, drying is 48 hours under 60 ℃, obtains m (CH
3SiO
3/2)-n (TiO
2) gel, the concentration of above-mentioned dilute hydrochloric acid is 0.04 mol;
F, press nano-copper sulfide barium dust and m (CH
3SiO
3/2)-n (TiO
2) mass ratio of gel is 1: 20 ratio, with above-mentioned nano-copper sulfide barium viscous fluid and m (CH
3SiO
3/2)-n (TiO
2) the gel mixing, under 50 ℃ of temperature, stirred 2 hours, evenly be coated on the dacron membrane substrate then, coating finishes and puts into baking oven, drying is 4～7 hours under 70～100 ℃, obtains the cured film that dacron membrane supports, and slowly uncovers cured film, cured film is placed the middle extruding of cylinder of two slow rotation, obtain containing the isolated film of nano-copper sulfide barium, the surface of described cylinder is coated with one deck silicone, and the surface temperature of described cylinder is 80～90 ℃.
Compared with prior art, the invention has the advantages that the isolated film and the preparation method that contain nano-copper sulfide barium, this infrared absorption major ingredient that contains the isolated film of nano-copper sulfide barium is the nano-copper sulfide barium that granularity is not more than 100 nanometers, and this isolated film base material that contains nano-copper sulfide barium is m (CH
3SiO
3/2)-n (TiO
2) gel, nano-copper sulfide barium is scattered in n-Hexadecane methyl bromination ammonium solution earlier, forms nano-copper sulfide barium viscous fluid, nano-copper sulfide barium viscous fluid and m (CH with the polyvinyl alcohol viscous fluid again
3SiO
3/2)-n (TiO
2) the gel mixing, evenly being coated on the dacron membrane substrate, dry, separation obtains; CH
3SiO
3/2-TiO
2Base material is owing to there is TiO
2Can increase substantially the specific refractory power of film, to the strong BaCu that absorbs of near infrared ray
2S
2Nano-powder is combined in the cured film, BaCu
2S
2Nano-particles filled plays the dual function that absorbs infrared rays and improve the mechanical property of materials in the gap of base material; This base material combines organic and characteristic inorganic materials, characteristics with excellent combination properties such as machinery, chemistry, thermally-stabilised, anti-photoirradiations, therefore should isolated film be a kind of stable performance, exotic materials with strong near infrared absorption characteristic, in military and solar device, be expected to be applied.Preparation method of the present invention is that to have equipment simple, the advantage that production cost is lower, easy to operate, combined coefficient is high.
Description of drawings
Fig. 1 is the XRD figure spectrum of nano-copper sulfide barium dust;
Fig. 2 is the stereoscan photograph of nano-copper sulfide barium dust;
Fig. 3 be the nano-copper sulfide barium dust see through spectrum.
Embodiment
Describe in further detail below in conjunction with the present invention of accompanying drawing embodiment.
Cupric nitrate and nitrate of baryta be dissolved in deionized water is made into cupric nitrate and nitrate of baryta concentration all is 0.10 mol cupric nitrate/nitrate of baryta mixed solution, sodium sulphite is made into concentration 0.20 mol sodium sulfide solution, and the pH value of regulating cupric nitrate/nitrate of baryta mixed solution and sodium sulfide solution with dilute hydrochloric acid or ammoniacal liquor is 6～8 stand-by; 2 liters of cupric nitrates/nitrate of baryta mixed solution is packed in the automiser spray of ultrasonic atomizing device, 2 liters of sodium sulfide solutions are packed in the reaction container of ultrasonic atomizing device, the surface-area of sodium sulfide solution is 30 square centimeters and (can be 18 square centimeters in the reaction container, 50 square centimeters etc.), be 20W at ultrasonic power, frequency is 50KHz, flow rate of liquid is under 100 milliliters/hour in the ullrasonic spraying head, cupric nitrate/nitrate of baryta mixing solutions is atomized to sodium sulfide solution, be to stir contact reacts under 50 rev/mins in stir speed (S.S.), reaction finished still aging 8 hours, obtained reaction soln; Reaction soln is filtered, obtain solid materials, the washed with de-ionized water solid materials of 3 times of volumes of first usefulness solid materials 3 minutes, raw spirit with 4 times of volumes of solid materials cleaned solid materials 3 minutes again, solid materials after cleaning is put into baking oven, drying is 85 hours under drying temperature is 80 ℃, obtains dried material; Take out dried material, in every gram dried material, add 20 milliliters of raw spirits, with Ceramic Balls wet-milling 2h, solid-liquid separation after the wet-milling, solid is put into baking oven, drying is 5 hours under drying temperature is 90 ℃, drying finishes, and material is used the zirconia ball dry grinding 1h of Φ 5mm more earlier with the zirconia ball dry grinding 2h of Φ 25mm, cross how many mesh sieves, obtain the nano-copper sulfide barium powder that granularity is not more than 100 nanometers; Through X-ray powder diffraction experiment, obtain nano-copper sulfide barium powder XRD figure spectrum as shown in Figure 1, scanning electron microscope analysis obtains as shown in Figure 2 granularity at the following crystal phase structure of 100nm; N-Hexadecane methyl brometo de amonio is dissolved in 50 ℃ the water, the n-Hexadecane methyl bromination ammonium solution that is made into mass percentage concentration 30% is stand-by, polyvinyl alcohol is dissolved in 90 ℃ the water, stirred 3 hours, the water white polyvinyl alcohol viscous fluid that is made into mass percentage concentration 30% is stand-by; 1: 2 ratio of mass ratio in nano-copper sulfide barium powder and n-Hexadecane methyl brometo de amonio, nano-copper sulfide barium powder is poured in the above-mentioned n-Hexadecane methyl bromination ammonium solution, stir, again in 1: 10 the ratio of mass ratio of nano-copper sulfide barium powder and polyvinyl alcohol, add above-mentioned polyvinyl alcohol viscous fluid, stirred 7 hours under 90 ℃ of temperature, it is stand-by to obtain nano-copper sulfide barium viscous fluid; 1: 1.5 in molar ratio ratio, butyl (tetra) titanate and ethanol are mixed, be 1: 1 ratio in butyl (tetra) titanate and Glacial acetic acid-methyl ethyl diketone aluminum chelating agent mol ratio then, add Glacial acetic acid-methyl ethyl diketone aluminum chelating agent that Glacial acetic acid and methyl ethyl diketone al mole ratio are preparation in 1: 1, under the magnetic agitation, be 1: 0.5 ratio in the mol ratio of butyl (tetra) titanate and hydrochloric acid, dropwise add concentration and be the dilute hydrochloric acid hydrolysis reaction 4 hours of 0.04 mol, obtain the butyl (tetra) titanate hydrolyzed solution; In silicon alkoxide Union carbide A-162, ethanol (MTES) and 1: 1.5: 0.5 ratio of hydrochloric acid mol ratio, MTES, ethanol and dilute hydrochloric acid are mixed, under the magnetic agitation, it is 1: 0.5 ratio in the mol ratio of MTES and hydrochloric acid, dropwise add concentration and be the dilute hydrochloric acid hydrolysis reaction 48 hours of 0.04 mol, be 1: 0.25 ratio again in the mol ratio of MTES and hydrochloric acid, dropwise add concentration and be the dilute hydrochloric acid hydrolysis reaction 4 hours of 0.04 mol, obtain the MTES hydrolyzed solution; Pressed butyl (tetra) titanate and MTES mol ratio 1: 12, the butyl (tetra) titanate hydrolyzed solution is mixed with the MTES hydrolyzed solution, reaction is 0.5 hour under the stirring, and the reaction knot finishes, and is put in the baking oven, and drying is 48 hours under 60 ℃, obtains m (CH
3SiO
3/2)-n (TiO
2) gel; Press nano-copper sulfide barium dust and m (CH
3SiO
3/2)-n (TiO
2) mass ratio of gel is 1: 20 ratio, with nano-copper sulfide barium viscous fluid and m (CH
3SiO
3/2)-n (TiO
2) the gel mixing, under 50 ℃ of temperature, stirred 2 hours, evenly be coated on the dacron membrane substrate then, coating finishes and puts into baking oven, drying is 4～7 hours under 70～100 ℃, obtain the cured film that dacron membrane supports, slowly uncover cured film, in the sepn process of cured film and dacron membrane substrate, prevent the fracture of cured film as far as possible, place two slow rotation surfaces to be coated with one deck silicone cured film, surface temperature is the middle extruding of 80～90 ℃ cylinder, obtains containing the isolated film of nano-copper sulfide barium, need by producing, the spacing of two cylinders can be regulated at 50～1000 μ m.Should isolated film be 60～70% to the visible light transmissivity of 400nm-1300nm, to the infrared light rejection rate of 1400nm-2500nm be more than 90% as shown in Figure 3 see through spectrum.
Embodiment 2
Substantially the same manner as Example 1, difference was pressed butyl (tetra) titanate and silicon alkoxide Union carbide A-162 mol ratio 1: 4, and the butyl (tetra) titanate hydrolyzed solution is mixed with silicon alkoxide Union carbide A-162 hydrolyzed solution.
Embodiment 3
Substantially the same manner as Example 1, difference was just pressed butyl (tetra) titanate and silicon alkoxide Union carbide A-162 mol ratio 1: 19, and the butyl (tetra) titanate hydrolyzed solution is mixed with silicon alkoxide Union carbide A-162 hydrolyzed solution.
Claims (3)
1. the isolated film and the preparation method that contain nano-copper sulfide barium, wherein the molecular formula of nano-copper sulfide barium powder is BaCu
2S
2Its crystal phase structure is stable yellow copper structure, and this nano-copper sulfide barium powder has strong near-infrared absorbing characteristic.
2. the matrix of isolated film is organically-modified silicon alkoxide Union carbide A-162 (MTES) with butyl (tetra) titanate (Tetrabutyl orthotitanate) as precursor, the CH that forms after hydrolysis and polymerization
3SiO
3/2-TiO
2The base compound organic-inorganic materials.
3. the present invention solves the problems of the technologies described above the technical scheme that adopts and is: contain isolated film and the preparation method of nano-copper sulfide barium, its step is as follows:
1), dacron membrane put into the Ultrasonic Cleaners that contains deionized water/dehydrated alcohol mixed solution clean, fully remove grease and the dirt on surface, and be put in the baking oven dryly, it is stand-by to obtain clean dacron membrane;
2), with cupric nitrate (Cu (NO
3)
2) and nitrate of baryta (Ba (NO
3)
2) be dissolved in deionized water respectively and be made into cupric nitrate and the nitrate of baryta solution that concentration is 0.1 mol, stand-by 6～8 with the pH value of dilute hydrochloric acid or ammoniacal liquor regulator solution; Simultaneously with sodium sulphite (Na
2S) be dissolved in deionized water and be made into the sodium sulfide solution that concentration is 0.2 mol, stand-by 6～8 with the pH value of dilute hydrochloric acid or ammoniacal liquor regulator solution;
3), with Cu (NO
3)
2With Ba (NO
3)
2Mixing solutions is packed in the automiser spray of ultrasonic atomizing device, the ion ratio of Cu and Ba is 1, sodium sulfide solution is packed in the reaction container of ultrasonic atomizing device, the volume ratio of cupric nitrate/nitrate of baryta solution and sodium sulfide solution is 1: 1 (total Cu adds that Ba ion and the ratio of S ion are 1: 2), be 20W at ultrasonic power, frequency is 50KHz, flow rate of liquid is under 100 milliliters/hour in the ullrasonic spraying head, with the copper nitrate solution spray atomization to sodium sulfide solution, stir contact reacts at reaction container, the contact reacts area 30cm of little mist vapour and liquid level
2, stirring catalytic stir speed (S.S.) is 50 rev/mins, stirs contact reacts and finishes still aging 8 hours, obtains reaction soln;
4), reaction soln filters, obtain solid materials, solid materials is put into the washed with de-ionized water 3 minutes of 3 times of solid materials volumes earlier, cleaned 3 minutes with the raw spirit of 4 times of solid materials volumes again after the taking-up, solid materials after cleaning is put into oven drying, drying temperature is 80 ℃ of following dryings 5 hours, obtains dried material;
5), add 20 milliliters of raw spirits in every gram dried material, with Ceramic Balls wet-milling 2h, solid-liquid separation after the wet-milling, solid is put into oven drying, and drying temperature is 90 ℃ of following dryings 5 hours, and drying finishes, solid is used the zirconia ball dry grinding 2h of Φ 25mm earlier, with the zirconia ball dry grinding 1h of Φ 5mm, obtain the nano-copper sulfide barium dust again. through the X-ray powder diffraction experiment, obtain the stable chalcopyrite phase powder BaCu of crystal phase structure
2S
2Material, scanning electron microscope analysis obtain granularity less than 100nm;
6), n-Hexadecane methyl brometo de amonio is dissolved in 50 ℃ the water, the n-Hexadecane methyl bromination ammonium solution that is made into mass percentage concentration 30% is stand-by, according to nano-copper sulfide powder and 1: 2 ratio of n-Hexadecane methyl brometo de amonio mass ratio, the nano-copper sulfide aluminium powder form is put into n-Hexadecane methyl bromination ammonium solution, after stirring, stand-by; In nano-copper sulfide powder and 1: 10 ratio of polyvinyl alcohol mass ratio, pour the polyvinyl alcohol viscous fluid into and mix again, under 90 ℃ of temperature, stirred 7 hours, obtain viscous liquid;
7), the hydrolysis of butyl (tetra) titanate: according to following molar ratio: (Tetrabutyl orthotitanate): (ethanol): (dilute hydrochloric acid)=1: 1.5: 0.5, butyl (tetra) titanate is mixed with ethanol, in mixing solutions, add Glacial acetic acid and aluminium acetylacetonate simultaneously, with as sequestrant, Glacial acetic acid is identical with aluminium acetylacetonate cumulative volume and butyl (tetra) titanate, room temperature is sealed under the magnetic agitation, and pointwise adds dilute hydrochloric acid then, carries out the butyl (tetra) titanate hydrolysis reaction 4 hours;
8), the hydrolysis of MTES: will be according to following molar ratio: (MTES): (ethanol): (dilute hydrochloric acid)=1: 1.5: 1, mix, room temperature is sealed under the magnetic agitation, and remaining dilute hydrochloric acid pointwise is joined in the above-mentioned mixing liquid again, carries out the first step MTES mixed hydrolysis reaction 48 hours.The concentration of dilute hydrochloric acid is 0.04 volumetric molar concentration.Then continue to add dilute hydrochloric acid again, carry out the reaction of second one-step hydrolysis, the second step dilute hydrochloric acid add-on is half of the first step amount; The room temperature hydrolysis time in second step 4 hours;
9), be 4～19: 1 according to MTES and Tetrabutyl orthotitanate molar ratio, the colloidal sol that mixing step g and h make mixes and stirs hydrolysis 0.5 hour;
10), after hydrolysis finishes, stop to stir, open mouth after, gel was put in 60 ℃ of baking ovens dry 48 hours because the volatilization of ethanol in the gel, after drying, gel becomes, and very silk fabric is close, and is stand-by;
11), with the nano-copper sulfide barium dust n-Hexadecane methyl bromination ammonium solution that has prepared in the f step, pour in the gel dense in the j step, under 50 ℃ of temperature, stirred 2 hours, obtain viscous liquid; Wherein the nano-copper sulfide barium dust is 1: 20 ratio with (MTES/Tetrabutyl orthotitanate) mass ratio;
12), there is not the preparation of supporting isolated thick film: above-mentioned viscous liquid evenly is coated on the clean dacron membrane substrate surface with rod pipe machinery, the dacron membrane that coating finishes is put into oven drying, 70～100 ℃ dryings 4～7 hours, obtain the cured film that dacron membrane supports; Firmly slowly uncover thick film, carry out separating of film and terylene, obtain the original shape of isolated film.In the sepn process of film and substrate, prevent the fracture of film as far as possible. carry out planarizing process subsequently. in the middle of will putting into the cylinder of two slow rotation from the isolated film that substrate is uncovered, bowl temperature is constant at 80～90 ℃. and cylinder surface is coated with one deck silicone, and at 50～1000 mu m range adjustable distances.Obtaining final isolated film through like this extruding, it is very even to have very high surface smoothness and a thickness.Should evenly contain nano-copper sulfide barium by isolated film, nano-copper sulfide barium can effectively absorb near infrared light can be with transition regime under sunlight.
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|---|---|---|---|---|
| CN115160621A (en) * | 2022-06-30 | 2022-10-11 | 广东聚航新材料研究院有限公司 | Preparation method of infrared heat-shielding PET (polyethylene terephthalate) film |
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| JPH06312489A (en) * | 1993-04-30 | 1994-11-08 | Daicel Chem Ind Ltd | Near infrared absorption polycarbonate resin laminate and molded form thereof |
| CN102863155A (en) * | 2012-09-25 | 2013-01-09 | 宁波大学 | Preparation method of solar thermal shield glass |
-
2013
- 2013-05-28 CN CN201310219042.XA patent/CN103274446B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06312489A (en) * | 1993-04-30 | 1994-11-08 | Daicel Chem Ind Ltd | Near infrared absorption polycarbonate resin laminate and molded form thereof |
| CN102863155A (en) * | 2012-09-25 | 2013-01-09 | 宁波大学 | Preparation method of solar thermal shield glass |
Non-Patent Citations (1)
| Title |
|---|
| 曾小兰等: "有机硅/TiO2透明涂层的性能研究", 《厦门大学学报（自然科学版）》, vol. 50, no. 5, 30 September 2011 (2011-09-30), pages 878 - 882 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160621A (en) * | 2022-06-30 | 2022-10-11 | 广东聚航新材料研究院有限公司 | Preparation method of infrared heat-shielding PET (polyethylene terephthalate) film |
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