CN1267496C - Vanadium dioxide series sun heat reflection intelligent temp./control high molecular sheet (plate) material - Google Patents
Vanadium dioxide series sun heat reflection intelligent temp./control high molecular sheet (plate) material Download PDFInfo
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- CN1267496C CN1267496C CN 200410051967 CN200410051967A CN1267496C CN 1267496 C CN1267496 C CN 1267496C CN 200410051967 CN200410051967 CN 200410051967 CN 200410051967 A CN200410051967 A CN 200410051967A CN 1267496 C CN1267496 C CN 1267496C
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- powder
- molecular
- molecular sheet
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- 239000000463 material Substances 0.000 title claims abstract description 67
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical class [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 title description 4
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 14
- 239000000049 pigment Substances 0.000 claims abstract description 10
- 229920004934 Dacron® Polymers 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims abstract description 7
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 6
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 4
- 239000004417 polycarbonate Substances 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920004933 Terylene® Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000005287 vanadyl group Chemical group 0.000 claims description 6
- 238000001149 thermolysis Methods 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 4
- 239000002019 doping agent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000012782 phase change material Substances 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007909 melt granulation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to an intelligent solar heat temperature control high-molecular sheet (plate) material of a vanadium dioxide and dopant series powder phase change material. The high-molecular sheet (plate) material comprises a high-molecular material and a composite pigment. The high-molecular sheet (plate) material is different from the existing solar heat reflection high polymers that the high-molecular sheet (plate) material can reflect infrared light in an all wave band at more than phase change temperature Tc of (V1-xMx)O2. Besides, the high-molecular sheet (plate) material has high reflection efficiency and favorable cooling effect. In addition, the infrared light can penetrate through the high-molecular sheet (plate) material in the all wave band at less than Tc, and the high-molecular sheet (plate) material has high infrared light transmissivity and favorable heat insulating efficiency. As a result, the intelligent temperature control is realized. Meanwhile, most of visual light can penetrate through the material, and favorable transparence is kept. In the high-molecular sheet (plate) material, high molecular materials including organic glass, polycarbonate, modified dacron, dacron and the like are used for manufacturing the sheet (plate) material, and the material can be used as the material for building doors and windows, and doors and windows of vehicles and ships so as to perform the function for reducing the use of air conditioners. The implementation of the high-molecular sheet (plate) material is favorable to energy saving and environment protection.
Description
Technical field
The present invention relates to a kind of solar heat reflection and transmission intelligent temperature control polymer sheet (plate) material automatically, particularly relate to a kind of VO
2And mix the powder-modified solar heat of Mo or W hotchpotch series reflection and transmission intelligent temperature control polymer sheet (plate) material automatically.It belongs to the polymer modification technical field.
Background technology
The wave band of sunlight is divided into UV-light (0.2-0.4 μ m), visible light (0.4-0.8 μ m) and near infrared light (0.8-2.6 μ m), and its energy distribution is approximately UV-light 5%, visible light 45% and near infrared light 50%.Solar light irradiation is when body surface, and object mainly absorbs the energy of near infrared light and its surface temperature is raise.In summer, solar radiation is when metal sheet or building surface, and surface temperature can reach 70-80 ℃, needs this moment reflects infrared light that the body surface temperature is reduced; And in the winter time,, need to see through the infrared light insulation because temperature is low.Though at present the solar heat reflecting and heat insulating macromolecule membrane is arranged, not seeing has reflects infrared light at high temperature, can see through the macromolecular material of infrared light when low temperature again.The present invention invented a kind of price quite, high temperature can reflects infrared light, low temperature sees through the infrared light and the material of visible light transmissive simultaneously, can realize intelligent temperature control.This material is more far better than the material property of existing reflection solar heat, can accomplish cool in summer and warm in winterly, plays few air-conditioning of use, save energy and protect environment.
VO
2Be converted to high temperature four directions metallographic phase mutually by low temperature monocline semi-conductor in the time of about 68 ℃, its transformation temperature Tc can regulate by mixing, and as whenever mixing 1% Mo or W atom, Tc reduces 11 or 26 ℃ respectively, makes that this material is suitable for using under the room temperature.VO
2Be accompanied by the sudden change of infrared light (λ=0.7-20 μ m) transmissivity and reflectivity during the series phase transformation.All wave band reflects infrared light when temperature is higher than Tc, all wave band sees through infrared light when temperature is lower than Tc, and this variation is reversible, thereby realizes intelligent temperature control.The present invention proposes for the first time with VO
2Series powder and superpolymer are compound, give good solar insulation of superpolymer and intelligent temperature control usefulness.If as the glass of this material replacing is installed on the door and window of car, ship, will effectively reduce room temp in summer in the door and window of construction industry and transport trade, improve room temp in the winter time, can save and even not use air-conditioning, not only save energy but also protect environment.
The patent No. is that the patent of invention of ZL 00117321.9 has been invented a kind of VO
2The preparation method of nano-powder and hotchpotch nano-powder thereof.This method is with V
2O
5, hydrochloric acid, oxalic acid and NH
4HCO
3Be starting raw material, synthetic presoma vanadyl (IV) basic carbonate ammonium and Mo or W doping presoma, this chemical doping method makes Mo or W ion evenly enter the precursor lattice, then precursor thermolysis in containing the oxygen inert atmosphere is got (V
1-xM
x) O
2Powder.The Mo of this powder and W ion evenly enter VO
2Lattice demonstrates (V
1-xM
x) O
2Intrinsic crystal property and with the performance of infrared light effect.Particularly importantly, this chemical doping method greatly reduces existing VO
2Powder, mix the VO of Mo or W
2Powder is by the preparation cost of the traditional method of consolidating prepared in reaction; Simultaneously, the granularity of powder can be controlled from the nano level to the micron order by the pyrolytic process of precursor.This has guaranteed VO
2And hotchpotch powder price is lower, and material infrared light excellent performance is for realizing that the present invention prepares solar heat intelligent temperature control polymer sheet (plate) material and provides material base.
Summary of the invention
The object of the present invention is to provide a kind of vanadium dioxide intelligent temperature control macromolecular sheet material or sheet material, this material is solar heat reflection rate height when high temperature, and when low temperature the transmissive solar heat, simultaneously can see through visible light.
Vanadium dioxide solar heat intelligent temperature control macromolecular sheet material of the present invention or sheet material are made up of macromolecular material and composite pigment, and the shared parts by weight of each component are as follows:
Macromolecular material 100-400;
Composite pigment 38-102;
Wherein macromolecular material is synthetic glass, polycarbonate, modification dacron terylene or dacron terylene; Composite pigment is separately by (V
1-xM
x) O
2Powder is formed, or by (V
1-xM
x) O
2Powder and Rutile type Titanium Dioxide are formed, or by (V
1-xM
x) O
2Form in powder and the oxide powder and zinc, wherein M=Mo or W, 0≤x＜0.045, the globule size of powder is nano level, submicron order, micron order.
The present invention relates to MO
2And the hotchpotch nano level, submicron order and micron-sized powder and preparation thereof, its preparation method is similar to Chinese patent ZL 00117321.9.With V
2O
5, oxalic acid and hydrochloric acid are raw material, preparation VOCl
2Solution is then with VOCl
2Solution and NH
4HCO
3Reaction obtains vanadyl (IV) basic carbonate ammonium presoma; If at VOCl
2Add MoCl in the solution
2Or the reduzate of ammonium molybdate or WOCl
2, again with NH
4HCO
3Reaction can be mixed molybdenum, be mixed vanadyl (IV) the basic carbonate ammonium presoma of tungsten; With VOCl
2Solution and ammonium tungstate and NH
4HCO
3Mixture reaction also can obtain to mix tungsten vanadyl (IV) basic carbonate ammonium presoma.Presoma is broken or not broken, containing under the oxygen protection of inert gas, can obtain (the V of different-grain diameter then 500 ℃ of-900 ℃ of thermolysiss
1-xM
x) O
2Powder.Wherein powder granularity can be by the degree of crushing of presoma, thermolysis heat-up rate and temperature of reaction control.
Macromolecular sheet material of the present invention or preparation of plates technology are as follows: with the even back of each mixing of materials hot melt granulation, be drawn into sheet material then, the about 2mm of thickness by prescription; Perhaps make sheet material with injection moulding process, thickness is greater than 2mm.The mensuration of the infrared reflectivity of gained material, the detection method of defined in the employing MIL STD.
The vanadium dioxide macromolecular sheet material or the sheet material that adopt technique scheme to make have following advantage:
1. in superpolymer, introduce (V with phase transition function
1-xM
x) O
2Powder, can be when temperature be higher than Tc all wave band (0.7-20 μ m) reflects infrared light, infrared light reflection efficient height, good cooling effect; All wave band sees through infrared light when temperature is lower than Tc, and infrared light sees through the efficient height, high insulating effect, thus realize intelligent temperature control.Simultaneously can see through visible light, indoor have brightness preferably.
2. control temperature is by (V
1-xM
x) O
2Transformation temperature Tc decision, can adjust as required.
3. every mechanical property of vanadium dioxide series solar heat intelligent temperature control macromolecular sheet material or sheet material can keep the index of original macromolecular material, and the intensity that has is also strengthened to some extent.Especially use (V
1-xM
x) O
2Nano-powder can improve the packing ratio of stopping composition, improves the rheological of material in the course of processing, improves material shielding effect to corrosive medium in application process.
The present invention has a extensive future, and is widely used at the door and window of buildings, automobile, train and boats and ships, and both save energy was protected environment again.
Embodiment
Embodiment 1-5
Vanadium dioxide solar heat intelligent temperature control macromolecular sheet material or sheet material are made up of macromolecular material and composite pigment, and the shared weight of each component is as shown in table 1.
(V
1-xM
x) O
2The synthetic method of powder:
Use V
2O
5, oxalic acid and hydrochloric acid reaction prepare VOCl
2Solution, this solution and bicarbonate of ammonia or volatile salt are at CO then
2Stirring reaction under the air-flow protection, synthetic vanadyl (IV) basic carbonate ammonium presoma.If the molybdenum presoma is mixed in preparation, can be at VOCl
2Add MoCl in the solution
2Or the ammonium molybdate reduzate, the same building-up reactions of carrying out.If the tungsten presoma is mixed in preparation, can be at VOCl
2Add WOCl in the solution
2, the same reaction; Or in bicarbonate of ammonia or volatile salt, add ammonium tungstate solution, the same reaction.Mo/V or W/V ratio in doping vanadyl (IV) the basic carbonate ammonium are determined by Mo/V in the reaction system or W/V ratio.Presoma is crushed to different grain size, then at oxygen containing N
2Or the pyrolysis that in Reaktionsofen, heats up under the Ar gas shiled, controlling different heat-up rates and different pyrolysis temperatures, insulation 0.5h promptly gets (V
1-xM
x) O
2Powder, it the results are shown in table 2.
Vanadium dioxide series solar heat intelligent temperature control macromolecular sheet material or preparation of plates method:
By prescription with each mixing of materials evenly after, hot melt granulation is made sheet material (the about 2mm of thickness) with drawing then; Make sheet material (thickness is greater than 2mm) with injection moulding process.Measure its infrared reflectivity, it the results are shown in table 1.
Table 1 VO
2The composition weight of series solar heat intelligent temperature control macromolecular sheet material or sheet material
| Raw material (gram) | Embodiment | ||||
| 1 | 2 | 3 | 4 | 5 | |
| Macromolecular material (consumption) | Synthetic glass 400 | Synthetic glass 400 | Polycarbonate 300 | Modification dacron terylene 200 | Dacron terylene 1OO |
| (V 1-xM x)O 2Pigment (consumption) | Nanometer VO 2 1OO | Submicron VO 2 100 | Micron V 0.983W 0.017O 2 70 | Nanometer V 0.983W 0.017O 2 38 | Nanometer V 0.970W 0.030O 2 17 |
| Other pigment (consumption) | Titanium dioxide 2 | Zinc oxide 1.5 | |||
| Tc(℃) | ～68 | ～68 | ～33 | ～33 | ～39 |
| The solar heat reflection rate, % | 93 | 90 | 81 | 84 | 85 |
(V under the different thermolysis conditions of table 2
1-xM
x) O
2Powder
| Precursor particle size (μ m) | Heat-up rate | Thermostat temperature (℃) | Powder granularity | Granular |
| ≤2 | Fast | 550 | ＜30nm | Spherical |
| ≤2 | Fast | 700 | ＜100nm | Spherical |
| ≤1O | Middling speed | 800 | ＜500nm | Torispherical |
| About 20 | At a slow speed | 900 | ＞1μm | Torispherical |
Claims (2)
1, a kind of vanadium dioxide solar heat intelligent temperature control macromolecular sheet material or sheet material is characterized in that this sheet material or sheet material is made up of macromolecular material and composite pigment, and the shared parts by weight of each component are as follows:
Macromolecular material 100～400,
Composite pigment 38～102;
Wherein macromolecular material is synthetic glass, polycarbonate, modification dacron terylene or dacron terylene; Composite pigment is separately by (V
1-xM
x) O
2Powder is formed, or by (V
1-xM
x) O
2Powder and Rutile type Titanium Dioxide are formed, or by (V
1-xM
x) O
2Powder and oxide powder and zinc are formed, wherein M=Mo or W, and 0≤x＜0.045, the globule size of powder is nano level, submicron order or micron order.
2, vanadium dioxide solar heat intelligent temperature control macromolecular sheet material as claimed in claim 1 or sheet material is characterized in that described (V
1-xM
x) O
2Powder be vanadyl (IV) basic carbonate ammonium and mix molybdenum or the tungsten presoma in oxygen containing inert atmosphere at the powder of 500 ℃～900 ℃ of thermolysis gained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410051967 CN1267496C (en) | 2004-10-28 | 2004-10-28 | Vanadium dioxide series sun heat reflection intelligent temp./control high molecular sheet (plate) material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410051967 CN1267496C (en) | 2004-10-28 | 2004-10-28 | Vanadium dioxide series sun heat reflection intelligent temp./control high molecular sheet (plate) material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1624041A CN1624041A (en) | 2005-06-08 |
| CN1267496C true CN1267496C (en) | 2006-08-02 |
Family
ID=34764083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410051967 Expired - Fee Related CN1267496C (en) | 2004-10-28 | 2004-10-28 | Vanadium dioxide series sun heat reflection intelligent temp./control high molecular sheet (plate) material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1267496C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807321B (en) * | 2005-12-31 | 2013-07-03 | 中科能（青岛）节能工程有限公司 | Highly energy-saving coating glass automatically adjusting light according to environment temperature and multi-layed assembled glass body |
| KR20120118303A (en) * | 2011-04-18 | 2012-10-26 | 삼성코닝정밀소재 주식회사 | Energy saving window and pair-glass |
| CN103183891B (en) * | 2013-04-02 | 2014-12-03 | 扬州大学 | Ultraviolet adsorption visible and transparent organic glass based on ZnO quantum dot and preparation thereof |
| CN107603102B (en) * | 2017-09-15 | 2019-11-08 | 四川大学 | Organic glass and preparation method thereof |
| CN107652604B (en) * | 2017-10-27 | 2019-07-16 | 四川大学 | Organic glass production system |
-
2004
- 2004-10-28 CN CN 200410051967 patent/CN1267496C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1624041A (en) | 2005-06-08 |
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Granted publication date: 20060802 Termination date: 20131028 |