CN102643563A - Transparent thermal insulation material and preparation method thereof - Google Patents
Transparent thermal insulation material and preparation method thereof Download PDFInfo
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- CN102643563A CN102643563A CN2012100914155A CN201210091415A CN102643563A CN 102643563 A CN102643563 A CN 102643563A CN 2012100914155 A CN2012100914155 A CN 2012100914155A CN 201210091415 A CN201210091415 A CN 201210091415A CN 102643563 A CN102643563 A CN 102643563A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
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- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/90—Passive houses; Double facade technology
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a transparent thermal insulation material, which is characterized in that: the material is codoped by cross-group elements. A preparation method of the material has the characteristics of simple process and cost saving, and is specially used for preparing composite wolfram oxygen chloride powder with a chemical formula being CsxNyWO3-ZCIC, wherein Cs is cesium; N is Sn or Sb or Bi; W is wolfram; O is oxygen; and X, Y, Z and C are positive numbers and meet the following conditions that: X is less than or equal to 1.0, Y is less than or equal to 1.0, Y/X is less than or equal to 1.0, Z is less than or equal to 0.6, and C is less than or equal to 0.1. A transparent thermal insulation film prepared by the composite wolfram oxygen chloride powder has the characteristics of high transparency and high thermal insulation, is applied to paste on glasses of buildings and automobiles so as to separate infrared wave bands with wavelength of 800-2000nm, contributes to realizing effects of thermal insulation and energy conservation, and also can be used for a combined type base plate of an electronic component.
Description
Technical field
The invention relates to a kind of transparent insulate material and method for making thereof, the made transparent heat-insulating film of particularly this transparent insulate material has high transparent and splendid infrared rays barrier properties concurrently.
Background technology
In order to realize the purpose of carbon reduction, in the prior art, on glass the borrowing usually of buildings and automobile sticked the effect that one deck lagging material is reached heat-insulating and energy-saving.And the rerum natura of MOX has good effect of heat insulation, has been widely used in as intercepting ultrared material.
For example, the U.S. the 5th, 385, No. 751 patents disclose a kind of Tungsten oxide 99.999 infrared rays barrier material of doped with fluorine, but method for making has the higher shortcoming of producing apparatus costliness and manufacturing cost because be to use chemical Vapor deposition process (Chemical Vapor Deposition).
9-12338 number open case of Japan Di Tekaiping discloses a kind of infrared rays barrier films; Comprise the compound tungsten oxide of forming by the element-specific of W elements and periodictable IVA family etc.; But method for making is to use sputter (Sputtering) method; The transparent glass substrate that needs to be applied to carry the infrared rays barrier films is exposed in the high temperature electricity slurry, is prone to cause the infrared rays barrier films in forming process, to receive the influence of the high energy ion bundle in the electricity slurry and defective occurs; And, in order to reduce the defect concentration of infrared rays barrier films, need provide annealing device to heat-treat, the higher shortcoming of processing procedure complicacy and manufacturing cost is also arranged.
The Japan spy opens 2003-121884 number and discloses the method for making that case discloses a kind of tungsten trioxide powder, and its method steps comprises: tungsten hexafluoride is dissolved in the alcohol, from solution, isolates throw out and under 100～500 ℃ of conditions of temperature, the throw out heating is made tungsten trioxide powder.And the purposes of said tungsten trioxide powder is applicable to as intercepting infrared material and uses.
No. 2006/0178254 open case of the U.S. discloses a kind of method for making of compound tungsten oxide, and its method steps comprises:
A) choose hydrate powder, tungsten hexachloride powder or ammonium tungstate powder wherein a kind of of tungsten trioxide powder, Tungsten oxide powder, tungsten oxide;
B) choose and contain M element monomer or compound powder;
Said M element comprises elements such as H, He, basic metal, earth alkali metal or rare earth class;
C) mixing step a) and the powder of step b) and adds ethanol or water is processed the tungsten oxide hydrate, dry then this tungsten oxide hydrate by a certain percentage;
D) the dry tungsten oxide hydrate of crossing of step c) is carried out following two-stage thermal treatment:
D-1) in the reducing gas environment, for example feed hydrogen (H
2) under the condition, carry out fs thermal treatment for 100～850 ℃ with sintering temperature;
D-2) after wait temporarily returns to room temperature, in inert gas environment, for example feed under argon gas (Ar) condition again, carry out subordinate phase thermal treatment for 650～1200 ℃ with sintering temperature;
E) carry out the refinement milled processed to accomplishing heat treated compound tungsten oxide of two-stage, and make the compound tungsten oxide particulate that general expression is MxWyOz.
The prepared compound tungsten oxide particulate of method for making according to above-mentioned open case has and fully covers infrared capable, is applicable to as intercepting infrared material to use.But, because need carry out the thermal treatment of two-stage, the complicated shortcoming of processing procedure is arranged still on method for making in the processing procedure of said compound tungsten oxide.
Summary of the invention
For solving the problem that exists in the above-mentioned prior art; It is a kind of adjustable and have the composition metal tungsten oxychlorination thing and a method for making thereof of the heat insulation double effects of high transparent height that main purpose of the present invention is to provide; In processing procedure, only need carry out one step thermal treatment, simply reach characteristics with low cost so have processing procedure, and; Prepared composition metal tungsten oxychlorination thing (below; Abbreviate compound tungsten oxychlorination thing as), have high transparent and high heat insulation double effects concurrently, be applicable to as intercepting infrared material and use.
Compound tungsten oxychlorination thing of the present invention; Be to utilize caesium (Cs) element and stanniferous (Sn) or antimony (Sb) or one or more metallic element muriates of bismuth (Bi); Codoped under suitable proportion forms compound tungsten oxychlorination thing material with tungsten chloride ethanolic soln codeposition, and its chemical formula is Cs
xN
yWO
3-ZCl
C, wherein Cs is a caesium; N is tin (Sn) or antimony (Sb) or bismuth (Bi); W is a tungsten; O is an oxygen; X, Y, Z, C are positive number, and meet following condition:
X≤1.0; Y≤1.0; Y/X≤1.0; Z≤0.6 and C≤0.1;
And; Caesium (Cs) in the said compound tungsten oxychlorination thing material is emitted a unbound electron easily; Arrange in pairs or groups adulterated tin (Sn) or antimony (Sb) or bismuth (Bi) metallic element emitted four to five unbound electrons; Have the differing absorption wavelength region separately, but both has strong especially receptivity for the common wave band of IR wavelength 800～2000nm.
The method for making of compound tungsten oxychlorination thing of the present invention comprises following each step:
A. getting tungsten hexachloride is dissolved in ethanol and is modulated into solution A;
B. the muriate of getting cesium chloride (CsCl) and stanniferous (Sn) or the antimony (Sb) or bismuth (Bi) metallic element of an amount of (ratio) mixes with water together and is modulated into solution B;
C. solution A and solution B are generated throw out with co-deposition method;
D. the throw out of step c is carried out the thermal treatment of single sintering and make said compound tungsten oxychlorination powder.
The method for making of compound tungsten oxychlorination thing of the present invention is under the environment that feeds a certain proportion of hydrogen or argon gas, carries out the single sintering thermal treatment of 450～800 ℃ of sintering temperatures.In thermal treatment, feeding the purpose of hydrogen and/or argon gas, is for fear of causing the compound tungsten oxide of part to be reduced into Tungsten oxide 99.999 (WO
3), weaken the near-infrared absorbing characteristic; And feed the weathering resistance that hydrogen and argon gas can elongate composite tungsten oxychlorination things simultaneously.
The method for making of compound tungsten oxychlorination thing of the present invention is applicable to that chemical formula is Cs
xN
yWO
3-ZCl
CCompound tungsten oxychlorination thing material; Wherein N is tin (Sn) or antimony (Sb) or bismuth (Bi) metallic element; Satisfy the N metallic element to the codoped ratio (Y/X) of Cs element for to be less than or equal under the condition of 1.0 (they being Y/X≤1.0); As long as the addition of adjustment N metallic element, the N metallic element will change the codoped ratio (Y/X) of Cs element thereupon, under suitable High Temperature Furnaces Heating Apparatus heat-treat condition; The rerum natura of prepared compound tungsten oxychlorination thing material will present different infrared rays rejection rates along with the variation of codoped ratio (Y/X).When the N metallic element is higher to the codoped ratio (Y/X) of Cs element, the infrared rays rejection rate (effect of heat insulation) of prepared compound tungsten oxychlorination thing material is relatively higher.Therefore, method for making of the present invention can be processed the adjustable compound tungsten oxychlorination thing of different degree of thermal insulation according to the different purposes demands on the market.
Compound tungsten oxychlorination thing of the present invention; Contain the chlorine element, the infrared rays rejection rate surpasses 70% (promptly＞70%), is applicable to process high transparent thermal isolation film; Can be affixed on the effect of the realization heat-insulating and energy-saving on glass of buildings and automobile, also can be used for the combined type substrate of electronic component.
The method for making of compound tungsten oxychlorination thing of the present invention has following characteristics:
1. only need the thermal treatment of single sintering in the method for making, processing procedure simply reaches the saving cost;
2. according to the prepared compound tungsten oxide of method for making, have excellent infrared rays rejection rate and visible light penetration coefficient concurrently;
3. according to the prepared compound tungsten oxide of method for making, have long-term quality stability, can utilize on the confession industry.
Description of drawings
Fig. 1 is the life test trend map of compound tungsten oxychlorination thing particulate of the present invention;
Fig. 2 is the flow chart of steps of compound tungsten oxychlorination thing method for making of the present invention;
Fig. 3 is the penetration rate spectrum figure of compound tungsten oxychlorination thing particulate of the present invention.
Embodiment
Compound tungsten oxychlorination thing of the present invention; Be to utilize caesium (Cs) element and stanniferous (Sn) or antimony (Sb) or bismuth (Bi) metallic element muriate, under suitable proportion, codoped forms compound tungsten oxychlorination thing material; Its rerum natura possesses preferable infrared rays wave band barrier properties; For specific wavelength is the light of 800～2000nm, and especially the infrared rays wave band of wavelength 800～1000nm more has special excellent receptivity; And its rerum natura also possesses preferable visible light penetration coefficient, is to be applicable to as intercepting the transparent high lagging material of ultrared height.
And, compound tungsten oxychlorination thing of the present invention, as shown in Figure 1 through the result of life test, have long-term quality stability, can utilize on the confession industry.
Compound tungsten oxychlorination thing of the present invention, chemical formula is Cs
xN
yWO
3-ZCl
C, wherein Cs is a caesium; N is tin (Sn) or antimony (Sb) or bismuth (Bi); W is a tungsten; O is an oxygen; X, Y, Z, C are positive number, and meet following condition:
X≤1.0；Y≤1.0；Y/X≤1.0；
Z≤0.6 and C≤0.1;
When the coexistence of N element and caesium (Cs) element, and satisfy the N element codoped ratio (Y/X) of caesium (Cs) element is less than or equal to 1.0, be i.e. Y/X≤1.0, the high transparent and high heat insulation effect that multiplies each other of compound tungsten oxychlorination thing tool of the present invention; When said codoped ratio (Y/X) greater than 1.0, the transparency and the effect of heat insulation of said compound tungsten oxychlorination thing are then relatively poor.
Compound tungsten oxychlorination thing of the present invention; Contain the chlorine element; And striding family and tin (Sn) or antimony (Sb) or bismuth (Bi) metallic element codoped with caesium (Cs) element processes; Its transparent heat-insulated effect obviously is superior to the composition metal tungsten oxyhalogenation thing of other congeners or its combination, is applicable to process high transparent thermal isolation film, can be affixed on the effect of reaching heat-insulating and energy-saving on glass of buildings and automobile.For example, compound tungsten oxychlorination thing of the present invention, its effect of heat insulation are superior to using the compound tungsten oxyhalogenation thing of the F of halogen family, Br, I or At element.
As shown in Figure 2, compound tungsten oxychlorination thing method for making of the present invention comprises following each step:
A. getting tungsten hexachloride is dissolved in ethanol and is modulated into solution A;
B. get the cesium chloride (CsCl) of an amount of (ratio) and the muriate of containing metal element and become solution B with the water hybrid modulation together;
Wherein, said metallic element be selected from the colony that constituted by tin (Sn) or antimony (Sb) or bismuth (Bi) wherein one or more;
C. solution A and solution B are comprised tungsten oxychloride (WOCl at least with the co-deposition method generation
4) and muriatic throw out;
Wherein, the sedimentary composition of said muriate is decided according to the composition of solution B, except that comprising the cesium chloride throw out, also comprise tin chloride, antimony chloride or bismuth chloride wherein one or more;
D. the throw out to step c carries out the thermal treatment of single sintering to make the sintering powder;
Before heat-treating, can implement filtering solvent step and drying step in advance to the throw out of step c.
When carrying out the filtering solvent step, be to utilize centrifuging or filtration method that the throw out of step c is imposed to remove solvent treatment.
When carrying out drying step, be the throw out of filtering solvent to be inserted in the environment of 115～145 ℃ of temperature heat drying 1 hour.
When carrying out the single sintering step, insert in tube furnace or the block furnace (hereinafter to be referred as High Temperature Furnaces Heating Apparatus) with the throw out of step c or through the throw out of drying treatment and to carry out high temperature sintering, sintering condition is the temperature rise rate with 2～10 ℃/min, feeds hydrogen (H simultaneously
2) and rare gas element argon gas (Ar) for example.At hydrogen (H
2) under the situation as reducing gas, the sintering temperature of High Temperature Furnaces Heating Apparatus is risen to 450～800 ℃ of temperature from room temperature, and lasting thermal treatment 1～2 hour; After treating the cooling cooling, promptly making chemical formula is Cs
xN
yWO
3-ZCl
CCompound tungsten oxychlorination thing sintering powder (below, abbreviate compound tungsten oxychlorination powder as);
When carrying out the shock heating processing of single sintering; The temperature rise rate of High Temperature Furnaces Heating Apparatus is controlled at 2～10 ℃ of PMs; And keep fixed temperature compound tungsten oxychlorination thing is carried out the sintering thermal treatment of the scheduled time, have the drying of reaching and annealed purpose for compound tungsten oxychlorination thing.Through above-mentioned heat treated compound tungsten oxychlorination powder, have the chemical constitution stability, and variability dwindles, can not generate the compound tungsten oxychlorination thing of improper element ratio, have more good near infrared range absorption characteristic.
Compound tungsten oxychlorination powder of the present invention is the raw material that is used to process the transparent thermal isolation film of height, and its step further comprises:
E. prepared compound tungsten oxychlorination powder being carried out fine-powdered grinds;
F. get the compound tungsten oxychlorination thing fine powder of an amount of step e, after adding cakingagent and special formulation auxiliary agent,, process slurry (or claiming coating fluid) again through after stirring and the attrition process;
Adding the purpose of auxiliary agent, is to be to help made compound tungsten oxide fine powder can reach homodisperse.Employed auxiliary agent, comprise coupler, interfacial agent, dispersion agent, high molecular polymer modification agent or UV light absorber wherein one or more combine.
G. the coating fluid with step f is coated on the transparent substrate polyethylene terephthalate film (PET film) with the wet type coating method, forms a transparent heat-insulated film.
For example; The compound tungsten oxychlorination thing fine powder of step e is added in the toluene solvant; Be mixed with compound tungsten oxychlorination thing fine powder and account for the solution of 20wt% (weight ratio); And the high-molecular type dispersing agent of adding 6wt%, utilize 1mm yttrium zirconium pearl to grind and disperse, obtain the dispersion liquid of the particle diameter of compound tungsten oxychlorination thing less than 80nm.
Said dispersion liquid and acryl resin (marque SSM7, the South Asia Plastics Company produces) are mixed, be mixed with the coating fluid that dispersion liquid accounts for 20wt% (weight ratio).The mode of this coating fluid with the wet type coating is coated on the transparent substrate, and this transparent substrate can be glass, polyethylene terephthalate film (PET), Polyclear N 100 (PEN), polycarbonate (PC), SE (PVC), Vestolen PP 7052 (PP), Vilaterm (PE), ROHM resin (Acrylic Resin), aromatic polyester (Polyarylate; PAr), aromatic polyester (CycloOlefin Polymer; Macromolecule membrane such as COP) in 120 ℃ of dryings 2 minutes, obtains transparent heat-insulated film.
According to the prepared transparent heat-insulated film of above step, have excellent infrared rays high barrier and visible light high-penetrability.Below, enumerate embodiment and further specify the present invention.
Assessing each item rerum natura of transparent heat-insulated film of the present invention, is according to following testing method.
1. visible light penetration coefficient (VLT%) test:
Adopt Japanese trader Tokyo Denshoku Co., the model that Ltd. produces is the light transmittance test machine (Haze Meter) of TC-HIII, according to JIS K7705 testing standard, tests the light transmission rate and the haze value of transparent heat-insulated film.The visible light penetration coefficient is high more, represents the transparency of transparent heat-insulated film good more.
2. infrared rays (IR cut%) rejection rate test:
The model that adopts Japanese trader HOYA to produce is a LT-3000 infrared rays rejection rate test machine, according to JIS R3106 testing standard, and the infrared rays rejection rate of test polyester film.Test result is higher for the infrared rays rejection rate, represents the effect of heat insulation of polyester film good more.
3. transparent and heat insulation combined index (that is, VLT%+IR cut%) is by above-mentioned two kinds of sum totals that record the data addition, and the higher expression of numerical value is transparent and effect of heat insulation is better.
4. compound tungsten oxide life test:
Transparent heat-insulated film is with deterioration accelerator (Accelerated weathering tester; Q-PANNEL produces) irradiation; Model is 313NM N.120.SOLAREYE; Took out a built-in testing visible light penetration coefficient (VLT%) and infrared rays (IR cut%) rejection rate in per 100 hours, ended up to 1000 hours.
Embodiment 1
Getting tungsten hexachloride and ethanol is mixed with the pH value and is about 0 blue solution A; Other gets cesium chloride (CsCl) and butter of antimony (SbCl
3) be mixed with clear solution B with water together with 1 mole of ratio to 0.1 mole.A, two kinds of solution of B are produced throw out with co-deposition method.Reaction formula is following:
2WCl
6+C
2H
5OH+3H
2O→WOCl
4↓+WO
2Cl
2↓+6HCl+C
2H
5OH；
WOCl
4↓+WO
2Cl
2↓+C
2H
5OH+CsCl+SbCl
3+3H
2O→2WO
3↓+Cs
++Sb
+3+Cl
-+6HCl+C
2H
5OH。
Then; The throw out of being obtained being positioned in the High Temperature Furnaces Heating Apparatus, and feeding the argon gas and the hydrogen of certain flow, is under the condition of 2 ℃ of PMs at the temperature rise rate of High Temperature Furnaces Heating Apparatus; High Temperature Furnaces Heating Apparatus is risen to 485～515 ℃ (with 500 ℃ of expressions of medial temperature) from room temperature, and lasting thermal treatment 1 hour.
Thermal treatment promptly makes the pH value and is about 7 the compound tungsten oxide that contains caesium, antimony element after accomplishing, and its reaction formula is following:
2WOCl
4+2WO
2Cl
2+2Cs
++Sb
+3+2Cl
-+6H
2O→2Cs
xSb
yWO
3Cl+10HCl+H
2(X≤1，y≤1)。
At last; Compound tungsten oxide powder is added the solution that is mixed with weight ratio 20% in the toluene solvant; And the high-molecular type dispersing agent of adding weight ratio 6%, utilize 1mm yttrium zirconium pearl to grind and disperse to obtain containing the compound tungsten oxychlorination thing grinding dispersion liquid of particle diameter less than 80nm.
This is ground dispersion liquid be made into weight ratio 20% coating fluid, this coating fluid is coated on the PET film with the mode that wet type is coated with,, obtain transparent heat-insulated film in 120 ℃ of dryings 2 minutes with acryl resin (marque SSM7, the South Asia Plastics Company produces).Measure the penetration coefficient (being VLT% and IR cut%) of 300～2000nm wavelength, the result lists in table 1.
Embodiment 2
With embodiment 1, but get cesium chloride and butter of antimony (SbCl
3) be mixed with clear solution B with water together with 1 mole of ratio to 0.5 mole.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Embodiment 3
With embodiment 2, but use tin trichloride (SnCl
3) replacement butter of antimony (SbCl
3) preparation clear solution B.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1; The result of its life test trend map then lists in Fig. 1.
Embodiment 4
With embodiment 2, but use Trichlorobismuthine (BiCl
3) replacement butter of antimony (SbCl
3) preparation clear solution B.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Embodiment 5
With embodiment 1, but get cesium chloride and butter of antimony (SbCl
3) be mixed with clear solution B with 1 mole of ratio and water to 0.7 mole.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1 and Fig. 3.
Embodiment 6
With embodiment 5, remove solvent treatment but throw out imposed with filtration method, and obtain comprising the wet mud throw out of tungsten chloride, cesium chloride, butter of antimony, and the calcining temperature of High Temperature Furnaces Heating Apparatus is risen to 785～815 ℃ (800 ℃ of medial temperatures) from room temperature.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Embodiment 7
With embodiment 5, but change the temperature rise rate of High Temperature Furnaces Heating Apparatus into PM 10 ℃.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Embodiment 8
With embodiment 3, but get cesium chloride and tin trichloride (SnCl
3) be mixed with clear solution B with water together with 1 mole of ratio to 0.7 mole.。
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Embodiment 9
With embodiment 1, but get cesium chloride and butter of antimony (SbCl
3) be mixed with clear solution B with water together with 1 mole of ratio to 1.0 moles.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Comparative example 1
With embodiment 5, but change the temperature rise rate of High Temperature Furnaces Heating Apparatus into PM 15 ℃.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Comparative example 2
With embodiment 1, but only get cesium chloride and water is mixed with clear solution B.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1 and Fig. 3.
Comparative example 3
With embodiment 1, but only get cesium chloride and water is mixed with clear solution B, and the calcining temperature of High Temperature Furnaces Heating Apparatus is risen to 785～815 ℃ (800 ℃ of medial temperatures) from room temperature.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1 and Fig. 3.
Comparative example 4
With embodiment 5, but change two-stage thermal treatment into, when carrying out the High Temperature Furnaces Heating Apparatus thermal treatment of fs, feed the hydrogen (H of certain flow
2), be under the condition of 2 ℃ of PMs at the temperature rise rate of High Temperature Furnaces Heating Apparatus, High Temperature Furnaces Heating Apparatus is risen to 485～515 ℃ (following with average 500 ℃ of expressions) from room temperature, and lasting thermal treatment 1 hour; After treating that room temperature is got back in the temperature cooling; Carry out the High Temperature Furnaces Heating Apparatus thermal treatment of subordinate phase, under the condition of the argon gas that only feeds certain flow, with 2 ℃ of temperature rise rates of PM; High Temperature Furnaces Heating Apparatus is risen to 785 ℃～815 ℃ (800 ℃ of medial temperatures) from room temperature, and lasting thermal treatment 1 hour.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Comparative example 5
With solid tungstic oxide (WO
3) and solid carbonic acid caesium (Cs
2CO
3) uniform mixing.Then, mixed powder being positioned in the High Temperature Furnaces Heating Apparatus, and feeding the argon gas and the hydrogen of certain flow, is under the condition of 2 ℃ of PMs at the temperature rise rate of High Temperature Furnaces Heating Apparatus, and High Temperature Furnaces Heating Apparatus is risen to 485～515 ℃ (average 500 ℃) from room temperature, and lasting thermal treatment 1 hour.
Thermal treatment promptly makes compound tungsten oxide after accomplishing, and is accredited as the not halogen-containing compound tungsten oxide of six reef knot crystalline substances with the energy depressive spectroscopy of X-ray diffractometer and sweep electron microscope.
At last, measure the transparent heat-insulated film that makes with the embodiment 1 method penetration coefficient to 300～2000nm wavelength, the result lists in table 1.
Comparative example 6
With embodiment 5, prepare clear solution B but use sodium-chlor (NaCl) to replace cesium chloride.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
Comparative example 7
With embodiment 1, but get cesium chloride and butter of antimony (SbCl
3) be mixed with clear solution B with water together with 1 mole of ratio to 1.1 moles.
Measure the penetration coefficient of obtained transparent heat-insulated film to 300～2000nm wavelength, the result lists in table 1.
The result:
1, the transparent heat-insulated film that makes of embodiment 3, via 1000 hours long-time irradiation test, according to the transparent heat-insulated film life test trend map of Fig. 1, obviously the variation for infrared rays wave band rejection rate and visible light penetration coefficient kept below 10%.Therefore, the transparent heat-insulated film of embodiment 3 has long-term quality stability, can utilize on the confession industry.
2, for the visible light penetration coefficient and the infrared rays rejection rate of wavelength 300～2000nm light; Transparent and heat insulation combined index (VLT%+IR cut%) according to table 1; The transparent heat-insulated film that embodiment 1-9 processes is all above 160, and all is lower than 150 as the transparent heat-insulated film that the comparative example 1-7 of control group processes.
Confirm thus; Compound tungsten oxychlorination thing of the present invention is applicable to as intercepting ultrared lagging material, and is used in and processes transparent heat-insulated film; Infrared rays wave band for wavelength 1000～2000nm; Have excellent barrier properties,, also show to possess preferable visible light penetration coefficient for wavelength 400～600nm visible light wave range.
3, the compound tungsten oxychlorination thing of embodiment 2-4; Chloride element and select different tin (Sn) for use or antimony (Sb) or bismuth (Bi) metallic element and caesium (Cs) element codoped; And satisfy the condition of codoped ratio Y/X≤1.0, made transparent heat-insulated film is according to the test result of table 1; Visible light penetration coefficient scope is between 70～72, and infrared rays rejection rate scope is between 91～92.
Confirm that thus compound tungsten oxychlorination thing of the present invention can be selected tin (Sn) or antimony (Sb) or bismuth (Bi) metallic element and caesium (Cs) element codoped for use, and be applicable to and process transparent heat-insulating film.
4, comparative example 5 uses not halogen-containing compound tungsten oxide to process transparent heat-insulated film, according to the transparent and heat insulation combined index of table 1, and the transparent heat-insulated film of obviously processing far away from embodiment 1-9.
So, in the composition of compound tungsten oxychlorination thing of the present invention,, and have preferable infrared rays wave band barrier properties because contain the chlorine element.
5, analyze the penetration rate spectrum figure of comparison diagram 3; The transparent heat-insulated film that embodiment 5 makes; With respect to the transparent heat-insulated film that the comparative example 2 and the comparative example 3 of control group are processed, have excellent visible light wave range (400～600nm) through characteristics and infrared rays wave band (1000～2000nm) barrier properties.
And the compound tungsten oxychlorination thing of embodiment 5 is chloride element and selects antimony (Sb) metallic element for use and caesium (Cs) element codoped.The compound tungsten oxychlorination thing of comparative example 2-3, then chloride element and caesium metallic element, the antimony that undopes (Sb) metallic element.
Confirm thus; Compound tungsten oxychlorination thing of the present invention; Utilize the result of caesium (Cs) element and tin (Sn) or antimony (Sb) or bismuth (Bi) metallic element codoped; Have the effect of multiplying each other for prepared transparent heat-insulated film, can obviously promote the infrared rays wave band barrier properties and the visible light penetration coefficient characteristic of transparent heat-insulated film.
6, the compound tungsten oxychlorination thing of embodiment 1,2,5,9 and comparative example 7; Select antimony (Sb) metallic element and caesium (Cs) element codoped for use; And the antimony (Sb) of embodiment 1,2,5,9 between 0.1～1.0, satisfies the condition of Y/X≤1.0 to the codoped ratio ranges of caesium (Cs), but 7 of comparative examples are not.
According to the test result of table 1, satisfy under the condition of Y/X≤1.0, heal greatly when the ratio of Y/X, the visible light penetration coefficient of made transparent heat-insulated film reduces relatively, and the infrared rays group then raises at a distance from rate (effect of heat insulation); And the compound tungsten oxychlorination thing of comparative example 7 does not satisfy the condition of Y/X≤1.0, is not suitable for processing high transparent thermal isolation film.
Therefore; Compound tungsten oxychlorination thing method for making of the present invention can be according to the demand of different purposes, under the condition that satisfies Y/X≤1.0; Mat is regulated and control different Y/X ratios (or claiming the codoped ratio) and is processed the compound tungsten oxychlorination thing of tool different qualities, and processes the high transparent heat-insulating film that is suitable for different purposes.
7, the transparent heat-insulated film that makes of embodiment 5 and embodiment 6 according to the transparent and heat insulation combined index of table 1, with respect to the transparent heat-insulated film that the comparative example 4 of control group is processed, has excellent visible light wave band through characteristic and infrared rays wave band barrier properties.
Difference between the three is that compound tungsten oxychlorination thing is being imposed in the processing procedure of high-temperature calcination, and embodiment 5 and embodiment 6 impose the thermal treatment of single sintering, and feed hydrogen (H simultaneously
2) and argon gas (Ar), impose two-stage thermal treatment with respect to comparative example 4, and feed argon gas when feeding hydrogen and carrying out subordinate phase thermal treatment when carrying out fs thermal treatment.
Confirm that thus compound tungsten oxychlorination thing method for making of the present invention only need be carried out the thermal treatment of single sintering, and fed hydrogen (H simultaneously
2) and argon gas (Ar), just help to make the compound tungsten oxychlorination thing that makes to have good near infrared range absorption characteristic, the tool processing procedure simply reaches cost-effective characteristics.
8, the transparent heat-insulated film that makes of embodiment 5 and embodiment 6 according to the transparent and heat insulation combined index of table 1, shows that sintering temperature is high more, and the transparency of prepared compound tungsten oxychlorination thing powder is good more.
9, same situation; The transparent heat-insulated film that embodiment 5 and embodiment 7 make; According to the transparent and heat insulation combined index of table 1,, have excellent visible light wave band through characteristic and infrared rays wave band barrier properties with respect to the transparent heat-insulated film that the comparative example 1 of control group is processed.
Difference between the three is compound tungsten oxychlorination thing to be imposed in the processing procedure of high temperature sintering, setting different temperature rise rate conditions respectively.Embodiment 5 sets 2 ℃/min of temperature rise rate and embodiment 7 sets 10 ℃/min of temperature rise rate, sets 15 ℃/min of temperature rise rate with respect to comparative example 1.
Confirm that thus compound tungsten oxychlorination thing method for making of the present invention when carrying out the thermal treatment of single sintering, is controlled at 2～10 ℃ of PMs with the temperature rise rate of High Temperature Furnaces Heating Apparatus, helps to make compound tungsten oxychlorination thing of the present invention to have more good near infrared range absorption characteristic.
Table 1: the method for manufacture of each embodiment and comparative example and physical result thereof
Annotate: on behalf of tungsten hexachloride, 1.A be dissolved in ethanol (WCl
6+ C
2H
5OH) mixed solution;
2.B be to represent metal chloride, and add water and be mixed into solution;
3. transparent and heat insulation combined index is represented with VLT%+IR cut%.
Claims (6)
1. the method for making of a transparent insulate material is exclusively used in and makes the transparent insulate material with obstruct wavelength 800～2000nm infrared rays wave band characteristic, it is characterized in that, comprises following each step:
A. getting tungsten hexachloride is dissolved in ethanol and is modulated into solution A;
B. the muriate of getting an amount of cesium chloride and stanniferous or antimony or bismuth metallic element mixes with water together and is modulated into solution B;
C. solution A and solution B are generated throw out with co-deposition method;
D. the throw out of step c is carried out the sintering thermal treatment of 450～800 ℃ of sintering temperatures, making chemical formula is Cs
xN
yWO
3-ZCl
CCompound tungsten oxychlorination powder, wherein Cs is a caesium; N is tin or antimony or bismuth; W is a tungsten; O is an oxygen; X, Y, Z, C are positive number, and meet following condition:
X≤1.0；
Y≤1.0；
Y/X≤1.0；
Z≤0.6 and C≤0.1.
2. the method for making of transparent insulate material as claimed in claim 1 wherein, when carrying out steps d, is under the environment that feeds hydrogen and argon gas, to carry out sintering thermal treatment.
3. according to claim 1 or claim 2 the method for making of transparent insulate material wherein, when carrying out steps d, is that the condition with 2～10 ℃ of temperature rise rate PMs rises to 450～800 ℃ of sintering temperatures from room temperature, and lasting thermal treatment 1～2 hour.
4. the method for making of transparent insulate material as claimed in claim 1 wherein, under the condition that satisfies Y/X≤1.0, is regulated and control different Y/X ratios when carrying out step b, can make to have the different compound tungsten oxychlorination powders that intercept infrared rays wave band characteristic.
5. transparent insulate material, method for making according to claim 1 makes, and has the characteristic that intercepts wavelength 800～2000nm infrared rays wave band, and chemical formula is Cs
xN
yWO
3-ZCl
C, wherein Cs is a caesium; N is tin or antimony or bismuth; W is a tungsten; O is an oxygen; X, Y, Z, C are positive number, and meet following condition:
X≤1.0；
Y≤1.0；
Y/X≤1.0；
Z≤0.6 reaches
C≤0.1。
6. transparent insulate material as claimed in claim 5 has the characteristic that intercepts wavelength 800～1000nm infrared rays wave band.
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