CN105293578B - Method for manufacturing light shielding material and method for manufacturing light shielding structure - Google Patents

Abstract

The invention provides a light shielding material, a light shielding structure and a manufacturing method thereof. The light shielding structure includes: a transparent base material and a film, the film is provided on the transparent base material, and the film has multiple dispersions, wherein multiple dispersions The body is doped tungsten carbonate, as shown in formula (I): M _x WC _y O _z formula (I); where M is the dopant, and the dopant contains at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3. In this structure, multiple dispersions can be evenly distributed in the film, thereby having good penetration in the visible light band and taking into account the effect of blocking infrared light.

Description

Light-shielding body material manufacturing method and light-shielding structure manufacturing method

technical field

The invention relates to a light-shielding material, a light-shielding structure and a manufacturing method thereof, in particular to a light-shielding material capable of shielding infrared light, a light-shielding structure and a manufacturing method thereof.

Background technique

In today's global environment, due to the extensive use of fossil energy, the greenhouse effect is gradually becoming serious. The main reason is that the heat energy generated by visible light and near-infrared light stays in the earth, which makes the earth's temperature increase year by year. . Therefore, energy saving and carbon reduction has become an increasingly important issue.

The wavelength distribution of solar radiation is 300-2500 nanometers (nm), of which the ultraviolet part accounts for 14%, the visible part accounts for 40%, and the infrared part accounts for 44%. Traditional glass has a light-transmitting effect, but its thermal insulation performance is poor, so scientists and engineers try to coat the windows of cars and buildings with a metal film that can shield infrared light, such as metals containing silver or aluminum Thin films, etc., metal thin films use reflection to achieve the effect of shielding. However, the metal film will block electromagnetic waves, which will have adverse effects on the electronic products in the car, such as GPS, ETC, mobile communication devices, etc. In addition, generally, physical vapor deposition (PVD) or chemical vapor deposition (CVD) is used to make metal thin films, and the process cost and product price are very expensive.

In the past, dark pigments (dye or pigment) were also used to block sunlight, but this product has poor visible light penetration and has almost no blocking effect on infrared light.

At present, some commercially available products use ceramic compounds such as LaB ₆ , ATO (antimony tin oxide) or ITO (indium tin oxide) to make heat insulation films, but LaB ₆ will absorb visible light and cause the color to be too dark; The penetration rate of visible light is good, but the shielding effect on infrared light is less obvious.

In addition, there are still powders or films of tungsten oxide compounds doped with alkali metal elements on the market as infrared shielding materials or electrochromic components, but due to the nature of the materials, the visible light transmittance and infrared shielding There are still inconsistencies.

Contents of the invention

Therefore, the object of the present invention is to provide a light-shielding body material, a light-shielding structure and a manufacturing method that can moderately block visible light, shield infrared light, and not reflect sunlight, and is expected to solve the above-mentioned various problems.

According to the embodiment of the structure of the present invention, a kind of light-shielding body material is proposed, which is doped tungsten oxycarbide shown in formula (I), and doped tungsten oxycarbide is composed of dopant and carbon allotrope Doped with tungsten-containing compounds to form:

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3.

Other examples in the aforementioned embodiments are as follows: the aforementioned dopant can be selected from alkali metals (AlkaliMetals), alkaline earth metals (Alkaline Earth Metals), rare earth metals (Rare Earth Metals), boron (B), carbon (C) , Fluorine (F), Aluminum (Al), Silicon (Si), Phosphorus (P), Sulfur (S), Chlorine (Cl), Titanium (Ti), Vanadium (V), Chromium (Cr), Manganese (Mn) , iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), bromine (Br) , zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In) , tin (Sn), antimony (Sb), tellurium (Te), iodine (I), hafnium (Hf), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) , Gold (Au), Mercury (Hg), Thallium (Tl), Lead (Pb), Bismuth (Bi), Polonium (Po) and Astatin (At). The aforementioned carbon allotrope can be selected from the group consisting of carbon black, graphite, carbon nanotube and graphene. The aforementioned light-shielding body material is granular, and the particle size of the light-shielding body material is 1 nanometer (nm) to 1000 nanometers (nm). The aforementioned light-shielding body material is granular, and the particle size of the light-shielding body material is 1 nanometer (nm) to 150 nanometers (nm).

According to an embodiment of the method of the present invention, a method for manufacturing a light-shielding body material is proposed, the steps of which include: preparing a powder, wherein the powder includes a dopant, a tungsten-containing compound, and a carbon allotrope. Abrasive particles are added to the powder to form a mixed powder. The mixed powder is ground to obtain the starting material. Utilize mixed gas heat treatment initial raw material, form doped tungsten oxycarbide, as shown in formula (I):

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3.

Other examples in the aforementioned method implementation are as follows: the aforementioned tungsten-containing compound may be tungsten trioxide powder or tungsten dioxide powder. The aforementioned dopants can be selected from alkali metals (Alkali Metals), alkaline earth metals (Alkaline Earth Metals), rare earth metals (Rare Earth Metals), boron (B), carbon (C), fluorine (F), aluminum (Al) , silicon (Si), phosphorus (P), sulfur (S), chlorine (Cl), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co) , nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), bromine (Br), zirconium (Zr), niobium (Nb) , molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb) , tellurium (Te), iodine (I), hafnium (Hf), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg) , thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po) and astatite (At). The aforementioned carbon allotrope can be selected from the group consisting of carbon black, graphite, carbon nanotube and graphene. The aforementioned abrasive grains can be made of silicon carbide. The weight ratio of the abrasive particles to the powder in the aforementioned mixed powder may be 8:1. In the aforementioned step of grinding the mixed powder, a high-energy ball mill can be used to grind for 30 minutes to 6 hours. The aforementioned mixed gas may include hydrogen, methane and argon. The aforementioned heat treatment temperature may be 100° C. to 1000° C., and the heat treatment time may be 1 hour to 12 hours.

According to the embodiment of another structure of the present invention, a light shielding structure is proposed, which includes: a transparent substrate and a film, the film is arranged on the transparent substrate, and the film has a plurality of doped tungsten oxycarbides, as shown in the formula ( I) Shown:

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3.

Other examples in the aforementioned embodiments are as follows: the thickness of the aforementioned film may be from 0.5 micrometers (μm) to 200 micrometers (μm).

According to the embodiment of another method of the present invention, a method for manufacturing a light-shielding structure is proposed, wherein the steps of the manufacturing method include: preparing a plurality of doped tungsten oxycarbide, and the doped tungsten oxycarbide is shown in formula (I):

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3. A solvent is added to uniformly disperse a plurality of doped tungsten oxycarbides in the solvent. The medium is added to obtain a dispersion. Spread the dispersion on a transparent substrate. Solidifies the medium of the dispersion to form a thin film.

Other examples in the aforementioned embodiment are as follows: the aforementioned medium can be selected from polyester resin, PI resin, polycarbonate resin, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, poly Styrene resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, polypropylene resin, acrylic resin, fluororesin, silicone resin, phenoxy resin, polyethylene terephthalate resin, One of the group consisting of polyurethane resin, urea resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyether resin, polyamide, acrylic resin, epoxy resin and UV curing resin .

Description of drawings

Fig. 1 is a flow chart of the manufacturing method of the light-shielding body material of the present invention.

FIG. 2 is a flow chart of the manufacturing method of the light-shielding structure of the present invention.

FIG. 3A is a light shielding structure according to an embodiment of the present invention.

FIG. 3B is a side view of a light shielding structure according to another embodiment of the present invention.

Fig. 4 is a particle size-frequency diagram of the light-shielding body material of the present invention.

FIG. 5 is a wavelength-transmittance graph of the light shielding structure of the present invention.

detailed description

Since there are no effective free electrons in tungsten trioxide (WO ₃ ), the absorption and reflection properties in the visible and near-infrared regions are poor, and it cannot be effectively used as a light shielding material. When the atomic ratio of oxygen to tungsten in tungsten trioxide is less than 3, it represents an oxygen-deficient state or has oxygen vacancies. It can be seen that free electrons are generated in tungsten oxide; especially when the atomic ratio of oxygen to tungsten is less than 2.2, it will A crystalline phase of tungsten dioxide (WO ₂ ) appears. Therefore, the present invention enters the crystal lattice of tungsten trioxide by adding dopants and carbon to obtain the chemical stability of the material, and controls the atomic ratio of oxygen to tungsten to be less than 3, so that a necessary amount of free electrons is generated in tungsten oxide , as an effective light-shielding material.

Please refer to FIG. 1 , which is a flowchart of a method for manufacturing a light-shielding body material of the present invention. It can be known from FIG. 1 that the steps include: step 100, preparing powder, wherein the powder includes dopant, tungsten-containing compound and carbon allotrope. Step 110, adding abrasive particles to the powder to form a mixed powder. Step 120, grinding the mixed powder to obtain the initial raw material. In step 130, the initial raw material is heat-treated with a mixed gas to form doped tungsten oxycarbide, and the formed doped tungsten oxycarbide is shown in formula (I):

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3.

The above-mentioned tungsten-containing compound can be selected from tungsten trioxide powder and/or tungsten dioxide powder; in addition, the source of dopant M is oxide, hydroxide, carbonate, tungstate, chlorine containing chemical element M Compound salts, nitrates, sulfates, oxalates or nitrogen oxides, etc.

The above-mentioned dopant (M) can be selected from alkali metals (Alkali Metals), alkaline earth metals (Alkaline Earth Metals), rare earth metals (Rare Earth Metals), boron (B), carbon (C), fluorine (F), aluminum (Al), silicon (Si), phosphorus (P), sulfur (S), chlorine (Cl), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), bromine (Br), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), iodine (I), hafnium (Hf), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po) and astatite (At). When the amount of dopant added increases, the amount of free electrons also increases, so the effect of light shielding also increases, but when the value of x is close to 1, the effect gradually reaches saturation.

In addition, in order to moderately regulate the amount of free electrons in the doped tungsten oxycarbide material, the chemical stability of the material itself and the effectiveness of sunlight shielding, the present invention adds an appropriate amount of carbon allotrope to replace part of the oxygen content. The aforementioned carbon allotrope can be selected from the group consisting of carbon black, graphite, carbon nanotube and graphene. Therefore, the formed doped tungsten oxycarbide exhibits excellent shielding characteristics for the wavelength range of the whole solar spectrum, and is quite effective for insulating solar heat energy.

In the aforementioned step 120, in order to obtain uniformly mixed doped tungsten oxycarbide, the present invention weighs an appropriate amount of raw materials containing W, M and C and puts them into a ball mill jar, and the built-in diameters are 5mm and 10mm. Pure silicon carbide abrasive particles, the weight ratio of the abrasive particles to the powder is 8:1, and after ball milling with a high-energy ball mill for 30 minutes to 6 hours, a uniformly mixed powder can be obtained.

In the aforementioned step 130, the mixed powder is heat-treated in an inert and/or reducing gas environment, the temperature of the heat treatment is 100°C-1000°C, and the time is 1 hour-12 hours; the inert and/or reducing mixed gas includes any proportion of Argon (Ar), nitrogen (N ₂ ), hydrogen (H ₂ ) or methane (CH ₄ ), generally using hydrogen (5vol%) + methane (5vol%) + argon (90vol%) is a better condition .

Please refer to FIG. 2 , which is a flowchart of the manufacturing method of the light-shielding structure of the present invention, and its steps include: Step 200 , preparing a plurality of dispersions, wherein the plurality of dispersions are doped tungsten oxycarbide. Step 210, adding a solvent so that the plurality of dispersions are evenly dispersed in the solvent. Step 220, adding a medium to obtain a dispersion. Step 230, coating the dispersion on the transparent substrate. Step 240, curing the dispersion medium to form a thin film.

The plurality of dispersions in the above step 200 are doped tungsten oxycarbides prepared by the manufacturing method in FIG. 1 .

The solvent in the above step 210 is prepared by mixing toluene and dispersant at a weight ratio of 6:1.

The medium in the above step 220 can be selected from polyester resin, PI resin, polycarbonate resin, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polyvinyl alcohol Butyral resin, ethylene-vinyl acetate copolymer, polypropylene resin, acrylic resin, fluororesin, silicone resin, phenoxy resin, polyethylene terephthalate resin, polyurethane resin, urea resin, One of acrylonitrile-butadiene-styrene copolymer (ABS resin), polyether resin, polyamide, acrylic resin, epoxy resin and UV curing resin.

The coating method in the above step 230 is that the dispersion liquid containing multiple dispersions can be evenly coated on the surface of the transparent substrate. The coating method includes: wire bar coating method, gravure coating method, spray coating Cloth, dip, slot, spin, rod, roll, or knife coater.

The above-mentioned transparent substrate can be selected from PET, acrylic resin, polyurethane, polycarbonate, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride or fluororesin or glass according to different purposes.

Please refer to FIG. 3A , which is a side view of a light shielding structure according to an embodiment of the present invention. It can be seen from FIG. 3A that the light-shielding structure 300 of the present invention includes: a transparent substrate 310 and a film 320. The film 320 is disposed on the transparent substrate 310. The thickness of the film 320 is between 0.5 micrometers (μm) and 200 micrometers (μm). Between, and there are multiple dispersions 321 in the film 320, wherein the multiple dispersions 321 are doped tungsten oxycarbide, as shown in formula (I):

M _x WC _y O _z formula (I);

Wherein M is a dopant containing at least one chemical element, W is tungsten, C is carbon, O is oxygen, and 0<x≦1, 0<y≦1, 0<z≦3.

Please refer to FIG. 3B , which is a side view of a light shielding structure according to another embodiment of the present invention. It can be seen from FIG. 3B that the light-shielding structure 300 of the present invention includes: two transparent substrates 310 and a film 320, and the film 320 is arranged between the two transparent substrates 310; One of the group consisting of alcohol, diisocaprylate and polyvinyl butyraldehyde makes the dispersion viscous and adheres the two transparent substrates 310 together; first stretch the viscous dispersion It is formed into a thin film 320, and then the thin film 320 is placed between two transparent substrates 310, and the light shielding structure 300 shown in FIG. 3B is formed by hot pressing. This embodiment can be used for explosion-proof glass.

Another embodiment of the light-shielding structure 300 of the present invention (not shown in the accompanying drawings) disperses a plurality of dispersions 321 in the transparent substrate 310, firstly immersing the transparent substrate 310 in the aforementioned dispersion liquid, and then increasing The temperature makes the transparent base material 310 into a molten state, and the dispersion 321 is mixed with the molten transparent base material 310 , and formed into a plate shape or a film shape after cooling down. For example: the transparent substrate 310 is made of PET resin, after it is immersed in the dispersion liquid, the surface of the PET resin has multiple dispersions 321, and then heated to the melting temperature of PET, mixed and cooled, and a composite material containing multiple dispersions 321 can be prepared. PET resin.

When the aforementioned dispersion 321 has a hexagonal crystal structure, its transmittance in the visible light region and absorption in the far infrared region are also better. If the dispersion 321 has an amorphous phase, tetragonal or cubic tungsten bronze structure, its transmittance in the visible light region and absorption effect in the far infrared region are poor.

Since the film 320 of the present invention can absorb a large amount of energy in the near-infrared and far-infrared regions, as well as part of the energy in the visible light region, the appearance of the film 320 is blue to green.

When the particle size of the dispersion 321 is too large, due to geometric scattering or Mie scattering (Mie scattering), the thin film 320 made of the dispersion 321 is formed in the visible light region similar to frosted glass and cannot obtain clear transparency; The particle size of the inventive dispersion 321 is controlled between 1 nanometer and 1000 nanometers, which can avoid the above-mentioned phenomenon, and can obtain clear images when used in the optical field.

Please refer to FIG. 4 , which is a particle size-frequency diagram of the light-shielding body material of the present invention. The particle size of the light-shielding material (dispersion) of the present invention is measured by a particle size analyzer (Mastersizer, Malvern, UK), and the particle size is measured by Laser Diffraction Scattering (ISO 13320 specification). When the laser beam passes through the dispersed particle sample, scattered light signals of different angles and intensities are generated, and the scattered light spectrum is measured and recorded at the same time, and then the particle size distribution of the scattered light spectrum is analyzed and calculated. It can be seen from Fig. 4 that, taking the atomic ratio Cs:W:C=0.32:1:0.4 of the light-shielding material as an example, the distribution of the particle size-frequency diagram after heat treatment at 500°C/1hr is shown in Fig. 4. The horizontal axis is the particle size, the unit is nanometer (nm), the vertical axis is the frequency, the unit is %; the particle size of the light shielding material prepared in the figure is all less than 140 nanometers (nm), the result after statistical calculation shows that: D ₅₀ (median diameter; the equivalent particle diameter of the largest particle when the cumulative distribution is 50% in the curve of Fig. 4) is 54nm, _D90 (the equivalent particle diameter of the largest particle when the cumulative distribution is 90% in the curve of Fig. 4 ) is 110nm.

Please refer to FIG. 5 , which is a wavelength-transmittance diagram of the light shielding structure of the present invention. The light-shielding body material of Fig. 4 (light-shielding material atomic ratio Cs:W:C=0.32:1:0.4) is coated on the PET film, forms the light-shielding body structure of the present invention, and its wavelength-transmittance curve is as follows As shown in Figure 5, the horizontal axis is the wavelength of light in the figure, and the unit is nanometer (nm), and the vertical axis is the transmittance, and the unit is %; As can be seen from Figure 5, the wavelength of its light-transmitting part is the light of 380nm-780nm ( For example, the transmittance of visible light with a wavelength of 500nm is 69%), the transmittance of infrared light with a wavelength of 1000nm is 3%, and the transmittance of infrared light with a wavelength of 1500nm is 1%. The light has good penetration, and has excellent shielding properties in the infrared region.

The following examples are given to describe the present invention in more detail.

comparative example

Optical properties of a PET film having a thickness of 23 μm as a transparent substrate were used in the comparative example. The light transmittance in the entire solar spectrum range (300nm-2500nm) is more than 89.2%, the transmittance in the visible region is about 90%, and the transmittance in the infrared region is about 85%. The shielding effect of sunlight is not good.

Example 1

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 500°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 50 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was The optical transmittance spectrum of this structure is shown in Figure 5, and its optical properties are listed in Table 1, wherein the average transmittance of visible light is 65%, and the shading coefficient (SC) is 0.42.

Example 2

Weigh 231.84g of tungsten trioxide, 31g of sodium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm. The weight ratio of abrasive particles to powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 500°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 53 m ² /g.

The chemical composition of the powder was analyzed with an energy dispersive spectrometer (EDS). The result shows that Na:W:C=0.9:1:0.2, which is the atomic ratio, indicating that Na and C have been doped into tungsten oxide during the heat treatment process. form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 70%, and the shading coefficient (SC) is 0.45.

Example 3

Weigh 231.84g of tungsten trioxide, 13.9g of indium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm. The weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 500°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 51 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS). The result shows that In:W:C=0.1:1:0.4, which is the atomic ratio, indicating that In and C have been doped into tungsten oxide during the heat treatment process. form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 55%, and the shading coefficient (SC) is 0.50.

Example 4

Weigh 231.84g of tungsten trioxide, 8.4g of calcium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm. The weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 500°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 54 m ² /g.

The chemical composition of the powder was analyzed with an energy dispersive spectrometer (EDS). The result shows that Ca:W:C=0.15:1:0.2, which is an atomic ratio, indicating that Ca and C have been doped into tungsten oxide during the heat treatment process. form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 62%, and the shading coefficient (SC) is 0.45.

Example 5

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 750°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 46 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 68%, and the shading coefficient (SC) is 0.40.

Example 6

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 1000°C, and the time is 1 hour; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 42 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 62%, and the shading coefficient (SC) is 0.42.

Example 7

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 750°C, and the time is 5 hours; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 41 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, in which the average visible light transmittance is 67%, and the shading coefficient (SC) is 0.41.

Example 8

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 750°C, and the time is 10 hours; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 38 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing the slurry with the acrylic resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then dried with hot air at 100°C for 10 minutes to obtain the translucent and blue light-shielding film of the present invention, the thickness of which was Its optical properties are listed in Table 1, wherein the average visible light transmittance is 64%, and the shading coefficient (SC) is 0.42.

Example 9

Weigh 231.84g of tungsten trioxide, 45.09g of cesium oxide, and 12g of carbon black and put them into a ball mill jar, which contains two specifications of high-purity silicon carbide abrasive particles with a diameter of 5mm and 10mm, and the weight of the abrasive particles and powder The ratio is 8:1, and after 1 hour of ball milling with a high-energy ball mill, the initial raw material of uniformly mixed light-shielding material powder can be obtained. The initial raw material is heat-treated in a mixed gas environment, the temperature of the heat treatment is 750°C, and the time is 5 hours; the mixed gas is H ₂ (5vol%)+CH ₄ (5vol%)+Ar (90vol%), and the pressure is 1 atmospheric pressure. A light-shielding material powder was obtained, and the specific surface area of this powder was 41 m ² /g.

The chemical composition of the powder was analyzed by energy dispersive spectrometer (EDS), and the result shows that Cs:W:C=0.32:1:0.4, which is the atomic ratio, showing that Cs and C have been doped into tungsten oxide during the heat treatment process, form new compounds.

Fully mix the powder of the light-shielding material with toluene and dispersant, the weight ratio of powder, toluene, and dispersant is 3:6:1; then perform ultrasonic dispersion and grinding to obtain a slurry with an average particle size of 60nm; The light-shielding material dispersion of the present invention can be obtained by mixing this slurry with UV resin at a weight ratio of 1:9.

The light-shielding material dispersion was coated on the PET film of the comparative example by doctor blade coating method, and then the resin was cured with ultraviolet light to obtain the translucent and blue light-shielding film of the present invention, with a thickness of 10 μm; Its optical properties are listed in Table 1, wherein the average transmittance of visible light is 70%, and the shading coefficient (SC) is 0.40.

Table 1

The above-mentioned shading coefficient (Shading Coefficient; SC) is the ratio of each example (1-9) and the comparative example (PET film with a thickness of 23 μm) in the same light irradiation environment. The smaller the value of the shading coefficient, the better the "shading" effect of the embodiment on the light.

In summary, the light-shielding body material, light-shielding structure and manufacturing method of the present invention have the following advantages:

First, the M _x WC _y O _z in the light-shielding material and the light-shielding structure is doped tungsten carbide, and the light-shielding structure made of this light-shielding material can have both high visible light transmittance and High infrared shielding.

Second, the manufacturing method is different from the wet process used in the prior art. The present invention is an all-dry process, which can not only avoid highly corrosive or highly polluting by-products produced in the process, but also the initial high-energy ball milling process Powder, alloying occurs, forming homogeneously mixed starting materials at the molecular level.

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Any person skilled in the art should be able to make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection of an invention shall be defined by the claims.

Claims (13)

1. a kind of smooth baffle material manufacturing method, its step are included：

A () prepares powder, wherein powder includes alloy, Tungstenic compound and carbon allotrope；

B () adds abrasive grains in powder, form mixed-powder；

C () ground and mixed powder, obtains initial feed；And

D () forms the oxidation of coal tungsten of doping, as shown in formula (I) using mixed gas heat treatment initial feed：

M_xWC_yO_zFormula (I)；

Wherein M is alloy, and alloy includes at least one chemical element, and W is tungsten, and C is carbon, and O is oxygen, and 0 ＜ x≤1,0 ＜ y ≤ 1,0 ＜ z≤3.

2. smooth baffle material manufacturing method according to claim 1, wherein Tungstenic compound be tungsten trioxide powder or Tungsten dioxide powder.

3. smooth baffle material manufacturing method according to claim 1, wherein alloy are selected from alkali metal, alkaline earth gold Category, rare earth metal, boron, fluorine, aluminum, silicon, phosphorus, sulfur, chlorine, titanium, vanadium, chromium, manganese, ferrum, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, Zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, stannum, antimony, tellurium, iodine, hafnium, tantalum, rhenium, osmium, iridium, platinum, gold, hydrargyrum, thallium, lead, bismuth, polonium One kind in the group constituted by Ji Astatine.

4. smooth baffle material manufacturing method according to claim 1, wherein carbon allotrope are selected from carbon black, stone One kind in the group constituted by ink, CNT and Graphene.

5. smooth baffle material manufacturing method according to claim 1, the wherein material of abrasive grains are carborundum.

6. smooth baffle material manufacturing method according to claim 1, the wherein abrasive grains of mixed-powder and powder Weight ratio is 8：1.

7. smooth baffle material manufacturing method according to claim 1, wherein step (c) grind 30 using high energy ball mill Minute was to 6 hours.

8. smooth baffle material manufacturing method according to claim 1, wherein mixed gas include hydrogen, methane and argon Gas.

9. smooth baffle material manufacturing method according to claim 1, the wherein heat treatment temperature of step (d) are 100 DEG C To 1000 DEG C, heat treatment time is 1 hour to 12 hours.

10. smooth baffle material manufacturing method according to claim 1, wherein the oxidation of coal tungsten for adulterating is graininess, and The particle diameter of the oxidation of coal tungsten of doping is 1 nanometer to 1000 nanometers.

11. smooth baffle material manufacturing methods according to claim 10, wherein the oxidation of coal tungsten for adulterating is graininess, and The particle diameter of the oxidation of coal tungsten of doping is 1 nanometer to 150 nanometers.

A kind of 12. smooth masking structure manufacture methods, its step are included：

A () prepares the oxidation of coal tungsten of multiple doping, shown in the oxidation of coal tungsten such as formula (I) of doping：

M_xWC_yO_zFormula (I)；

Wherein M is alloy, and alloy includes at least one chemical element, and W is tungsten, and C is carbon, and O is oxygen, and 0 ＜ x≤1,0 ＜ y ≤ 1,0 ＜ z≤3；

B () adds solvent, make the oxidation of coal tungsten of doping be dispersed in solvent；

C () adds medium, obtain dispersion liquid；

D () Coating dispersions are on transparent base；And

E () solidifies the medium of dispersion liquid, form thin film.

13. smooth masking structure manufacture methods according to claim 12, wherein medium selected from polyester resin, PI resins, Polycarbonate resin, polyvinyl resin, Corvic, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene tree Fat, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, acrylic resin, acrylic resin, fluororesin, silicone Resin, phenoxy resin, pet resin, poly- amino resins, urea resin, acrylonitrile-butadiene-benzene In the group constituted by ethylene copolymer, polyether resin, polyamide, acryl resin, epoxy resin and UV solidified resins one Kind.