CN110330813B - Color TiO2Near-infrared reflection pigment and preparation method thereof - Google Patents

Color TiO2Near-infrared reflection pigment and preparation method thereof Download PDF

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CN110330813B
CN110330813B CN201910382579.5A CN201910382579A CN110330813B CN 110330813 B CN110330813 B CN 110330813B CN 201910382579 A CN201910382579 A CN 201910382579A CN 110330813 B CN110330813 B CN 110330813B
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pigment
tio
carrying
ball milling
grinding
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CN110330813A (en
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袁乐
卿小龙
毕美
翁小龙
黄刚
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Sichuan Zhiyi Industrial Co ltd
University of Electronic Science and Technology of China
Xihua University
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Sichuan Zhiyi Industrial Co ltd
University of Electronic Science and Technology of China
Xihua University
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Abstract

The application provides a colored TiO2Near-infrared reflective pigment and preparation method thereof, wherein the chemical formula of the pigment is Ti1‑m‑ nFemMonO2(ii) a The method comprises the following steps: step S1: preparing TiO with preset mass fraction2Raw material, Fe3+Impurities and Mo6+Impurities; step S2: carrying out ball milling and grinding treatment on the prepared material in sequence; step S3: carrying out solid phase synthesis on the ground grinding material to completely convert anatase type into rutile type; step S4: carrying out secondary grinding and sieving on the reactant after solid-phase synthesis to obtain the colored TiO2A near infrared reflective pigment. By this application, the existing inverse can be solvedThe near infrared reflectivity of the jet type energy-saving pigment is low, the color is single, the energy-saving effect is poor, and the like.

Description

Color TiO2Near-infrared reflection pigment and preparation method thereof
Technical Field
The application relates to the technical field of inorganic oxide near-infrared high-reflection materials, in particular to colored TiO2Near-infrared reflective pigments and methods for their preparation.
Background
The inorganic oxide pigment has good temperature and chemical stability, so that the inorganic oxide pigment is widely applied to the fields of building outer walls, automobiles, industrial equipment surfaces, plastics, color masterbatch and the like, and has wide application prospect. The spectral reflection characteristic of the pigment is an important parameter for representing the performance of various inorganic pigments and is one of the inherent attributes of the inorganic pigment, and the color tone and the brightness of the pigment are directly determined by the reflection characteristic of the visible light wave band (400 nm-700 nm) of the solar spectrum; the reflection characteristics at the near-infrared end of the spectrum (700nm to 2500nm) are closely related to the solar heat absorption/reflection properties of the pigment. At present, in the total solar energy reaching the ground, a visible light region accounts for about 50% of the total solar radiation energy, an infrared region accounts for about 43%, and 95% of the infrared radiation energy is concentrated in the range of 0.72-2.5 um in wavelength, namely in the near infrared range. Therefore, the coating with high near infrared reflectivity can reflect most of the energy of sunlight, reduce the temperature of the surface of an object and avoid many adverse effects caused by the increase of the surface temperature.
In the prior art, Shendali invented a high infrared reflection heat insulation coating for exterior wall buildings and its preparation method (Chinese patent CN 103)881484A), the research of the research adopts titanium dioxide to prepare the reflective heat-insulating pigment, and the product of the invention has no toxicity and good reflectivity. Although titanium dioxide as a white pigment has high reflectivity (more than 60%) in a visible light-near infrared band, a white (or light-colored) high-reflection coating formed by the titanium dioxide has the defects of visual attractiveness, poor pollution resistance and short service life because of the discordance of color tone and environment, and is difficult to meet the building aesthetic requirements when used as an energy-saving material; at present, the research on near infrared reflection pigments mainly takes light color as a main part, but with the improvement of the living standard of people, more requirements on the color of a coating are made. Colored pigments are preferred, however, the common colored pigments absorb more near infrared sunlight (have low reflectivity), which is a bottleneck in developing colored near infrared reflective pigments. For example, chinese patent document CN102181217A discloses a color reflective thermal insulation coating, which uses five pigments of chrome iron black, chrome iron red, cobalt blue, titanium yellow, and cobalt green to replace the conventional commonly used pigments such as carbon black, iron oxide red, organic yellow, phthalocyanine green, and phthalocyanine blue, and although the color requirement of exterior wall decoration can be satisfied, the near infrared reflectivity of the prepared coating is low (26.95% -63.16%), and it is difficult to satisfy the building energy saving requirement. Therefore, increasing the color range of the pigment and improving the reflectivity of the near infrared band are two important directions for the research of the high-reflection energy-saving material at present. Based on the research direction, the Sarasama Vishnu et al uses praseodymium ions to prepare doped Y in later period2Ce2O7The pigment is brownish red after being doped with praseodymium ions, but the near infrared reflectivity of the pigment is only 57.5 percent; the patent document CN107556801A also discloses an iron red near-infrared high-reflection material and a preparation method thereof, wherein the chemical formula of the iron red near-infrared high-reflection material is Ti0.8Fe0.2O2Its near infrared reflectance is also only 51.28%.
In summary, it is a mainstream direction of current research to dope a substrate to obtain a color, but the reflectivity of the current pigment prepared by doping is low, and some doping materials contain harmful heavy metals (such as cadmium red, chromium green, cobalt blue, cadmium stannate, lead chromate and the like), so that the harm to health and environment is large. The prepared pigment still has the problem of single color and cannot meet the requirements of the current paint on color.
Disclosure of Invention
The present application provides a colored TiO2The near-infrared reflection pigment and the preparation method thereof solve the problems of low near-infrared reflectivity, single color, poor energy-saving effect and the like of the existing reflection type energy-saving pigment.
In order to solve the above problems, the present application discloses a colored TiO2A near infrared reflective pigment having the formula Ti1-m-nFemMonO2(ii) a Wherein m is 0.014-0.06 and n is 0.002-0.018.
Meanwhile, the application also discloses a method for preparing the colored TiO2A method of near-infrared reflecting pigments, the method comprising:
step S1: preparing TiO with preset mass fraction2Raw material, Fe3+Impurities and Mo6+Impurities;
step S2: carrying out ball milling and grinding treatment on the prepared material in sequence;
step S3: carrying out solid phase synthesis on the ground grinding material to completely convert anatase type into rutile type;
step S4: carrying out secondary grinding and sieving on the reactant after solid-phase synthesis to obtain the colored TiO2A near infrared reflective pigment.
Optionally, the step S1 includes:
preparing TiO with the mass fraction of 95.2 to 99.1 percent20.7 to 3 percent of Fe2O30.2 to 1.8 percent of MoO3。
Preferably, the step S1 includes:
preparing TiO with the mass fraction of 96.2 to 99.05 percent20.7 to 3 percent of Fe2O30.25 to 0.8 percent of MoO3。
Preferably, the step S1 includes:
preparing 98.9 mass percent of TiO20.75% of Fe2O30.375% MoO3。
Optionally, the ball milling treatment step includes:
the prepared material was added to a ball mill pot and ball milled for several hours using a wet process.
Optionally, the ball milling treatment step includes:
adding the prepared materials into a ball milling tank, adding 50ml of ethanol, and carrying out ball milling for 4 hours by adopting a wet method, wherein the material-ball ratio is 1: 4, the rotating speed is 500 r/min.
Optionally, the step of grinding treatment includes:
and drying and crushing the slurry subjected to ball milling treatment, and then grinding.
Optionally, the step S3 includes:
and (3) putting the ground grinding material into a high-temperature sintering furnace, carrying out solid-phase synthesis reaction, and carrying out heat preservation and calcination at 1000 ℃ for 120min to completely convert the anatase type into the rutile type.
Optionally, the step S4 includes:
carrying out superfine grinding on the reactant after the solid phase synthesis, and sieving the reactant by using a 200-mesh filter screen to obtain the colored TiO2A near infrared reflective pigment.
Compared with the prior art, the method has the following advantages:
provides a colored TiO2Preparation method of near-infrared reflection pigment, using several environment-friendly elements Fe and Mo to make TiO2The pigment is codoped and modified, the color range is adjusted by coloring elements and the reflectivity of the coating is improved by compensating elements, the color control range is improved, and the TiO can be kept2The high near-infrared reflection characteristic of the matrix greatly improves the solar heat reflection capability of the pigment, reduces the heat accumulation on the using surface of the pigment, has wide application prospect in the energy-saving coating field, and can better realize the coordination of energy-saving effect and visual attractiveness.
Drawings
FIG. 1 is a process for preparing a colored TiO2A flow chart of the steps of a method of near infrared reflective pigments;
FIG. 2 shows colored TiO prepared by different mass fraction ratios2Color plate images of near infrared reflective pigments and their control groups;
FIG. 3 shows codoped TiO compounds prepared at different ratios2A comparison plot of the average reflectance of near infrared reflective pigments;
FIGS. 4 to 7 show co-doped TiO compounds prepared at different ratios2A graph comparing the reflectance of a near infrared reflective pigment to its single doped control.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, the present application is described in further detail with reference to the accompanying drawings and the detailed description.
Due to TiO2The high refractive index crystal form (rutile type) has good solar reflection effect and other characteristics and is widely applied, and based on the requirements of different application backgrounds on color and spectral reflection characteristics, for example, (Cr, Sb) codoped TiO prepared by Zou J et al in Dyes and Pigments 109(2014) 113-2Pigment, TiO doped by multicomponent method2The pigment is subjected to modification design, the color of the pigment is gradually changed from bright yellow to orange yellow along with the continuous increase of the doping amount of the metal elements, but the reflectivity of the pigment in a near infrared band is gradually reduced to 50 percent; rui Yang et al in Solar Energy Materials&Solar Cells published co-doping Fe and N to MgTiO3In the middle, the color is changed from white to dark red, but the reflectivity of the sample can only reach 53 percent in the wave band of 700nm-2500 nm. The existing co-doping research has a certain improvement effect, but the ideal effect cannot be achieved, the relationship between the color range and the reflectivity cannot be reasonably regulated, and the higher reflectivity cannot be achieved.
Aiming at the problems of the prior art, the application provides a new technical scheme, two impurities (n-type and p-type matching) with different valence states are selected for doping modification, a non-ferrous metal ion is used as an n-type (p-type) coloring impurity, the characteristic absorption of low-energy visible light photons is formed by introducing an impurity energy level in a forbidden band, and TiO is further regulated and controlled2And (4) color. On the other hand, to avoid high impurity doping concentrationsThe phenomena of the increase of the concentration of free carriers of the sample and the reduction of the near infrared reflectivity are caused, p-type (n-type) compensation impurities are introduced, and TiO is reduced through the neutralization effect2The concentration of electrons (holes) in the matrix has the effects of weakening the absorption of free carriers in a near-infrared band and enhancing the near-infrared reflectivity of the sample.
Example (b):
the embodiment of the application provides a colored TiO2A near infrared reflective pigment having the formula Ti1-m- nFemMonO2(ii) a Wherein m is 0.014-0.06 and n is 0.002-0.018.
Referring to FIG. 1, the examples of the present application also show the preparation of a colored TiO2A flow chart of steps of a method of near-infrared reflecting pigments, the method may comprise:
step S1: preparing materials: preparing TiO with preset mass fraction2Raw material, Fe3+Impurities and Mo6+Impurities;
in an optional embodiment of the present application, it is shown that the step S1 specifically may include:
preparing TiO with the mass fraction of 95.2 to 99.1 percent20.7 to 3 percent of Fe2O30.2 to 1.8 percent of MoO3。
In a preferred embodiment of the present application, the step S1 includes:
preparing TiO with the mass fraction of 96.2 to 99.05 percent20.7 to 3 percent of Fe2O30.25 to 0.8 percent of MoO3。
Step S2: carrying out ball milling and grinding treatment on the prepared material in sequence;
the ball milling treatment comprises the following steps:
the prepared material was added to a ball mill pot and ball milled for several hours using a wet process.
When the concrete implementation is realized, the method can comprise the following steps: adding the prepared materials into a ball milling tank, adding 50ml of ethanol, and carrying out ball milling for 4 hours by adopting a wet method, wherein the material-ball ratio is 1: 4, the rotating speed is 500 r/min.
Grinding treatment: and drying and crushing the slurry subjected to ball milling treatment, and then grinding.
Step S3: carrying out solid phase synthesis on the ground grinding material to completely convert anatase type into rutile type;
the steps can be specifically as follows: and (3) putting the ground grinding material into a high-temperature sintering furnace, carrying out solid-phase synthesis reaction, and carrying out heat preservation and calcination at 1000 ℃ for 120min to completely convert the anatase type into the rutile type.
Step S4: carrying out secondary grinding and sieving on the reactant after solid-phase synthesis to obtain the colored TiO2A near infrared reflective pigment.
The steps can be specifically as follows: carrying out superfine grinding on the reactant after the solid phase synthesis, and sieving the reactant by using a 200-mesh filter screen to obtain the colored TiO2A near infrared reflective pigment.
According to the purpose of the present application and the technical means adopted, the steps S1-S4 are Fe3+And Mo6+Double doped TiO2To develop colored TiO with high near infrared reflectivity2A pigment.
When the coloring impurity is Fe3+When the compensating impurity is Mo6+；
When the coloring impurity is Mo6+When the compensating impurity is Fe3+。
When implemented, by colouring impurity Fe3+(Mo6+) The doping of (2) introduces an impurity level to cause TiO2The change in the energy band width causes a change in the visible light absorption spectrum, changing the color of the matrix. However, as the doping concentration of the colored impurities increases, the concentration of free carriers in the sample increases, thereby reducing the near-infrared reflectance of the sample. Therefore, the application introduces a certain proportion of high valence Mo6+(lower valence Fe)3+) As the compensation impurities, the addition of the compensation impurities can reduce the concentration of holes (electrons) in the matrix, and play a role in reducing free carriers, so that the near-infrared reflectivity of the sample is improved.
Meanwhile, the coloring impurities and the compensating impurities in the embodiment of the application can play roles in regulating and controlling whiteColoured TiO2The visible light absorption spectrum and the color effect of the pigment further widen the regulation and control range of the color. The unique advantages of the method are that the color regulation range is improved, and TiO can be kept2The high near-infrared reflection characteristic of the matrix greatly improves the solar heat reflection capability of the pigment, reduces the heat accumulation on the using surface of the pigment, has wide application prospect in the energy-saving coating field, and can better realize the coordination of energy-saving effect and visual attractiveness.
Next, in order to further verify the feasibility of the embodiment of the present application, two experimental groups and three control groups are designed to illustrate the technical solution of the embodiment of the present application.
Experiment group one: preparing 98.875% TiO according to mass fraction20.75% of Fe2O30.375% MoO3(ii) a Adding the prepared raw materials into a ball milling tank, adding 50ml of ethanol, and carrying out ball milling for 4 hours by adopting a wet method, wherein the material-ball ratio is 1: 4, the rotating speed is 500 r/min. And drying and crushing the ball-milled slurry, and then grinding. And (3) putting the ground grinding material into a high-temperature sintering furnace, carrying out solid-phase synthesis reaction, and calcining at the temperature of 1000 ℃ for 120min to convert the anatase type into the rutile type. And grinding and sieving for the second time after the solid-phase reaction is finished. Ultra-fine grinding the reactant of solid phase synthesis, and sieving with 200 mesh sieve to obtain Fe3+、Mo6+Co-doped TiO2A near infrared reflective pigment.
Experiment group two: preparing 96.75 percent TiO according to mass fraction22.5% of Fe2O30.75% MoO3. The step of processing the prepared raw materials refers to experiment group one, which is not described herein any more, and Fe is obtained3+、Mo6+Co-doped TiO2A near infrared reflective pigment.
Control group one: preparing 98.5-100% TiO according to mass fraction2Separately, 0% of MoO was prepared30.375% MoO30.75% of MoO31.5% MoO3. The prepared raw materials are marked as sample 1-1, sample 1-2, sample 1-3 and sample 1-4 in sequence and are added with different materials respectivelyThe subsequent treatment steps of the ball milling tank are carried out according to the experiment group I, which is not repeated herein, so that Mo is obtained6+Single doped TiO2A near infrared reflective pigment.
Control group two: preparing 97.75-99.25% TiO according to mass fraction20.75% of Fe2O3Separately, 0% of MoO was prepared30.375% MoO30.75% of MoO31.5% MoO3. The prepared raw materials are sequentially marked as a sample 2-1, a sample 2-2 (namely an experiment group I), a sample 2-3 and a sample 2-4, and are respectively added into different ball milling tanks, and the subsequent processing steps refer to the experiment group I, which is not repeated herein, so that Fe is obtained3+、Mo6+Co-doped TiO2A near infrared reflective pigment.
Control group three: preparing 96-97.5 percent of TiO according to mass fraction22.5% of Fe2O3Separately, 0% of MoO was prepared30.375% MoO30.75% of MoO31.5% MoO3. The prepared raw materials are sequentially marked as a sample 3-1, a sample 3-2, a sample 3-3 (namely an experiment group two) and a sample 3-4, and are respectively added into different ball milling tanks, and the subsequent processing steps refer to the experiment group one, which is not repeated herein, so that Fe is obtained3+、Mo6+Co-doped TiO2A near infrared reflective pigment.
In summary, the embodiment of the present application compares two experimental groups with three control groups, and the characteristics of the present application include:
(1) the phase structure of the prepared pigment is rutile type with high refractive index, and a good solar energy reflection effect can be achieved.
(2) Through Fe3+、Mo6+The co-doped prepared TiO2 near-infrared reflection pigment has various colors in different proportions, such as: red, orange, yellow, green, indigo, and the like. Referring to FIG. 2, it shows the color TiO prepared by different mass fraction ratios in the examples of the present application2A color palette of near infrared reflective pigments; the color palette image has been grey scale processed in fig. 2.
(3) Single doped TiO2Plane of near infrared reflection pigmentThe average reflectivity decreases with increasing concentration, and the co-doped TiO is used in the present application2The average reflectance of the near infrared reflective pigments increases and then decreases as their concentration increases. Therefore, higher average reflectivity can be obtained only by controlling the co-doping ratio well. As a preferred embodiment of the present application, 98.875% TiO by mass fraction is prepared20.75% of Fe2O30.375% MoO3(ii) a Under the mass fraction ratio, the prepared color TiO2Near infrared reflecting pigments, i.e. Fe3+、 Mo6+Co-doped TiO2The average reflectivity of the near infrared reflection pigment can reach more than 95 percent.
Referring to FIG. 3, co-doped TiO compounds prepared at different ratios are shown2Graph comparing the average reflectance of near infrared reflective pigments. In fig. 3, X ═ 0 represents control group one; x ═ 0.0075 represents control group two; x is 0.025 for control group III, X means Fe2O3Y represents MoO3Mass fraction of (c).
(4) Referring to FIGS. 4 to 7, codoped TiO compounds prepared at different ratios are shown2A graph comparing the reflectance of a near infrared reflective pigment to its single doped control. From the comparison results, it was found that the prepared TiO was codoped2The reflectivity of the near infrared reflection pigment is better than that of single doping under the condition of a certain mixture ratio. X in FIGS. 4 to 7 represents Fe2O3Y represents MoO3Mass fraction of (c).
The embodiments in the present specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The above-mentioned colored TiO provided by the present application2The near infrared reflection pigment and the preparation method thereof are introduced in detail, the principle and the implementation mode of the application are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the application; also, to one of ordinary skill in the art, in light of the teachings of this applicationIt is to be understood that changes may be made in the particular embodiments and applications described above, and in view of the above, the description is not intended to limit the scope of the invention.

Claims (6)

1. Color TiO2The near-infrared reflection pigment is characterized by being applied to the field of energy-saving coatings, the energy-saving principle is that the near-infrared reflectivity is enhanced, and the chemical formula of the pigment is Ti1-m-nFemMonO2(ii) a Wherein m is 0.014-0.06, n is 0.002-0.018; the pigment passes 98.875% TiO20.75% of Fe2O30.375% MoO3Preparing to obtain; the average reflectance of the pigment is greater than 95%;
wherein the preparation method of the pigment comprises the following steps:
step S1: preparing 98.875 percent of TiO according to mass fraction20.75% of Fe2O30.375% MoO3；
Step S2: sequentially adding the prepared materials into a ball milling tank, adding 50ml of ethanol, and carrying out ball milling and grinding treatment;
step S3: carrying out solid phase synthesis on the ground grinding material to completely convert anatase type into rutile type;
step S4: carrying out secondary grinding and sieving on the reactant after solid-phase synthesis to obtain the colored TiO2A near infrared reflective pigment.
2. The pigment according to claim 1, wherein in the preparation method of the pigment, the step of ball milling treatment comprises:
and adding the prepared materials into a ball milling tank, and carrying out ball milling for 4 hours by using a wet method.
3. The pigment according to claim 2, wherein the step of ball milling comprises, in the method of preparing the pigment:
adding the prepared materials into a ball milling tank, and carrying out ball milling for 4 hours by adopting a wet method, wherein the material-ball ratio is 1: 4, the rotating speed is 500 r/min.
4. The pigment according to claim 1, characterized in that in the preparation method of the pigment, the step of grinding treatment comprises:
and drying and crushing the slurry subjected to ball milling treatment, and then grinding.
5. The pigment according to claim 1, wherein in the method for producing the pigment, the step S3 comprises:
and (3) putting the ground grinding material into a high-temperature sintering furnace, carrying out solid-phase synthesis reaction, and carrying out heat preservation and calcination at 1000 ℃ for 120min to completely convert the anatase type into the rutile type.
6. The pigment according to claim 1 or 5, wherein in the preparation method of the pigment, the step S4 comprises:
carrying out superfine grinding on the reactant after the solid phase synthesis, and sieving the reactant by using a 200-mesh filter screen to obtain the colored TiO2A near infrared reflective pigment.
CN201910382579.5A 2019-05-09 2019-05-09 Color TiO2Near-infrared reflection pigment and preparation method thereof Expired - Fee Related CN110330813B (en)

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CN110734651A (en) * 2019-10-23 2020-01-31 广东丰霖新材料科技有限公司 brownish red pigment, and preparation method and application thereof
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6042236A (en) * 1983-08-10 1985-03-06 Asahi Kasei Kogyo Kk Yellow inorganic pigment
CN1037494A (en) * 1988-05-10 1989-11-29 北京有色金属研究总院 Yellow series inorganic pigment
JPH0543235A (en) * 1991-08-08 1993-02-23 Mitsubishi Materials Corp Production of titanium oxide-based yellow pigment
JP2003160741A (en) * 2001-11-28 2003-06-06 Sanyu:Kk Inorganic white pigment
CN102127342A (en) * 2010-12-24 2011-07-20 陕西理工学院 Method for preparing pitchy pigment capable of reflecting infrared rays and heat insulating paint
CN102134407A (en) * 2010-12-23 2011-07-27 北京大学 Nano corundum type inorganic pigment and preparation method thereof
CN102181217A (en) * 2011-04-14 2011-09-14 广州立邦涂料有限公司 Colorized reflection heat insulation coating and color card thereof
CN103493144A (en) * 2011-04-28 2014-01-01 法国圣戈班玻璃厂 Transparent electric conductor
CN103589195A (en) * 2013-10-24 2014-02-19 陕西理工学院 Preparation method of cinereous pigment capable of reflecting infrared rays and heat-insulating paint
CN103881484A (en) * 2012-12-20 2014-06-25 广州市久美化工有限公司 High-infrared-reflection heat-insulation coating for exterior wall building and preparation method thereof
CN107556801A (en) * 2017-08-23 2018-01-09 华南理工大学 A kind of rust near-infrared high reflection material and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6042236A (en) * 1983-08-10 1985-03-06 Asahi Kasei Kogyo Kk Yellow inorganic pigment
CN1037494A (en) * 1988-05-10 1989-11-29 北京有色金属研究总院 Yellow series inorganic pigment
JPH0543235A (en) * 1991-08-08 1993-02-23 Mitsubishi Materials Corp Production of titanium oxide-based yellow pigment
JP2003160741A (en) * 2001-11-28 2003-06-06 Sanyu:Kk Inorganic white pigment
CN102134407A (en) * 2010-12-23 2011-07-27 北京大学 Nano corundum type inorganic pigment and preparation method thereof
CN102127342A (en) * 2010-12-24 2011-07-20 陕西理工学院 Method for preparing pitchy pigment capable of reflecting infrared rays and heat insulating paint
CN102181217A (en) * 2011-04-14 2011-09-14 广州立邦涂料有限公司 Colorized reflection heat insulation coating and color card thereof
CN103493144A (en) * 2011-04-28 2014-01-01 法国圣戈班玻璃厂 Transparent electric conductor
CN103881484A (en) * 2012-12-20 2014-06-25 广州市久美化工有限公司 High-infrared-reflection heat-insulation coating for exterior wall building and preparation method thereof
CN103589195A (en) * 2013-10-24 2014-02-19 陕西理工学院 Preparation method of cinereous pigment capable of reflecting infrared rays and heat-insulating paint
CN107556801A (en) * 2017-08-23 2018-01-09 华南理工大学 A kind of rust near-infrared high reflection material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Photocatalytic Activity of Mo+Fe Co-doped Titanium Dioxide Nanoparticles Prepared by Sol-Gel Method;LIU Hailin et al.;《Journal of Wuhan University of Technology-Mater. Sci. Ed.》;20130208;第28卷(第1期);44-47 *
Synthesis and enhanced photocatalytic activity of molybdenum,iron,and nitrogen triple-doped titanian anopowders;Nursev Erdogan et al.;《Ceramics International》;20160727;16766-16774 *
Synthesis, physicochemical properties and visible light photocatalytic studies of molybdenum, iron and vanadium doped titanium dioxide;Hayat Khan et al.;《Reac Kinet Mech Cat》;20131017;393-414 *

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