CN109337275B - Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof - Google Patents

Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof Download PDF

Info

Publication number
CN109337275B
CN109337275B CN201811046574.7A CN201811046574A CN109337275B CN 109337275 B CN109337275 B CN 109337275B CN 201811046574 A CN201811046574 A CN 201811046574A CN 109337275 B CN109337275 B CN 109337275B
Authority
CN
China
Prior art keywords
reddish brown
composite material
filler
asa
mixing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811046574.7A
Other languages
Chinese (zh)
Other versions
CN109337275A (en
Inventor
韩爱军
姚凌云
叶明泉
陈昕
丁成
杨计玲
张羽
张奎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN201811046574.7A priority Critical patent/CN109337275B/en
Publication of CN109337275A publication Critical patent/CN109337275A/en
Application granted granted Critical
Publication of CN109337275B publication Critical patent/CN109337275B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a manganese tungstate doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and a preparation method thereof, wherein the reddish brown composite material comprises the following components in percentage by weight: ASA resin, 84.05-90.35, reddish brown filler, 9-15, coupling agent A, 0.05-0.20, coupling agent B, 0.1-0.25 and lubricant, 0.5, wherein the reddish brown filler is represented by the general formula Mn0.7Zn0.3MoxW1‑xO4Wherein x is 0.0, 0.1, 0.3 or 0.5. The manganese tungstate-doped modified ASA reddish brown composite material has good thermal aging resistance and is environment-friendly, and ASA plastic products are reddish brown and have widened chromatograms.

Description

Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of infrared composite materials, and particularly relates to a manganese tungstate modified ASA (acrylonitrile styrene acrylate) doped reddish brown composite material with good heat aging resistance and environmental friendliness and a preparation method thereof.
Background
Plastics can be rapidly aged when being irradiated by sunlight outdoors, and besides ultraviolet rays and oxygen in the air cause the ageing of the plastics, the ageing of the plastics by near infrared light in the sunlight also has a remarkable influence. Since the near infrared region (700-2500nm) accounts for 52% of the total energy in the whole solar spectrum, the accumulation of the energy in the near infrared region to the surface of the plastic can cause the temperature of the surface of the plastic to rise sharply, thereby accelerating the aging process, i.e. the aging of the plastic due to heat. Therefore, if the reflectivity of the plastic in the near infrared band can be improved, the surface temperature of the plastic product under the irradiation of sunlight can be reduced, which is beneficial to delaying the aging of the plastic product. An effective way to improve the reflectivity of plastic products in the near-infrared band is to add near-infrared reflective pigments in the preparation process.
At present, scholars at home and abroad have carried out some researches on the heat aging resistance of ASA resin. For example, after ASA resin, ketone resin, inorganic additive, styrene grafted maleic anhydride, antioxidant and light stabilizer are mixed uniformly by zhuangdiangdong, a double-screw extruder is used to prepare the heat-resistant ASA plastic alloy, and the plastic alloy has good heat resistance and mechanical strength on the basis of keeping good weather resistance and mechanical properties of the original ASA resin (CN 103497474-heat-resistant ASA plastic alloy and preparation method thereof, 2014). As mentioned above, research institutions generally improve the heat aging resistance of ASA plastic products by adding some organic additives such as antioxidants, light stabilizers and the like, and endow the products with various colors by adding colorants.
However, the prior art has problems that: the infrared composite material improves the thermal aging resistance of plastics by adding a thermal modifier, and endows the product with color by adding a coloring agent, and most of the additives contain toxicity and cannot meet the requirement of environmental protection.
Disclosure of Invention
The invention aims to provide a manganese tungstate-doped modified ASA reddish brown composite material which is good in heat-resisting aging resistance and environment-friendly, and simultaneously endows ASA plastic products with reddish brown colors and widens the color spectrum.
The invention also aims to provide a preparation method of the manganese tungstate-modified ASA-doped reddish brown composite material.
The technical solution for realizing the purpose of the invention is as follows:
a manganese tungstate doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material comprises the following components in percentage by weight:
84.05-90.35 parts of ASA resin,
9 to 15 parts of reddish brown filler,
0.05 to 0.20 percent of coupling agent A,
0.1 to 0.25 percent of coupling agent B,
the lubricant, 0.5,
wherein the red brown filler is represented by the general formula Mn0.7Zn0.3MoxW1-xO4Wherein x is 0.0, 0.1, 0.3 or 0.5.
Preferably, the coupling agent A is gamma-aminopropyltriethoxysilane.
The coupling agent B is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
The lubricant is liquid paraffin.
The technical solution for realizing another purpose of the invention is as follows:
a preparation method of a manganese tungstate doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material comprises the following steps:
(10) preparing reddish brown filler, namely uniformly mixing raw materials of the reddish brown filler, performing hydrothermal treatment, washing and drying to obtain reddish brown filler powder for later use;
the (10) step of preparing the red-brown filler comprises the following steps:
(11) mixing raw materials: firstly MnCO3Adding into dilute hydrochloric acid with pH 3 and stirring evenly; then adding Zn thereto5(OH)6(CO3)2Continuously stirring to generate a large amount of white blocky precipitates; ultrasonically dispersing for 5min to disperse the massive precipitate into fine particles to form uniform MnCO3-Zn5(OH)6(CO3)2-a HCl suspension; mixing Na2WO4·2H2O and Na2MoO4·2H2Dissolving O in deionized water, preparing mixed solution with the concentration of 0.02-0.04 mol/L and 0-0.02 mol/L respectively, and then adding the mixed solution into MnCO3-Zn5(OH)6(CO3)2Stirring for 15min in HCl suspension to mix well; adjusting the pH value to 5 by using dilute hydrochloric acid with the pH value of 1, and transferring the solution to a reaction kettle;
in the raw material mixing step (11), MnCO3The proportion of the mixed solution to dilute hydrochloric acid is 1 g of MnCO3300ml of dilute hydrochloric acid.
(12) Hydrothermal treatment: putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 6 hours;
(13) washing: taking out the reaction kettle, naturally cooling at room temperature, and washing with deionized water and absolute ethyl alcohol for 2 times respectively;
(14) and (3) drying: drying the washed powder in an oven; the drying temperature is 100 ℃, and the drying time is 2-4 h.
(20) And (3) doping manganese tungstate, namely dissolving a coupling agent A, B according to a ratio, adding the mixture into reddish brown filler powder, mixing and drying to obtain a reddish brown filler solid, mixing the reddish brown filler solid with ASA resin, adding ethyl acetate, mixing, molding and airing to obtain the finished reddish brown composite material.
The step (20) of doping manganese tungstate comprises the following steps:
(21) preparation of a filler solid: dissolving the coupling agents A and B in absolute ethyl alcohol according to a ratio to form a mixed solution, adding the mixed solution into the reddish brown filler powder, uniformly mixing, and drying in an oven to fully volatilize the absolute ethyl alcohol to obtain a reddish brown filler solid;
in the step of preparing the (21) filler solid, the total weight ratio of the absolute ethyl alcohol to the coupling agent is 100: 1.
(22) Resin mixing: adding the reddish brown filler solid into the ASA resin and uniformly mixing;
(23) and (3) preparing a finished product: and adding ethyl acetate which is uniformly mixed with the lubricant into the uniformly mixed ASA resin and reddish brown filler solid mixture, fully mixing under a grinding condition, forming, and airing in a natural environment to obtain the finished reddish brown composite material.
In the step of preparing the finished product in the step (23), the weight ratio of the ethyl acetate to the ASA is 1: 1.5.
Compared with the prior art, the invention has the following remarkable advantages:
1. the heat-resistant aging performance is good: compared with the existing ASA resin, the prepared composite material can improve the near-infrared solar reflectance by 28.31 percent, has better performance of blocking heat accumulation on the surface of a plastic product, thereby reducing the surface temperature of the plastic product and effectively delaying the aging of the plastic product;
2. the composite material is reddish brown: the manganese tungstate-doped modified ASA resin can endow ASA plastic products with reddish brown color, and reduces the addition of coloring agents;
3. the method is environment-friendly: does not contain heavy metal oxide and toxic additive, is beneficial to environmental protection and human health;
the invention is described in further detail below with reference to the figures and the detailed description.
Drawings
FIG. 1 is a graph of the near infrared reflectance spectra of manganese tungstate doped modified ASA red-brown composites prepared in examples 1-4 and a comparative example of pure ASA plastic.
Detailed Description
To facilitate further understanding of the invention by those skilled in the art, 4 examples are illustrated.
Wherein, Na2MoO4·2H2O，Na2WO4·2H2O，MnCO3，Zn5(OH)6(CO3)2Hydrochloric acid, ASA resin, coupling agent a: gamma-aminopropyltriethoxysilane, coupling agent B: isopropyl tris (dioctyl pyrophosphato acyloxy) titanate and liquid paraffin were all commercially available materials.
Example 1
(1) Preparation of reddish brown filler: mixing the raw materials of MnCO according to the proportion shown in Table 13Adding into dilute hydrochloric acid with pH 3 and stirring evenly (1 g MnCO)3300ml of dilute hydrochloric acid); then adding Zn thereto5(OH)6(CO3)2Continuously stirring to generate a large amount of white blocky precipitates; ultrasonic dispersing for 5min to disperse the lump precipitate into fine particles to form uniform MnCO3-Zn5(OH)6(CO3)2-a HCl suspension; mixing Na2WO4·2H2Dissolving O in deionized water to prepare a solution with the concentration of 0.04mol/L, and then adding the solution into MnCO3-Zn5(OH)6(CO3)2Stirring for 15min in HCl suspension to mix well; adjusting the pH value to 5 by using dilute hydrochloric acid with the pH value of 1, and transferring the solution to a reaction kettle; putting the reaction kettle into an oven, and preserving heat for 6 hours at 150 ℃; naturally cooling at room temperature, and washing with deionized water and anhydrous ethanol for 2 times; the washed powder was dried in an oven at 100 ℃ for 3 h.
(2) Preparing a manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material: according to the proportion of the red-brown composite material shown in the table 2, the coupling agents A and B are dissolved in absolute ethyl alcohol (the total weight ratio of the absolute ethyl alcohol to the coupling agent is 100:1) to form a mixed solution; adding the mixed solution into a reddish brown filler to uniformly mix the coupling agent and the filler, and then placing the mixture in an oven at 80 ℃ for drying for 2 hours to fully volatilize absolute ethyl alcohol to obtain the brown filler; adding the treated brown filler into ASA resin, mixing uniformly, adding an ethyl acetate solvent (the weight ratio of ethyl acetate to ASA is 1:1.5) which is mixed uniformly with a lubricant, and grinding uniformly to disperse the mixture fully; and (3) placing the mixture into a mold to be molded into a sheet shape, and airing the sheet in a natural environment to obtain the reddish brown composite material of the embodiment 1.
The examples 2,3 and 4 were prepared according to the above procedure, and the ratios of the raw materials are shown in tables 1 and 2.
TABLE 1 general formula Mn0.7Zn0.3MoxW1-xO4The proportion and the ingredient table of the reddish brown filler raw materials
Figure 1
TABLE 2 Red-brown composite material ratio
Figure 2
Figure RE-GDA0001892423320000051
To examine the near infrared reflection properties of the manganese tungstate-doped modified ASA red-brown composite material of the present invention and to evaluate the heat aging resistance thereof, the red-brown composite material in the example shown in table 2 was compared with a material (comparative example) prepared from a commercially available ASA resin in the same manner as in the example. Wherein the instrument for measuring reflectivity is ultraviolet-visible-near infrared spectrophotometer (Shimadzu corporation, Japan, UV-3600), BaSO4As a reference, the test wavelength interval was 1 nm.
FIG. 1 shows Mn prepared in examples 1 to 40.7Zn0.3MoxW1-xO4NIR spectra of/ASA reddish brown composites and of comparative pure ASA plastics. As can be seen from the figure, Mn0.7Zn0.3MoxW1-xO4The reflectivity of the/ASA red-brown composite material is higher than that of pure ASA plastic in a near infrared band (780-2500 nm). As can be seen from Table 3, the near infrared solar reflectance of example 4 is as high as 63.29%, which is much greater than 34.98% for pure ASA plastic (comparative). This indicates that the pigment Mn is reflected by a reddish brown near-infrared reflection0.7Zn0.3MoxW1-xO4The modification can greatly improve the reflection of the ASA plastic to solar energy in a near infrared region, and effectively reduce the accumulation of heat on the surface of a plastic product, thereby slowing down the aging of the outdoor ASA plastic product.
Wherein, the near infrared solar reflectance is calculated by the standard ASTM G-159-98, and the calculation formula is as follows:
Figure BDA0001793453390000052
wherein r (λ) is the experimentally measured reflectance at the wavelength λ, i (λ) (W · m)-2·nm-1) Is the standard radiation intensity of sunlight at wavelength lambda (obtained by the standard ASTM G-159-98).
TABLE 3 near-Infrared solar reflectance of manganese tungstate doped modified ASA Red-Brown composite
Figure BDA0001793453390000053
Testing the colorimetric value L of the composite material*，a*，b*The instrument is NH310 type color difference instrument of Shenzhen Sanenchi company, and the color difference instrument is based on the measurement principle of CIE color space, and each color has its specific L*，a*，b*Value of wherein L*Representing a luminance in the range of 0-100, L*The magnitude of the value represents the brightness level. a is*The value (-128- +128) indicates the green-red phase nature of the pigment, with negative values indicating the green phase and positive values indicating the red phase. b*The value (-128- +128) indicates the blue-yellow phase behavior of the pigment, with negative values indicating the blue phase and positive values indicating the yellow phase. Before testing, the instrument is respectively subjected to blackboard correction and whiteboard correction, the testing position is changed during testing, the measurement interval is 1-2s, and the average value of the three testing results is taken.
TABLE 4 manganese tungstate doped modified ASA reddish brown composite material L*，a*，b*Value of
Examples 1 2 3 4
L* 50.5 46.21 42.83 40.71
a 5.96 11.39 16.11 18.49
b* 10.50 18.78 18.10 18.22
L*: brightness; a is*: green-red index; b*: blue-yellow index;
table 4 shows L of manganese tungstate-doped modified ASA red-brown composite material*，a*，b*The value is obtained. As seen from the table, a of examples 1 to 4*The values are positive values, which indicates that the composite material shows a red phase; b*The values are also positive, indicating that the composite material exhibits a yellow phase; l is*Decreasing values, indicating a gradual darkening of the composite, L*，a*，b*The effect of the value is finally manifested in that the color of the composite is reddish brown.
According to the manganese tungstate-doped modified ASA (acrylonitrile-styrene-acrylate) reddish brown composite material, the heat reflection of ASA plastics to the sun can be greatly improved through the modification of manganese tungstate doping, the surface temperature of the plastic products is reduced, the aging of the plastic products is effectively slowed down, the plastic products are endowed with reddish brown colors, and the addition of coloring agents is reduced. The raw materials and the finished product do not contain heavy metal oxides and toxic additives, are beneficial to environmental protection and human health, and can be widely used for manufacturing outdoor plastic devices.

Claims (5)

1. A preparation method of a manganese tungstate doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material comprises the following steps:
(10) preparing reddish brown filler, namely uniformly mixing raw materials of the reddish brown filler, performing hydrothermal treatment, washing and drying to obtain reddish brown filler powder for later use;
(20) the manganese tungstate modified ASA resin is prepared by dissolving a coupling agent A, B according to a ratio, adding the solution into reddish brown filler powder, mixing and drying to obtain a reddish brown filler solid, mixing the reddish brown filler solid with the ASA resin, adding ethyl acetate, mixing, molding and airing to obtain a finished reddish brown composite material;
the manganese tungstate doped modified ASA red-brown composite material comprises the following components in percentage by weight:
84.05-90.35 parts of ASA resin,
9 to 15 parts of reddish brown filler,
0.05 to 0.20 percent of coupling agent A,
0.1 to 0.25 percent of coupling agent B,
the lubricant, 0.5,
wherein the red brown filler is represented by the general formula Mn0.7Zn0.3MoxW1-xO4Wherein x is 0.0, 0.1, 0.3 or 0.5;
characterized in that the step (10) of preparing the reddish brown filler comprises the following steps:
(11) mixing raw materials: firstly MnCO3Adding into dilute hydrochloric acid with pH 3 and stirring evenly; then adding Zn thereto5(OH)6(CO3)2Continuously stirring to generate a large amount of white blocky precipitates; ultrasonically dispersing for 5min to disperse the massive precipitate into fine particles to form uniform MnCO3-Zn5(OH)6(CO3)2-a HCl suspension; mixing Na2WO4·2H2O and Na2MoO4·2H2Dissolving O in deionized water, preparing mixed solution with the concentration of 0.02-0.04 mol/L and 0-0.02 mol/L respectively, and then adding the mixed solution into MnCO3-Zn5(OH)6(CO3)2Stirring for 15min in HCl suspension to mix well; adjusting the pH value to 5 by using dilute hydrochloric acid with the pH value of 1, and transferring the solution to a reaction kettle;
(12) hydrothermal treatment: putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 6 hours;
(13) washing: taking out the reaction kettle, naturally cooling at room temperature, and washing with deionized water and absolute ethyl alcohol for 2 times respectively;
(14) and (3) drying: drying the washed powder in an oven; the drying temperature is 100 ℃, and the drying time is 2-4 h.
2. The method for preparing a reddish brown composite material according to claim 1, wherein in the step of (11) mixing the raw materials, MnCO is added3The proportion of the mixed solution to dilute hydrochloric acid is 1 g of MnCO3300ml of dilute hydrochloric acid.
3. The preparation method of the reddish brown composite material according to claim 1, wherein the (20) step of doping the manganese tungstate modified ASA resin comprises:
(21) preparation of a filler solid: dissolving the coupling agents A and B in absolute ethyl alcohol according to a ratio to form a mixed solution, adding the mixed solution into the reddish brown filler powder, uniformly mixing, and drying in an oven to fully volatilize the absolute ethyl alcohol to obtain a reddish brown filler solid;
(22) resin mixing: adding the reddish brown filler solid into the ASA resin and uniformly mixing;
(23) and (3) preparing a finished product: and adding ethyl acetate which is uniformly mixed with the lubricant into the uniformly mixed ASA resin and reddish brown filler solid mixture, fully mixing under a grinding condition, forming, and airing in a natural environment to obtain the finished reddish brown composite material.
4. The method for preparing reddish brown composite material according to claim 3, wherein in the step of preparing (21) filler solid, the total weight ratio of absolute ethyl alcohol to coupling agent is 100: 1.
5. The method for preparing reddish brown composite material according to claim 3, wherein in the step of preparing the final product (23), the weight ratio of the ethyl acetate to the ASA is 1: 1.5.
CN201811046574.7A 2018-09-08 2018-09-08 Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof Active CN109337275B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811046574.7A CN109337275B (en) 2018-09-08 2018-09-08 Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811046574.7A CN109337275B (en) 2018-09-08 2018-09-08 Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109337275A CN109337275A (en) 2019-02-15
CN109337275B true CN109337275B (en) 2020-10-20

Family

ID=65305070

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811046574.7A Active CN109337275B (en) 2018-09-08 2018-09-08 Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109337275B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745149A (en) * 2003-10-20 2006-03-08 住友金属矿山株式会社 Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle
WO2009096165A1 (en) * 2008-01-31 2009-08-06 Panasonic Corporation Optical information recording medium, method for manufacturing the same, and target thereof
CN106963951A (en) * 2017-02-27 2017-07-21 上海师范大学 Graphene oxide/manganese tungstate/polyethylene glycol nano-hybrid material and its preparation
CN108083324A (en) * 2017-12-25 2018-05-29 畅的新材料科技（上海）有限公司 A kind of doped stannum oxide material of near-infrared reflection and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745149A (en) * 2003-10-20 2006-03-08 住友金属矿山株式会社 Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle
WO2009096165A1 (en) * 2008-01-31 2009-08-06 Panasonic Corporation Optical information recording medium, method for manufacturing the same, and target thereof
CN106963951A (en) * 2017-02-27 2017-07-21 上海师范大学 Graphene oxide/manganese tungstate/polyethylene glycol nano-hybrid material and its preparation
CN108083324A (en) * 2017-12-25 2018-05-29 畅的新材料科技（上海）有限公司 A kind of doped stannum oxide material of near-infrared reflection and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Microwave-assisted synthesis and characterisation of divalent metal tungstate nanocrystalline minerals: ferberite, hubnerite, sanmartinite, scheelite and stolzite";J. Theo Kloprogge等;《Materials Chemistry and Physics》;20041231;第88卷;第438-443页 *

Also Published As

Publication number Publication date
CN109337275A (en) 2019-02-15

Similar Documents

Publication Publication Date Title
KR102263303B1 (en) Surface-treated infrared absorbing fine particles, surface-treated infrared absorbing fine particle powder, infrared absorbing fine particle dispersion using the surface-treated infrared absorbing fine particle, infrared absorbing fine particle dispersion, and manufacturing method thereof
CN107043516B (en) With the dark heat-proof ABS resin composition for improving weatherability
CN109734126A (en) A kind of preparation method of high-weatherability titanium dioxide
Li et al. Preparation and characterization of transparent Al doped ZnO/epoxy composite as thermal-insulating coating
CN107558175A (en) A kind of preparation method of glass/zinc oxide
JP5898397B2 (en) Near-infrared shielding polyester resin composition, near-infrared shielding polyester resin laminate, molded article and method for producing the same
CN110330813B (en) Color TiO2Near-infrared reflection pigment and preparation method thereof
CN109337275B (en) Manganese tungstate-doped modified ASA (acrylonitrile styrene acrylate) reddish brown composite material and preparation method thereof
CN105936680B (en) A kind of rare earth compounding and its preparation method and application
JP2021031828A (en) Deep color infrared reflective fiber containing no metal component, manufacturing method thereof and woven fabric using the same
CN111039323B (en) Bi doped with iron/terbium element3YO6Inorganic pigment and preparation method and application thereof
CN105542527A (en) Improved ultraviolet-proof coating and preparation method thereof
CN111607328A (en) Preparation process of nano heat-insulating coating
CN111500097A (en) Environment-friendly art pigment and preparation method thereof
US11034803B2 (en) Color masterbatch composition for dark textiles or engineering plastics and article produced therefrom
TWI509038B (en) Infra. red low-temperature-rise pigment composition and infra. red low-temperature-rise material
CN114410233B (en) Packaging adhesive film and preparation method and application thereof
El‐naggar et al. PVC polymer/ZnO/NiO/Co3O4 nanocomposites: toward improved optical properties
CN113969032B (en) Ultraviolet shielding acrylic tannic acid composite material and preparation method and application thereof
CN112358285B (en) Preparation method for preparing Mn ion-doped zirconium silicate black pigment by non-hydrolytic sol-gel method
CN105349146A (en) YAB/SiO2 near-infrared micro-nano luminescent material and preparation method and application thereof
CN110684356A (en) Antistatic dust-absorbing silicone rubber product and manufacturing method thereof
CN103965675B (en) A kind of high infrared reflection dark material and preparation method thereof
CN117106323B (en) Organic-inorganic composite functional pigment dispersion
CN116162364B (en) Preparation method of cobalt-free rare earth purple inorganic pigment

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant