CN114958033B - High near infrared reflection color pigment and application thereof - Google Patents

High near infrared reflection color pigment and application thereof Download PDF

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CN114958033B
CN114958033B CN202210371282.0A CN202210371282A CN114958033B CN 114958033 B CN114958033 B CN 114958033B CN 202210371282 A CN202210371282 A CN 202210371282A CN 114958033 B CN114958033 B CN 114958033B
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pigment
lial
moo
near infrared
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CN114958033A (en
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孙晓琦
冯罗
章美琪
杨奕婕
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Xiamen Institute of Rare Earth Materials
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0003—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/60—Planning or developing urban green infrastructure

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Abstract

The invention relates to the technical field of pigments, and discloses a high near infrared reflection color pigment and application thereof, wherein the pigment has a chemical general formula: liAl (LiAl) 1‑x M x (MoO 4+δ ) 2 The doping amount x is 0-0.4; the material is prepared from raw materials including Li source, al source, mo source and M source by a solid phase reaction method. The invention meets the aesthetic demands of people on various colors; the synthesized pigment has higher near infrared reflectivity (R%), can realize the regulation and control of pigment color and reflectivity by changing doping concentration, and can be used as a high-performance cold material for the fields of building outer walls, vehicle and ship exteriors or paint cans.

Description

High near infrared reflection color pigment and application thereof
Technical Field
The invention relates to the technical field of pigments, in particular to a high near infrared reflection color pigment and application thereof.
Background
With the rapid development of economy and technology, the process of urban treatment accelerates the use of materials such as asphalt, glass and the like and air conditioners, so that the temperature of urban centers is 3-5 ℃ higher than that of peripheral areas. The urban heat island effect is generated by a large amount of energy consumption and heat accumulation, and becomes a topic of great concern, and has potential influence on energy consumption and vegetation growth, and even causes a certain harm to life and human health of residents. The urban heat island effect is closely related to factors such as building density, vegetation area and the like, and if the building can emit more sunlight, more energy can be saved, and the urban heat island effect is relieved. Therefore, attention has been paid to how to effectively block heat transfer of sunlight on the surface and roof of a building.
The ceramic pigment with high near infrared reflectivity can effectively reflect solar energy (with the proportion of 52 percent) at 700-2500nm, thereby reducing energy consumption and slowing downUrban heat island effect. Generally, most of traditional inorganic pigments contain toxic heavy metal elements, have single color, and cannot meet aesthetic requirements of people on building materials. The color and reflection properties of pigments are changed by doping, and have become a research hotspot for researchers. The doping of transition metals or rare earth elements is an effective means for changing the color of pigments, and commonly used chromophores mainly include Fe, cr, bi, RE, etc., and various researchers have studied inorganic pigments such as LiRE (MoO) 4 ) 2 、Y 3-x Ce x Al 5 O 12 ，Sr 1-x RE x CuSi 4 O 10+δ (re=pr, nd, sm), etc., can replace conventional architectural coatings. Therefore, research and preparation of pigments which can not only show higher near infrared reflectivity, but also meet the diversity of colors are technical problems to be solved in the field at present.
Disclosure of Invention
The invention aims to provide a high near infrared reflection color pigment and application thereof, wherein the synthesized pigment has low toxic metal content, higher near infrared reflectivity and more various colors.
In order to achieve the technical purpose and achieve the technical effect, the invention discloses a high near infrared reflection color pigment, which has the chemical general formula:
LiAl 1-x M x (MoO 4+δ ) 2 ；
wherein: m is selected from at least one of Fe, pr, ho, nd, er and Ce.
Wherein, the value range of x in the chemical formula is as follows: x is more than 0 and less than or equal to 0.4.
Wherein the pigment has a triclinic structure of a P-1 space group.
Wherein, the pigment is prepared from raw materials including Li source, al source, mo source and M source by a solid phase reaction method.
The invention also discloses a preparation method of the high near infrared reflection color pigment, which comprises the following steps:
step 1: according to LiAl 1-x M x (MoO 4+δ ) 2 The stoichiometric ratio of each element of the raw materials of a Li source, an Al source, a Mo source and an M source is weighed;
step 2: mixing the raw materials weighed in the step 1, adding the raw materials into an agate mortar for grinding, adding acetone as a wet grinding medium until the acetone volatilizes, and repeating the operation for 3-5 times to obtain mixed powder;
step 3: drying the mixed powder ground in the step 2 in an air oven to obtain dried powder;
step 4: placing the powder obtained in the step 3 into a crucible, roasting in a muffle furnace, heating to 400 ℃ from room temperature, reacting for 2 hours, heating to 650 ℃ again, and preserving heat for 4 hours to obtain a sample;
step 5: grinding the sample obtained in the step 4 for 3-5 times to obtain the color pigment.
Wherein the Li source is provided by at least one of carbonate and molybdate containing Li element;
the M source is provided by at least one of carbonate, oxide, chloride, nitrate and sulfate containing M element;
the Al source is provided by at least one of oxides, chlorides, nitrates and sulfates containing Al elements;
the Mo source is provided by oxide or molybdate containing Mo element.
Preferably, the Li source is provided by a carbonate containing Li element;
the M source is provided by an oxide containing M element;
the Al source is provided by oxide containing Al element;
the Mo source is provided by oxide containing Mo element.
The invention also discloses application of the high near infrared reflection color pigment in building exterior wall coating, vehicle and ship exterior coating and paint can coating.
The invention has the following beneficial effects:
(1) Provides a series of LiAl (MoO) doped with Fe, pr, ho, nd, er, ce 4 ) 2 The near infrared reflecting pigment is prepared by doping Fe, pr, ho,the Nd, er and Ce elements successfully change the pigment color from white to various colors such as green, light purple, pink, yellow and the like, and can meet the aesthetic demands of people on various colors;
(2) The pigment synthesized by the invention has higher near infrared reflectivity (R%), can realize the regulation and control of pigment color and reflectivity by changing doping concentration, and can be used as a high-performance cold material to be applied to the fields of building outer walls, vehicle and ship exteriors or paint cans.
Drawings
FIG. 1 shows the synthesis of (a) LiAl according to example 3 of the present invention 1-x Fe x (MoO 4+δ ) 2 XRD diffraction pattern of pigment, x=0-0.4; (b) 2 theta = 26.0 ° -27.5 ° of the XRD diffraction pattern.
FIG. 2 shows LiAl synthesized in example 3 of the present invention 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) SEM images of pigments.
FIG. 3 shows LiAl synthesized in example 3 of the present invention 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) particle size distribution profile of the pigment.
FIG. 4 shows LiAl synthesized in example 4 of the present invention 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) the absorption spectrum of the pigment, and the inset is the ultraviolet-visible reflection spectrum.
FIG. 5 shows LiAl synthesized in example 4 of the present invention 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) absorption limit diagram of the compound.
FIG. 6 shows LiAl synthesized in example 4 of the present invention 1-x Fe x (MoO 4+δ ) 2 Colorimetric parameter diagram of the pigment.
FIG. 7 shows LiAl synthesized in example 4 of the present invention 1-x Fe x (MoO 4+δ ) 2 Near infrared reflectance plot of pigment.
FIG. 8 shows LiAl synthesized in example 4 of the present invention 1-x Fe x (MoO 4+δ ) 2 Near infrared solar reflectance plot of pigment.
FIG. 9 shows LiAl synthesized in example 5 of the present invention 1-x M x (MoO 4+δ ) 2 (m=fe, pr, ho, nd, er, ce) pigment.
FIG. 10 is a diagram showing the pigment produced in example 5 of the present invention.
FIG. 11 shows LiAl synthesized in example 5 of the present invention 0.8 M 0.2 (MoO 4 ) 2 Near infrared reflectance plot of (m=pr, ho, nd, er, ce) pigment.
FIG. 12 LiAl synthesized in example 5 of the present invention 0.8 Fe 0.2 (MoO 4 ) 2 And LiAl 0.8 Pr 0.2 (MoO 4 ) 2 Respectively with the alkyd resin in the presence or absence of TiO 2 Infrared thermal imaging patterns of infrared heating at different times on a galvanized sheet with a base coating, wherein (1) and (3) are non-coated with TiO 2 The galvanized sheet (2) and (4) are coated with TiO 2 The galvanized sheet (1) and (2) are coated with LiAl 0.8 Fe 0.2 (MoO 4 ) 2 The galvanized sheet (3) and (4) are coated with LiAl 0.8 Pr 0.2 (MoO 4 ) 2 A galvanized sheet of pigment.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention provides a high near infrared reflection color pigment LiAl 1-x M x (MoO 4+δ ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the M source is the corresponding oxide of Fe, pr, ho, nd, er and Ce.
Pigment LiAl 1-x M x (MoO 4+δ ) 2 A triclinic structure having a P-1 space group.
The pigment is prepared from raw materials including a Li source, an Al source, a Mo source and an M source by a solid phase reaction method.
Example 2
The present invention provides a high near infrared reflective color pigment LiAl of example 1 1-x M x (MoO 4+δ ) 2 The preparation method of (2) comprises the following steps:
step 1: according to LiAl 1-x M x (MoO 4+δ ) 2 The stoichiometric ratio of each element of the raw materials of a Li source, an Al source, a Mo source and an M source is weighed;
step 2: mixing the raw materials weighed in the step 1, adding the raw materials into an agate mortar for grinding, adding acetone as a wet grinding medium until the acetone volatilizes, and repeating the operation for 3-5 times to obtain mixed powder;
step 3: drying the mixed powder ground in the step 2 in an air oven to obtain dried powder;
step 4: placing the powder obtained in the step 3 into a crucible, roasting in a muffle furnace, heating to 400 ℃ from room temperature, reacting for 2 hours, heating to 650 ℃ again, and preserving heat for 4 hours to obtain a sample;
step 5: grinding the sample obtained in the step 4 for 3-5 times to obtain the color pigment.
Wherein:
the Li source is provided by at least one of carbonate and molybdate containing Li element;
the M source is provided by at least one of carbonate, oxide, chloride, nitrate and sulfate containing M element;
the Al source is provided by at least one of oxides, chlorides, nitrates and sulfates containing Al elements;
the Mo source is provided by oxide or molybdate containing Mo element.
Preferably, the Li source is provided by a carbonate containing Li element;
the M source is provided by an oxide containing M element;
the Al source is provided by oxide containing Al element;
the Mo source is provided by oxide containing Mo element.
Example 3
To further investigate the effect of different doping levels x on the crystal structure of the high near infrared reflective color pigment, liAl was prepared in this example by the preparation method described in example 2 1-x Fe x (MoO 4+δ ) 2 Pigment, wherein the doping amount x has the following range: 0 < x.ltoreq.0.4, and the results are shown in FIG. 1 and Table 1.
TABLE 1LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) unit cell parameters and strain of pigment
FIG. 1 shows the main peak shape and LiAl (MoO) 4 ) 2 The standard card (PDF No. 72-0753) of (C) matches well, indicating that the sample has better crystallinity at a calcination temperature of 650 ℃. The aluminum lithium molybdate belongs to a triclinic system structure, the space group is P-1, and LiAl is added along with the increase of doping concentration 1-x Fe x (MoO 4+δ ) 2 The pigment sample has a slight difference in the relative intensities of the (020) and (002) peaks, the difference in the relative intensities of the strongest diffraction peak (002) and the weaker (002) peak begins to decrease, and the crystal plane (002) shifts to a low angle. At a doping concentration of 0.4, the intensities of the (020) and (002) peaks are substantially the same. The above shows that the crystal forms of the aluminum lithium molybdate with different doping concentrations of Fe can grow in an oriented mode, and the morphology of various pigments can be different.
Table 1 shows LiAl 1-x Fe x (MoO 4+δ ) 2 Information such as cell parameters of (x=0 to 0.4). From the above table, it can be seen that Fe 3+ The introduction of (a) affects the unit cell volume increase of the sample, mainly due to the ionic radius ofFe of (2) 3+ (coordination number CN is 6) replaces the ion radius of +.>Al of (2) 3+ (coordination number CN is 6), so that the unit cell volume is increased, and diffraction peaks are shifted to low angles.
As can be seen from fig. 2, liAl (MoO 4 ) 2 The morphology of the pigment sample has obvious crystal faces at the calcining temperature of 650 ℃, which indicates that the solid solution has better crystallinity. Sample particles with different doping concentrations all show irregular polyhedrons and different particle sizes and are accompanied by agglomeration.
FIG. 3 shows LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0 to 0.4) particle size distribution of pigment, and detailed information of D10, D50, D90 of pigment samples is shown in table 2.
TABLE 2 LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) D10, D50, D90 of pigment powder
sample D10 D50 D90
x＝0 125.36 247.31 487.89
x＝0.1 386.58 729.61 1377.02
x＝0.2 339.90 634.73 1185.29
x＝0.3 278.79 512.30 941.40
x＝0.4 287.33 537.89 106.96
From the particle size distribution map, it can be observed that the particle sizes of all samples are normally distributed and uniformly distributed. Undoped LiAl (MoO) 4 ) 2 The samples had D10, D50 and D90 of 125.36nm,247.31nm and 487.89nm, respectively. The other samples had larger effective particle sizes D50 than the undoped sample, ranging from 500-750 nm. The good particle size distribution is the guarantee of uniform distribution and pure color of the later-stage coating.
Example 4
In order to further investigate the optical properties of the pigments according to the invention, the present example was carried out with LiAl prepared in example 2, example 3 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) pigment, and the absorption spectrum of the pigment is characterized and analyzed, and the results are shown in fig. 4, 5, 6, 7, 8, table 3 and table 4.
FIG. 4 is LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) absorption spectrum and ultraviolet-visible reflection spectrum of pigment, liAl prepared 1-x Fe x (MoO 4+δ ) 2 The sample has higher reflectivity in the visible light region of 380-700nm, which indicates LiAl 1-x Fe x (MoO 4+δ ) 2 The color of the sample may be biased towards a light color.
With Fe 3+ The doping amount of (c) increases, the visible light reflectivity tends to gradually decrease, and pure LiAl (MoO) 4 ) 2 The absorbance of the sample at 270-400nm has a suddenly decreasing trend, fe 3+ The incorporation of ions causes the inflection point of the band to move in a direction in which the band is longer. All samples have strong absorbance in the ultraviolet and blue regions, so LiAl 1-x Fe x (MoO 4+δ ) 2 The color of the sample gradually changes from white to yellow-green.
Table 3 shows LiAl 1-x Fe x (MoO 4+δ ) 2 The decrease in the L x value from 97.22 to 89.15, which indicates a decrease in the brightness of the pigment, is observed from the table.
TABLE 3 LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) color coordinates of pigment, forbidden bandwidth
sample L* a* b* C* H° Eg(eV)
x＝0 97.22 -1.20 2.39 2.67 63.34 3.89
x＝0.1 95.14 -2.48 9.19 9.52 74.90 3.24
x＝0.2 92.83 -4.07 14.93 15.47 74.75 3.14
x＝0.3 90.91 -5.13 20.26 20.90 75.79 3.07
x＝0.4 89.15 -5.89 25.36 26.04 76.92 3.03
FIG. 5 is LiAl 1-x Fe x (MoO 4+δ ) 2 Absorption Limit diagram of (x=0-0.4) compound, liAl 1-x Fe x (MoO 4+δ ) 2 The absorption limit of the pigment red-shifts with an increase in the Fe concentration, thus making the forbidden band width Eg smaller, and Eg decreases from 3.89eV to 3.03eV. The change in forbidden band width may be due to the presence of Al 3p And O 2p Fe is introduced between tracks 3d Rails, the acting force between the two rails is reduced, and in addition, fe 3+ The ion undergoes d-d transition, mainly represented by 430nm and 480-650nm 6 A 1 → 4 E, 4 A 1 Transition mode.
FIG. 6 LiAl synthesized 1-x Fe x (MoO 4+δ ) 2 The colorimetric parameters of the pigments show a variation of the L x a b parameters of the pigments, when x=0, the L x value is 97.22, close to white.
As the Fe doping concentration increases, the a value decreases from-1.20 to-5.89, indicating that the pigment color is greenish, but the increase is smaller; the increase in b from 2.39 to 25.36 indicates a yellow color of the pigment with a greater increase. The saturation C increases from 2.67 to 26.04 indicating a more full color of the pigment. All color samples had a hue angle H deg. in the yellow region (70-105 deg.), so the color presented was yellow.
FIG. 7 is a synthetic LiAl 1-x Fe x (MoO 4+δ ) 2 Near infrared reflectance of pigment, FIG. 8 is a graph of synthetic LiAl 1-x Fe x (MoO 4+δ ) 2 Near infrared solar reflectance plot of pigment, table 4 is a synthetic LiAl 1-x Fe x (MoO 4+δ ) 2 The reflectivity of the pigment at 1100nm, the average reflectivity, and the near infrared solar reflectivity.
TABLE 4 LiAl 1-x Fe x (MoO 4+δ ) 2 (x=0-0.4) near infrared reflectance and near infrared solar reflectance of pigment at 1100nm
sample R％(1100nm) R％ R*％
x＝0 90.38 96.40 92.18
x＝0.1 92.77 98.34 94.19
x＝0.2 90.16 98.31 92.27
x＝0.3 87.94 96.85 89.84
x＝0.4 87.12 95.51 88.76
The results show that Fe-doped LiAl (MoO 4 ) 2 The reflectivity of the pigment will be altered compared to the undoped sample.
The reflectance of pigment (x=0.1-0.2) at 1100nm decreases from 92.77% to 87.12% with increasing doping amount, the near infrared average reflectance increases from 96.40% to 98.34%, then from 98.34% to 95.51%; the near infrared solar reflectance increased from 92.18% to 94.19% and then gradually decreased to 88.76%.
As described above, the doping of Fe can improve the reflective properties of the pigment, and an increase in doping concentration also reduces the reflectivity. Compared with the traditional pigment, the prepared LiAl 1-x Fe x (MoO 4+δ ) 2 The pigment has more excellent reflection properties.
NiTiO 3 @TiO 2 About 60% of R, biPr 0.5 Cr 0.5 TiO 3 R% is 91.5%, Y 3 Al 5-x Fe x O 12 The R% of the (x= 0.0,0.5,1.0,1.5,2.0,3.0) series of pigments is between 68.08 and 86.47%. Compared with yellow-green pigment with similar color, the synthesized LiAl 0.8 Fe 0.2 (MoO 4+δ ) 2 The near solar reflectance of the pigment is as high as 92.27%.
Example 5
To further characterize the color of the synthesized pigment under specific use conditions, the present example uses LiAl synthesized in example 1 and example 2 1-x M x (MoO 4+δ ) 2 (M=Fe, pr, ho, nd, er, ce; x=0-0.4) pigment as experimental object, liAl is synthesized 1-x Fe x (MoO 4+δ ) 2 、LiAl 1-x Pr x (MoO 4+δ ) 2 、LiAl 1-x Ho x (MoO 4+δ ) 2 、LiAl 1-x Nd x (MoO 4+δ ) 2 、LiAl 1-x Er x (MoO 4+δ ) 2 、LiAl 1-x Ce x (MoO 4+δ ) 2 。
FIG. 9 is early stageCalcining at 650 ℃ for 4 hours to synthesize LiAl 1-x M x (MoO 4+δ ) 2 (m=fe, pr, ho, nd, er, ce) pigment, fig. 10 is a physical diagram of a synthetic pigment, and table 5 is information about the value of L.
LiAl 1-x Pr x (MoO 4+δ ) 2 The color of the pigment is green, the color gradually deepens along with the increase of Pr doping concentration, the L value of the pigment is more than 95, the red-green chromaticity a value is changed from-3.60 to-5.60, and the b value is increased from 9.30 to 12.29.
LiAl 1-x Nd x (MoO 4+δ ) 2 The pigment was light purple in color, the brightness L value decreased from 92.88 to 86.19 with increasing Nd concentration, the a value increased from-2.08 to 0.42, and the b value slowly decreased from x=0.1 to 0.3 to-3.99, and significantly decreased to-9.23 when x=0.4.
LiAl 1-x Er x (MoO 4+δ ) 2 The pigment color is pink, the brightness L is 94-96, the value of a is gradually increased from 3.88 to 8.95, and the value of b is in the range of-0.72-0.14.
The above three pigments are cold color pigments.
LiAl 1-x Ho x (MoO 4+δ ) 2 And LiAl 1-x Ce x (MoO 4+δ ) 2 The pigments are all yellow warm pigments.
LiAl 1-x Ho x (MoO 4+δ ) 2 Brightness L value ratio LiAl of pigment 1-x Ce x (MoO 4+δ ) 2 High pigment, indicating LiAl 1- x Ho x (MoO 4+δ ) 2 The pigment color is lighter; liAl (LiAl) 1-x Ce x (MoO 4+δ ) 2 Yellow-green value of pigment b.value LiAl 1-x Ho x (MoO 4+δ ) 2 Pigment is bigger, indicating LiAl 1-x Ce x (MoO 4+δ ) 2 The pigment is darker yellow.
LiAl 1-x Ho x (MoO 4+δ ) 2 The a-value of the pigment varies between-2.98 and-3.10, liAl 1-x Ce x (MoO 4+δ ) 2 The a-value of the pigment is then varied from-1.17 to 5.95.
Table 5L a b values for the synthetic pigments
The above results show that different doping metal elements can lead to white powder LiAl (MoO 4 ) 2 The invention has the advantages that various colors are presented, the color spectrum of the near infrared reflecting inorganic pigment is enriched, and the color diversity requirement of modern people can be met.
FIG. 11 is LiAl 0.8 M 0.2 (MoO 4 ) 2 Near infrared reflectance plot of (m=pr, ho, nd, er, ce) pigment, table 6 is LiAl 0.8 M 0.2 (MoO 4 ) 2 Calculation data of near infrared reflectance and near infrared solar reflectance of (m=pr, ho, nd, er, ce) pigment.
TABLE 6 LiAl 0.8 M 0.2 (MoO 4 ) 2 Near infrared reflectance and near infrared solar reflectance of (m=pr, ho, nd, er, ce) pigments
sample R％(1100nm) R*％ Eg
LiAl 0.8 Pr 0.2 (MoO 4 ) 2 90.48 90.29 3.67
LiAl 0.8 Nd 0.2 (MoO 4 ) 2 90.23 87.83 3.81
LiAl 0.8 Er 0.2 (MoO 4 ) 2 96.57 95.67 3.83
LiAl 0.8 Ho 0.2 (MoO 4 ) 2 91.72 92.29 3.77
LiAl 0.8 Ce 0.2 (MoO 4 ) 2 99.09 98.05 3.56
As can be seen, the cold color pigments, such as green LiAl 0.8 Pr 0.2 (MoO 4 ) 2 Light purple LiAl 0.8 Nd 0.2 (MoO 4 ) 2 And pink LiAl 0.8 Er 0.2 (MoO 4 ) 2 The reflectivity at 1100nm is 90.48%, 90.23% and 96.57%, respectively, and the near infrared solar reflectivity Rx% is highUp to 90.29%, 87.83% and 95.67%; in the warm color pigment, liAl 0.8 Ho 0.2 (MoO 4 ) 2 And LiAl 0.8 Ce 0.2 (MoO 4 ) 2 R% of 92.29% and 98.05%, respectively, are capable of reflecting a substantial portion of solar energy, can be used as a near infrared reflecting material, and expand applications in thermal insulation.
Example 6
To further characterize the usability of the synthesized pigments in practical applications, the present example was followed by LiAl synthesized in example 5 0.8 Fe 0.2 (MoO 4 ) 2 And LiAl 0.8 Pr 0.2 (MoO 4 ) 2 The following experiments were performed for the subjects.
Pigments with high solar reflectivity in the paint can reflect infrared part sunlight generating heat to a great extent so as to achieve the effect of energy saving and cooling. To evaluate the suitability of design pigments, liAl was developed in design 0.8 Fe 0.2 (MoO 4 ) 2 And LiAl 0.8 Pr 0.2 (MoO 4 ) 2 With or without pigment coating with TiO 2 And (3) carrying out infrared heat radiation on the galvanized sheet.
In the coating process, the pigment and alkyd resin are uniformly mixed according to the proportion of 1:1.5 to prepare the water-based metal antirust paint decorative paint, the water-based metal antirust paint decorative paint is coated on a galvanized sheet with the thickness of 10cm multiplied by 8cm, the coated sheet is naturally dried and then dispersed on a heat insulation plate, the thickness of the coating is measured by a QNix 8500 thickness meter, and the thickness of each coating is measured to be about 110-120 mu m.
And (3) carrying out image acquisition on the smear through an infrared thermal imager, wherein the shooting time interval is 3min, the temperature recording mode is set to be a temperature highest point marking mode, the distance between the galvanized sheet and the infrared lamp is kept at 25cm, and in a thermal imaging experiment, the total exposure time of the galvanized sheet under the infrared lamp with the power of 100w is 10min.
From FIG. 12, it is shown that the temperature maximum is always at no TiO 2 Substrate LiAl 0.8 Pr 0.2 (MoO 4 ) 2 Sample (3). During the same heat radiation time interval, the smear surfaceThe rate of rise of the temperature of (a) was gradually slowed from an initial 42.7 c to 54.8 c and then slowly to 65.8 c. No TiO 2 Smear of substrate is compared with TiO 2 The higher the temperature of the smear surface of the substrate, the description of TiO 2 The reflectivity of the smear can be improved.
For the absence of TiO 2 LiAl of the substrate 0.8 Fe 0.2 (MoO 4 ) 2 And LiAl 0.8 Pr 0.2 (MoO 4 ) 2 The smears ((1) and (3)) have a surface temperature of (1) 5 to 6℃lower than that of (3), mainly due to LiAl 0.8 Fe 0.2 (MoO 4 ) 2 Near infrared reflectance ratio LiAl of (C) 0.8 Pr 0.2 (MoO 4 ) 2 High, more infrared radiant heat can be reflected. In general, both pigments have good near infrared reflection performance and can be used as a cold color system inorganic pigment with high near infrared reflection.
In summary, the invention provides an application of the high near infrared reflection color pigment in building exterior wall coating, vehicle and ship exterior coating and paint can coating, the pigment has higher near infrared reflectivity, liAl 1-x M x (MoO 4+δ ) 2 (m=fe, pr, ho, nd, er, ce) pigments appear yellowish green, pale purple, pink, yellow, etc., with rich color properties.
When the doping element is Fe, all the samples of the doping amount are triclinic, and at a lower doping concentration Fe doped sample pigments have a higher near infrared reflectance (x=0.2, r% =98.13), and as the doping concentration increases, the color of all the sample pigments deepens.
LiAl 0.8 Pr 0.2 (MoO 4 ) 2 、LiAl 0.8 Nd 0.2 (MoO 4 ) 2 And LiAl 0.8 Er 0.2 (MoO 4 ) 2 The pigment has R% at 1100nm of 90.48%, 90.23% and 96.57%, respectively, up to 90.29%, 87.83% and 95.67%. In the warm color pigment, liAl 0.8 Ho 0.2 (MoO 4 ) 2 And LiAl 0.8 Ce 0.2 (MoO 4 ) 2 R% of 92.29% and 98.05%, respectively. The excellent reflective properties allow all the pigments prepared to have good heat insulating properties and to be used as a new type of "cold" pigment.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (5)

1. A high near infrared reflective color pigment, characterized by: the chemical general formula of the pigment is as follows:
LiAl 1-x M x (MoO 4+δ ) 2，
the M is at least one of Fe, pr, ho, nd, er and Ce;
the value range of x is as follows: x is more than 0 and less than or equal to 0.4;
wherein, the pigment is prepared from raw materials including Li source, al source, mo source and M source by a solid phase reaction method:
the preparation method comprises the following steps:
step 1: according to LiAl 1-x M x (MoO 4+δ ) 2 The stoichiometric ratio of each element of the raw materials of a Li source, an Al source, a Mo source and an M source is weighed;
step 2: mixing the raw materials weighed in the step 1, adding the raw materials into an agate mortar for grinding, adding acetone as a wet grinding medium until the acetone volatilizes, and repeating the operation for 3-5 times to obtain mixed powder;
step 3: drying the mixed powder ground in the step 2 in an air oven to obtain dried powder;
step 4: placing the powder obtained in the step 3 into a crucible, roasting in a muffle furnace, heating to 400 ℃ from room temperature, reacting for 2 hours, heating to 650 ℃ again, and preserving heat for 4 hours to obtain a sample;
step 5: grinding the sample obtained in the step 4 for 3-5 times to obtain the color pigment.
2. The high near infrared reflective color pigment of claim 1, wherein: the pigment has a triclinic structure of the P-1 space group.
3. The high near infrared reflective color pigment of claim 1, wherein:
the Li source is provided by at least one of carbonate and molybdate containing Li element;
the M source is provided by at least one of carbonate, oxide, chloride, nitrate and sulfate containing M element;
the Al source is provided by at least one of oxides, chlorides, nitrates and sulfates containing Al elements;
the Mo source is provided by oxide or molybdate containing Mo element.
4. The high near infrared reflective color pigment of claim 1, wherein:
the Li source is provided by carbonate containing Li element;
the M source is provided by an oxide containing M element;
the Al source is provided by oxide containing Al element;
the Mo source is provided by oxide containing Mo element.
5. Use of the highly near infrared reflective color pigments according to any of claims 1 to 4 in exterior wall coatings for buildings, exterior coatings for vehicles and ships, paint can coatings.
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