CN116178991A - Fe (Fe) 2 O 3 -Cr 2 O 3 Preparation method of high near infrared reflection pigment and application of pigment in coating - Google Patents
Fe (Fe) 2 O 3 -Cr 2 O 3 Preparation method of high near infrared reflection pigment and application of pigment in coating Download PDFInfo
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- CN116178991A CN116178991A CN202310196543.4A CN202310196543A CN116178991A CN 116178991 A CN116178991 A CN 116178991A CN 202310196543 A CN202310196543 A CN 202310196543A CN 116178991 A CN116178991 A CN 116178991A
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- 239000000049 pigment Substances 0.000 title claims abstract description 127
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- 239000011248 coating agent Substances 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 16
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
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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
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
-
- 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
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
Abstract
The invention discloses Fe 2 O 3 ‑Cr 2 O 3 The preparation method of the high near infrared reflection pigment comprises the following steps: weighing Fe according to a molar ratio 2 O 3 And Cr (V) 2 O 3 Powder, adding a certain amount of Al 2 O 3 Or TiO 2 Mixing the powder uniformly, calcining the mixed powder, and refining the powder to the required size after heat preservation. Fe obtained by the invention 2 O 3 ‑Cr 2 O 3 The high near infrared reflection pigment has good microscopic morphology, the agglomeration is not obvious, and the reflectivity of the pigment to the near infrared band is as high as 76.68%.
Description
Technical Field
The invention relates to an infrared reflection pigment, in particular to Fe 2 O 3 -Cr 2 O 3 A preparation method of a high near infrared reflective pigment and application thereof in paint.
Background
Pigments are colored, finely divided, powdery materials that are generally insoluble in water, oils, solvents, resins, and the like, and can be dispersed in a variety of media. It has masking power, tinting strength, relatively stable to light, and is used in preparing paint, etc. The pigment is an important component in the paint formulation, can lead the paint to have basic functions of coloring, covering, corrosion prevention, protection and the like, and can lead some special paint to have multiple functions of electric conduction, camouflage, photochromism, photoluminescence, thermochromism and the like. After the paint formulation designer has properly selected the pigment, the paint product is designed to have the proper cost, high application performance and good ecological performance. Near infrared reflective pigments (Near-infrared Reflective Pigments) are pigments that absorb and reflect light of a wavelength in the visible region to exhibit a desired color, while reflecting a substantial amount of light in the Near infrared region to reduce the surface temperature of an object.
The near infrared reflecting paint is similar to common paint in composition and consists of four kinds of material including base material, pigment, functional stuffing and assistant, and the components with great influence on the optical performance of the paint are base material and pigment and stuffing. The base material, namely the film forming material, is the most important component in the paint and plays a leading role in the performance of the paint and the paint film. The film-forming material forms a film and simultaneously, with evaporation of water molecules (or solvent molecules) in the coating, the binder molecules in the solution or the polymer particles in the emulsion are brought into close proximity to each other to coalesce the pigment and filler to form a continuous coating and bond the coating to the substrate to form a uniform, continuous and tough protective film. The properties of the base material play a decisive role in the hardness, flexibility, abrasion resistance, impact resistance, water resistance, heat resistance, weather resistance and other physicochemical properties of the coating film formed, and also determine the state of the coating and the manner in which the coating film is cured.
The resin used for the near infrared reflective coating has a smaller near infrared light absorption, and is required to have high transparency, light transmittance of 80% or more, and low solar energy absorptivity. Since some of the groups in the resin absorb heat, the resin is designed to contain as few groups as possible such as c—o-C, C =o, -OH, etc. In addition, since near infrared reflective coating is mainly applied to petroleum tanks, automobile and aircraft housings, ship decks, and roofs and walls of warehouses or buildings, it is also required to be excellent in acid and alkali resistance, water resistance, weather resistance, temperature resistance, and adhesion.
Pigments are one of the important factors affecting the reflective properties of near infrared reflective coatings. In general, the higher the reflectance value of the pigment in a near infrared reflective coating, the more reflective the coating. In recent years, due to rapid development of pigment preparation technology, pigment powder with different particle sizes can be prepared, and the nano pigment has better reflection performance in the near infrared band. Among the infrared reflective pigments, black pigments are most widely used. The black pigment is a very important variety in the color matching of the paint, and various colors with different brightness can be obtained by adding the black pigment with different proportions on the basis of the existing colors. For example, the iron-red paint can be added with black pigment with different proportions to obtain purple-brown with different depths; black pigments with different proportions are added into the white paint, so that grays with different depths can be obtained; and black pigments with different proportions are added into the yellow paint, so that dark green with different depths can be obtained.
However, the black paint has certain magnetism, and is easy to agglomerate after being thinned, so that the infrared reflection performance is affected.
Disclosure of Invention
In order to solve the problems, the invention adopts a solid phase reaction method to prepare Fe 2 O 3 -Cr 2 O 3 The high near infrared reflective pigment comprises the following specific operations: weighing Fe according to a molar ratio 2 O 3 And Cr (V) 2 O 3 Powder, adding a certain amount of Al 2 O 3 Or TiO 2 Mixing the powder uniformly, calcining the mixed powder, and refining the powder to the required size after heat preservation.
The chromium oxide has the advantages of high tinting strength, high thermal stability, good corrosion resistance and the like, is a basic component of various pigments with different crystal forms, and has been widely used as an important inorganic pigment for a long time. Cr (Cr) 2 O 3 The P-type semiconductor material with corundum structure has a forbidden band width of about 3.5eV, can form solid solution with various transition metal ions, further change microstructure and spectral characteristics of the material, and presents various colors such as black, dark green and the like. Cr is added to 2 O 3 With Cr 2 O 3 After mixing and calcining, a black pigment can be prepared. Cr by component doping 2 O 3 The pigment is modified, and the purpose of preparing the high near infrared reflection pigment can be achieved.
In the method of the invention, cr is used as 2 O 3 The molar amount of (2) is 1 unit, and Fe is added 2 O 3 The molar amount of (1) to (0.9) units, al 2 O 3 TiO is (0.01-0.03) units 2 Is (0.01-0.07) units. Al (Al) 3+ And Ti is 4+ The doping element can increase the reflectivity of the pigment and the wavelength of the reflected wave.
The calcination temperature and time are critical to the chemical reaction of the pigment, and the reasonable temperature control is carried out according to the characteristics of raw materials.
The powder is agglomerated by chemical reaction during calcination, so that the powder after calcination is subjected to refinement treatment in the last step, a ball mill can be adopted for refinement, ethanol is added into the ball mill as a medium, the ball milling time is controlled, and the powder is refined to an average particle size of 1.5-3.5 mu m.
Fe obtained by the invention 2 O 3 -Cr 2 O 3 The high near infrared reflection pigment has good microscopic morphology, the agglomeration is not obvious, and the reflectivity of the pigment to the near infrared band is as high as 76.68%.
Drawings
FIG. 1 is a near infrared reflectance spectrum of the pigment obtained in examples S1 to S5.
FIG. 2 is a graph showing the average reflectance of the pigments obtained in examples S1 to S5.
FIG. 3 shows the near infrared reflectance spectra of the pigments obtained in examples S3, S6 to S8.
FIG. 4 shows the average reflectivities of the pigments obtained in examples S3, S6 to S8.
FIG. 5 shows the near infrared reflectance spectra of the pigments obtained in examples S3 and S9 to S12.
FIG. 6 shows the average reflectivities of the pigments obtained in examples S3 and S9 to S12.
FIG. 7 is a graph showing the infrared reflectance of the pigment obtained in example S3 at different calcination temperatures.
FIG. 8 shows the average reflectance of pigments obtained in example S3 by changing the calcination temperature to 950 ℃,1000 ℃, 1100 ℃, 1150 ℃.
FIG. 9 shows the infrared reflectance of the pigment obtained in example S3 with the incubation times of 0.5h, 4h, and 6h.
FIG. 10 shows the average reflectance of the pigment obtained in example S3 with the incubation times of 0.5h, 4h and 6h.
FIG. 11 shows the infrared reflectance of the pigment obtained in example S3 after the ball milling time was changed to 3min, 6min, 10min, 15min, 60min and the obtained pigment was sieved.
FIG. 12 shows the average reflectance of the pigment obtained in example S3 after the ball milling time was changed to 3min, 6min, 10min, 15min, 60min and the mixture was sieved.
FIG. 13 is an XRD pattern of the pigments obtained in examples S3, S6 and S11.
FIG. 14 is an SEM image of the pigment obtained in examples S3 (a), S6 (b) and S11 (c).
Detailed Description
The invention is described below in connection with examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Table 1 shows Fe in examples S1 to S12 2 O 3 -Cr 2 O 3 Raw materials of the high near infrared reflection pigment. The raw materials of examples S1 to S12 are weighed according to the molar ratio, mixed and calcined at 1050 ℃, the calcined powder is added into a ball mill after heat preservation for 2 hours, ball milling is carried out for 30 minutes after ethanol is added, and particles with the particle size of 1.5-1.6 mu m are selected.
TABLE 1 raw material compositions for examples S1 to S12
FIG. 1 is a near infrared reflectance spectrum of the pigments obtained in examples S1 to S5, showing that the reflectance at a wavelength of 700nm is low, the reflectance of all pigments tends to increase with increasing wavelength, and the reflectance is between 700 and 1176nm with Fe 2 O 3 /Cr 2 O 3 The molar ratio is reduced by increasing, the reflectivity is between 1176 and 2500nm along with Fe 2 O 3 /Cr 2 O 3 The molar ratio increases with increasing molar ratio.
FIG. 2 is a graph showing the average reflectance of the pigments obtained in examples S1 to S5, showing that the average reflectance of the pigments follows Fe 2 O 3 /Cr 2 O 3 The molar ratio increases gradually and then decreases slowly. Fe in example S3 2 O 3 /Cr 2 O 3 At a molar ratio of 0.50, the pigment obtained by calcination has a highest average reflectance in the near infrared range of 72.53%.
FIG. 3 shows the near infrared reflectance spectra of the pigments obtained in examples S3, S6 to S8. The reflectivity has a tendency to be obviously increased along with the increase of the wavelength in most of the wavelength ranges from 700nm to 2500nm, and the change of the reflectivity along with the increase of the wavelength is more gentle between the wavelength ranges from 842nm to 972nm and from 1434nm to 1852 nm. Examples S6 to S8 were doped with Al in the wavelength range 700nm to 1185nm 2 O 3 The reflectivity of the pigment of (2) is higher than that of example S3 without Al doping 2 O 3 Is reduced in the pigment of example S8, al 2 O 3 /Cr 2 O 3 The reflectance was the lowest at a molar ratio of 0.03; doping Al in 1185-2500 nm range 2 O 3 Is less doped with Al 2 O 3 To some extent, al of example S6 2 O 3 /Cr 2 O 3 The reflectance was highest with a molar ratio of 0.01.
FIG. 4 shows the average reflectance of the pigments obtained in examples S3 and S6 to S8, and it can be seen that Al is contained in the pigment obtained in example S6 2 O 3 /Cr 2 O 3 Molar ratio of 0.01, compared with the Al without addition 2 O 3 In example S3 of (2), the average reflectance in the near infrared band was increased to 73.60%. However, with the pigments obtained in example S7 and example S8, al was present 2 O 3 /Cr 2 O 3 The average reflectance gradually decreased with continued increase in the molar ratio, and the pigment obtained in example S8 had an average reflectance in the near infrared band of only 68.78%.
FIG. 5 shows the near infrared reflectance spectra of the pigments obtained in examples S3 and S9 to S12. As can be seen from the graph, between the wavelength range of 700-1203 nm, tiO 2 The doping of the (C) significantly improves the reflectivity of the pigment, and the TiO has the wavelength of 1203-2500 nm 2 The doping of (3) does not significantly improve the reflectivity of the pigment.
FIG. 6 shows the average reflectivities of the pigments obtained in examples S3 and S9 to S12. As can be seen from the figure, tiO in the pigment 2 /Cr 2 O 3 At a molar ratio of less than 0.05, the pigment has an average reflectance in the near infrared band with TiO 2 The pigment obtained in example S11 was the highest with increasing doping amountCan reach 76.68 percent. However, when TiO is present in the feedstock 2 /Cr 2 O 3 When the molar ratio is more than 0.05, the near infrared average reflectivity of the pigment is reduced; tiO in the pigment obtained in example S12 2 /Cr 2 O 3 At a molar ratio of 0.07, the pigment had a near infrared average reflectance of 71.36%, indicating excessive TiO 2 The doping level adversely affects the near infrared reflectance properties of the pigment.
The other conditions of example S3 were kept unchanged, the calcination temperature was changed to 950 ℃,1000 ℃, 1100 ℃, 1150 ℃, and the corresponding pigment was obtained and tested for infrared band reflectance. As shown in FIG. 7, the reflectance of the pigment obtained at different calcination temperatures is gradually increased with the increase of the wavelength, the reflectance of the pigment obtained at 1000℃is higher between 700 and 1226nm, and the reflectance obtained at 1050℃and 1100℃and 1150℃are higher in the wavelength range of 1226 to 2500 nm.
FIG. 8 shows the average reflectance of pigments obtained in example S3 by changing the calcination temperature to 950 ℃,1000 ℃, 1100 ℃, 1150 ℃ and it can be seen that the average reflectance of pigments increases and decreases with increasing calcination temperature. When the calcining temperature is 1050 ℃, the average reflectivity of the obtained pigment in the near infrared band is highest and reaches 72.53 percent, which is mainly due to the fact that the calcining temperature is too low, the solid phase reaction speed is low, the solid phase reaction is insufficient, the generated crystal amount is small, the crystal grains are small, the crystal development is incomplete, and the near infrared reflection performance of the pigment is poor. Too high a calcination temperature can exacerbate the erosion and dissolution of the liquid phase crystals, degrade the quality of the pigment, and also affect the reflective properties of the pigment.
The other conditions of example S3 were kept unchanged, and the incubation times were changed to 0.5h, 4h, 6h to obtain the corresponding pigments and the infrared band reflectances were tested as shown in fig. 9. As can be seen from the graph, the reflectivity of the pigment after heat preservation for 6 hours is greatly reduced within the wavelength range of 700 nm-1326 nm, which is obviously lower than that of the pigment after heat preservation for a short time, and the average reflectivity within the wavelength range can be reduced when the heat preservation time is too long, and the reflectivity of the pigment after heat preservation for 0.5 hours is obviously lower than that of other pigments with longer heat preservation time within the wavelength range of 1326 nm-2500 nm.
FIG. 10 shows that the average reflectance of the pigment obtained after the incubation time was changed to 0.5h, 4h, and 6h in example S3, and the average reflectance of the pigment was increased and then decreased with the increase of the incubation time. When the heat preservation time is 2 hours, the average reflectivity of the calcined pigment in the near infrared band is highest and reaches 64.91 percent, which is mainly because the heat preservation time is too short, the reaction is not fully carried out, the crystallinity is not high, the heat preservation time is too long, the grain size is easily increased, the grains are abnormally grown, and the reflectivity is reduced.
The other conditions of example S3 were kept unchanged, and the ball milling time was changed to 3min, 6min, 10min, 15min, 60min, and pigment particles with median particle diameter were retained after sieving, and the infrared band reflectance and the average reflectance were respectively tested, as shown in fig. 11 and fig. 12. As can be seen from fig. 11, the reflectivity of the pigments all showed a tendency to gradually rise with an increase in wavelength. As can be seen from fig. 12, the median particle diameter of the pigment powder, which was not subjected to the grinding treatment after calcination, was about 3.34 μm, and the median particle diameter of the pigment gradually decreased with the increase of the ball milling time, and accordingly, the average reflectance of the pigment showed a tendency to increase first and then decrease. When the ball milling time is less than 30min, the reflectivity of the pigment increases along with the extension of the ball milling time; when the ball milling time exceeds 30 minutes, the reflectance of the pigment decreases with the increase of the ball milling time. When the ball milling time was 30min, the average reflectance of the pigment in the near infrared band was 72.53% at the highest, and the median particle diameter of the pigment was about 1.58. Mu.m.
FIG. 13 is an XRD pattern of the pigments obtained in examples S3, S6 and S11, showing that the pigments obtained in examples S3, S6 and S11 all have corundum crystal structures and that no diffraction peaks of other impurity phases appear, indicating that Al and Ti ions both enter Cr 2 O 3 The crystal lattice forms a solid solution, but there is a relatively large difference in the intensity of each doped diffraction peak in the XRD pattern, with the intensity of doped titanium being highest, the intensity of doped aluminum being second highest, and the intensity of undoped aluminum being lowest.
Table 2 shows the pigment unit cell parameters and grain sizes calculated using XRD data, with undoped pigment grain sizes around 37nm, and aluminum doped test pigments and titanium doped pigment grain sizes at 62nm and 41nm, respectively. This is due toHexacoordinated trivalent chromium ion Cr 3+ Radius (61.5 pm) of Ti 4+ The radius (60.5 pm) is relatively close, so Ti 4+ Is easier to replace Cr 2 O 3 Cr in lattice 3+ 。
TABLE 2 unit cell parameters and grain size of the pigments obtained in examples S3, S6 and S11
FIG. 14 is an SEM image of the pigment obtained in examples S3 (a), S6 (b) and S11 (c), showing that the pigment particles were 1 to 5 μm in size, regular in shape and less noticeable in agglomeration.
The pigment obtained in example S3 has an average reflectance of up to 72.53% in the wavelength band of 700nm to 2500 nm. EXAMPLE S6 doping with Al 2 O 3 /Cr 2 O 3 Al in a molar ratio of 0.01 2 O 3 The near infrared average reflectivity of the pigment can reach 73.60%; EXAMPLE S11 TiO-doped 2 /Cr 2 O 3 TiO with molar ratio of 0.05 2 The average reflectance of the pigment reached 76.68%, indicating that Fe 2 O 3 -Cr 2 O 3 Adding proper amount of Al into the system pigment 2 O 3 And TiO 2 The near infrared reflectivity of the pigment can be improved.
Calcination has a great influence on the near infrared reflectivity of the pigment, and the average reflectivity of the pigment is firstly increased and then reduced along with the increase of the calcination temperature; pigment average reflectance also shows a similar trend with longer incubation time. When the calcining temperature is 1050 ℃ and the heat preservation time is 2 hours, the pigment reaches the highest near infrared average reflectivity.
The median particle diameter of the pigment gradually decreases along with the increase of the ball milling time, and the average reflectivity is increased and then decreased along with the increase of the median particle diameter; when the ball milling time is 30min, the median particle size of the pigment is about 1.58 μm, and the pigment reaches the highest average reflectivity.
The foregoing is only illustrative of the present invention and is not to be construed as limiting thereof, but rather as various modifications, equivalent arrangements, improvements, etc., within the spirit and principles of the present invention.
Claims (5)
1. Fe (Fe) 2 O 3 -Cr 2 O 3 A method for preparing a high near infrared reflective pigment, characterized in that the method comprises the following operations: weighing Fe according to a molar ratio 2 O 3 And Cr (V) 2 O 3 Powder, adding a certain amount of Al 2 O 3 Or TiO 2 Mixing the powder uniformly, calcining the mixed powder, and refining the powder to the required size after heat preservation.
2. The method according to claim 1, wherein Fe 2 O 3 And Cr (V) 2 O 3 The molar ratio of (1) to (0.9) 1; al (Al) 2 O 3 And Cr (V) 2 O 3 The molar ratio of (1) is (0.01-0.03); tiO (titanium dioxide) 2 And Cr (V) 2 O 3 The molar ratio of (2) is (0.01-0.07): 1.
3. The method according to claim 1, wherein the calcination temperature is 950 ℃ to 1150 ℃ and the incubation time is 0.5 to 6 hours.
4. The method according to claim 1, wherein the heat-preserved powder is refined by a ball mill to an average particle size of 1.5-3.5 μm.
5. A silicone resin coating with high near infrared reflection, characterized in that the silicone resin coating is added with Fe prepared by the method of any one of claims 1-4 2 O 3 -Cr 2 O 3 High near infrared reflective pigments.
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