CN109082140B - Preparation method of composite high-infrared-reflection nano pigment - Google Patents

Preparation method of composite high-infrared-reflection nano pigment Download PDF

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CN109082140B
CN109082140B CN201810975319.4A CN201810975319A CN109082140B CN 109082140 B CN109082140 B CN 109082140B CN 201810975319 A CN201810975319 A CN 201810975319A CN 109082140 B CN109082140 B CN 109082140B
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lafeo
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CN109082140A (en
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仝玉萍
李克亮
张天宇
赵顺波
王晗晗
朱海弘
张新中
张海龙
严亮
马军涛
梅婉婉
刘焕强
徐凯
霍洪媛
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North China University of Water Resources and Electric Power
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • 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
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention discloses a preparation method of a composite high-infrared-reflection nano pigment, which comprises the following steps: 1) dispersing P123 and deionized water in a proper amount of absolute ethyl alcohol for magnetic stirring; 2) adding LaFeO after P123 is fully dissolved3Setting stirring temperature, adding butyl titanate after the temperature of the stirrer is stable, and dropwise adding ammonia water to adjust the pH value; 3) after the reaction is finished, washing for several times by using water and ethanol respectively until impurities are completely removed, clarifying the upper-layer solution, and centrifuging to obtain a precipitate; 4) drying the precipitate obtained in the step 3), calcining the dried precipitate in a furnace, and grinding the calcined precipitate to obtain the composite high infrared reflection nano pigment. In a word, the composite high infrared reflection nano pigment prepared by the method combines LaFeO3And TiO2The paint has the advantages of no toxicity, strong coloring capability, high infrared reflectivity, good chemical stability and the like.

Description

Preparation method of composite high-infrared-reflection nano pigment
Technical Field
The invention relates to the technical field of pigments for buildings, ceramics, textiles and the like, in particular to a preparation method of a composite high-infrared-reflection nano pigment.
Background
In recent years, pigments have been widely used in the fields of construction, ceramics, textiles, and the like. The performance requirements of pigments are also increasing. Most of traditional inorganic pigments are white and light-colored, so that white light pollution is easily caused, toxic components are contained, and the environment is polluted, and the traditional pigment with single performance cannot meet the requirements of various industries, so that the preparation of novel nanoscale sub-nanoscale materials to replace the traditional pigment with single performance is a hotspot of research in the field of current materials. Therefore, a green synthesis method is sought, and the composite high infrared reflection nano pigment with small size, good dispersibility, good fire resistance, good corrosion resistance, good saturation and uniform particle size distribution is obtained in a relatively mild environment.
Common TiO 22The pigment is a high infrared reflection heat insulation pigment, is white loose powder, has strong ultraviolet shielding effect, and has good dispersibility and durability. But because the appearance of the film is white, the film is easy to cause white pollution and also injures human retina to a certain extent.
Patent application No. 201510060090.8 discloses a high infrared reflection nanopigment. Although the pigment has the advantages of good thermal stability, good light stability and high infrared reflectivity, the variety of the required raw materials is various, so that the operation steps in the preparation process are complicated, the quality is difficult to ensure in large-scale production, and the industrial production is not facilitated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of inorganic-inorganic composite high-infrared-reflection nano pigment, which prepares active TiO by using active TiO2With pigmentsLaFeO3The high infrared reflection environment-friendly inorganic pigment is synthesized at a lower temperature.
The technical scheme of the invention is that the preparation method of the composite high infrared reflection nanometer pigment comprises the following steps:
1) dispersing a surfactant and deionized water in a proper amount of absolute ethyl alcohol for magnetic stirring;
2) adding LaFeO after the surfactant is fully dissolved3Setting the stirring temperature, adding butyl titanate after the temperature of the stirrer is stable, dropwise adding ammonia water to adjust the pH value, and reacting for 3-4 h;
3) after the reaction is finished, washing for several times by using water and ethanol respectively until impurities are completely removed, clarifying the upper-layer solution, and centrifuging to obtain a precipitate;
4) drying the precipitate obtained in the step 3) at 70-80 ℃, calcining the dried precipitate in a furnace at 400-500 ℃ for 1-3 h, and grinding to obtain the composite high infrared reflection nano pigment.
Further, after grinding in the step 4), mixing and soaking the obtained pigment and the film-forming additive for 2-3 hours at the temperature of 34-47 ℃ according to the mass ratio of 2 (2-5), and adding an alternating magnetic field, wherein the central magnetic field of the alternating magnetic field is 2400Gs, and the alternating frequency is 10 Hz; the mixing and adhesion of the film-forming assistant to the precipitate can be improved by adding the alternating magnetic field under the condition, the storage stability of the composite high infrared reflection nano pigment can be improved by soaking the film-forming assistant, and the film-forming performance of the pigment can be improved.
Further, the preparation method of the film-forming assistant comprises the following steps:
s1: selecting 7-10 parts of dodecyl alcohol ester, 4-6 parts of polyoxyethylene fatty acid ester, 6-9 parts of perfluoroalkyl acrylate, 0.3-0.5 part of hexamethylene diisocyanate, 1-2 parts of dicumyl peroxide, 0.8-1.5 parts of methyl ethyl ketone peroxide, 0.5-0.8 part of activated carbon powder, 5-7 parts of ethanol, 3-4 parts of propylene glycol and 1-2 parts of nano titanium dioxide powder in parts by weight;
s2, mixing dodecyl alcohol ester, polyoxyethylene fatty acid ester, perfluoroalkyl acrylate and hexamethylene diisocyanate at the temperature of 23-31 ℃, heating to the temperature of 64-78 ℃, dropwise adding dicumyl peroxide, stirring at 800-1000 rpm for 5-7 min, and cooling to room temperature at the speed of 2 ℃/min to form a mixture A for later use;
s3, mixing ethanol, propylene glycol and methyl ethyl ketone peroxide, controlling the temperature to be 35-45 ℃, and performing microwave treatment for 3-5 min by adding 180-300W of microwave power and 2150MHz of microwave frequency to form a mixture B for later use; the mixing degree of ethanol, propylene glycol and methyl ethyl ketone peroxide can be effectively improved by adding microwaves under the condition, so that the performance of the film-forming additive is improved;
and S4, mixing the mixture A obtained in the step S2 and the mixture B obtained in the step S3, adding 0.5-fold weight of deionized water, uniformly mixing, adding activated carbon powder and nano titanium dioxide powder, performing high-voltage pulse electric field and ultrasonic combined dispersion, performing high-voltage pulse electric field treatment for 15-30 min at 25-40 ℃, heating to 2-3 ℃ every 3-5 min, and applying ultrasonic treatment for 1-2 min to obtain the film-forming aid, wherein the ultrasonic conditions comprise that the ultrasonic power is 150-260W, the ultrasonic frequency is 20-70 kHz, the electric field intensity is 20-55 KV/cm, and the number of pulses is 2-7. The mixing degree of the mixture A and the mixture B can be obviously improved through the high-voltage pulse electric field and ultrasonic combined dispersion, and the performance of the film forming additive can be enhanced by adding the activated carbon powder and the nano titanium dioxide powder in the proportion; the film-forming assistant prepared by the method can obviously improve the weather resistance, scrub resistance, stability and the like of the composite high infrared reflection nano pigment.
Further, the surfactant described in step 1) is preferably P123.
Further, ammonia water is dripped in the step 2) to adjust the pH value to 8, and the reaction is carried out for 3 hours.
Further, the drying conditions in step 4) are specifically: drying at 80 ℃ for 1h, and calcining under the conditions of: calcining at 500 deg.C for 1 h.
Further, LaFeO described in step 2)3Obtained by the following method: placing the beaker filled with deionized water on a constant-temperature magnetic stirrer, and adjusting the temperature of the magnetic stirrer to 60 +/-10 ℃;when the temperature of the magnetic stirrer rises to and stabilizes to 60 +/-10 ℃, dissolving glycine in deionized water, adding ferric nitrate and lanthanum nitrate into the solution in sequence after the glycine is fully dissolved, and stirring for 120 +/-10 min after the glycine is fully dissolved; and after stirring, pouring the mixed solution into an evaporating dish, putting the evaporating dish on a universal electric furnace, heating and stirring at 120 +/-10 ℃, enabling the solution to perform self-propagating combustion reaction in the process to generate loose powder, putting the loose powder into an agate mortar for grinding, and calcining the obtained powder at the temperature of 600-900 ℃ after grinding.
Further, LaFeO described in step 2)3In the preparation process of (3), the added lanthanum nitrate and ferric nitrate are respectively calculated by La and Fe, and the molar weight of the glycine is 2 times of the sum of the molar weights of the La and the Fe.
Furthermore, the calcination temperature is 700-800 ℃.
Further, the calcination temperature was 750 ℃. LaFeO3In the preparation process, the matrix is not completely calcined at 600 ℃ and 700 ℃, impurity peaks disappear along with the rise of temperature, the baseline tends to be stable, the peak shape tends to be sharp, and the crystallinity becomes better and better. Compared with 900 ℃, the characteristic peak value of 900 ℃ at 800 ℃ is higher, the peak shape is sharper, but from the aspect of energy saving, the relative calcination temperature is 750-800 ℃ which is lower.
Further, stirring treatment is carried out in the step 2) through a pigment preparation device, wherein the pigment preparation device comprises a main body, a main shaft, a stirring disc, a feeding device, a support plate and a material liquid port boss; the feeding device comprises a main body, a feeding device, a main shaft, a motor, two stirring disks, a feeding device, a liquid feeding boss and a liquid discharging boss, wherein the feeding device is arranged at the upper end of the main body;
the stirring disc is embedded in the main shaft through a swinging fixture block, and the swinging fixture block is used for enabling the stirring disc to swing up and down and limiting transversely;
the two material liquid port bosses are respectively positioned at the left end and the right end of the lower end of the sliding rail on the support plate, a material liquid port is arranged on the material liquid port boss, and a sealing elastic ring is arranged on the outer side of the circumference of the material liquid port;
be equipped with the elastic fit groove that matches with the sliding rail in the middle of the feeding device medial surface, the elastic fit groove left and right sides is equipped with the feed liquid interface that matches with feed liquid mouth position, the feed liquid interface circumference outside is equipped with the sealed recess that matches with sealed elastic ring position, and feeding device goes up the top surface center and is equipped with the interpolation mouth. The device can be swung up and down through the matching of the counterweight ball and the hollow groove while rotating along with the rotation of the main shaft under the action of the stirring disc, more sufficient stirring is carried out by utilizing the stirring main blade and the stirring auxiliary blade, meanwhile, the solution enters the feeding device to wash the additive through the butt joint of the two material liquid ports, the accuracy of the additive is ensured, the residue of the additive is avoided, and the tightness of a material liquid port and a material liquid port during butt joint is ensured through the elastic matching groove, the sealing elastic ring and the sealing groove.
The working method of the pigment preparation device comprises the steps of adding deionized water into the main body through the feed inlet, and adding the surfactant, absolute ethyl alcohol and LaFeO3And butyl titanate is respectively added into the four feeding devices, the opening device firstly presses down the feeding devices of the surfactant and the absolute ethyl alcohol to the boss of the feed liquid port, the feed liquid port is in butt joint with the feed liquid port, and simultaneously, the sealing elastic ring and the sealing groove are occluded and sealed, so that the deionized water generates rotary force through stirring, the convection between the two feed liquid ports and the inside of the main body is realized, and after the surfactant is fully dissolved, the LaFeO is pressed down3The feeding device is provided with stirring temperature, and the feeding device which presses the butyl titanate is stabilized at the stirring temperatureAmmonia water is dripped into the material port to adjust the pH value, and the mixture is stirred after reacting for 3 to 4 hours; during the period, the stirring disc rotates along with the main shaft through the characteristic of the swing fixture block, and simultaneously swings up and down through the action of the counterweight balls and the hollow groove, so that the stirring effect is improved through the stirring main blade and the stirring auxiliary blade.
The invention has the beneficial effects that:
(1) the invention uses LaFeO3Pigments and TiO2Compounding, and taking the advantages of the two into full play through the synergistic effect of the two to synthesize LaFeO3/TiO2A nanocomposite pigment. The composite high infrared reflection nano pigment obtained by the invention combines LaFeO3And TiO2Excellent performance, rich color, high infrared reflectivity, no toxicity, etc.
(2) The film-forming assistant prepared by the invention can obviously improve the weather resistance, scrub resistance, stability and the like of the composite high infrared reflection nano pigment; the mixing and adhesion of the film forming additive to the precipitate can be improved by adding the alternating magnetic field, the storage stability of the composite high infrared reflection nano pigment is improved, and the film forming property of the pigment is improved.
(3) The pigment preparation device provided by the invention can rotate along with the main shaft and can swing up and down through the matching of the counterweight balls and the hollow groove under the action of the stirring disc, the stirring main blade and the stirring auxiliary blade are utilized to stir more fully, the accuracy of the additive amount is ensured, the additive residue is avoided, the device is simple and convenient to use, the stirring effect is good, and the accuracy of the additive amount can be simply and conveniently improved.
In a word, the preparation method is simple, the raw materials are easy to obtain, the synthesis temperature is low, the process is simple and controllable, and the method is suitable for large-scale production.
Drawings
FIG. 1 shows LaFeO calcined at 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C3XRD pattern of (a).
FIG. 2 shows LaFeO calcined at 700 deg.C, 750 deg.C, 800 deg.C3XRD pattern of (a).
FIG. 3 shows LaFeO prepared at different pH values3/TiO2XRD pattern and LaFeO3XRD pattern of the matrix.
FIG. 4 shows LaFeO prepared with different surfactants3/TiO2XRD pattern of (a).
FIG. 5 shows LaFeO prepared at different pH values3/TiO2SEM photograph of (a): (a) pH 7(b) pH 8(c) pH 9.
FIG. 6 shows LaFeO prepared with different surfactants3/TiO2SEM photograph of (a): (a) p123(b) PVP (c) Triton x-100.
FIG. 7 is a schematic view of the external appearance of the manufacturing apparatus of the present invention.
FIG. 8 is a schematic view of the internal structure of the manufacturing apparatus of the present invention.
FIG. 9 is a top view of the stirring disk of the present invention.
Fig. 10 is a schematic structural view of the feeding device of the present invention.
The device comprises a main body, 11 feed inlets, 12 discharge outlets, 2 main shafts, 21 motors, 3 stirring discs, 31 hollow grooves, 32 counterweight balls, 33 stirring main blades, 34 stirring auxiliary blades, 35 swinging fixture blocks, 4 feeding devices, 41 feed liquid interfaces, 42 sealing grooves, 43 elastic matching grooves, 44 adding ports, 5 support plates, 51 sliding rails, 6 feed liquid port bosses, 61 feed liquid ports and 62 sealing elastic rings.
Detailed Description
Example 1
LaFeO3The preparation method comprises the following steps:
first, a beaker containing 150ml of deionized water was placed on a constant temperature magnetic stirrer, and the temperature of the magnetic stirrer was adjusted to 60 ℃. When the temperature of the magnetic stirrer rises to and stabilizes to 60 ℃, 3.002g of glycine is dissolved in deionized water, 4.04g of ferric nitrate and 4.33g of lanthanum nitrate are sequentially added into the solution after the glycine is fully dissolved, and stirring is carried out for 2 hours after the full dissolution. After stirring, pouring the mixed solution into an evaporating dish, heating the evaporating dish on a universal electric furnace at 120 ℃, enabling the liquid to rapidly expand, then enabling the solution to be violently combusted in the evaporating dish, discharging a large amount of pungent smoke, generating fluffy powder at the combustion position in the process, putting the fluffy powder into an agate mortar for grinding, calcining the obtained powder at 600 ℃ for 2 hours after grinding, and grinding the powder into powderThe shape of LaFeO is obtained3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
0.6g P123 and 2ml deionized water are dispersed in 250ml absolute ethyl alcohol for magnetic stirring, and 0.05g LaFeO is added after P123 is fully dissolved3The stirring temperature of the matrix is set to be 60 ℃. When the temperature of the stirrer is stabilized at 60 ℃, 2.5ml of butyl titanate is added, and when the butyl titanate is fully dissolved, timing is started to allow the butyl titanate to react for 3 hours. During this process, the pH was adjusted to 8 by dropwise addition of ammonia. TiO formed by hydrolysis of butyl titanate2Coated on the surface of lanthanum ferrite. Then washing with water and ethanol for several times respectively until the impurities are completely removed and the upper solution is clear. The precipitate was obtained by centrifugation and dried at 70 ℃. After drying, putting the mixture into a furnace to calcine for 1h at 500 ℃, and grinding the mixture to obtain the composite high infrared reflection nano pigment.
Example 2
LaFeO3The preparation method comprises the following steps:
in contrast to example 1, the temperature of the magnetic stirrer was adjusted to 50 ℃; stirring for 130min after fully dissolving; heating at 110 deg.C in a universal electric furnace; calcining the obtained powder for 2h at the temperature of 700 ℃, and grinding the powder into powder to obtain LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
dispersing 0.5g PVP and 2ml deionized water in 250ml absolute ethyl alcohol for magnetic stirring, adding 0.05g LaFeO after P123 is fully dissolved3The stirring temperature of the matrix is set to be 60 ℃. When the temperature of the stirrer is stabilized at 60 ℃, 2.5ml of butyl titanate is added, and when the butyl titanate is fully dissolved, timing is started to allow the butyl titanate to react for 3.5 hours. During this process, the pH was adjusted to 8 by dropwise addition of ammonia. TiO formed by hydrolysis of butyl titanate2Coated on the surface of lanthanum ferrite. Then washing with water and ethanol for several times respectively until the impurities are completely removed and the upper solution is clear. The precipitate was obtained by centrifugation and dried at 75 ℃. After drying, putting the mixture into a furnace to calcine for 2 hours at 450 ℃, and grinding the mixture to obtain the composite high infrared reflection nano pigment.
Example 3
LaFeO3The preparation method comprises the following steps:
in contrast to example 1, the temperature of the magnetic stirrer was adjusted to 70 ℃; stirring for 110min after fully dissolving; heating at 130 deg.C in a universal electric furnace; calcining the obtained powder for 2h at the temperature of 800 ℃, and grinding the powder into powder to obtain LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
5ml of triton x-100 and 2ml of deionized water are dispersed in 250ml of absolute ethyl alcohol for magnetic stirring, and 0.05g of LaFeO is added after P123 is fully dissolved3The stirring temperature of the matrix is set to be 60 ℃. When the temperature of the stirrer is stabilized at 60 ℃, 2.5ml of butyl titanate is added, and when the butyl titanate is fully dissolved, timing is started to allow the butyl titanate to react for 4 hours. During this process, the pH was adjusted to 8 by dropwise addition of ammonia. TiO formed by hydrolysis of butyl titanate2Coated on the surface of lanthanum ferrite. Then washing with water and ethanol for several times respectively until the impurities are completely removed and the upper solution is clear. The precipitate was obtained by centrifugation and dried at 80 ℃. And after drying, calcining the mixture in a furnace at 400 ℃ for 3 hours, and grinding the mixture to obtain the composite high infrared reflection nano pigment.
Example 4
LaFeO3The preparation method comprises the following steps:
different from the embodiment 1, the obtained powder is calcined for 2h at the temperature of 900 ℃ and then is ground into powder, thus obtaining LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
in the process, the pH was adjusted to 7 by adding dropwise ammonia, in contrast to example 1.
Example 5
LaFeO3The preparation method comprises the following steps:
different from the embodiment 1, the obtained powder is calcined for 2h at the temperature of 750 ℃ and then is ground into powder, thus obtaining LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
in the process, the pH was adjusted to 9 by adding dropwise ammonia, in contrast to example 1.
Example 6
LaFeO3The preparation method comprises the following steps:
different from the embodiment 1, the obtained powder is calcined for 2h at the temperature of 750 ℃ and then is ground into powder, thus obtaining LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
different from the embodiment 1, after grinding, the obtained pigment and the film-forming additive are mixed and soaked for 2h at the temperature of 34 ℃ according to the mass ratio of 2:3, and an alternating magnetic field is added, wherein the central magnetic field of the alternating magnetic field is 2400Gs, and the alternating frequency is 10 Hz; the mixing and adhesion of the film-forming assistant to the precipitate can be improved by adding the alternating magnetic field under the condition, the storage stability of the composite high infrared reflection nano pigment can be improved by soaking the film-forming assistant, and the film-forming performance of the pigment can be improved.
The preparation method of the film-forming additive comprises the following steps:
s1: selecting 7 parts of dodecyl alcohol ester, 4 parts of polyoxyethylene fatty acid ester, 6 parts of perfluoroalkyl acrylate, 0.3 part of hexamethylene diisocyanate, 1 part of dicumyl peroxide, 0.8 part of methyl ethyl ketone peroxide, 0.5 part of activated carbon powder, 5 parts of ethanol, 3 parts of propylene glycol and 1 part of nano titanium dioxide powder in parts by weight;
s2, mixing dodecyl alcohol ester, polyoxyethylene fatty acid ester, perfluoroalkyl acrylate and hexamethylene diisocyanate at the temperature of 23 ℃, heating to 64 ℃, dropwise adding dicumyl peroxide, stirring at 800rpm for 5min, and cooling to room temperature at the speed of 2 ℃/min to form a mixture A for later use;
s3, mixing ethanol, propylene glycol and methyl ethyl ketone peroxide, controlling the temperature at 35 ℃, and performing microwave treatment for 3min by using microwave with the microwave power of 180W and the microwave frequency of 2150MHz to form a mixture B for later use; the mixing degree of ethanol, propylene glycol and methyl ethyl ketone peroxide can be effectively improved by adding microwaves under the condition, so that the performance of the film-forming additive is improved;
s4, mixing the mixture A of the step S2 and the mixture B of the step S3, adding deionized water with the weight 0.5 times that of the mixture, uniformly mixing, adding activated carbon powder and nano titanium dioxide powder, carrying out high-voltage pulse electric field and ultrasonic combined dispersion, carrying out high-voltage pulse electric field treatment for 15min at 25 ℃, heating to 2-3 ℃ every 3min, and applying ultrasonic treatment for 1min to obtain the film-forming aid after the high-voltage pulse electric field and the ultrasonic combined dispersion, wherein the ultrasonic conditions are that the ultrasonic power is 150W, the ultrasonic frequency is 20kHz, the high-voltage pulse electric field conditions are that the electric field strength is 20KV/cm, and the pulse number is 2. The mixing degree of the mixture A and the mixture B can be obviously improved through the high-voltage pulse electric field and ultrasonic combined dispersion, and the performance of the film forming additive can be enhanced by adding the activated carbon powder and the nano titanium dioxide powder in the proportion; the film-forming assistant prepared by the method can obviously improve the weather resistance, scrub resistance, stability and the like of the composite high infrared reflection nano pigment.
Example 7
LaFeO3The preparation method comprises the following steps:
different from the embodiment 1, the obtained powder is calcined for 2h at the temperature of 750 ℃ and then is ground into powder, thus obtaining LaFeO3And (4) nanocrystals.
The preparation method of the composite high infrared reflection nano pigment comprises the following steps:
different from the embodiment 1, after grinding, the sediment and the film-forming additive are mixed and soaked for 2.5h at the temperature of 41 ℃ according to the mass ratio of 2:4, and an alternating magnetic field is added, wherein the central magnetic field of the alternating magnetic field is 2400Gs, and the alternating frequency is 10 Hz.
The preparation method of the film-forming additive comprises the following steps:
s1: selecting 9 parts of dodecyl alcohol ester, 5 parts of polyoxyethylene fatty acid ester, 7 parts of perfluoroalkyl acrylate, 0.4 part of hexamethylene diisocyanate, 2 parts of dicumyl peroxide, 1.2 parts of methyl ethyl ketone peroxide, 0.7 part of activated carbon powder, 6 parts of ethanol, 3 parts of propylene glycol and 2 parts of nano titanium dioxide powder in parts by weight;
s2, mixing dodecyl alcohol ester, polyoxyethylene fatty acid ester, perfluoroalkyl acrylate and hexamethylene diisocyanate at the temperature of 27 ℃, heating to 73 ℃, dropwise adding dicumyl peroxide, stirring at 950rpm for 6min, and cooling to room temperature at the speed of 2 ℃/min to form a mixture A for later use;
s3, mixing ethanol, propylene glycol and methyl ethyl ketone peroxide, controlling the temperature at 39 ℃, and performing microwave treatment for 4min by using microwave power of 270W and microwave frequency of 2150MHz to form a mixture B for later use; the mixing degree of ethanol, propylene glycol and methyl ethyl ketone peroxide can be effectively improved by adding microwaves under the condition, so that the performance of the film-forming additive is improved;
s4, mixing the mixture A of the step S2 and the mixture B of the step S3, adding deionized water with the weight 0.5 times that of the mixture, uniformly mixing, adding activated carbon powder and nano titanium dioxide powder, carrying out high-voltage pulse electric field and ultrasonic combined dispersion, carrying out high-voltage pulse electric field treatment for 20min at 35 ℃, heating to 3 ℃ every 4min, and applying ultrasonic treatment for 2min to obtain the film-forming aid after the high-voltage pulse electric field and the ultrasonic combined dispersion, wherein the ultrasonic power is 240W, the ultrasonic frequency is 50kHz, the high-voltage pulse electric field conditions are 45KV/cm in electric field intensity and 6 pulses are counted.
In the preparation process of the composite high infrared reflection nano pigment, stirring treatment is carried out through a pigment preparation device, as shown in fig. 1 and 2, the pigment preparation device comprises a main body 1, a main shaft 2, a stirring disc 3, a feeding device 4, a carrier plate 5 and a material liquid port boss 6; a feed inlet 11 is formed in the center of the upper top surface of a main body 1, a discharge outlet 12 is formed in the center of the lower bottom surface of the main body 1, a main shaft 2 is located in the center of the inside of the main body 1, the upper end of the main shaft 2 is connected with the upper top surface of the main body 1 through a motor 21, two stirring disks 3 are arranged, the two stirring disks 3 are arranged on the main shaft 1 at equal intervals from top to bottom, four support plates 5 are arranged and are respectively located in the front, back, left and right middle parts of the side surface of the main body 1, a sliding rail 51 is arranged in the middle of the support plate 5;
as shown in fig. 3, a hollow groove 31 is formed at the far end of the circumference of the stirring disc 3, a counterweight ball 32 is arranged in the hollow groove 31, a plurality of stirring main blades 33 are arranged on the upper top surface and the lower bottom surface of the stirring rotary disc 3 at equal intervals, a plurality of stirring auxiliary blades 34 are arranged on the left side surface and the right side surface of each stirring main blade 33 at equal intervals, the stirring disc 3 is embedded in the main shaft 2 through a swinging fixture block 35, and the swinging fixture block 35 is used for enabling the stirring disc 3 to swing up and down and limiting transversely;
as shown in fig. 1, two feed liquid port bosses 6 are provided, which are respectively located at the left and right ends of the lower end of the sliding rail 51 on the support plate 5, a feed liquid port 61 is provided on the feed liquid port boss 6, and a sealing elastic ring 62 is provided outside the circumference of the feed liquid port 61;
as shown in fig. 4, an elastic fitting groove 43 matched with the sliding rail 51 is arranged in the middle of the inner side surface of the feeding device 4, material liquid ports 41 matched with the material liquid ports 61 are arranged on the left side and the right side of the elastic fitting groove 43, a sealing groove 42 matched with the sealing elastic ring 62 is arranged on the outer side of the circumference of the material liquid port 41, and an adding port 44 is arranged in the center of the upper top surface of the feeding device 4.
The working method of the pigment preparation device comprises the steps of adding deionized water into the main body 1 through the feed inlet 11, and adding the surfactant, the absolute ethyl alcohol and the LaFeO3And butyl titanate are respectively added into the four feeding devices 4, the device is opened, the feeding devices 4 of the surfactant and the absolute ethyl alcohol are firstly pressed down to the position of the feed liquid port boss 6, the feed liquid port 61 is in butt joint with the feed liquid port 41, meanwhile, the sealing elastic ring 62 and the sealing groove 42 are occluded and sealed, deionized water generates a rotary force through stirring, the convection between the two feed liquid ports 61 of the deionized water and the inside of the main body 1 is realized, and after the surfactant is fully dissolved, LaFeO is pressed down3The stirring temperature is set, the feeding device 4 of the butyl titanate is pressed when the stirring temperature is stabilized, ammonia water is dripped through the feeding hole 11 to adjust the pH value, and stirring is completed after reaction for 3-4 hours; meanwhile, the stirring disc 3 rotates along with the main shaft 2 through the characteristic of the swing fixture 35, and the stirring disc 3 swings up and down through the action of the counterweight balls 32 and the hollow groove 31, so that the stirring effect is improved through the stirring main blade 33 and the stirring auxiliary blade 34.
XRD test
LaFeO is obtained by calcining precursor powder3Nanocrystalline, LaFeO at 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C respectively in figure 13XRD pattern of nanocrystals. When the XRD pattern is compared with that of the standard graphic card JCPDSNO.74-2203, the characteristic peak of lanthanum ferrite can be found from 600 ℃. Impurity peaks appear at 600 ℃ and 700 ℃, and the XRD pattern and the standard chart are respectively compared with JCPDS NO.22-641 and JCPDS NO.2-915 to find that the impurity peak is La2O3And Fe2O3Indicating incomplete calcination of the matrix at 600 ℃ and 700 ℃. With the rise of the temperature, impurity peaks disappear, the baseline tends to be stable, the peak shape tends to be sharp, and the crystallinity is better and better. The characteristic peak value of 900 ℃ is higher and the peak shape is sharper at 800 ℃ compared with 900 ℃, but the 800 ℃ with lower relative calcination temperature is still selected from the aspect of energy saving.
As can be seen from FIG. 2, the impurities mixed in the lanthanum ferrite are removed at the calcination temperature of 750 ℃ to obtain the lanthanum ferrite nanocrystal with good crystallinity, and the particle size of the nanoparticle obtained by increasing the peak value is larger, the particle size is smaller, the specific surface area of the particle is larger, the specific surface energy is higher, and the material dispersibility is better, so that a uniform coating is easily formed in the use process, the adhesion is strong, and the chromaticity is uniform. In order to lay a good foundation for the subsequent coating of the matrix, the temperature of 750 ℃ is determined to be the better temperature for preparing the lanthanum ferrite pigment by the self-propagating combustion method.
Figure 3 is a XRD pattern of the product at different pH values. The matrix with the temperature of 750 ℃ and the balance of compounded LaFeO3/TiO2. As can be seen from the figure, LaFeO3The diffraction peak of the matrix is narrow and sharp, and the crystal crystallinity is good. Compounded LaFeO3/TiO2Crystals, starting from pH 7 images, show TiO in each curve2Characteristic peaks (. DELTA.marked TiO)2Characteristic peak) of TiO2Has been successfully coated with LaFeO3On the substrate. Shows that the LaFeO can be successfully prepared by the method3/TiO2A nanocomposite pigment. LaFeO in pH 7, pH 8, pH 9 images3All the characteristic peaks of (A) are obviously weakened because of TiO2Wraps up LaFeO3The result produced. LaFeO in pH 9 image3The peak of (A) is extremely low as compared with the substrate, indicating that TiO is likely2The coating is too thick, so that the composite pigment obtained by us is very likely to be TiO2White rather than colored is represented. The specific coating effect needs to be further analyzed by SEM.
Figure 4 is an XRD analysis pattern of different surfactant products.From the figure it is clear that different surfactants have different effects on the experiment: the samples coated with PVP and P123 showed significant TiO2Characteristic peaks (. DELTA.marked TiO)2Characteristic peak) indicating TiO2Has been successfully compounded in LaFeO3On the substrate; the sample using triton is not greatly different from the matrix, and TiO does not appear2Characteristic peak of (2). Whereas PVP compares to P123, sample TiO using P1232The characteristic peak of (A) is higher, and the peak type is sharper. This indicates that the coating effect is better with P123 than with PVP under the same conditions.
SEM test
The product was subjected to structural testing by scanning electron microscopy, and FIG. 5 is an SEM image of the product prepared at different pH values, from which it can be seen that pH values to TiO2The coating effect is obviously influenced. Wherein, the graph a and the graph c have poor dispersity and a large amount of agglomeration, and the graph c is more obvious; and the dispersion of the graph b is better, obvious spheroidal particles appear, and the particle size is about 30 nm. The surface of the particle is rough and has a plurality of small projections, and the small projections are coated TiO when viewed by combining XRD2. Thus, a pH of 8 is preferred.
FIG. 6 is an SEM image of a product made with different surfactants, from which it can be seen that different surfactants are on TiO2The coating effect is obviously influenced, wherein the product in the figure a has good dispersibility, is spherical-like, uniform in size and rough in surface, and has a plurality of small particle bulges on the surface, and the small particles on the surface are coated TiO by combining with an XRD characteristic peak2. And the graph b and the graph c have poor dispersity and uneven size. Thus, the preferred surfactant is P123.
Color test
The data in table 1 are the results of colorimetric analysis of samples at different pH values. The following conclusions are drawn from the analysis results: the pigment produced at pH 9, with highest L (lightness), also had good brightness for samples at pH 7 and pH 8. pH 7 and pH 8 samples are reddish (a high) and pH 9 samples are yellowish (b high). According to the current society, such pink pigments should be popular.
TABLE 1LaFeO3/TiO2Color coordinate graph of nano composite pigment
Figure BDA0001777265170000131
The mechanism of the invention is as follows:
LaFeO3the matrix is a structure with strong chemical stability, insoluble in water, ethanol and acid. And TiO 22Is a high infrared reflection heat insulation pigment, and has the single disadvantage that white light pollution is easily caused due to the white appearance of the pigment, and the retina of a person is injured. Therefore, the high infrared reflection heat insulation color pigment with excellent comprehensive performance can be compounded by effectively combining the two.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A preparation method of a composite high infrared reflection nano pigment is characterized by comprising the following steps:
1) dispersing a surfactant and deionized water in a proper amount of absolute ethyl alcohol for magnetic stirring;
2) adding LaFeO after the surfactant is fully dissolved3Setting the stirring temperature, adding butyl titanate after the temperature of the stirrer is stable, dropwise adding ammonia water to adjust the pH value, and reacting for 3-4 h;
3) after the reaction is finished, washing for several times by using water and ethanol respectively until impurities are completely removed, clarifying the upper-layer solution, and centrifuging to obtain a precipitate;
4) drying the precipitate obtained in the step 3) at 70-80 ℃, calcining the dried precipitate in a furnace at 400-500 ℃ for 1-3 h, and grinding to obtain the composite high infrared reflection nano pigment;
after grinding in the step 4), mixing and soaking the obtained pigment and the film-forming additive for 2-3 hours at the temperature of 34-47 ℃ according to the mass ratio of 2 (2-5), and adding an alternating magnetic field, wherein the central magnetic field of the alternating magnetic field is 2400Gs, and the alternating frequency is 10 Hz;
the preparation method of the film-forming additive comprises the following steps:
s1: selecting 7-10 parts of dodecyl alcohol ester, 4-6 parts of polyoxyethylene fatty acid ester, 6-9 parts of perfluoroalkyl acrylate, 0.3-0.5 part of hexamethylene diisocyanate, 1-2 parts of dicumyl peroxide, 0.8-1.5 parts of methyl ethyl ketone peroxide, 0.5-0.8 part of activated carbon powder, 5-7 parts of ethanol, 3-4 parts of propylene glycol and 1-2 parts of nano titanium dioxide powder in parts by weight;
s2, mixing dodecyl alcohol ester, polyoxyethylene fatty acid ester, perfluoroalkyl acrylate and hexamethylene diisocyanate at the temperature of 23-31 ℃, heating to the temperature of 64-78 ℃, dropwise adding dicumyl peroxide, stirring at 800-1000 rpm for 5-7 min, and cooling to room temperature at the speed of 2 ℃/min to form a mixture A for later use;
s3, mixing ethanol, propylene glycol and methyl ethyl ketone peroxide, controlling the temperature to be 35-45 ℃, and performing microwave treatment for 3-5 min by adding 180-300W of microwave power and 2150MHz of microwave frequency to form a mixture B for later use; the mixing degree of ethanol, propylene glycol and methyl ethyl ketone peroxide can be effectively improved by adding microwaves under the condition, so that the performance of the film-forming additive is improved;
s4, mixing the mixture A obtained in the step S2 and the mixture B obtained in the step S3, adding 0.5-fold weight of deionized water, uniformly mixing, adding activated carbon powder and nano titanium dioxide powder, performing high-voltage pulse electric field and ultrasonic combined dispersion, performing high-voltage pulse electric field treatment for 15-30 min at 25-40 ℃, heating to 2-3 ℃ every 3-5 min, and applying ultrasonic treatment for 1-2 min to obtain the film-forming aid, wherein the ultrasonic conditions comprise that the ultrasonic power is 150-260W, the ultrasonic frequency is 20-70 kHz, the electric field intensity is 20-55 KV/cm, and the number of pulses is 2-7;
the step 2) is carried out stirring treatment through a pigment preparation device, wherein the pigment preparation device comprises a main body (1), a main shaft (2), a stirring disc (3), a feeding device (4), a support plate (5) and a material liquid port boss (6); the feeding device is characterized in that a feeding hole (11) is formed in the center of the upper top surface of the main body (1), a discharging hole (12) is formed in the center of the lower bottom surface of the main body (1), the main shaft (2) is located in the center of the inside of the main body (1), the upper end of the main shaft (2) is connected with the upper top surface of the main body (1) through a motor (21), two stirring disks (3) are arranged, the two stirring disks (3) are arranged on the main shaft (1) at equal intervals from top to bottom, four support plates (5) are arranged and are respectively located in the front, back, left and right middle parts of the side surface of the main body (1), a sliding rail (51) is arranged in the middle of each support plate (5), the feeding device (4) is located;
the stirring disc is characterized in that a hollow groove (31) is formed in the far end of the circumference of the stirring disc (3), a counterweight ball (32) is arranged in the hollow groove (31), a plurality of stirring main blades (33) are arranged on the upper top surface and the lower bottom surface of the stirring disc (3) at equal intervals, a plurality of stirring auxiliary blades (34) are arranged on the left side surface and the right side surface of each stirring main blade (33) at equal intervals, the stirring disc (3) is embedded in the main shaft (2) through a swinging clamping block (35), and the swinging clamping block (35) is used for enabling the stirring disc (3) to swing up and down and limit;
the two material liquid port bosses (6) are respectively positioned at the left end and the right end of the lower end of the sliding rail (51) on the support plate (5), the material liquid port boss (6) is provided with a material liquid port (61), and the outer side of the circumference of the material liquid port (61) is provided with a sealing elastic ring (62);
be equipped with in the middle of feeding device (4) medial surface with elastic matching groove (43) that sliding rail (51) match, the elastic matching groove (43) left and right sides is equipped with feed liquid interface (41) with feed liquid mouth (61) position matching, feed liquid interface (41) circumference outside is equipped with sealed recess (42) with sealed elastic ring (62) position matching, and feeding device (4) are gone up the top surface center and are equipped with interpolation mouth (44).
2. The preparation method of the composite high infrared reflection nanometer pigment according to claim 1, characterized in that ammonia water is dripped in the step 2) to adjust the pH value to 8, and the reaction is carried out for 3 hours.
3. The preparation method of the composite high infrared reflection nanometer pigment according to claim 1, characterized in that the drying conditions in the step 4) are specifically as follows: drying at 80 ℃ for 1h, and calcining under the conditions of: calcining at 500 deg.C for 1 h.
4. The method for preparing the composite high infrared reflection nano pigment according to claim 1, wherein the LaFeO in the step 2)3Obtained by the following method: placing the beaker filled with deionized water on a constant-temperature magnetic stirrer, and adjusting the temperature of the magnetic stirrer to 60 +/-10 ℃; when the temperature of the magnetic stirrer rises to and stabilizes to 60 +/-10 ℃, dissolving glycine in deionized water, adding ferric nitrate and lanthanum nitrate into the solution in sequence after the glycine is fully dissolved, and stirring for 120 +/-10 min after the glycine is fully dissolved; and after stirring, pouring the mixed solution into an evaporating dish, putting the evaporating dish on a universal electric furnace, heating and stirring at 120 +/-10 ℃, enabling the solution to generate self-propagating combustion reaction in the process to generate loose powder, and calcining the obtained powder at the temperature of 600-900 ℃ to obtain the catalyst.
5. The method for preparing the composite high infrared reflection nano pigment according to claim 4, wherein the LaFeO in the step 2)3In the preparation process, the stirring temperature of the magnetic stirrer is 60 +/-10 ℃.
6. The method for preparing the composite high infrared reflection nano pigment according to claim 4, wherein the LaFeO in the step 2)3In the preparation process of (3), the added lanthanum nitrate and ferric nitrate are respectively calculated by La and Fe, and the molar weight of the glycine is 2 times of the sum of the molar weights of the La and the Fe.
7. The preparation method of the composite high infrared reflection nanometer pigment according to claim 4, characterized in that the calcining temperature is 700-800 ℃.
8. The preparation method of the composite high infrared reflection nanometer pigment according to claim 4, characterized in that the calcining temperature is 750 ℃.
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