CN112175416A - Superfine cristobalite in-situ coated gamma-Ce2S3Preparation method of bright red pigment and product prepared by preparation method - Google Patents
Superfine cristobalite in-situ coated gamma-Ce2S3Preparation method of bright red pigment and product prepared by preparation method Download PDFInfo
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Abstract
The invention discloses an in-situ wrapped gamma-Ce superfine cristobalite2S3The preparation method of the scarlet pigment comprises the steps of firstly introducing a cerium source and a silicon source into a microemulsion system, carrying out precipitation reaction, centrifuging, washing and drying to obtain coating pigment precursor powder, and then carrying out vulcanization treatment and high-temperature calcination to obtain the superfine cristobalite in-situ coating gamma-Ce2S3A bright red pigment.In addition, the product prepared by the preparation method is also disclosed. The invention synchronously synthesizes the gamma-Ce core colorants by a simple and controllable preparation process2S3Pigment particles and cristobalite coating layer crystals are coated in situ to form inner nuclear pigments gamma-Ce2S3Pigment particles are uniformly stacked and embedded in the garnet-like seed coating structure in the cristobalite coating layer, so that the high-temperature stability and the acid corrosion resistance of the pigment are greatly improved, and the application field of the pigment is greatly expanded.
Description
Technical Field
The invention relates to the technical field of inorganic pigments, in particular to a coated gamma-Ce2S3A method for preparing a pigment and a product prepared by the method.
Background
Rare earth double half type sulfide gamma-Ce2S3The environment-friendly red pigment not only presents a bright red color, but also presents stable color and strong tinting strength, and is more critical to environmental protection and no toxicity, so the red pigment is considered to be a preferred material for replacing the traditional toxic pigments such as cadmium sulfoselenide and the like. The French Rona Planck company developed gamma-Ce first in 19952S3Red pigment and related products thereof have been widely applied in the fields of plastics, rubber, high-grade paint and the like, but the application in high-temperature industries such as ceramics and the like is rarely reported, mainly because of gamma-Ce2S3The high temperature resistance and the acid etching resistance of the alloy are poor. In an air atmosphere, gamma-Ce2S3Heated to 350 ℃ and oxidized; in liquid phase environment, gamma-Ce2S3Is very easy to react with H+Bind to release unpleasant H2And S. Thus, γ to Ce2S3The application of the red pigment in the high-temperature fields of ceramics and the like is greatly limited. At present, researchers commonly adopt a wrapping modification technology from gamma to Ce2S3The surface of the pigment is coated with one or more layers of transparent high-temperature stable substances so as to improve the high-temperature stability and the acid corrosion resistance of the pigment. For gamma-Ce2S3The existing coating mode of pigment coating adopts a liquid phase method to directly coat the ready-made gamma-Ce2S3Commercial pigment powder or pigment precursor powder is wrapped, and the wrapping pigment or wrapping layer crystal prepared by the methodThe body is only adsorbed on the surface of the pigment particles, or the obtained coating material is amorphous, thereby leading to gamma-Ce2S3The temperature stability of the coating pigment is improved very limitedly (less than 550 ℃), which is far from meeting the use requirements of high-temperature fields such as ceramics. Therefore, it is urgently needed to develop a new wrapping material and wrapping technology to solve the existing gamma-Ce2S3The stable temperature of the coating pigment is low, thereby promoting the environment-friendly gamma-Ce2S3The development and application of the scarlet pigment in the high-temperature fields of ceramics and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the superfine cristobalite in-situ coated gamma-Ce2S3The preparation method of the scarlet pigment synchronously synthesizes the gamma-Ce core colorants through a simple and controllable preparation process2S3Pigment particles and cristobalite coating layer crystals are coated in situ to form inner nuclear pigments gamma-Ce2S3The pigment particles are uniformly stacked and embedded in the quasi-pomegranate seed coating structure in the cristobalite coating layer, thereby greatly improving gamma-Ce2S3The high temperature resistance and the acid corrosion resistance of the pigment expand the application field. The invention also aims to provide a product prepared by the preparation method.
The purpose of the invention is realized by the following technical scheme:
the invention provides superfine cristobalite in-situ coated gamma-Ce2S3The preparation method of the scarlet pigment comprises the following steps:
(1) dissolving a silicon source and water-soluble cerium salt in water according to the molar ratio of Ce to Si of 1: 3-10 to obtain a silicon-containing cerium ion solution, and then adding the silicon-containing cerium ion solution into an oil phase solvent A to stir to prepare a microemulsion A; adding the precipitator into an oil phase solvent B with the same composition as the oil phase solvent A, and stirring to prepare a microemulsion B; mixing the microemulsion A and the microemulsion B according to the volume ratio of 1-2: 1-2, and carrying out precipitation reaction to obtain a coating pigment precursor solution;
(2) adding a demulsifier into the coating color precursor solution for demulsification, standing to obtain a precipitate, and performing centrifugal separation, alcohol washing, water washing and drying to obtain coating color precursor powder;
(3) adding a vulcanization assistant into the coating pigment precursor powder, grinding and mixing uniformly, and then carrying out vulcanization treatment in a vulcanization atmosphere to obtain the gamma-Ce core colorants2S3Pigment particles; then removing the sulfuration atmosphere, continuing heating and calcining under the inert protective atmosphere, synchronously forming a cristobalite transparent shell wrapping layer in situ and forming inner core toners gamma-Ce2S3Uniformly stacking pigment particles and embedding the pigment particles in a pomegranate seed-like coating structure in a coating layer to obtain a coating pigment with the average particle size of 1-2.0 mu m and a core pigment gamma-Ce2S3Superfine cristobalite in-situ coated gamma-Ce with average particle size of pigment particles of 150-200 nm2S3A bright red pigment.
In the scheme, the water-soluble cerium salt is Ce (SO)4)2·4H2O、Ce2(SO4)3·8H2O、(NH4)2Ce(NO3)6、Ce(NO3)3·6H2O、CeCl3·7H2O or Ce (AC)3·nH2O; the silicon source is tetraethoxysilane or Na2SiO3·9H2O; the oil phase solvent A and the oil phase solvent B are composed of cyclohexane, triton and n-hexanol according to a volume ratio of 10-35: 1-12: 2-12; the precipitator is ammonia water or NaOH solution; the demulsifier is acetone.
Further, the concentration of the silicon-containing cerium ion solution in the step (1) is 0.2-1.5 mol/L; according to the volume ratio of the silicon-containing cerium ion solution to the oil phase solvent A being 1: 4-10, and the precipitator to the oil phase solvent B being 1: 4-10.
Further, the stirring time for preparing the microemulsion A and the microemulsion B in the step (1) is 3-6 hours respectively, and the precipitation reaction time is 3-5 hours; the standing time in the step (2) is 10-20 min; drying for 24-32 h at the temperature of 90-100 ℃.
Further, the invention isThe auxiliary agent for the sulfuration in the step (3) is Na2CO3Or Na3PO4The vulcanization atmosphere is Ar + CS2Or N2+CS2With Ar or N2Bubbling CS2Form loading, Ar or N2The air flow is 100-300 mL/min; the inert protective atmosphere is Ar or N2。
Further, the temperature of the vulcanization treatment in the step (3) is 600-950 ℃, and the time of the vulcanization treatment is 1-4 h; the calcination temperature is 1100-1300 ℃ under the inert protective atmosphere, and the heat preservation time is 1-4 h.
The purpose of the invention is realized by the following technical scheme:
the superfine cristobalite is utilized to wrap gamma-Ce in situ2S3The product prepared by the preparation method of the scarlet pigment has the chromaticity parameters of a being more than or equal to 35, L being 37-45 and b being 24-28; after being soaked in concentrated hydrochloric acid with the concentration of 12mol/L for 24 hours, the color parameters of the calcined product at 700-900 ℃ in the air atmosphere are a > 30, L > 34 and b > 20, and the product is subjected to heat treatment at the temperature of room temperature-1200 ℃, wherein the mass change is less than 2 wt%.
The invention has the following beneficial effects:
(1) the invention adopts superfine cristobalite in-situ coated gamma-Ce prepared by a microemulsion method2S3The reaction process of the bright red pigment is carried out in a specific nano-scale reaction tank of a microemulsion system, the raw material mixing reaches the molecular or atomic level, the coating efficiency is high, the coating is uniform and compact, the granularity of the obtained pigment product is fine, the distribution is uniform, the color development effect of the pigment is greatly enhanced, and the higher actual use requirement can be met; in the formed pomegranate seed-like coating structure, the compact cristobalite coating layer can isolate external strong acid corrosion and avoid O2Ensuring the gamma-Ce of the inner core colorant under the high temperature2S3The pigment particles are not oxidized at high temperature, so that the high-temperature stability and the acid corrosion resistance of the pigment are greatly improved, and the application field of the pigment is greatly expanded.
(2) The invention adopts an in-situ coating method to synchronously synthesize the coloring agent particles and the coating layer crystals, and the coloring agent particles and the coating layer crystals are firstly synthesized under the liquid phase conditionStep by step synthesizing a precursor, and then synchronously synthesizing gamma-Ce in the process of one-time heat treatment2S3And a wrapping layer, solves the problem of gamma-Ce in the ex-situ wrapping process2S3The problems of acid decomposition and heat treatment oxidation in the pretreatment of finished pigment are solved, and the existing gamma-Ce is broken through2S3The pigment packaging technology bottleneck realizes the gamma-Ce2S3The red pigment is still red after being calcined at 900 ℃, keeps the original crystal structure without decomposition, and has excellent acid resistance and high temperature resistance.
(3) The preparation method has the advantages of simple and easily-controlled process, simple required equipment and low cost, and is beneficial to industrial production popularization and application. In addition, the gamma-Ce provided by the invention2S3The pigment product is a green environment-friendly nontoxic pigment, can greatly meet the requirement of the ceramic pigment on the environment in the actual use process, and realizes the sustainable development of the pigment.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 shows an in-situ coated ultrafine cristobalite-containing gamma-Ce prepared according to an embodiment of the present invention2S3XRD patterns of the scarlet color materials;
FIG. 2 shows in-situ coated superfine cristobalite gamma-Ce prepared according to the embodiment of the invention2S3TEM image of a bright red pigment;
FIG. 3 shows an in-situ coated ultrafine cristobalite-containing gamma-Ce in accordance with an embodiment of the present invention2S3XRD patterns of the scarlet color calcined at different temperatures.
Detailed Description
The first embodiment is as follows:
this example shows an in-situ coated form of ultrafine cristobalite [ gamma ] -Ce2S3The preparation method of the scarlet pigment comprises the following steps:
(1) 6.07gCe (SO) was added in a molar ratio Ce: Si of 1: 34)2·4H2Dissolving O in 5mL of water, and adding 9.37g of ethyl orthosilicate to obtain a silicon-containing cerium ion solution; then adding the above solution containing silicon and cerium ions into the solution 28Stirring for 3 hours at room temperature in an oil phase solvent A consisting of mL of cyclohexane, 8mL of triton and 7mL of hexanol to obtain a microemulsion A; adding 5mL of concentrated ammonia water into an oil phase solvent B consisting of 28mL of cyclohexane, 8mL of triton and 7mL of hexanol, and stirring for 3h at room temperature to prepare a microemulsion B; mixing the microemulsion A and the microemulsion B, and stirring at room temperature for reaction for 3h to obtain a coating pigment precursor solution;
(2) adding acetone into the coating pigment precursor solution for demulsification, standing for 10min to obtain precipitate, performing centrifugal separation, alcohol washing, water washing, and drying at 90 deg.C for 24 hr to obtain coating pigment precursor powder;
(3) mixing 0.16gNa2CO3Adding the powder of the wrapping pigment precursor into the powder, grinding and mixing uniformly, placing the mixture into an atmosphere furnace, and loading the mixture into CS in an Ar bubbling mode2Maintaining the flow of Ar gas at 100mL/min, and carrying out vulcanization treatment at 900 ℃ for 2.5h to obtain gamma-Ce2S3Inner core toner particles; then close CS2Continuously heating to 1300 ℃ under Ar protective atmosphere, carrying out calcination treatment, keeping the temperature for 2h, and cooling to room temperature along with the furnace to obtain the superfine cristobalite in-situ coated gamma-Ce2S3A bright red pigment.
Example two:
this example shows an in-situ coated form of ultrafine cristobalite [ gamma ] -Ce2S3The preparation method of the scarlet pigment comprises the following steps:
(1) 4.34gCe (NO) in a molar ratio Ce: Si of 1: 73)3·6H2Dissolving O in 6mL of water, and adding 14.58g of ethyl orthosilicate to obtain a silicon-containing cerium ion solution; then adding the silicon-cerium-containing ion solution into an oil phase solvent A consisting of 32mL of cyclohexane, 9mL of triton and 8mL of hexanol, and stirring for 4 hours at room temperature to obtain a microemulsion A; dissolving 0.8g of NaOH in 6mL of water, adding the dissolved NaOH into an oil phase solvent B consisting of 32mL of cyclohexane, 9mL of triton and 8mL of n-hexanol, and stirring for 4 hours at room temperature to prepare a microemulsion B; mixing the microemulsion A and the microemulsion B, and stirring and reacting for 4 hours at room temperature to obtain a coating pigment precursor solution;
(2) adding acetone into the coating pigment precursor solution for demulsification, standing for 15min to obtain precipitate, performing centrifugal separation, alcohol washing, water washing, and drying at 90 deg.C for 32h to obtain coating pigment precursor powder;
(3) mixing 0.16gNa3PO4Adding the powder of the coating pigment precursor into the powder, grinding and mixing uniformly, placing the mixture in an atmosphere furnace, and adding N2Loading into CS in the form of bubbles2And hold N2The gas flow is 150mL/min, and the gamma-Ce is obtained by sulfurizing treatment for 3h at the temperature of 800 DEG C2S3Inner core toner particles; then close CS2In N at2Continuously heating to 1200 ℃ under the protective atmosphere, carrying out calcination treatment, keeping the temperature for 3h, and cooling to room temperature along with the furnace to obtain the superfine cristobalite in-situ coated gamma-Ce2S3A bright red pigment.
Example three:
this example shows an in-situ coated form of ultrafine cristobalite [ gamma ] -Ce2S3The preparation method of the scarlet pigment comprises the following steps:
(1) 3.73g of CeCl was added in a molar ratio of Ce to Si of 1 to 103·7H2O was dissolved in 10mL of water and 28.42g of Na was added2SiO3·9H2O, obtaining a silicon-containing cerium ion solution; then adding the silicon-cerium-containing ion solution into an oil phase solvent A consisting of 35mL of cyclohexane, 11mL of triton and 10mL of hexanol, and stirring for 5 hours at room temperature to obtain a microemulsion A; adding 10mL of concentrated ammonia water into an oil phase solvent B consisting of 35mL of cyclohexane, 11mL of triton and 10mL of hexanol, and stirring for 5 hours at room temperature to prepare a microemulsion B; mixing the microemulsion A and the microemulsion B, and stirring and reacting for 5 hours at room temperature to obtain a coating pigment precursor solution;
(2) adding acetone into the coating color precursor solution for demulsification, standing for 20min to obtain precipitate, performing centrifugal separation, alcohol washing, water washing, and drying at 100 deg.C for 24 hr to obtain coating color precursor powder;
(3) mixing 0.08gNa3PO4And 0.08gNa2CO3Adding the powder of the wrapping pigment precursor into the powder, grinding and mixing uniformly, placing the mixture into an atmosphere furnace, and loading the mixture into CS in an Ar bubbling mode2And maintaining the flow rate of Ar gas at 250mL/min, sulfurizing at 920 deg.c for 2 hr to obtain gamma-Ce2S3Inner core toner particles; then close CS2Continuously heating to 1250 ℃ under Ar protective atmosphere, preserving heat for 4 hours, and cooling to room temperature along with the furnace to obtain the superfine cristobalite in-situ coated gamma-Ce2S3A bright red pigment.
As shown in figure 1, the phase composition of the wrapping pigment prepared by the embodiment of the invention is cristobalite and gamma-Ce2S3. As can be seen from FIG. 2, the coating pigment has a structure similar to that of pomegranate seed, and nano-scale gamma-Ce is embedded in the cristobalite transparent shell matrix2S3Pigment particles, wherein the average particle size of the coating pigment is 1-2.0 mu m, and the inner nuclear pigment gamma-Ce2S3The average particle size of the toner particles is 150-200 nm.
The chromaticity parameters of the wrapping pigment prepared by the embodiment of the invention are shown in table 1, and after being soaked in 12mol/L concentrated hydrochloric acid for 24 hours, the wrapping pigment is subjected to heat treatment at the temperature of room temperature to 1200 ℃, the mass change is less than 2 wt%, and no obvious thermal effect exists.
TABLE 1 color parameters of the coating colors obtained in the examples of the invention
With uncoated commercial gamma-Ce2S3The red pigment is a comparative example, and the chromaticity parameters of the wrapping pigment prepared in the first embodiment of the invention after being soaked in 12mol/L concentrated hydrochloric acid for 24 hours and calcined for 30min at different temperatures in an air atmosphere are shown in Table 2.
TABLE 2 index of corrosion and high temperature resistance of wrapping color of inventive example and comparative example
The results in Table 2 and FIG. 2 show that the ultrafine cristobalite in-situ coated gamma-Ce prepared in the embodiment of the invention2S3The bright red pigment has excellent qualityDifferent high temperature resistance and acid corrosion resistance.
Claims (8)
1. Superfine cristobalite in-situ coated gamma-Ce2S3The preparation method of the scarlet pigment is characterized by comprising the following steps:
(1) dissolving a silicon source and water-soluble cerium salt in water according to the molar ratio of Ce to Si of 1: 3-10 to obtain a silicon-containing cerium ion solution, and then adding the silicon-containing cerium ion solution into an oil phase solvent A to stir to prepare a microemulsion A; adding the precipitator into an oil phase solvent B with the same composition as the oil phase solvent A, and stirring to prepare a microemulsion B; mixing the microemulsion A and the microemulsion B according to the volume ratio of 1-2: 1-2, and carrying out precipitation reaction to obtain a coating pigment precursor solution;
(2) adding a demulsifier into the coating color precursor solution for demulsification, standing to obtain a precipitate, and performing centrifugal separation, alcohol washing, water washing and drying to obtain coating color precursor powder;
(3) adding a vulcanization assistant into the coating pigment precursor powder, grinding and mixing uniformly, and then carrying out vulcanization treatment in a vulcanization atmosphere to obtain the gamma-Ce core colorants2S3Pigment particles; then removing the sulfuration atmosphere, continuing heating and calcining under the inert protective atmosphere, synchronously forming a cristobalite transparent shell wrapping layer in situ and forming inner core toners gamma-Ce2S3Uniformly stacking pigment particles and embedding the pigment particles in a pomegranate seed-like coating structure in a coating layer to obtain a coating pigment with the average particle size of 1-2.0 mu m and a core pigment gamma-Ce2S3Superfine cristobalite in-situ coated gamma-Ce with average particle size of pigment particles of 150-200 nm2S3A bright red pigment.
2. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 12S3The preparation method of the scarlet pigment is characterized by comprising the following steps: the water-soluble cerium salt is Ce (SO)4)2·4H2O、Ce2(SO4)3·8H2O、(NH4)2Ce(NO3)6、Ce(NO3)3·6H2O、CeCl3·7H2O or Ce (AC)3·nH2O; the silicon source is tetraethoxysilane or Na2SiO3·9H2O; the oil phase solvent A and the oil phase solvent B are composed of cyclohexane, triton and n-hexanol according to a volume ratio of 10-35: 1-12: 2-12; the precipitator is ammonia water or NaOH solution; the demulsifier is acetone.
3. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 12S3The preparation method of the scarlet pigment is characterized by comprising the following steps: the concentration of the silicon-containing cerium ion solution in the step (1) is 0.2-1.5 mol/L; according to the volume ratio of the silicon-containing cerium ion solution to the oil phase solvent A being 1: 4-10, and the precipitator to the oil phase solvent B being 1: 4-10.
4. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 12S3The preparation method of the scarlet pigment is characterized by comprising the following steps: the stirring time for preparing the microemulsion A and the microemulsion B in the step (1) is 3-6 hours respectively, and the precipitation reaction time is 3-5 hours; and (3) standing for 10-20 min in the step (2), and drying at the temperature of 90-100 ℃ for 24-32 h.
5. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 12S3The preparation method of the scarlet pigment is characterized by comprising the following steps: the auxiliary agent for the sulfuration in the step (3) is Na2CO3Or Na3PO4The vulcanization atmosphere is Ar + CS2Or N2+CS2With Ar or N2Bubbling CS2Form loading, Ar or N2The air flow is 100-300 mL/min; the inert protective atmosphere is Ar or N2。
6. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 1 or 52S3The preparation method of the scarlet pigment is characterized by comprising the following steps: the vulcanization part in the step (3)The treating temperature is 600-950 ℃, and the vulcanizing treatment time is 1-4 h; the calcination temperature is 1100-1300 ℃ under the inert protective atmosphere, and the heat preservation time is 1-4 h.
7. In-situ coated gamma-Ce prepared from the ultrafine cristobalite as claimed in any one of claims 1 to 62S3The product is prepared by the preparation method of the scarlet pigment.
8. The ultrafine cristobalite in-situ coated gamma-Ce according to claim 72S3The product prepared by the preparation method of the scarlet pigment is characterized in that: the chromaticity parameters of the wrapping pigment are a is more than or equal to 35, L is 37-45, and b is 24-28; after being soaked in concentrated hydrochloric acid with the concentration of 12mol/L for 24 hours, the color parameters of the calcined product at 700-900 ℃ in the air atmosphere are a > 30, L > 34 and b > 20, and the product is subjected to heat treatment at the temperature of room temperature-1200 ℃, wherein the mass change is less than 2 wt%.
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