CN108946818B - Preparation method of black inorganic ceramic pigment - Google Patents
Preparation method of black inorganic ceramic pigment Download PDFInfo
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
The invention discloses a blackMethod for preparing inorganic ceramic pigment, the black ceramic pigment has YMn1‑xFexO3The structure of (1), wherein: x is more than or equal to 0.05 and less than or equal to 0.30; the preparation method of the black ceramic pigment comprises the following steps: (1) respectively dissolving corresponding yttrium nitrate, manganese nitrate and ferric nitrate in distilled water according to the molar ratio of Y, Mn to Fe to obtain a mixed solution; (2) adding the mixed solution into an aqueous solution of glycine; (3) stirring for more than 1h at 60 ℃ by using a magnetic stirrer, and then burning and concentrating at 100-120 ℃ to obtain precursor powder; (4) calcining the mixture in a muffle furnace at the temperature of 650-900 ℃ for 2-4 h to obtain the black ceramic pigment with the perovskite structure; the preparation method is simple, raw materials are easy to obtain, the obtained product has good particle dispersibility, uniform particle size distribution, low synthesis temperature and simple and controllable process, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of ceramic pigments, and particularly relates to a preparation method of a black inorganic ceramic pigment.
Background
In recent years, a black pigment is increasingly demanded in the market for a pigment which can realize a clearer hue than red, and a black pigment which can realize a clearer blue hue is strongly demanded.
At present, the building sanitary ceramics in China have become the most important production base of the building sanitary ceramics in the world after the rapid development for more than ten years, the ceramic ink-jet production technology developed in recent years is vigorously developed in China, the ceramic ink-jet technology is greatly developed and applied in the field of building ceramic production, the ink-jet printing equipment is directly applied to the ceramic production line, the decoration method and the technique of the building sanitary ceramics are greatly enriched and expanded, the production efficiency is powerfully improved, and various beautiful patterns in the nature are promoted to be organically combined into the field of building ceramic decoration through a computer.
Inkjet printing is a non-contact digital printing technology that was successfully developed in the late 70 s of the twentieth century. It can spray ink onto various medium surfaces through nozzles on a printing head, and realizes non-contact, high-speed and low-noise printing of monochromatic or colored characters or images. Early in the 21 st century, the company FERRO developed an oil-based ink suitable for ink-jet printing on ceramics. Since then, the development of over a decade has led to the widespread use of inkjet printing technology in the architectural ceramics. As a brand new ceramic decoration concept, the color printing technology for ceramic decoration can make full use of abundant computer data, and introduces the digital technology into the traditional architectural ceramic products, so that the ceramic decoration embodies fashionable characteristics following the era step, meets the requirements of people on individuation, and pushes the ceramic decoration technology to a brand new stage.
However, because of the particularity of the ink-jet printing process, the requirement on the pigment in the ink is particularly severe, the pigment still needs to be stable at 1250 ℃ and maintain stable color development in the current common glaze base glaze, the particle size of the pigment is less than 1 micron, and many traditional ceramic pigments cannot develop color or change color after being finely ground until the particle size D90 is less than 1 micron, so that the current ceramic ink-jet printing pigments are few in variety and mainly have blue, brown, yellow, chrome-tin red and the like; the traditional ceramic pigment production process is synthesized by solid-phase reaction between raw materials at high temperature, and a color body mainly exists in the solid-phase reaction between the raw materials, but the traditional ceramic pigment production process is simple and extensive, the uniform mixing degree of the raw materials is very low, and the prepared black pigment can not be subjected to color development or color change under the glaze surface or transparent glaze of an archaized brick fired at 1200 ℃ after being crushed to 1 micron.
The patent application with the application number of 201110327956.9 discloses a black high-temperature resistant ceramic toner and a preparation method thereof. It is made up by using black inorganic ceramic pigment, styrene-acrylic resin, polypropylene wax, charge regulating agent, dimethyl dichlorosilane and hexamethyldisilazane through the processes of mixing, tabletting, coarse pulverizing, air-flow pulverizing, grading and sieving. The ceramic ink powder is high temperature resistant, but the manufacturing process is complex, and the ceramic ink powder is not beneficial to mass production.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of a black inorganic ceramic pigment.
The technical scheme of the invention is as follows: a method for preparing a black inorganic ceramic pigment having YMn1-xFexO3The structure of (1), wherein: x is more than or equal to 0.05 and less than or equal to 0.30; the preparation method of the black ceramic pigment comprises the following steps:
respectively dissolving corresponding yttrium nitrate, manganese nitrate and ferric nitrate in distilled water according to the molar ratio of Y, Mn to Fe to obtain a mixed solution;
adding the mixed solution obtained in the step into an aqueous solution of glycine;
stirring the mixed solution in the step for more than 1h at 60 ℃ by using a magnetic stirrer, and then burning and concentrating at 100-120 ℃ to obtain precursor powder;
and finally, directly calcining the precursor powder obtained in the step by using a muffle furnace at the temperature of 650-900 ℃ for 2-4 h to obtain the black ceramic pigment with the perovskite structure.
Further, before the precursor powder is calcined by a muffle furnace, pouring the precursor powder into a pigment coating agent to be soaked for 1-2 h, and then filtering and air-drying the soaked precursor powder;
further, the pigment coating agent is prepared by a coating agent preparation device, the coating agent preparation device mainly comprises a stirring main cabin, a first stirring auxiliary cabin and a second stirring auxiliary cabin, the structures of the stirring main cabin, the first stirring auxiliary cabin and the second stirring auxiliary cabin are completely the same, only the stirring main cabin is explained at present, the stirring main cabin comprises a variable pressure port, a variable pressure valve, a material inlet and outlet, a pressure valve, a liquid inlet valve, a liquid level meter, a liquid outlet valve, a liquid outlet, a stirring device and a base, the top of the base is connected with the bottom of the cabin body through the stirring device, the top of the cabin body is connected with the bottom of the variable pressure valve through the material inlet and outlet, the variable pressure port is arranged on the left side of the variable pressure valve, the pressure valves are arranged on the front end surface of the cabin body near the top, the two liquid inlets are respectively arranged on the, the liquid level meter is arranged at the left end of the cabin body, the liquid outlet valve is arranged at the right end of the cabin body close to the bottom, and the liquid outlet is connected with the liquid outlet valve; a main blade fan, an auxiliary blade fan and a rotary table are arranged outside the stirring device, a rotary shaft and a motor are arranged in the stirring device, the motor is positioned in the stirring device, the top of the motor is connected with the bottom of the rotary table through the rotary shaft, the rotary table is positioned at the top of the stirring device, the top of the rotary table is respectively connected with the main blade fan and the auxiliary blade fan, and the main blade fan is coated at the top of the auxiliary blade fan; the first stirring auxiliary cabin and the second stirring auxiliary cabin are symmetrically arranged about the main stirring cabin, and liquid outlets of the first stirring auxiliary cabin and the second stirring auxiliary cabin are respectively connected with two liquid inlets of the main stirring cabin through pipelines.
Further, the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 80-85: 100, adding the mixture into a main stirring cabin, and stirring the mixture for 50-60 min under the pressure of 0.3-0.5 MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and an ethanol solvent are mixed according to a mass ratio of 7-10: 3-5: 1-1.8: 3-4: 40, stirring the mixture in the auxiliary stirring cabin I for 30-40 min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 2-3 h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent are mixed according to the mass ratio of 10-13: 8-10: 3-5: mixing the mixed solution B obtained in the step B in a proportion of 60, adding the mixed solution B into a stirring auxiliary cabin II, stirring the mixed solution B at normal temperature for 20-25 min to obtain a mixed solution c, dropwise adding the mixed solution c with the volume of one fourth of the mixed solution B to the main cabin at a constant speed while continuously stirring the mixed solution B obtained in the step B, and stirring the mixed solution B at normal temperature and normal pressure for reaction for 2-3 h after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.1 to-0.12 MPa, and regulating the temperature to 55 to 65 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 4-6 times, and then drying the powder for 3-4 hours under the pressure of 0.1-0.2 MPa to obtain the pigment coating agent powder
Further, the black ceramic pigment has a structure of YMn1-xfex o3, wherein: x is more than or equal to 0.15 and less than or equal to 0.20;
further, the black ceramic pigment has a structure of YMn1-xfex o3, wherein: x is 0.15;
preferably, the calcination temperature in the step is 900 ℃;
preferably, the calcination time in the step is 3-4 h;
further, the black ceramic pigment is a low-molecular, low-toxicity or even non-toxic inorganic substance;
further, the stirring speed in the step is 80-100 r/min;
in the preparation method, the stirring time is preferably 1.5-2 h, the reaction time is less than 1h, and the product cannot be subjected to sufficient diffusion reaction, so that the phase of the product is not uniform.
In the production method of the present invention, the temperature for concentration is required to be 100 ℃ or higher, and in order to sufficiently burn the precursor powder and obtain a fluffy precursor powder, the temperature is preferably 120 ℃. The calcination temperature of the precursor is 650-900 ℃, and 900 ℃ is preferred.
In the preparation method, the calcination time of the precursor is preferably more than 2 hours, more preferably 2-4 hours, and still more preferably 3-4 hours.
The invention has the beneficial effects that:
1. the black inorganic pigment of the invention is doped with ions and enters the perovskite structure to form a single stable solid solution which is difficult to dissolve out and has the advantages of good thermal stability and chemical stability;
2. the product of the invention does not contain toxic elements such as lead, chromium and the like, and is green and environment-friendly;
3. the preparation method is simple, raw materials are easy to obtain, the obtained product has good particle dispersibility, uniform particle size distribution, low synthesis temperature and simple and controllable process, and is suitable for large-scale production.
Drawings
Fig. 1 is a calcined X-ray diffraction pattern of YMn1-xfex o3 of a black ceramic pigment of perovskite structure at a high temperature of 800 ℃, wherein X is 0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, the abscissa is diffraction angle and the ordinate is diffraction intensity;
FIG. 2 is an XRD pattern of YMn1-xFexO3 powder of black ceramic pigment with perovskite structure at different temperatures when X is 0.15;
FIG. 3 is a schematic view of a liquid mixing and stirring apparatus according to the present invention;
wherein, 1-stirring main cabin, 2-stirring auxiliary cabin I, 3-stirring auxiliary cabin II, 11-pressure changing port, 12-pressure changing valve, 13-material inlet and outlet, 14-pressure valve, 15-liquid inlet, 16-liquid inlet valve, 17-liquid level meter, 18-liquid outlet valve, 19-liquid outlet, 20-stirring device, 21-base, 201-main blade fan, 202-auxiliary blade fan, 203-turntable, 204-rotating shaft, 205-motor;
FIG. 4 is a schematic view of the internal structure of a stirring device in the coating agent preparing apparatus of the present invention.
Detailed description of the preferred embodiment
The technical solution of the present invention is further described with reference to the following specific examples, but the scope of the claims is not limited thereto.
Example 1
3.83g of yttrium nitrate, 2.87g of manganese nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving glycine 3.01g in 50ml water to obtain solution 2, adding solution 1 into solution 2, stirring at 60 deg.C to obtain clear solution 3, stirring with ultrasonic vibration at 80 rpm for 2 hr, and stirring at 120 deg.CConcentrating and burning to generate loose powder, namely a precursor, pouring the powder into the pigment coating agent to be soaked for 1h, then filtering the soaked precursor powder, air-drying, calcining the air-dried precursor powder at 900 ℃ for 4h, and grinding again to obtain a final sample YMnO3。
Example 2
3.83g of yttrium nitrate, 2.73g of manganese nitrate, 0.21g of ferric nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution 3 is clear, stirring at 90 r/min for 2 hours by utilizing ultrasonic oscillation, then concentrating and burning at 120 ℃ to generate loose powder, namely a precursor, pouring the powder into a pigment coating agent, soaking for 1 hour, then filtering the soaked precursor powder, air-drying, calcining the air-dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain a final sample YMn0.95Fe0.05O3。
Example 3
3.83g of yttrium nitrate, 2.59g of manganese nitrate, 0.41g of iron nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 100 rpm for 2 hours by utilizing ultrasonic oscillation, then concentrating and burning at 120 ℃, pouring the powder into a pigment coating agent, soaking for 1 hour, then filtering the soaked precursor powder, drying in the air, calcining the dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain a final sample YMn0.9Fe0.1O3。
Example 4
3.83g of yttrium nitrate, 2.44g of manganese nitrate, 0.61g of ferric nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving glycine 3.01g in 50ml water to obtain solution 2, adding solution 1 into solution 2, stirring at 60 deg.C to obtain clear solution 3, stirring at 90 rpm for 2 hr by ultrasonic oscillation, concentrating and combusting at 120 deg.C, adding powder into pigment coating agentSoaking for 1h, filtering the soaked precursor powder, air-drying, calcining the air-dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain the final sample YMn0.85Fe0.15O3。
Example 5
3.83g of yttrium nitrate, 2.87g of manganese nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 80 rpm for 2 hours by utilizing ultrasonic oscillation, then concentrating and burning at 120 ℃ to obtain precursor powder, pouring the precursor powder into a pigment coating agent, soaking for 1 hour, and then filtering and air-drying the soaked precursor powder; the pigment coating agent is prepared by a coating agent preparation device which mainly comprises a stirring main cabin 1, a stirring auxiliary cabin I2 and a stirring auxiliary cabin II 3, wherein the stirring main cabin 1, the stirring auxiliary cabin I2 and the stirring auxiliary cabin II 3 have the same structure, only the stirring main cabin 1 is explained at present, the stirring main cabin 1 comprises a pressure changing port 11, a pressure changing valve 12, a material inlet and outlet 13, a pressure valve 14, a liquid inlet 15, a liquid inlet valve 16, a liquid level meter 17, a liquid outlet valve 18, a liquid outlet 19, a stirring device 20 and a base 21, the top of the base 21 is connected with the bottom of the cabin body through the stirring device 20, the top of the cabin body is connected with the bottom of the pressure changing valve 12 through the material inlet and outlet 13, the pressure changing port 11 is arranged on the left side of the pressure changing valve 12, the pressure valve 14 is arranged at the position close to the top of the front end surface of the cabin body, the, the liquid level meter 17 is arranged at the left end of the cabin body, the liquid outlet valve 18 is arranged at the right end of the cabin body close to the bottom, and the liquid outlet 19 is connected with the liquid outlet valve 18; a main blade fan 201, an auxiliary blade fan 202 and a turntable 203 are arranged outside the stirring device 20, a rotating shaft 204 and a motor 205 are arranged in the stirring device 20, the motor 205 is positioned in the stirring device 20, the top of the motor 205 is connected with the bottom of the turntable 203 through the rotating shaft 204, the turntable 203 is positioned at the top of the stirring device 20, the top of the turntable 203 is respectively connected with the main blade fan 201 and the auxiliary blade fan 202, and the main blade fan 201 is covered on the top of the auxiliary blade fan 202; the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are symmetrically arranged about the main stirring cabin 1, and liquid outlets 19 of the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are respectively connected with two liquid inlets 13 of the main stirring cabin 1 through pipelines;
the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 80: mixing according to the proportion of 100, adding into a main stirring cabin, and then stirring for 50min under the pressure of 0.3MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and ethanol solvent are mixed according to a mass ratio of 7:3:1: 3: 40, stirring for 30min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. mixing butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent according to a mass ratio of 10:8:3: 60, adding the mixture into a stirring auxiliary cabin II, stirring for 20min at normal temperature to obtain a mixed solution c, continuously stirring the mixed solution B obtained in the step B, dropwise adding the mixed solution c with the volume of one fourth of the mixed solution B to the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.1 MPa, and regulating the temperature to 55 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 4 times, and then drying for 3 hours under the pressure of 0.1MPa to obtain pigment coating agent powder;
calcining the air-dried precursor powder at 650 ℃ for 2 hours, and grinding again to obtain a final sample YMnO3
Example 6
3.83g of yttrium nitrate, 2.59g of manganese nitrate, 0.41g of iron nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 100 rpm for 2 hours by using ultrasonic oscillation, then concentrating and burning at 120 ℃ to obtain precursor powder, pouring the precursor powder into a pigment coating agent, soaking for 1 hour, and then filtering and air-drying the soaked precursor powder; the pigment coating agent is prepared by a coating agent preparation device which mainly comprises a stirring main cabin 1, a stirring auxiliary cabin I2 and a stirring auxiliary cabin II 3, wherein the stirring main cabin 1, the stirring auxiliary cabin I2 and the stirring auxiliary cabin II 3 have the same structure, only the stirring main cabin 1 is explained at present, the stirring main cabin 1 comprises a pressure changing port 11, a pressure changing valve 12, a material inlet and outlet 13, a pressure valve 14, a liquid inlet 15, a liquid inlet valve 16, a liquid level meter 17, a liquid outlet valve 18, a liquid outlet 19, a stirring device 20 and a base 21, the top of the base 21 is connected with the bottom of the cabin body through the stirring device 20, the top of the cabin body is connected with the bottom of the pressure changing valve 12 through the material inlet and outlet 13, the pressure changing port 11 is arranged on the left side of the pressure changing valve 12, the pressure valve 14 is arranged at the position close to the top of the front end surface of the cabin body, the, the liquid level meter 17 is arranged at the left end of the cabin body, the liquid outlet valve 18 is arranged at the right end of the cabin body close to the bottom, and the liquid outlet 19 is connected with the liquid outlet valve 18; a main blade fan 201, an auxiliary blade fan 202 and a turntable 203 are arranged outside the stirring device 20, a rotating shaft 204 and a motor 205 are arranged in the stirring device 20, the motor 205 is positioned in the stirring device 20, the top of the motor 205 is connected with the bottom of the turntable 203 through the rotating shaft 204, the turntable 203 is positioned at the top of the stirring device 20, the top of the turntable 203 is respectively connected with the main blade fan 201 and the auxiliary blade fan 202, and the main blade fan 201 is covered on the top of the auxiliary blade fan 202; the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are symmetrically arranged about the main stirring cabin 1, and liquid outlets 19 of the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are respectively connected with two liquid inlets 13 of the main stirring cabin 1 through pipelines;
the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 80: mixing according to the proportion of 100, adding into a main stirring cabin, and then stirring for 50min under the pressure of 0.3MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and ethanol solvent are mixed according to a mass ratio of 7:3:1: 3: 40, stirring for 30min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. mixing butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent according to a mass ratio of 10:8:3: 60, adding the mixture into a stirring auxiliary cabin II, stirring for 20min at normal temperature to obtain a mixed solution c, continuously stirring the mixed solution B obtained in the step B, dropwise adding the mixed solution c with the volume of one fourth of the mixed solution B to the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.1 MPa, and regulating the temperature to 55 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 4 times, and then drying for 3 hours under the pressure of 0.1MPa to obtain pigment coating agent powder;
calcining the air-dried precursor powder at 800 ℃ for 3 hours, and grinding again to obtain a final sample YMn0.9Fe0.1O3
Example 7
3.83g of yttrium nitrate, 2.30g of manganese nitrate, 0.81g of ferric nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 80 rpm for 2 hours by utilizing ultrasonic oscillation, then concentrating and burning at 120 ℃ to obtain precursor powder, pouring the precursor powder into a pigment coating agent, soaking for 1 hour, and then filtering and air-drying the soaked precursor powder; the pigment coating agent is prepared by a coating agent preparation device which mainly comprises a stirring main cabin 1, a stirring auxiliary cabin I2 and a stirring auxiliary cabin II 3, wherein the stirring main cabin 1, the stirring auxiliary cabin I2 and the stirring auxiliary cabin II 3 have the same structure, only the stirring main cabin 1 is explained at present, the stirring main cabin 1 comprises a pressure changing port 11, a pressure changing valve 12, a material inlet and outlet 13, a pressure valve 14, a liquid inlet 15, a liquid inlet valve 16, a liquid level meter 17, a liquid outlet valve 18, a liquid outlet 19, a stirring device 20 and a base 21, the top of the base 21 is connected with the bottom of the cabin body through the stirring device 20, the top of the cabin body is connected with the bottom of the pressure changing valve 12 through the material inlet and outlet 13, the pressure changing port 11 is arranged on the left side of the pressure changing valve 12, the pressure valve 14 is arranged at the position close to the top of the front end surface of the cabin body, the, the liquid level meter 17 is arranged at the left end of the cabin body, the liquid outlet valve 18 is arranged at the right end of the cabin body close to the bottom, and the liquid outlet 19 is connected with the liquid outlet valve 18; a main blade fan 201, an auxiliary blade fan 202 and a turntable 203 are arranged outside the stirring device 20, a rotating shaft 204 and a motor 205 are arranged in the stirring device 20, the motor 205 is positioned in the stirring device 20, the top of the motor 205 is connected with the bottom of the turntable 203 through the rotating shaft 204, the turntable 203 is positioned at the top of the stirring device 20, the top of the turntable 203 is respectively connected with the main blade fan 201 and the auxiliary blade fan 202, and the main blade fan 201 is covered on the top of the auxiliary blade fan 202; the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are symmetrically arranged about the main stirring cabin 1, and liquid outlets 19 of the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are respectively connected with two liquid inlets 13 of the main stirring cabin 1 through pipelines;
the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 80: mixing according to the proportion of 100, adding into a main stirring cabin, and then stirring for 50min under the pressure of 0.3MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and ethanol solvent are mixed according to a mass ratio of 7:3:1: 3: 40, stirring for 30min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. mixing butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent according to a mass ratio of 10:8:3: 60, adding the mixture into a stirring auxiliary cabin II, stirring for 20min at normal temperature to obtain a mixed solution c, continuously stirring the mixed solution B obtained in the step B, dropwise adding the mixed solution c with the volume of one fourth of the mixed solution B to the main cabin at a constant speed, and stirring and reacting for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.1 MPa, and regulating the temperature to 55 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 4 times, and then drying for 3 hours under the pressure of 0.1MPa to obtain pigment coating agent powder;
calcining the air-dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain a final sample YMn0.8Fe0.2O3；
Example 8
3.83g of yttrium nitrate, 2.15g of manganese nitrate, 1.01g of ferric nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain a solution 1. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 100 rpm for 2 hours by using ultrasonic oscillation, then concentrating and burning at 120 ℃ to obtain precursor powder, pouring the precursor powder into a pigment coating agent, soaking for 2 hours, and then filtering and air-drying the soaked precursor powder; the pigment coating agent is prepared by a coating agent preparation device which mainly comprises a stirring main cabin 1, a stirring auxiliary cabin I2 and a stirring auxiliary cabin II 3, wherein the stirring main cabin 1, the stirring auxiliary cabin I2 and the stirring auxiliary cabin II 3 have the same structure, only the stirring main cabin 1 is explained at present, the stirring main cabin 1 comprises a pressure changing port 11, a pressure changing valve 12, a material inlet and outlet 13, a pressure valve 14, a liquid inlet 15, a liquid inlet valve 16, a liquid level meter 17, a liquid outlet valve 18, a liquid outlet 19, a stirring device 20 and a base 21, the top of the base 21 is connected with the bottom of the cabin body through the stirring device 20, the top of the cabin body is connected with the bottom of the pressure changing valve 12 through the material inlet and outlet 13, the pressure changing port 11 is arranged on the left side of the pressure changing valve 12, the pressure valve 14 is arranged at the position close to the top of the front end surface of the cabin body, the, the liquid level meter 17 is arranged at the left end of the cabin body, the liquid outlet valve 18 is arranged at the right end of the cabin body close to the bottom, and the liquid outlet 19 is connected with the liquid outlet valve 18; a main blade fan 201, an auxiliary blade fan 202 and a turntable 203 are arranged outside the stirring device 20, a rotating shaft 204 and a motor 205 are arranged in the stirring device 20, the motor 205 is positioned in the stirring device 20, the top of the motor 205 is connected with the bottom of the turntable 203 through the rotating shaft 204, the turntable 203 is positioned at the top of the stirring device 20, the top of the turntable 203 is respectively connected with the main blade fan 201 and the auxiliary blade fan 202, and the main blade fan 201 is covered on the top of the auxiliary blade fan 202; the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are symmetrically arranged about the main stirring cabin 1, and liquid outlets 19 of the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are respectively connected with two liquid inlets 13 of the main stirring cabin 1 through pipelines;
the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 83:100, adding into a main stirring cabin, and then stirring for 55min under the pressure of 0.4MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane group and ethanol solvent are mixed according to a mass ratio of 8:4:1.5: 3.4: 40, stirring for 35min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 3h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. b, mixing butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent according to a mass ratio of 11:9:4:4:60, adding the mixture into a stirring auxiliary cabin II, stirring the mixture for 25min at normal temperature to obtain a mixed solution c, continuously stirring the mixed solution B obtained in the step B, simultaneously dropwise adding the mixed solution c of which the volume is one fourth of the mixed solution B to a main cabin at a constant speed, and stirring the mixed solution B for reaction for 2h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.12 MPa, and regulating the temperature to 60 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 5 times, and then drying for 3 hours under the pressure of 0.2MPa to obtain pigment coating agent powder;
calcining the air-dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain a final sample YMn0.75Fe0.25O3。
Example 9
3.83g of yttrium nitrate, 2.01g of manganese nitrate, 1.21g of ferric nitrate and 1.49g of potassium chloride were dissolved in 100ml of water and stirred to obtain 1g of a solution. Dissolving 3.01g of glycine into 50ml of water to obtain a solution 2, pouring the solution 1 into the solution 2, stirring at 60 ℃ until the solution is clear 3, stirring at 100 rpm for 2 hours by using ultrasonic oscillation, then concentrating and burning at 120 ℃ to obtain precursor powder, pouring the precursor powder into a pigment coating agent, soaking for 2 hours, and then filtering and air-drying the soaked precursor powder; the pigment coating agent is prepared by a coating agent preparation device which mainly comprises a stirring main cabin 1, a stirring auxiliary cabin I2 and a stirring auxiliary cabin II 3, wherein the stirring main cabin 1, the stirring auxiliary cabin I2 and the stirring auxiliary cabin II 3 have the same structure, only the stirring main cabin 1 is explained at present, the stirring main cabin 1 comprises a pressure changing port 11, a pressure changing valve 12, a material inlet and outlet 13, a pressure valve 14, a liquid inlet 15, a liquid inlet valve 16, a liquid level meter 17, a liquid outlet valve 18, a liquid outlet 19, a stirring device 20 and a base 21, the top of the base 21 is connected with the bottom of the cabin body through the stirring device 20, the top of the cabin body is connected with the bottom of the pressure changing valve 12 through the material inlet and outlet 13, the pressure changing port 11 is arranged on the left side of the pressure changing valve 12, the pressure valve 14 is arranged at the position close to the top of the front end surface of the cabin body, the, the liquid level meter 17 is arranged at the left end of the cabin body, the liquid outlet valve 18 is arranged at the right end of the cabin body close to the bottom, and the liquid outlet 19 is connected with the liquid outlet valve 18; a main blade fan 201, an auxiliary blade fan 202 and a turntable 203 are arranged outside the stirring device 20, a rotating shaft 204 and a motor 205 are arranged in the stirring device 20, the motor 205 is positioned in the stirring device 20, the top of the motor 205 is connected with the bottom of the turntable 203 through the rotating shaft 204, the turntable 203 is positioned at the top of the stirring device 20, the top of the turntable 203 is respectively connected with the main blade fan 201 and the auxiliary blade fan 202, and the main blade fan 201 is covered on the top of the auxiliary blade fan 202; the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are symmetrically arranged about the main stirring cabin 1, and liquid outlets 19 of the first stirring auxiliary cabin 2 and the second stirring auxiliary cabin 3 are respectively connected with two liquid inlets 13 of the main stirring cabin 1 through pipelines;
the preparation method of the pigment coating agent comprises the following steps:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 85:100, adding into a main stirring cabin, and then stirring for 60min under the pressure of 0.5MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and ethanol solvent are mixed according to a mass ratio of 10:5:1.8: 4: 40, stirring for 40min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of one third of the volume of the slurry into the main cabin at a constant speed, and stirring and reacting for 3h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution b;
C. mixing butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent according to a mass ratio of 13:10:5: 60, adding the mixture into a stirring auxiliary cabin II, stirring for 25min at normal temperature to obtain a mixed solution c, continuously stirring the mixed solution B obtained in the step B, dropwise adding the mixed solution c with the volume of one fourth of the mixed solution B to the main cabin at a constant speed, and stirring and reacting for 3h at normal temperature and normal pressure after dropwise adding to obtain a mixed solution d;
C. then changing the pressure in the main cabin to-0.12 MPa, and regulating the temperature to 65 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the main cabin for 6 times, and then drying for 4 hours under the pressure of 0.2MPa to obtain pigment coating agent powder;
calcining the air-dried precursor powder at 900 ℃ for 4 hours, and grinding again to obtain a final sample YMn0.5Fe0.5O3。
Test examples
XRD test
XRD analysis was performed on the products prepared at different loadings, as shown in FIG. 1. The results show that: when the amount X of Fe is 0-0.30, the diffraction intensity of the peak continuously increases, the structure of the obtained product is completely consistent with that of the matrix, and the diffraction peak is not changed after the amount X is more than 0.30, so that the effect of X is best when the amount X is 0.3.
YMn at different calcination temperatures when the other conditions are the same1-xFexO3The XRD pattern of the resulting product is shown in FIG. 2. It can be seen that the product can be successfully synthesized at six temperatures, and the crystallinity of the product becomes better and better with the increase of the temperature, so 900 ℃ is selected as the preferred calcining temperature.
SEM test
Microstructure test of the product is carried out by a scanning electron microscope, and the material synthesized by the doping method has good dispersibility and uniform particle size distribution. For the pigment, the smaller the granularity is, the larger the specific surface of the particle is, the higher the specific surface energy is, and in addition, the material has good dispersibility, is easy to form a uniform coating in the use process, and has strong adhesive force and uniform chroma.
EDS analysis
The surface composition of the product is tested by an energy spectrometer, which shows that the doped product is composed of three elements of Y, Mn, Fe and O, the surface distribution is very uniform, and the chemical segregation phenomenon does not occur. It is also evident from the figure that: atomic ratio Y: (Mn + Fe) is about 1:1, in accordance with the stoichiometric ratio.
The pigment has a typical perovskite structure, is green and environment-friendly because of not containing toxic elements such as lead, cadmium and the like, has strong chromophoric ability and keeps relatively stable color tone in the firing process, can be used for coloring ceramics, glass and printing, and has attracted wide attention in recent years.
The preparation method of the invention saves energy and time, the raw materials are easy to obtain, and the obtained product has good ion dispersibility, uniform particle size distribution, no toxicity and no radioactivity; the synthesis temperature is low, the process is simple and controllable, and the method is suitable for large-scale production; and when the paint is painted on the ceramic and glass, the paint can fill the surface of the ceramic and glass, so that the ceramic and glass are firmer.
Coating agent test
By comparing the pigment without the coating agent with the fuel with the coating agent, the pigment with the coating agent has better thermal stability, smoother surface, acid resistance, corrosion resistance and illumination resistance compared with the pigment without the coating agent.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (2)
1. A method for preparing a black inorganic ceramic pigment, wherein the black ceramic pigment has YMn1-xFexO3The structure of (1), wherein: x is more than or equal to 0.05 and less than or equal to 0.30; the preparation method of the black ceramic pigment comprises the following steps:
(1) respectively dissolving corresponding yttrium nitrate, manganese nitrate and ferric nitrate in distilled water according to the molar ratio of Y, Mn to Fe to obtain a mixed solution;
(2) adding the mixed solution obtained in the step (1) into an aqueous solution of glycine;
(3) stirring the mixed solution in the step (2) for more than 1h at 60 ℃ by using a magnetic stirrer, and then carrying out combustion concentration at 100-120 ℃ to obtain precursor powder;
(4) finally, directly calcining the precursor powder obtained in the step (3) in a muffle furnace at the temperature of 650-900 ℃ for 2-4 h to obtain the black ceramic pigment with the perovskite structure;
before the precursor powder is calcined by a muffle furnace, pouring the precursor powder into a pigment coating agent to be soaked for 1-2 h, and then filtering and air-drying the soaked precursor powder;
the pigment coating agent is prepared by a coating agent preparation device, the coating agent preparation device mainly comprises a stirring main cabin (1), a first stirring auxiliary cabin (2) and a second stirring auxiliary cabin (3), the structures of the stirring main cabin (1), the first stirring auxiliary cabin (2) and the second stirring auxiliary cabin (3) are completely the same, the stirring main cabin (1) comprises a pressure changing port (11), a pressure changing valve (12), a material inlet and outlet (13), a pressure valve (14), a liquid inlet (15), a liquid inlet valve (16), a liquid level meter (17), a liquid outlet valve (18), a liquid outlet (19), a stirring device (20) and a base (21), the top of the base (21) is connected with the bottom of the cabin body through the stirring device (20), the top of the cabin body is connected with the bottom of the pressure changing valve (12) through the material inlet and outlet (13), the pressure changing port (11) is arranged on the left side of the pressure, the pressure valves (14) are arranged on the front end surface of the cabin body close to the top, the liquid inlets (15) are two in number and are respectively arranged on the left end and the right end of the cabin body close to the top, the liquid inlet valves (16) are two in number and are respectively arranged on the two liquid inlets (15), the liquid level meter (17) is arranged on the left end of the cabin body, the liquid outlet valve (18) is arranged on the right end of the cabin body close to the bottom, and the liquid outlet (19) is connected with the liquid outlet valve (18); a main blade fan (201), an auxiliary blade fan (202) and a rotating disc (203) are arranged outside the stirring device (20), a rotating shaft (204) and a motor (205) are arranged in the stirring device (20), the motor (205) is positioned in the stirring device (20), the top of the motor (205) is connected with the bottom of the rotating disc (203) through the rotating shaft (204), the rotating disc (203) is positioned at the top of the stirring device (20), the top of the rotating disc (203) is respectively connected with the main blade fan (201) and the auxiliary blade fan (202), and the main blade fan (201) is covered on the top of the auxiliary blade fan (202); the first stirring auxiliary cabin (2) and the second stirring auxiliary cabin (3) are symmetrically arranged about the main stirring cabin (1), and the first stirring auxiliary cabin (2) and a liquid outlet (19) of the second stirring auxiliary cabin (3) are respectively connected with two liquid inlets (15) of the main stirring cabin (1) through pipelines.
2. The preparation method of the black inorganic ceramic pigment according to claim 1, wherein the specific preparation method of the pigment coating agent is as follows:
A. mixing gamma-alumina and an ethanol solvent according to a mass ratio of 80-85: 100, adding the mixture into a stirring main cabin (1), and then stirring the mixture for 50-60 min under the pressure of 0.3-0.5 MPa to obtain slurry;
B. ethyl silicate, acrylate, polysiloxane, siloxane and an ethanol solvent are mixed according to a mass ratio of 7-10: 3-5: 1-1.8: 3-4: 40, adding the mixture into a first stirring auxiliary cabin (2), stirring for 30-40 min at normal temperature to obtain a mixed solution a, continuously stirring the slurry obtained in the step A, simultaneously dropwise adding the mixed solution a of which the volume is one third of that of the slurry into a main stirring cabin (1) at a constant speed, and after dropwise adding, stirring and reacting for 2-3 h at normal temperature and normal pressure to obtain a mixed solution b;
C. butyl acetate, benzoyl peroxide, chlorine dioxide, propyl methacrylate and an ethanol solvent are mixed according to the mass ratio of 10-13: 8-10: 3-5: mixing the mixed solution B obtained in the step B at a ratio of 60, adding the mixed solution c into the stirring auxiliary cabin II (3), stirring the mixed solution B at normal temperature for 20-25 min to obtain a mixed solution c, dropwise adding the mixed solution c of which the volume is one fourth of that of the mixed solution B into the stirring main cabin (1) at a constant speed while continuously stirring the mixed solution B obtained in the step B, and stirring the mixed solution c at normal temperature and normal pressure for reaction for 2-3 h after dropwise adding is finished to obtain a;
D. then changing the pressure in the main cabin (1) to-0.1-0.12 MPa, and regulating the temperature to 55-65 ℃ to recover the ethanol; then adding deionized water to repeatedly wash the powder in the stirring main cabin (1) for 4-6 times, and then drying for 3-4 h under the pressure of 0.1-0.2 MPa to obtain pigment coating agent powder;
E. mixing the pigment coating agent powder with an ethanol solvent according to the mass ratio of 1:50 to obtain a pigment coating agent;
wherein: x = 0.15;
the calcination temperature in the step (4) is 900 ℃;
the calcination time in the step (4) is 3-4 h;
the stirring speed in the step (3) is 80-100 r/min.
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