CN108864760B - Compound blue ceramic pigment Cu2Y2O5/TiO2Preparation method of (1) - Google Patents
Compound blue ceramic pigment Cu2Y2O5/TiO2Preparation method of (1) Download PDFInfo
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Abstract
The invention discloses a composite blue ceramic pigment Cu2Y2O5/TiO2The method for preparing the compound (A) is as follows,belongs to the technical field of ceramic pigments, and comprises the following steps of S1: adding butyl titanate into ethanol, and carrying out ultrasonic treatment for 1h to obtain a solution A; step S2, adding Cu2Y2O5And any dispersant are dispersed in deionized water to obtain a solution B; step S3, adding the solution A into the solution B, and standing for 12 h; step S4: and transferring the mixture into a reaction kettle, keeping the mixture in an oven at 180 ℃ for 6 hours, centrifuging, drying and grinding to obtain the composite blue ceramic pigment. The composite blue ceramic pigment prepared by the method has the advantages of large specific surface area, high temperature resistance, good chemical stability, bright color and the like.
Description
Technical Field
The invention relates to the technical field of ceramic pigments, in particular to a composite blue ceramic pigment Cu2Y2O5/TiO2The preparation method of (1).
Background
Blue is one of three primary colors of red, green and blue, has the shortest wavelength of 440-475 n nanometers, and belongs to short wavelength. The blue ceramic pigment is used for decorating ceramic products, and is also used as a colorant of ceramic colored glaze or a ceramic blank, which is an indispensable decorative material for ceramic decoration art. Most of the conventional blue pigments contain toxic heavy metals such as lead, chromium and the like, which have serious influence on the environment and individuals, and the conventional single-property pigments have failed to meet the requirements of various industries. Meanwhile, the material has the advantages that the size of the material is reduced to the nanometer level, and the material has the superior performance which is not compared with the conventional material. Therefore, a green synthesis method is required, and a high-performance nano blue pigment with small size, good dispersibility and uniform particle size distribution is imperatively obtained in a relatively mild environment.
TiO2Is a pigment with high infrared reflectivity, but its application is limited because it is susceptible to "white light" contamination, if TiO can be used2Effectively compounded with other substrates to synthesize a mesoporous and spheroidal core-shell structure with nano or submicron order, and on the one hand, the TiO is exerted2The high infrared reflection performance of the pigment can play the chromaticity of the color pigment on one hand, and the high infrared reflection color pigment is hopeful to be obtained. The method is a good development direction in combination with the problem that the current building energy consumption has increasingly serious influence on the environment and energy.
Application number 201610665535.X patent application discloses a preparation method of an antique blue pigment, belonging to the technical field of ancient ceramic pigments. The method adopts a coprecipitation-hydrothermal synthesis method, the prepared pigment has high purity and good crystallization condition, but the production period of the method is long, and the addition of the precipitator can cause the local concentration to be too high, generate agglomeration or have uneven composition, and is not beneficial to large-scale production.
Disclosure of Invention
Aiming at the technical problems, the invention provides a composite blue ceramic pigment Cu2Y2O5/TiO2The preparation method of (1).
The technical scheme of the invention is as follows:
compound blue ceramic pigment Cu2Y2O5/TiO2The preparation method comprises the following steps:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 20-30 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: mixing Cu2Y2O5Adding into deionized water, Cu2Y2O5The addition amount is 1.2-2.2g/ml, and solution B is obtained;
s3: preparation of solution C: and (4) adding the solution B obtained in the step (S2) into a stirring device, adding the solution A obtained in the step (S2) into the stirring device, stirring at the speed of 80-100r/min for 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, guiding the mixed liquid in the stirring device into a standing container after stirring is finished, and standing for 12h to obtain a solution C.
S4: obtaining a pigment: transferring the solution C obtained in the step S3 into a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment;
further, Cu described in step S22Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 23-25 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, adding the mixed solution a into a magnetic stirrer, heating to 60 ℃, stirring for 20min, heating and stirring the mixed solution a to be clear, then adjusting the heating temperature to 100-2Y2O5。
Further, the Cu (NO)3)2·3H2O and Y (NO)3)3·6H2The sum of the molar amounts of Cu ions and Y ions in O is 0.5 times the molar amount of glycine.
Further, the solution B described in the step S2 may be made of Cu2Y2O5And a dispersing agent is mixed according to the mass ratio of 20:1 to obtain a mixture c, and the mixture c is added into deionized water according to the amount of 1.5-2.5g/ml, wherein the dispersing agent is SDS or SDBS, and the SDS or SDBS has good emulsifying, foaming, permeating, decontaminating and dispersing performances.
Further, the molar ratio of the butyl titanate in the solution A to the metal ions in the solution B in the step S3 is 1:1, so that the utilization rate of the raw materials is improved, and the waste is reduced.
Further, the magnetic stirrer comprises: the stirring cylinder (1), the heating layer (2), the upper cover (3), the stirring rods (4), the liquid outlets (5), the electromagnetic seats (6) and the electronic device (7), wherein the heating layer (2) is fixed on the outer layer of the stirring cylinder (1), the center of the upper cover (3) is rotatably connected with the turntable (31) through a bearing, the stirring rods (4) are respectively provided with four parts, two stirring rods (4) are inserted from the position of the turntable (31) far away from the circle center and are fixed with the turntable (31) through threads, the other two stirring rods (4) are inserted from the position of the turntable (31) close to the circle center and are fixed with the turntable (31) through threads, the electromagnetic seats (6) are fixedly connected below the stirring cylinder (1), eight electromagnetic devices (61) are symmetrically arranged in the inner center of the electromagnetic seats (6), the inner rings are provided with four parts, the outer rings are provided with four parts, the liquid outlets (5) are fixed at the bottom of the right, the electronic device (7) is fixed below the electromagnetic seat (6).
Further, coil (21) is wound in the heating layer (2), and the stirring barrel is heated by adopting the eddy current heating effect, so that the heating is more uniform by utilizing the eddy current heating effect.
Further, a temperature sensor (11) is arranged at the bottom of the mixing drum (1), the temperature sensor (11) is electrically connected with the electronic device (7), and the temperature in the mixing drum is fed back in real time through the temperature sensor.
Furthermore, the electronic device (7) comprises a rectifier (71), a transformer (72), a transfer switch (73), a timer (74) and a display (75), wherein the rectifier (71) is fixed on the left side inside the electronic device (7) and is connected with an external alternating current power supply, the transformer (72) is electrically connected to the right side of the rectifier (71), the transfer switch (73) is electrically connected to the right side of the transformer (72), the timer (74) is fixed on the right side of the transfer switch (73), the display (75) is electrically connected to the right side of the timer (74), the transformer (72) respectively supplies power to the coil (21), the temperature sensor (11) and the electromagnetic device (61), the display (75) is electrically connected with the transfer switch (73) and the temperature sensor (11), and alternating current is converted into direct current through the rectifier, the stable magnetic force is generated through a direct current point to attract the stirring rod to rotate, the direct current generates an eddy current effect to heat the stirring barrel, the display is used for adjusting the stirring speed and the heating temperature and setting the heating time, the change-over switch is used for controlling the on-off of a circuit of the electromagnetic device, and the transformer provides different voltages for different power utilization elements.
Further, when the solution A is added into the stirring device in the step S3, an antioxidant can be added, wherein the antioxidant is added according to the volume of the solution B added into the stirring device by 0.2g/ml, and the antioxidant comprises the following components, by mass, 1 part of tea polyphenol palmitate, 0.2 part of ascorbic acid palmitate, 3 parts of pentamethylene, 0.5 part of poly α -olefin and 0.4 part of astaxanthin, so that the oxidation resistance of the pigment is improved, and the service life of the pigment is prolonged.
The invention has the beneficial effects that:
in the invention, Cu2Y2O5Blue pigment and TiO2The Cu is compounded, the advantages of the Cu and the Cu are brought into play to the best through the synergistic effect of the Cu and the Cu2Y2O5/TiO2A nanocomposite ceramic pigment. The composite blue ceramic pigment obtained by the invention combines Cu2Y2O5And TiO2Has the advantages of bright color, no color change at high temperature, and the like. In addition, 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; and the obtained product is low molecular and lowToxic or even non-toxic organic matters, no toxic elements such as lead, chromium and the like, environmental protection, good product particle dispersibility, uniform particle size distribution and good color rendering property.
Drawings
FIG. 1 is Cu2Y2O5X-ray diffraction patterns of different calcination temperatures (700, 750, 800 ℃);
FIG. 2 is Cu2Y2O5Different calcination temperatures (700, 750, 800 ℃) and TiO2A composite X-ray diffraction pattern;
FIG. 3 is an X-ray diffraction spectrum of a composite blue ceramic pigment with different molar amounts of butyl titanate and metal ions;
FIG. 4 is an X-ray diffraction pattern of composite blue ceramic pigments with different surfactants;
FIG. 5 shows Cu2Y2O5SEM images at 750 ℃ calcination;
FIG. 6 is an SEM image of a composite blue ceramic pigment with or without a surfactant added;
FIG. 7 is a SEM image of the substrate before and after coating at 750 deg.C;
FIG. 8 is an SEM image of a composite blue ceramic pigment with different molar amounts of butyl titanate and metal ions;
FIG. 9 is a block diagram of the magnetic stirrer of the present invention;
FIG. 10 is a top view of the turntable of the present invention;
FIG. 11 is a distribution diagram of the inventive electromagnetic machine.
The device comprises a stirring cylinder 1, a heating layer 2, an upper cover 3, a stirring rod 4, a liquid outlet 5, an electromagnetic seat 6, an electronic device 7, a turntable 31, an electromagnetic device 61, a coil 21, a temperature sensor 11, a rectifier 71, a transformer 72, a change-over switch 73, a timer 74 and a display 75.
Detailed Description
For the convenience of understanding the technical solution of the present invention, the following is further explained with reference to fig. 9 to 11, and the embodiments do not limit the scope of the present invention.
The first embodiment is as follows:
compound blue ceramic pigment Cu2Y2O5/TiO2The preparation method comprises the following steps:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 20 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: cu2Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 23 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding the mixed solution a into a magnetic stirrer, heating to 60 ℃ for 20min, heating and stirring the mixed solution a to be clear, adjusting the heating temperature to 100 ℃ again, stirring for 90min, allowing the mixed solution a to undergo a self-propagating combustion reaction during stirring to generate loose powder, placing the obtained powder into an industrial crucible for calcination, and adjusting the calcination temperature to 700 ℃ according to the mass of the powder in the crucible to finally obtain Cu, wherein the sum of the molar weight of Cu ions and Y ions in O is 0.5 times of the molar weight of glycine2Y2O5Mixing Cu2Y2O5Adding into deionized water, Cu2Y2O5The addition amount is 1.2/ml, and a solution B is obtained;
s3: preparation of solution C: adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, wherein the molar ratio of butyl titanate in the solution A to metal ions in the solution B is 1:1, the utilization rate of raw materials is improved, the waste is reduced, the stirring speed is 80r/min, the stirring time is 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, guiding mixed liquid in the stirring device into a standing container after the stirring is finished, and standing for 12h to obtain a solution C;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 to a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment.
Example two:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 25 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: cu2Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 24 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding the mixed solution a into a magnetic stirrer, heating to 60 ℃ for 20min, heating and stirring the mixed solution a to be clear, adjusting the heating temperature to 110 ℃ again, stirring for 100min, allowing the mixed solution a to undergo a self-propagating combustion reaction during stirring to generate loose powder, placing the obtained powder into an industrial crucible for calcination, wherein the calcination temperature is 750 ℃, and the calcination time is adjusted according to the mass of the powder in the crucible to finally obtain Cu2Y2O5，Cu2Y2O5Mixing the mixture c and a dispersing agent according to the mass ratio of 20:1 to obtain a mixture c, and adding the mixture c into deionized water according to the amount of 2g/ml, wherein the dispersing agent is SDS which has good emulsifying, foaming, permeating, decontaminating and dispersing performances;
s3: preparation of solution C: adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, wherein the molar ratio of butyl titanate in the solution A to metal ions in the solution B is 1:1, the utilization rate of raw materials is improved, the waste is reduced, the stirring speed is 90r/min, the stirring time is 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, guiding mixed liquid in the stirring device into a standing container after the stirring is finished, and standing for 12h to obtain a solution C;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 to a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment.
Example three:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 30 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: cu2Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 25 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding the mixed solution a into a magnetic stirrer, heating to 60 ℃ for 20min, heating and stirring the mixed solution a until the mixed solution a is clear, adjusting the heating temperature to 120 ℃ again, stirring for 110min, allowing the mixed solution a to undergo a self-propagating combustion reaction during stirring to generate loose powder, and placing the obtained powder into a magnetic stirrerCalcining in an industrial crucible at 800 deg.C for a time adjusted according to the mass of the powder in the crucible to obtain Cu2Y2O5Mixing Cu2Y2O5Adding into deionized water, Cu2Y2O5The addition amount is 2.2g/ml, and a solution B is obtained;
s3: preparation of solution C: adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, wherein the molar ratio of butyl titanate in the solution A to metal ions in the solution B is 1:1, the utilization rate of raw materials is improved, the waste is reduced, the stirring speed is 100r/min, the stirring time is 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, guiding mixed liquid in the stirring device into a standing container after the stirring is finished, and standing for 12h to obtain a solution C;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 to a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment.
Example four:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 20 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: cu2Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 25 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding the mixed solution a into a magnetic stirrer, heating to 60 ℃ for 20min, heating and stirring the mixed solution a to be clear, adjusting the heating temperature to 120 ℃ again, stirring for 110min, allowing the mixed solution a to undergo a self-propagating combustion reaction during stirring to generate loose powder, placing the obtained powder into an industrial crucible for calcination, wherein the calcination temperature is 800 ℃, and the calcination time is adjusted according to the mass of the powder in the crucible to finally obtain Cu2Y2O5Mixing Cu2Y2O5Mixing the mixture c and a dispersing agent according to the mass ratio of 20:1 to obtain a mixture c, and adding the mixture c into deionized water according to the amount of 2.5g/ml, wherein the dispersing agent is SDBS, and the SDBS has good emulsifying, foaming, penetrating, decontaminating and dispersing properties;
s3: preparation of solution C: adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, wherein the molar ratio of butyl titanate in the solution A to metal ions in the solution B is 1:1, the utilization rate of raw materials is improved, the waste is reduced, the stirring speed is 100r/min, the stirring time is 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, guiding mixed liquid in the stirring device into a standing container after the stirring is finished, and standing for 12h to obtain a solution C;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 to a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment.
As shown in fig. 9, the magnetic stirrer in step S1 includes: the stirring cylinder 1, the heating layer 2, the upper cover 3, the stirring rod 4, the liquid outlet 5, the electromagnetic seat 6 and the electronic device 7, wherein the heating layer 2 is fixed on the outer layer of the stirring cylinder 1, the coil 21 is wound inside the heating layer 2, the stirring cylinder 1 is heated by adopting the eddy current heating effect, the heating can be more uniform by utilizing the eddy current heating effect, the center of the upper cover 3 is rotatably connected with a turntable 31 through a bearing, as shown in figure 10, four stirring rods 4 are respectively arranged, wherein two stirring rods 4 are inserted from the position of the turntable 31 far away from the circle center, the upper end of each stirring rod is fixed with the turntable 31 through threads, the two stirring rods 4 are inserted from the position of the turntable 31 close to the circle center, the upper end of each stirring rod is fixed with the turntable 31 through threads, the electromagnetic seat 6 is fixedly connected below the stirring cylinder 1, as shown in figure 11, eight electromagnets 61 are symmetrically arranged at the inner center of the electromagnetic seat 6, the electronic device 7 is fixed below the electromagnetic seat 6, the temperature sensor 11 is arranged at the bottom of the mixing drum 1, the temperature sensor 11 is electrically connected with the electronic device 7, and the temperature in the mixing drum is fed back in real time through the temperature sensor 11; the electronic device 7 comprises a rectifier 71, a transformer 72, a transfer switch 73, a timer 74, a display 75, a rectifier 71 fixed on the left side of the inside of the electronic device 7 and connected with an external alternating current power supply, the transformer 72 is electrically connected on the right side of the rectifier 71, the transfer switch 73 is electrically connected on the right side of the transformer 72, the timer 74 is fixed on the right side of the transfer switch 73, the display 75 is electrically connected on the right side of the timer 74, the transformer 72 respectively supplies power for the coil 21, the temperature sensor 11 and the electromagnetic device 61, the display 75 is electrically connected with the transfer switch 73 and the temperature sensor 11, the alternating current is converted into direct current through the rectifier 71, stable magnetic force is generated through a direct current point to attract the stirring rod 4 to rotate, the direct current generates an eddy current effect to heat the stirring barrel 1, the display 75 is used for adjusting stirring speed and, the transfer switch 73 is used to control the on/off of the circuit of the electromagnet 61, and the transformer 72 provides different voltages for different electric elements.
Example five:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 30 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: cu2Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 25 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding the mixed solution a into a magnetic stirrer, heating to 60 ℃ for 20min, heating and stirring the mixed solution a to be clear, adjusting the heating temperature to 120 ℃ again, stirring for 110min, allowing the mixed solution a to undergo a self-propagating combustion reaction during stirring to generate loose powder, placing the obtained powder into an industrial crucible for calcination, wherein the calcination temperature is 800 ℃, and the calcination time is adjusted according to the mass of the powder in the crucible to finally obtain Cu2Y2O5Mixing Cu2Y2O5Adding into deionized water, Cu2Y2O5The addition amount is 2.2g/ml, and a solution B is obtained;
s3, preparing a solution C, namely adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, and adding an antioxidant into the solution A when the solution A is added into the stirring device, wherein the antioxidant is added according to the volume of the solution B added into the stirring device and is 0.2g/ml, the antioxidant comprises 1 part of tea polyphenol palmitate, 0.2 part of ascorbic acid palmitate, 3 parts of pentamethylene, 0.5 part of poly α -alkene and 0.4 part of astaxanthin, the oxidation resistance of the pigment is improved, the service life of the pigment is prolonged, the molar ratio of butyl titanate in the solution A to metal ions in the solution B is 1:1, the utilization rate of raw materials is improved, waste is reduced, the stirring speed is 100r/min, the stirring time is 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, and the mixed liquid in the stirring device is led out to a container to stand for 12h after stirring is finished, so that the solution C is obtained;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 to a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment.
As shown in fig. 9, the magnetic stirrer in step S1 includes: the stirring cylinder 1, the heating layer 2, the upper cover 3, the stirring rod 4, the liquid outlet 5, the electromagnetic seat 6 and the electronic device 7, wherein the heating layer 2 is fixed on the outer layer of the stirring cylinder 1, the coil 21 is wound inside the heating layer 2, the stirring cylinder 1 is heated by adopting the eddy current heating effect, the heating can be more uniform by utilizing the eddy current heating effect, the center of the upper cover 3 is rotatably connected with a turntable 31 through a bearing, as shown in figure 10, four stirring rods 4 are respectively arranged, wherein two stirring rods 4 are inserted from the position of the turntable 31 far away from the circle center, the upper end of each stirring rod is fixed with the turntable 31 through threads, the two stirring rods 4 are inserted from the position of the turntable 31 close to the circle center, the upper end of each stirring rod is fixed with the turntable 31 through threads, the electromagnetic seat 6 is fixedly connected below the stirring cylinder 1, as shown in figure 11, eight electromagnets 61 are symmetrically arranged at the inner center of the electromagnetic seat 6, the electronic device 7 is fixed below the electromagnetic seat 6, the temperature sensor 11 is arranged at the bottom of the mixing drum 1, the temperature sensor 11 is electrically connected with the electronic device 7, and the temperature in the mixing drum is fed back in real time through the temperature sensor 11; the electronic device 7 comprises a rectifier 71, a transformer 72, a transfer switch 73, a timer 74, a display 75, a rectifier 71 fixed on the left side of the inside of the electronic device 7 and connected with an external alternating current power supply, the transformer 72 is electrically connected on the right side of the rectifier 71, the transfer switch 73 is electrically connected on the right side of the transformer 72, the timer 74 is fixed on the right side of the transfer switch 73, the display 75 is electrically connected on the right side of the timer 74, the transformer 72 respectively supplies power for the coil 21, the temperature sensor 11 and the electromagnetic device 61, the display 75 is electrically connected with the transfer switch 73 and the temperature sensor 11, the alternating current is converted into direct current through the rectifier 71, stable magnetic force is generated through a direct current point to attract the stirring rod 4 to rotate, the direct current generates an eddy current effect to heat the stirring barrel 1, the display 75 is used for adjusting stirring speed and, the transfer switch 73 is used to control the on/off of the circuit of the electromagnet 61, and the transformer 72 provides different voltages for different electric elements.
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.
Experimental data
XRD test
Cu synthesized by calcining at different temperatures2Y2O5XRD analysis was performed as shown in FIG. 1. Therefore, the following steps are carried out: the complex peak exists at 700 ℃, and the diffraction peaks at 750 ℃ and 800 ℃ correspond to the standard map one by one, which shows that the Cu is synthesized2Y2O5Preferably, the calcination temperature is 750 ℃ in view of the combination.
Under the same conditions, the influence of the calcination temperature of the matrix on the product is preferred, as shown in FIG. 2, Cu2Y2O5With TiO2After compounding, with standard anatase TiO2Compared with XRD patterns (JCPDS: 21-1272), TiO appears in all the patterns2Characteristic peak. At a matrix temperature of 700 ℃ of Cu2Y2O5The characteristic peak is slightly higher than that of TiO2Probably because TiO2 does not coat Cu very well2Y2O5The surface of the crystal. TiO when the temperature of the substrate is 750 DEG C2The characteristic peak of the alloy is far higher than that of Cu2Y2O5Possibly due to too high a ratio of Ti4+ to metal ions. At a substrate temperature of 800 ℃, almost no Cu is seen2Y2O5Characteristic peak of (1), and TiO2The characteristic peak of (A) is significantly lower than that at a matrix temperature of 750 ℃.
The effect of the dispersant to metal ion ratio on the product, as shown in FIG. 3, is preferably compared to TiO2Compared with XRD patterns (JCPDS: 21-1272), TiO appears in all the patterns2Characteristic peaks and standard spectra Cu2Y2O5(JCPDS: 33-511) compared with Cu2Y2O5Characteristic peak of (2). When the ratio of Ti4+ to metal ions is 10:1, Cu2Y2O5The characteristic peaks were not apparent. When the ratio of Ti4+ to metal ions is 1:1, Cu2Y2O5The characteristic peak of the TiO is obvious2The peak value of (a) is also significant.
Under the same conditions, the effect of the dispersant on the product is preferred, as shown in FIG. 4, where SDS (SDS to metal ion 2:1) is added at the same time at a ratio of Ti4+ to metal ion of 1: 1. The XRD pattern of the SDS added with the surfactant shows an amorphous structure at 25.47 degrees, and compared with the XRD pattern without the surfactant, the SDS-added crystal is not good or bad simply by XRD, and further SEM analysis is needed.
SEM test
The microstructure of the product was tested by scanning electron microscopy, and as can be seen from FIG. 5, we can clearly see the Cu matrix2Y2O5Has good dispersibility, uniform particle distribution, no obvious agglomeration and uniform grain size. As can be seen from fig. 6, the grain sizes of the two are not very different, and the particle size is more uniform without the addition of active agent. As can be seen in fig. 7, the particles after coating are significantly more uniform in size and more spherical in shape than before. As can be seen from FIG. 8, the particle size of the particles in the ratio of 1:1 is slightly smaller than that in the ratio of 10:1, and the specific surface area is larger. Approximately spherical, spheroidal, TiO2A layer of shell is formed on the surface of the substrate uniformly.
Color test
For (Cu) obtained by experiment2Y2O5) The blue ceramic pigments were subjected to a color test and the results are shown in the following table.
As can be seen from the table, Cu was calcined2Y2O5The temperature of the crystals increases from 700 ℃ to 800 ℃, the L value also increases from 49.58 to 52.86 with the increase of the temperature, the brightness value of the product also tends to be bright, when the temperature increases from 700 ℃ to 750 ℃, the L value increase is not obvious, which shows that the brightness is hardly increased, when the temperature increases from 750 ℃ to 800 ℃, although the L value increase is not obvious, the a and b values have obvious change, L shows the brightness (brightness), the chromaticity value gradually increases, which shows that the product is brighter, the value of a is smaller and smaller with the increase of the temperature, which shows that the sample is greener, the b value is smaller and smaller, which shows that the matrix is blueish, wherein L is the brightness, the L is larger and the product is brighter, the a is the red-green change value, the product color is redder, the b is the yellow-blue change value, the b is the product color is more yellow, the temperature increases from 750 ℃ and the brightness is not obvious.
Claims (6)
1. Compound blue ceramic pigment Cu2Y2O5/TiO2The preparation method is characterized by comprising the following steps:
s1: preparation of solution a: adding butyl titanate into ethanol, mixing and stirring, wherein the addition amount of the butyl titanate is 0.034g/ml, the external temperature is 20-30 ℃ during mixing, and then carrying out ultrasonic treatment for 1h to obtain a solution A;
s2: preparation of solution B: mixing Cu2Y2O5Adding into deionized water, Cu2Y2O5The addition amount is 1.2-2.2g/ml, and solution B is obtained;
s3: preparation of solution C: adding the solution B obtained in the step S2 into a stirring device, adding the solution A obtained in the step S2 into the stirring device, stirring at the stirring speed of 80-100r/min for 1.2kg/h according to the total mass of the solution A and the solution B added into the stirring device, leading out mixed liquid in the stirring device into a standing container after stirring is finished, and standing for 12h to obtain a solution C;
s4: obtaining a pigment: transferring the solution C obtained in the step S3 into a reaction kettle, firstly drying in the reaction kettle at the oven temperature of 180 ℃ for 6 hours, then centrifuging the dried solution C to obtain a mixture b, then drying the mixture b to obtain a solid pigment, drying the mixture b at the temperature of 80 ℃ for 4 hours, then drying at the temperature of 90 ℃ for 2 hours, then putting the dried mixture b into a grinder for grinding, and grinding into powder to obtain the composite blue ceramic pigment;
cu described in step S22Y2O5The acquisition method comprises the following steps: dissolving glycine solid in distilled water at 23-25 deg.C, and adding Cu (NO)3)2·3H2O and Y (NO)3)3·6H2Adding O into the aqueous solution of glycine to obtain a mixed solution a, adding the mixed solution a into a magnetic stirrer, heating to 60 ℃, stirring for 20min, heating and stirring the mixed solution a to be clear, then adjusting the heating temperature to 100-2Y2O5；
The solution B in the step S2 can also be made of Cu2Y2O5Mixing the mixture with a dispersant according to the mass ratio of 20:1 to obtain a mixture c, and adding the mixture c into deionized water according to the amount of 1.5-2.5g/ml, wherein the dispersant is SDS or SDBS;
when the solution A is added into the stirring device in the step S3, an antioxidant can be added, wherein the addition amount of the antioxidant is added according to the volume of the solution B added into the stirring device and is 0.2g/ml, and the antioxidant comprises the following components, by mass, 1 part of tea polyphenol palmitate, 0.2 part of ascorbic acid palmitate, 3 parts of pentamethylene, 0.5 part of poly α -olefin and 0.4 part of astaxanthin;
the magnetic stirrer comprises: the stirring cylinder (1), the heating layer (2), the upper cover (3), the stirring rods (4), the liquid outlets (5), the electromagnetic seats (6) and the electronic device (7), wherein the heating layer (2) is fixed on the outer layer of the stirring cylinder (1), the center of the upper cover (3) is rotatably connected with the turntable (31) through a bearing, the number of the stirring rods (4) is four, two stirring rods (4) are inserted from the position of the turntable (31) far away from the circle center and the upper end of the stirring rods is fixed with the turntable (31) through threads, the other two stirring rods (4) are inserted from the position of the turntable (31) close to the circle center and the upper end of the stirring rods is fixed with the turntable (31) through threads, the electromagnetic seats (6) are fixedly connected below the stirring cylinder (1), eight electromagnetic devices (61) are symmetrically arranged in the inner center of the electromagnetic seats (6), the inner rings are four, the outer rings are provided with four liquid outlets (5), the electronic device (7) is fixed below the electromagnetic seat (6).
2. The composite blue ceramic pigment Cu as claimed in claim 12Y2O5/TiO2Characterized in that the Cu (NO) is3)2·3H2O and Y (NO)3)3·6H2The sum of the molar amounts of Cu ions and Y ions in O is 0.5 times the molar amount of glycine.
3. The composite blue ceramic pigment Cu as claimed in claim 12Y2O5/TiO2The method of (5) is characterized in that the molar ratio of the butyl titanate in the solution A to the metal ions in the solution B in the step S3 is 1: 1.
4. The composite blue ceramic pigment Cu as claimed in claim 12Y2O5/TiO2The preparation method is characterized in that a coil (21) is wound inside the heating layer (2), and the stirring drum is heated by adopting the eddy current heating effect.
5. The composite blue ceramic pigment Cu as claimed in claim 12Y2O5/TiO2The preparation method is characterized in that a temperature sensor (11) is arranged at the bottom of the mixing drum (1), and the temperature sensor(11) Is electrically connected with the electronic device (7).
6. The composite blue ceramic pigment Cu as claimed in claim 12Y2O5/TiO2The manufacturing method of the electronic device (7) is characterized in that the electronic device (7) comprises a rectifier (71), a transformer (72), a transfer switch (73), a timer (74) and a display (75), the rectifier (71) is fixed on the left side inside the electronic device (7) and is connected with an external alternating current power supply, the transformer (72) is electrically connected to the right side of the rectifier (71), the transfer switch (73) is electrically connected to the right side of the transformer (72), the timer (74) is fixed on the right side of the transfer switch (73), the display (75) is electrically connected to the right side of the timer (74), the transformer (72) respectively supplies power to the coil (21), the temperature sensor (11) and the electromagnet (61), and the display (75) is electrically connected with the transfer switch (73) and the temperature sensor (11).
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