CN107573064B - Zirconia ceramic micro-bead and preparation method thereof - Google Patents
Zirconia ceramic micro-bead and preparation method thereof Download PDFInfo
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Abstract
The invention relates to zirconia ceramic microspheres and a preparation method thereof. The preparation method of the zirconia ceramic microspheres comprises the following steps: mixing zirconium oxide powder, styrene and water to obtain a mixture, wherein the mass ratio of the zirconium oxide powder to the styrene is 50: 100-90: 100, and the mass ratio of the styrene to the water is 15: 100-25: 100; carrying out polymerization reaction on the mixture and an initiator under the condition of continuous stirring to obtain reaction liquid containing a microbead blank; separating solid from liquid of the reaction liquid containing the microbead blank, and drying to obtain a microbead blank; and sequentially carrying out binder removal and sintering on the micro-bead blank to obtain the zirconia ceramic micro-beads. The preparation method of the zirconia ceramic microspheres prepared by the method has good quality and high production efficiency.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to zirconia ceramic microspheres and a preparation method thereof.
Background
The zirconia ceramic micro-beads are mainly applied to the preparation of superfine powder and are matched with a sand mill, a stirring mill or a ball mill for use. At present, main preparation processes of zirconia ceramic microspheres include rolling forming and titration forming, wherein the rolling forming efficiency is high, but the prepared microspheres are low in quality, are damaged more and are easy to damage in the using process; although the quality of the microbeads prepared by titration molding is good, one microbead can be prepared by titration molding in one step, and batch production cannot be realized, so that the yield is low.
Disclosure of Invention
Accordingly, there is a need for a method for preparing zirconia ceramic microbeads with good quality and high production efficiency.
In addition, the zirconia ceramic microspheres are also provided.
A preparation method of zirconia ceramic microspheres comprises the following steps:
mixing zirconium oxide powder, styrene and water to obtain a mixture, wherein the mass ratio of the zirconium oxide powder to the styrene is 50: 100-90: 100, and the mass ratio of the styrene to the water is 15: 100-25: 100;
carrying out polymerization reaction on the mixture and an initiator under the condition of continuous stirring to obtain reaction liquid containing a microbead blank;
separating the solid from the liquid of the reaction liquid containing the microbead blank and then drying to obtain the microbead blank; and
and sequentially carrying out glue removal and sintering on the micro-bead blank to obtain the zirconia ceramic micro-bead.
The preparation method of the zirconia ceramic microspheres comprises the steps of mixing zirconia powder, styrene and water to obtain a mixture, controlling the mass ratio of the zirconia powder to the styrene to be 50: 100-90: 100, controlling the mass ratio of the styrene to the water to be 15: 100-25: 100, carrying out polymerization reaction on the mixture and an initiator under the condition of continuous stirring to generate volume shrinkage, so that the zirconia powder is subjected to formed intermolecular pressure to form a microsphere blank, carrying out solid-liquid separation, drying, glue discharging and sintering on reaction liquid containing the microsphere blank to obtain the zirconia ceramic microspheres, so that the zirconia ceramic microspheres have good mechanical strength, high density, high hardness, good wear resistance and good impact resistance, the produced products are regular in shape, less in damage and good in quality, and in addition, the preparation method is simple to operate, and compared with a titration forming method, the preparation method can be used for mass production at one time, and is beneficial to improving the production efficiency.
In one embodiment, the step of mixing zirconia powder, styrene and water specifically comprises: ball-milling and mixing the zirconia powder, the styrene and a dispersing agent to obtain a premix; the water is then mixed with the premix with constant stirring.
In one embodiment, in the step of polymerizing the mixture and the initiator under continuous stirring, the stirring speed is 1000 rpm to 2000 rpm.
In one embodiment, the step of mixing the water with the premix under continuous stirring and the step of polymerizing the mixture and the initiator under continuous stirring are both performed in an autoclave with a stirring blade, the water and the premix are continuously stirred by the stirring blade, and the mixture and the initiator are continuously stirred by the stirring blade.
In one embodiment, the ball milling and mixing time is 8-24 hours, and the mass ratio of the zirconia powder to the ball milling medium is 1: 3-1: 5.
In one embodiment, the step of polymerizing the mixture and the initiator under the condition of continuous stirring is specifically as follows: adding the initiator into the mixture under the condition of continuous stirring, and then continuously stirring until the temperature of the reaction system begins to decrease.
In one embodiment, the drying step is: drying for 1-10 hours at 40-100 ℃.
In one embodiment, the step of discharging the glue is specifically as follows: heating from room temperature to 450-750 ℃ at the heating rate of 5-30 ℃/min, and keeping the temperature for 1-2 hours.
In one embodiment, the sintering step is: heating from room temperature to 1350-1500 ℃ at the heating rate of 5-10 ℃/min, and sintering for 1-5 hours.
The zirconia ceramic microspheres prepared by the preparation method of the zirconia ceramic microspheres.
Drawings
Fig. 1 is a flowchart of a method for preparing zirconia ceramic beads according to an embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As shown in fig. 1, a method for preparing zirconia ceramic micro beads according to an embodiment includes the steps of:
step S110: and mixing the zirconium oxide powder, the styrene and the water to obtain a mixture.
Wherein the mass ratio of the zirconium oxide powder to the styrene is 50: 100-90: 100; the mass ratio of the styrene to the water is 15: 100-25: 100. If the zirconia powder is less, the ceramic microbead blank has larger molding shrinkage, so that the sintering is not compact, and if the zirconia powder is too much, the fluidity of the mixture is poor, so that the subsequent mixture is difficult to stir, and the spherical microbead blank cannot be formed in the subsequent polymerization reaction. The preparation method of the zirconia ceramic microspheres utilizes the incompatibility of styrene and water, so that two phases are incompatible during stirring to generate a spherical blank, if too much water is used, the blank of the microspheres is too small, the microspheres are too small, and if too little water is used, the mixture has no fluidity, and the spherical blank cannot be generated.
In this embodiment, step S110 specifically includes: ball-milling and mixing zirconia powder, styrene and a dispersing agent to obtain a premix; water was then mixed with the premix with constant stirring.
Because the styrene is in a liquid state, no additional water is needed for ball milling when the zirconium oxide powder, the styrene and the dispersing agent are mixed in a ball milling way. And the zirconia powder can be dispersed more uniformly by ball milling and mixing under the condition of adding the dispersing agent. Specifically, the ball milling and mixing time is 8-24 hours, and the mass ratio of the zirconia powder to the ball milling medium is 1: 3-1: 5.
Specifically, the step of mixing water with the premix under continuous stirring is performed in an autoclave equipped with a stirring paddle by which the water and the premix are stirred. More specifically, the step of mixing water with the premix under continuous stirring is: and (3) placing the premixed solution into a high-pressure reaction kettle, adding water under the condition of continuous stirring, and then continuously stirring for 10-60 minutes.
It should be noted that, firstly, the zirconia powder, the styrene and the dispersant are mixed to obtain the premix, and then the water and the premix are mixed to ensure that the zirconia powder can be more uniformly dispersed in the mixture, so that the subsequent styrene can fully wrap the zirconia powder in the polymerization reaction process, thereby ensuring the full utilization of the zirconia powder, improving the production efficiency, and simultaneously, the uniform dispersion of the zirconia powder is also beneficial to improving the quality of the subsequent zirconia ceramic microbeads and reducing the damage, therefore, the step S110 is not limited to the mode of firstly mixing the zirconia powder, the water and the dispersant to obtain the premix and then mixing the styrene and the premix. For example, the zirconia powder, styrene, the dispersant and water may be directly mixed while stirring in the autoclave.
Specifically, the dispersant is polyvinyl alcohol; the mass ratio of the dispersing agent to the zirconia powder is 0.5: 100-1.5: 100. The dispersant is not limited to polyvinyl alcohol, and for example, the dispersant may be polyethylene glycol or polyacrylic acid. As long as it can disperse the zirconia powder.
Furthermore, the median particle size of the zirconia powder is 0.3 to 0.5 μm.
Step S120: and carrying out polymerization reaction on the mixture and an initiator under the condition of continuous stirring to obtain a reaction solution containing the microbead blank.
In this embodiment, step S120 is specifically: adding the initiator into the mixture under the condition of continuous stirring, and then continuously stirring until the reaction system begins to cool. After the initiator is added, styrene starts to perform polymerization reaction and generates volume contraction, zirconium oxide powder is given with formed intermolecular pressure to form a microbead blank, heat is released in the polymerization reaction process, the temperature of a reaction system can reach 80-90 ℃, and the reaction is finished when the temperature of the reaction system starts to be reduced. Specifically, the temperature of the reaction system can be observed by using a thermometer.
Wherein, the step S120 is carried out in a high-pressure reaction kettle with a stirring paddle, and the mixture and the initiator are continuously stirred by the stirring paddle.
Specifically, the stirring speed is 1000 rpm to 2000 rpm. The diameter of the micro-bead blank can be controlled by controlling the stirring speed, and the subsequent particle size of the zirconia ceramic micro-beads can be controlled to be 0.1-1 mm by adjusting the stirring speed in the range.
The initiator is used for initiating the polymerization reaction of the styrene. Specifically, the initiator is dibenzoyl peroxide (BPO); the mass ratio of the initiator to the styrene is 0.1: 100-0.5: 100. The initiator is not limited to BPO, and may be TBPO (tert-butyl peroxy-2-ethylhexanoate), for example, as long as it can promote the polymerization of styrene.
Step S130: and (3) separating solid from liquid of the reaction liquid containing the microbead blank, and drying to obtain the microbead blank.
In the embodiment, a reaction solution containing the microbead blank is filtered by using a solid-liquid separation test paper; and then drying the microbead blank subjected to solid-liquid separation for 1 to 10 hours at the temperature of between 40 and 100 ℃.
Step S140: and sequentially carrying out binder removal and sintering on the micro-bead blank to obtain the zirconia ceramic micro-beads.
Specifically, the rubber discharging steps are as follows: heating from room temperature to 450-750 ℃ at the heating rate of 5-30 ℃/min, and keeping the temperature for 1-2 hours. Organic matters in the micro-bead green bodies are removed through binder removal, so that the micro-bead green bodies are prevented from cracking in the sintering process, the breakage rate of the zirconia ceramic micro-beads is reduced, and the production efficiency is improved.
Further, the step of discharging the gel is performed in vacuum. It should be noted that the purpose of the vacuum glue discharging is to improve the glue discharging efficiency, and therefore, the glue discharging step can also be performed in an air environment.
Specifically, the sintering step is as follows: heating from room temperature to 1350-1500 ℃ at the heating rate of 5-10 ℃/min, and sintering for 1-5 hours.
Because only one bead can be produced by titration molding and one-time titration, the batch production cannot be realized, the yield is low, the green body of the ceramic bead is not subjected to external pressure in the preparation process of rolling molding, the density of the green body is low, and the density of the bead obtained by later-stage sintering is low and the bead strength is poor.
The preparation method of the zirconia ceramic microspheres comprises the steps of mixing zirconia powder, styrene, a dispersing agent and water to obtain a mixture, controlling the mass ratio of the zirconia powder to the styrene to be 50: 100-90: 100, controlling the mass ratio of the styrene to the water to be 15: 100-25: 100, carrying out a polymerization reaction on the styrene to generate volume shrinkage under the condition of continuous stirring on the mixture and an initiator, so as to provide the zirconia powder with formed intermolecular pressure to form a microsphere blank, carrying out solid-liquid separation, drying, glue discharging and sintering on a reaction liquid containing the microsphere blank to obtain the zirconia ceramic microspheres, so that the zirconia ceramic microspheres have good mechanical strength, high compactness, high hardness, good wear resistance and good impact resistance, and the produced product has the advantages of small regularity and breakage and good quality, in addition, the preparation method is simple to operate, and compared with a titration forming method, the preparation method can be used for mass production at one time, and is beneficial to improving the production efficiency.
The zirconia ceramic microspheres of an embodiment are prepared by the preparation method of the zirconia ceramic microspheres, and have the advantages of high density, high hardness, high wear resistance, high mechanical strength, high impact resistance and regular shape, namely, the zirconia ceramic microspheres of the embodiment have high quality.
The following are specific examples (the following examples, unless otherwise specified, contain no other components not specifically indicated except for unavoidable impurities):
example 1
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconia powder, the styrene and the polyvinyl alcohol for 24 hours to obtain a premix, wherein the mass ratio of the zirconia powder to the styrene is 70:100, the mass ratio of the zirconia powder to a ball-milling medium is 1:4, the mass ratio of the polyvinyl alcohol to the zirconia powder is 1.5:100, and the median particle size of the zirconia powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 30 minutes after the water is added, then adding dibenzoyl peroxide, and continuing stirring at the stirring speed of 1500 rpm to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.1: 100; the mass ratio of styrene to water was 20: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into a drying oven to dry for 5 hours at 70 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 450 ℃ at the heating rate of 15 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 2 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.3 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The compactness of the zirconia ceramic microspheres of the embodiment is tested by adopting an Archimedes drainage method, and is shown in Table 1; the porosity of the zirconia ceramic microspheres of the present example was measured by mercury intrusion porosimetry, as shown in table 1; the zirconia ceramic beads of this example were tested for hardness according to "GB/T16534-1996 engineering ceramic Vickers hardness test method Standard" and are shown in Table 1.
The abrasion resistance of the zirconia ceramic microspheres of the present example was tested by a grinding method: weighing microbeads of unit weight, putting the microbeads into a ball milling tank, carrying out ball milling for 30 hours, cleaning, drying, weighing the weight of the microbeads after ball milling, subtracting the weight of the microbeads after ball milling from the weight of the microbeads before ball milling to obtain the weight loss of the microbeads, dividing the weight loss of the microbeads by the number of kilograms of the microbeads before ball milling and the ball milling time, and calculating to obtain the average equivalent abrasion of each kilogram of the microbeads per hour, wherein the average equivalent abrasion of each kilogram of the microbeads per hour is shown in table 1.
Example 2
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconium oxide powder, the styrene and the polyvinyl alcohol for 12 hours to obtain a premix, wherein the mass ratio of the zirconium oxide powder to the styrene is 50:100, the mass ratio of the zirconium oxide powder to a ball-milling medium is 1:3, and the mass ratio of the polyvinyl alcohol to the zirconium oxide powder is 1: 100.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 60 minutes after the water is added, then adding dibenzoyl peroxide, continuing stirring at the stirring speed of 1000 revolutions per minute to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.2: 100; the mass ratio of styrene to water was 15: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into a drying oven to dry for 10 hours at 40 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 750 ℃ at the heating rate of 30 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 3 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.2 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 3
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconium oxide powder, the styrene and the polyvinyl alcohol for 8 hours to obtain a premix, wherein the mass ratio of the zirconium oxide powder to the styrene is 90:100, the mass ratio of the zirconium oxide powder to a ball-milling medium is 1:5, the mass ratio of the polyvinyl alcohol to the zirconium oxide powder is 0.5:100, and the median particle size of the zirconium oxide powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuously stirring at a stirring speed, continuing to stir for 20 minutes after the water is added, then adding dibenzoyl peroxide, and continuing to stir at a stirring speed of 2000 revolutions per minute to enable styrene to carry out polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and completing the reaction to obtain reaction solution containing a microbead blank, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.5: 100; the mass ratio of styrene to water was 18: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into an oven to dry for 1 hour at 100 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 600 ℃ at the heating rate of 10 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating from room temperature to 1450 ℃ at the heating rate of 8 ℃/min, carrying out heat preservation sintering for 5 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.4 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 4
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconia powder, the styrene and the polyvinyl alcohol for 24 hours to obtain a premix, wherein the mass ratio of the zirconia powder to the styrene is 60:100, the mass ratio of the zirconia powder to a ball-milling medium is 1:4, the mass ratio of the polyvinyl alcohol to the zirconia powder is 1.5:100, and the median particle size of the zirconia powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 40 minutes after the water is added, then adding dibenzoyl peroxide, continuing stirring at the stirring speed of 1200 revolutions per minute to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.4: 100; the mass ratio of styrene to water was 25: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into an oven to dry for 8 hours at the temperature of 60 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 650 ℃ at the heating rate of 25 ℃/min under the vacuum condition, preserving the heat for 1.5 hours, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1350 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation sintering for 5 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.25 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 5
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconia powder, the styrene and the polyethylene glycol for 24 hours to obtain a premix, wherein the mass ratio of the zirconia powder to the styrene is 70:100, the mass ratio of the zirconia powder to a ball-milling medium is 1:4, the mass ratio of the polyethylene glycol to the zirconia powder is 1.5:100, and the median particle size of the zirconia powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 30 minutes after the water is added, then adding dibenzoyl peroxide, and continuing stirring at the stirring speed of 1500 rpm to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.1: 100; the mass ratio of styrene to water was 20: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into a drying oven to dry for 5 hours at 70 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 450 ℃ at the heating rate of 15 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 2 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.3 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 6
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconia powder, the styrene and the polyacrylic acid for 24 hours to obtain a premix, wherein the mass ratio of the zirconia powder to the styrene is 70:100, the mass ratio of the zirconia powder to a ball-milling medium is 1:4, the mass ratio of the polyacrylic acid to the zirconia powder is 1.5:100, and the median particle size of the zirconia powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 30 minutes after the water is added, then adding dibenzoyl peroxide, and continuing stirring at the stirring speed of 1500 rpm to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 0.1: 100; the mass ratio of styrene to water was 20: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into a drying oven to dry for 5 hours at 70 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 450 ℃ at the heating rate of 15 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 2 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.3 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 7
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) and ball-milling and mixing the zirconia powder, the styrene and the polyvinyl alcohol for 24 hours to obtain a premix, wherein the mass ratio of the zirconia powder to the styrene is 70:100, the mass ratio of the zirconia powder to a ball-milling medium is 1:4, the mass ratio of the polyvinyl alcohol to the zirconia powder is 1.5:100, and the median particle size of the zirconia powder is 0.3-0.5 mu m.
(2) Placing the premixed solution into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed solution under the condition of continuous stirring, continuing stirring for 30 minutes after the water is added, then adding tert-butyl peroxy-2-ethylhexanoate, and continuing stirring at the stirring speed of 1500 rpm to enable styrene to generate polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction solution containing a microbead blank after the reaction is finished, wherein the mass ratio of the tert-butyl peroxy-2-ethylhexanoate to the styrene is 0.1: 100; the mass ratio of styrene to water was 20: 100.
(3) And filtering the reaction liquid containing the microbead blank by using a funnel provided with filter test paper to perform solid-liquid separation, and then putting the microbead blank obtained by the solid-liquid separation into a drying oven to dry for 5 hours at 70 ℃.
(4) And (3) putting the dried microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 450 ℃ at the heating rate of 15 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(5) Putting the sagger filled with the bead blank subjected to gel removal in the step (4) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 2 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.3 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 8
The zirconia ceramic micro beads of this example were prepared in substantially the same manner as in example 1, except that the mass ratio of zirconia powder to styrene was 40: 100. The diameter of the obtained zirconia ceramic micro beads was measured to be 0.1mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was obtained by statistics and is shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 9
The zirconia ceramic beads of this example were prepared in substantially the same manner as in example 1, except that the mass ratio of zirconia powder to styrene was 1: 1. The diameter of the obtained zirconia ceramic micro beads was measured to be 0.5mm, and the proportion of the zirconia ceramic micro beads having a regular spherical shape and no breakage in this example was statistically obtained as shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 10
The zirconia ceramic micro beads of this example were prepared in substantially the same manner as in example 1 except that the mass ratio of styrene to water was 10: 100. The diameter of the obtained zirconia ceramic micro beads was measured to be 0.05mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was statistically obtained as shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres obtained in the example are shown in Table 1 by the same method as that of example 1
Example 11
The zirconia ceramic beads of this example were prepared in substantially the same manner as in example 1, except that the addition of dibenzoyl peroxide in step (2) was followed by stirring at a stirring speed of 800 rpm to polymerize styrene. The diameter of the obtained zirconia ceramic micro beads was measured to be 1mm, and the proportion of the zirconia ceramic micro beads having a regular spherical shape and no breakage in this example was found by statistics to be shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres obtained in the example are shown in Table 1 by the same method as that of example 1
Example 12
The procedure for preparing the zirconia ceramic beads of this example was substantially the same as that of example 1, except that the polymerization of styrene was carried out by continuing stirring at a stirring speed of 2200 rpm after adding dibenzoyl peroxide in step (2). The diameter of the obtained zirconia ceramic micro beads was measured to be 0.05mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was statistically obtained as shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 13
The procedure for producing zirconia ceramic beads of this example was substantially the same as in example 1, except that the median particle size of the zirconia powder was 0.6 to 0.8 μm. The diameter of the obtained zirconia ceramic micro beads was measured to be 0.4mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was obtained by statistics and is shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 14
The procedure for producing zirconia ceramic beads of this example was substantially the same as in example 1, except that the median particle size of the zirconia powder was 0.08 to 0.2 μm. The diameter of the obtained zirconia ceramic micro beads was measured to be 0.2mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was obtained by statistics and is shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Example 15
The preparation process of the zirconia ceramic microspheres of the present example is as follows:
(1) putting zirconium oxide powder, styrene and polyvinyl alcohol into a high-pressure reaction kettle with a stirring paddle, adding water into the premixed liquid under the condition of continuous stirring, continuing to stir for 30 minutes after the water is added, then adding dibenzoyl peroxide, continuing to stir at the stirring speed of 1500 revolutions per minute to enable the styrene to have polymerization reaction until the temperature of a reaction system in the high-pressure reaction kettle begins to drop, and obtaining reaction liquid containing a microbead blank after the reaction is finished, wherein the mass ratio of the zirconium oxide powder to the styrene is 70:100, the mass ratio of the zirconium oxide powder to a ball-milling medium is 1:4, the mass ratio of the polyvinyl alcohol to the zirconium oxide powder is 1.5:100, the median particle size of the zirconium oxide powder is 0.3-0.5 mu m, and the mass ratio of the dibenzoyl peroxide to the styrene is 0.1: 100; the mass ratio of styrene to water was 20: 100.
(2) Same as in step (3) of example 1.
(3) Same as in step (4) of example 1.
(4) Same as in step (5) of example 1.
The diameter of the obtained zirconia ceramic micro beads was measured to be 0.3mm, and the proportion of the zirconia ceramic micro beads having regular spherical shape and no breakage in the present example was obtained by statistics and is shown in table 1.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres of this example were measured by the same method as in example 1 and are shown in table 1.
Comparative example 1
The zirconia ceramic micro beads of comparative example 1 were prepared as follows:
(1) and (3) putting the zirconia powder into a rotating disc, spraying a PVA aqueous solution with the mass percentage of 15%, and rolling and molding the zirconia powder along with the rotation of the rotating disc to obtain a microbead blank. Wherein the median particle size of the zirconia powder is 0.3-0.5 μm.
(2) And (3) putting the microbead blank into a sagger, then putting the sagger into a vacuum degumming furnace, heating the sagger from room temperature to 450 ℃ at the heating rate of 15 ℃/min under the vacuum condition, preserving the heat for 1 hour, and then cooling the sagger along with the furnace.
(3) Putting the sagger filled with the bead blank subjected to gel removal in the step (2) into a muffle furnace, heating the sagger from room temperature to 1500 ℃ at the heating rate of 10 ℃/minute, carrying out heat preservation sintering for 2 hours, and then cooling along with the furnace to obtain the zirconia ceramic beads of the embodiment, wherein the diameter of the zirconia ceramic beads is 0.5 mm; the proportion of the zirconia ceramic microspheres which are regularly spherical in shape and have no breakage is shown in table 1 by statistics.
The density, porosity, hardness and equivalent wear of the zirconia ceramic microspheres obtained in comparative example 1 were measured by the same method as in example 1 and are shown in table 1, and the ratio of the zirconia ceramic microspheres obtained in comparative example 1, which are regular spheres and have no breakage, was statistically shown in table 1.
Table 1 shows the density, porosity, hardness and equivalent wear of the zirconia ceramic beads of examples 1 to 15 and comparative example 1, and the proportion of the zirconia ceramic beads having a regular spherical shape and no breakage.
TABLE 1
As can be seen from table 1, the zirconia ceramic beads of examples 1 to 7 and examples 11 to 14 all had a density of 98%, a porosity of at most 2%, a hardness of at least 1300MPa, and an equivalent wear of at most 0.0006%, and the proportion of the zirconia ceramic beads having a regular spherical shape and no breakage was at least 90%, whereas the zirconia ceramic of comparative example 1 had a density of 98% and a porosity of 2%, but had a hardness of only 1200MPa, an equivalent wear of at most 0.001%, a proportion of the zirconia ceramic beads having a regular spherical shape and no breakage of only 80%, and an equivalent wear was high, and the proportions of the zirconia ceramic beads having a regular spherical shape and no breakage were far inferior to those of examples 1 to 7, examples 13, and examples 14.
Although example 8 is different from example 1 only in the mass ratio of zirconia powder to styrene, the zirconia ceramic beads of example 1 have a diameter of 0.3mm, a compactness of 99%, a porosity of 1%, a hardness of 1350MPa, an equivalent wear of at most 0.0001%, and a proportion of zirconia ceramic beads that are regular spheres and have no breakage of 95%, whereas the zirconia ceramic beads of example 8 have a diameter of 0.2mm, and the zirconia ceramic beads that are regular spheres and have no breakage of both hardness and shape are lower than those of example 1 and have an equivalent wear higher than that of example 1; in example 9, which differs from example 1 only in the ratio of zirconia powder to styrene, the density, porosity and hardness were comparable to those of example 1, but the equivalent wear was much higher than that of example 1, and the ratio of regular spheres to no breakage was only 50%.
The difference from example 1 is only that the diameter of the zirconia ceramic beads of example 10 is only 0.05mm, and the density, hardness and proportion of the zirconia ceramic beads which are regular spheres and have no breakage are far inferior to example 1, and the porosity and equivalent wear are also far higher than example 1; and the difference from example 1 is only in example 15 in which the step of placing zirconia powder, styrene and polyvinyl alcohol in an autoclave with a stirring paddle was not preceded by a step of ball-milling zirconia powder, styrene and polyvinyl alcohol, and although the diameter of zirconia ceramic beads was comparable to example 1, the proportion of zirconia ceramic beads having a density, hardness and shape of regular spheres and no breakage was far inferior to example 1, and the porosity and equivalent wear were also far superior to example 1, which indicates that the proportion of zirconia powder to styrene, the proportion of styrene to water, the stirring rate and the mixing order at the time of polymerization had different degrees of influence on the particle size, density, porosity, hardness, shape and wear resistance of zirconia ceramic beads.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The preparation method of the zirconia ceramic microspheres is characterized by comprising the following steps:
mixing zirconium oxide powder, styrene and water to obtain a mixture, wherein the mass ratio of the zirconium oxide powder to the styrene is 50: 100-90: 100, and the mass ratio of the styrene to the water is 15: 100-25: 100;
carrying out polymerization reaction on the mixture and an initiator under the condition of continuous stirring to obtain reaction liquid containing a microbead blank;
separating the solid from the liquid of the reaction liquid containing the microbead blank and then drying to obtain the microbead blank; and
sequentially carrying out binder removal and sintering on the micro-bead blank to obtain zirconia ceramic micro-beads;
the method comprises the following steps of mixing zirconium oxide powder, styrene and water: ball-milling and mixing the zirconia powder, the styrene and a dispersing agent to obtain a premix; then mixing the water with the premix under continuous stirring;
in the step of carrying out polymerization reaction on the mixture and the initiator under the condition of continuous stirring, the stirring speed is 1000-2000 r/min.
2. The method for preparing zirconia ceramic microbeads according to claim 1, wherein said step of mixing said water with said premix under continuous stirring and said step of polymerizing said mixture and said initiator under continuous stirring are both performed in a high-pressure reaction tank with a stirring paddle, said water and said premix are continuously stirred by said stirring paddle, and said mixture and said initiator are continuously stirred by said stirring paddle.
3. The preparation method of zirconia ceramic microbeads according to claim 1, wherein the time for ball milling and mixing is 8-24 hours, and the mass ratio of zirconia powder to ball milling medium is 1: 3-1: 5.
4. The preparation method of the zirconia ceramic microspheres according to claim 1, wherein the step of polymerizing the mixture and the initiator under the condition of continuous stirring is specifically as follows: adding the initiator into the mixture under the condition of continuous stirring, and then continuously stirring until the temperature of the reaction system begins to decrease.
5. The method for preparing zirconia ceramic microbeads according to claim 1, wherein said drying step is: drying for 1-10 hours at 40-100 ℃.
6. The preparation method of zirconia ceramic microbeads according to claim 1, characterized in that the step of binder removal specifically comprises: heating from room temperature to 450-750 ℃ at the heating rate of 5-30 ℃/min, and keeping the temperature for 1-2 hours.
7. The method for preparing zirconia ceramic microbeads according to claim 1, wherein said sintering step is: heating from room temperature to 1350-1500 ℃ at the heating rate of 5-10 ℃/min, and sintering for 1-5 hours.
8. The zirconia ceramic microspheres prepared by the method for preparing zirconia ceramic microspheres of any one of claims 1 to 7.
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