CN115028447B - Phase separation-based submicron zirconia ceramic microsphere and preparation method and application thereof - Google Patents
Phase separation-based submicron zirconia ceramic microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a phase separation-based submicron zirconia ceramic microsphere and a preparation method and application thereof. The invention prepares the submicron zirconia ceramic microspheres based on the phase separation method, the phase separation process in the liquid drops is automatically carried out, the whole process flow is simpler, the labor cost is low, and the repeatability is high. The invention is suitable for the field of ceramic materials.
Description
Technical Field
The invention belongs to the field of ceramic materials, and particularly relates to a phase separation-based submicron zirconia ceramic microsphere and a preparation method and application thereof.
Background
The submicron ceramic microsphere is widely applied in the fields of composite materials, high-sensitivity sensors, toughening materials and the like. The existing preparation method of submicron microspheres comprises a stirring emulsification method (Xia Yanmin, xu Hui, su Zhiqing and Song Xiaofang. Polyacrylamide microsphere emulsion and a preparation method thereof [ P ]. Beijing market: CN108314758B, 2020-08-07.), a template method (Chengyeifei, she, zhao Kai, cui Xuefeng, zhang Litong. A submicron carbide ceramic hollow microsphere and a preparation method [ P ]. Shanxi, CN113045318A, 2021-06-29.), a hydrothermal method (Su Gaoshen, yan Xuemin. A monodisperse submicron silica microsphere and a preparation method [ P ]. North, CN106745009A, 2017-05-31.), a phase inversion method (Wu Bozhen, wang Fancheng. A submicron nylon 6/graphene functional microsphere [ P ]. Zhejiang, CN 6595 zxft 95A, 2020-6505-15-98. ], a multi-step method (6828-3498) of submicron nylon 6/graphene functional microsphere and a submicron oxide microsphere with controllable height [ CN 653476. 3476. Z27. Cndot, etc. However, the preparation methods have the defects of complex process, difficult control of the preparation process, high requirement on raw materials and the like.
Disclosure of Invention
The invention solves the technical problem of providing submicron zirconia ceramic microspheres based on phase separation and a preparation method and application thereof. The method has the advantages of cheap raw materials, complete phase separation, no need of fine regulation of the separation stage, and simple process flow.
In order to achieve the above object, the first aspect of the present invention provides the following solutions:
a preparation method of submicron zirconia ceramic microspheres based on phase separation is provided, wherein the submicron zirconia ceramic microspheres are obtained by phase separation, gelation reaction, ultrasonic dispersion, cleaning, drying and high-temperature sintering of zirconia precursor solution;
wherein the zirconia precursor solution is a mixed solution of zirconium oxychloride, polyoxyethylene, formamide, water and ethanol; and after the phase separation of the mixed solution, forming micron-sized gel microsphere pellets formed by aggregating a large number of micron-sized gel microspheres, and after ultrasonic dispersion of the micron-sized gel microsphere pellets, carrying out cleaning, drying and high-temperature sintering on the obtained micron-sized gel microspheres to obtain 500-1000nm submicron zirconia ceramic microspheres through volume shrinkage.
As an embodiment of the present invention, the zirconium oxychloride content of the zirconium oxide precursor solution is 30.7wt.% to 31.2wt.%; formamide content of 7.2-7.3 wt.%; polyethylene oxide content 7.3wt.% to 8.7wt.%; the content of absolute ethyl alcohol is 37.5wt.% to 38.1wt.%, and the content of deionized water is 15.9wt.% to 16.1wt.%.
As an embodiment of the present invention, the preparation steps of the micron-sized gel microsphere pellet are as follows: emulsifying a zirconium oxide precursor solution to obtain zirconium oxide precursor solution droplets with the diameter of 10-100 microns, and then carrying out phase separation and gelation in a constant temperature box at 60 ℃ to obtain the micron-sized gel microsphere pellets;
the diameter of the micron-sized gel microsphere pellets is 10-100 microns.
As an embodiment of the present invention, in the emulsifying step, the zirconia precursor solution is used as a dispersed phase, and an emulsion containing zirconia precursor solution droplets with a diameter of 10 to 100 micrometers in a continuous phase is obtained through an emulsifying apparatus.
As an embodiment of the present invention, the continuous phase solution is a simethicone solution with an oil-soluble surfactant content of 2-5 vol.%.
In a second aspect, the present invention provides submicron zirconia ceramic microspheres prepared by the method of the first aspect of the invention.
The third aspect of the present invention provides the submicron zirconia ceramic microspheres prepared by the method of the first aspect of the present invention, or the application of the submicron zirconia ceramic microspheres of the second aspect of the present invention in the fields of composite materials, high sensitivity sensors or toughened materials.
The technical scheme provided by the invention at least brings the following beneficial effects:
(1) The invention prepares the submicron zirconia ceramic microspheres based on the phase separation method, the phase separation process in the liquid drops is automatically carried out, the whole process flow is simpler, the labor cost is low, and the repeatability is high.
(2) The liquid drop phase separation process involved in the invention is complete separation, so that fine regulation and control on the phase separation intermediate stage are not needed. The method overcomes the defect of high requirement on the control of the preparation process in the existing preparation method of the submicron ceramic microspheres.
(3) The invention uses the phase separation method originally used for preparing the porous ceramic to prepare the submicron zirconia ceramic microspheres, obtains unexpected technical effects and promotes the further development of the preparation technology of the submicron ceramic microspheres.
Drawings
FIG. 1 is an optical microscope photograph showing the progress of phase separation of droplets in example 1.
Fig. 2 is a scanning electron microscope image of the micron-sized gel microsphere pellet prepared in example 1.
Fig. 3 is a scanning electron microscope image of the micron-sized gel spheres obtained by performing ultrasonic dispersion on the micron-sized gel microsphere pellets prepared in example 1.
FIG. 4 is a scanning electron microscope image of submicron zirconia ceramic microspheres prepared in example 1.
FIG. 5 is a scanning electron microscope photograph of the zirconia ceramic microspheres prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is intended to include the plural unless the context clearly indicates otherwise. In addition, the reagents or instruments used are not indicated by manufacturers, and are conventional products commercially available.
The invention provides a preparation method of submicron zirconia ceramic microspheres. A submicron zirconia ceramic microsphere, in the form of a sphere or a sphere-like shape, prepared according to an embodiment of the present invention is described below with reference to fig. 3. The particle size distribution of the submicron zirconia ceramic microspheres is 500-1000 nm.
Example 1
A process for preparing submicron zirconium oxide ceramic microspheres includes such steps as proportionally mixing the dispersed phase solution with the continuous phase solution, low-speed stirring for emulsifying to obtain the emulsified liquid drops containing 10-100 microns of dispersed phase solution. And (3) putting the emulsion in a constant temperature box at 60 ℃, and allowing the emulsion droplets to spontaneously undergo phase separation and gel reaction to obtain micron-sized gel microsphere pellets, wherein the diameter of the micron-sized gel microsphere pellets is 10-100 microns. And then ultrasonically dispersing, cleaning and drying the micron-sized gel microsphere pellets to obtain micron-sized gel microspheres, and then sintering the micron-sized gel microspheres at high temperature to obtain the submicron-sized zirconia ceramic microspheres. The preparation method comprises the following steps:
1) Preparing a dispersed phase: weighing 1.933g (31.2 wt.%), 0.45g (7.3 wt.%), 1g (16.1 wt.%) of deionized water and 2.367g (38.1 wt.%) of absolute ethyl alcohol, mixing thoroughly, stirring for 2h, adding 0.4ml (7.3 wt.%) of formamide into the solution, and stirring for 5min to obtain a solution;
2) Preparing a continuous phase: weighing 50ml of simethicone solution, adding 1ml of oil-soluble surfactant, and fully mixing the solution by using a magnetic stirrer;
3) Stirring and emulsifying: adding the dispersed phase solution into the continuous phase solution, and emulsifying by low-speed mechanical stirring to form dispersed phase emulsion droplets with the diameter of 10-100 microns in the continuous phase;
4) Aging: transferring the emulsion into a thermostat at 60 ℃ and standing for more than 24 hours to promote the emulsion to undergo phase separation and gel;
5) Ultrasonic treatment: and (4) placing the micron-sized gel microsphere pellets which are completely phase-separated and gelled in an ultrasonic instrument for ultrasonic dispersion to obtain the micron-sized gel microspheres.
6) Cleaning: and transferring the micron-sized gel microspheres into a glass bottle, and repeatedly washing with trichloroethylene, ammonia water, deionized water and propylene glycol monomethyl ether in sequence.
7) And (3) sintering: placing the micron-sized gel microspheres on a polytetrafluoroethylene film for drying, transferring the dried micron-sized gel microspheres into a crucible made of an alumina material, placing the crucible into a high-temperature sintering furnace for sintering, and respectively preserving heat for 1 hour at 200 ℃,380 ℃,500 ℃,750 ℃ and 900 ℃, preserving heat for 2 hours at 1200 ℃, wherein the heating rate before 600 ℃ is 1 ℃/min, and then the heating rate is 5 ℃/min; finally, cooling along with the furnace to obtain the 500-1000nm submicron zirconia ceramic microspheres.
Example 2
The difference from the embodiment 1 is that: the amount of polyethylene oxide added at the time of dispersion preparation was changed to 0.55g. At this time, the zirconium oxychloride content was 30.7wt.%, the polyethylene oxide content was 8.7wt.%, the deionized water content was 15.9wt.%, the anhydrous ethanol content was 37.5wt.%, and the formamide content was 7.2wt.%.
As can be seen from fig. 1, the emulsified zirconium oxide precursor solution droplets with a diameter of 10-100 microns undergo a phase separation process with time during the gelation process, and gel after the phase separation is completely performed; the micron-sized gel microsphere pellet obtained in the process is shown in fig. 2, and it can be seen from the figure that the micron-sized gel microsphere pellet is formed by gathering a large number of micron-sized gel microspheres; as shown in figure 3, the micron-sized gel microspheres obtained by dispersing the micron-sized gel microsphere pellets through an ultrasonic dispersion step have a volume shrinkage phenomenon in a sintering process, and the micron-sized gel microspheres have a sintering diameter of 500-1000 nm. After sintering, the submicron zirconia ceramic microspheres are mostly spherical or spheroidal. In example 1, the addition amount of polyoxyethylene is 0.45g (7.3 wt.%), the addition amount of zirconium oxychloride is 1.933g (31.2 wt.%), the content of deionized water is 1g (16.1 wt.%), the content of absolute ethyl alcohol is 2.367g (38.1 wt.%), and the content of formamide is 0.4ml (7.3 wt.%), the diameter of the obtained microspheres is smaller, and when the content of polyoxyethylene is 0.55g, the diameter of the microspheres is close to 1um, so that the content of polyoxyethylene in the reagent ratio of the method is 0.45g-0.55g, namely the content of zirconium oxychloride is 30.7wt.% to 31.2wt.%; formamide content of 7.2wt.% to 7.3wt.%; polyethylene oxide content from 7.3wt.% to 8.7wt.%; the content of anhydrous ethanol is 37.5-38.1 wt.%, and the content of deionized water is 15.9-16.1 wt.%. The method can be used for preparing the submicron zirconia ceramic microspheres more conveniently than the traditional method, has better dispersion degree and sphericity, and provides beneficial improvement for the application of the submicron zirconia ceramic microspheres in the fields of composite materials, high-sensitivity sensors, toughening materials and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (3)
1. A preparation method of submicron zirconia ceramic microspheres based on phase separation is characterized in that the submicron zirconia ceramic microspheres are obtained by phase separation, gelation reaction, ultrasonic dispersion, cleaning, drying and high-temperature sintering of zirconia precursor solution;
wherein the zirconia precursor solution is a mixed solution of zirconium oxychloride, polyoxyethylene, formamide, water and ethanol; after the phase separation is finished, the mixed solution forms micron-sized gel microsphere pellets formed by gathering a large number of micron-sized gel microspheres, and the micron-sized gel microsphere pellets obtained after ultrasonic dispersion are subjected to cleaning, drying and high-temperature sintering, and then are subjected to volume shrinkage to obtain 500-1000nm submicron zirconia ceramic microspheres;
the zirconium oxychloride content of the zirconium oxide precursor solution is 30.7-31.2 wt.%; formamide content of 7.2-7.3 wt.%; polyethylene oxide content from 7.3wt.% to 8.7wt.%; the content of anhydrous ethanol is 37.5-38.1 wt.%, and the content of deionized water is 15.9-16.1 wt.%;
the preparation steps of the micron-sized gel microsphere pellet are as follows: emulsifying a zirconium oxide precursor solution to obtain zirconium oxide precursor solution droplets with the diameter of 10-100 microns, and then carrying out phase separation and gelation in a constant temperature box at 60 ℃ to obtain the micron-sized gel microsphere pellets; the diameter of the micron-sized gel microsphere pellets is 10-100 microns;
in the emulsification step, the zirconium oxide precursor solution is used as a dispersed phase solution, and an emulsion containing 10-100 micron diameter zirconium oxide precursor solution droplets in a continuous phase solution is obtained through emulsification equipment;
the continuous phase solution is a simethicone solution with the oil-soluble surfactant content of 2-5 vol.%.
2. Submicron zirconia ceramic microspheres produced by the method of claim 1.
3. The submicron zirconia ceramic microsphere prepared by the method of claim 1 or the submicron zirconia ceramic microsphere of claim 2, which is applied in the fields of composite materials, high-sensitivity sensors or toughening materials.
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