CN108178656B - High-porosity porous ceramic microsphere and preparation method thereof - Google Patents
High-porosity porous ceramic microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-porosity porous ceramic microsphere and a preparation method thereof, belonging to the technical field of materials. The porous ceramic microspheres are prepared by mixing ceramic powder, a pore-forming agent and oleic acid in proportion, then ball-milling, then mixing with paraffin in proportion, heating and stirring uniformly at 80-120 ℃ to prepare wax slurry, then continuing to heat the wax slurry to 120-155 ℃, dropwise adding the wax slurry into a low-temperature liquid medium by using a syringe needle to solidify into microspheres, carrying out high-temperature dewaxing treatment on the solidified microspheres for 30-120 min by adopting a buried burning method, and finally calcining the biscuited ceramic microspheres at high temperature. The method has the advantages of simple process, low cost and good reproducibility, and the prepared inorganic porous ceramic microspheres have high porosity, can avoid the deterioration of the moisture-sensitive powder during the formation of the microspheres, and are particularly suitable for preparing the water-sensitive inorganic ceramic microspheres.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a porous ceramic material, and particularly relates to a high-porosity porous ceramic microsphere and a preparation method thereof.
Background
In recent years, the millimeter-scale ceramic microspheres have wide application in the fields of nuclear fuel elements, petroleum exploitation, chemical catalysis, separation and purification and the like. Compared with the traditional cylindrical pellet element, the ceramic microsphere fuel element serving as a fourth-generation nuclear fuel element can be densified under the action of irradiation and temperature, so that the problem of swelling and deformation of the cylindrical pellet due to irradiation can be effectively solved; in the field of oil exploitation, the ceramic microspheres can be used as a fracturing propping agent in oil-gas well fracturing operation, enter fractures along with fracturing fluid, prop open oil layer fractures and enlarge oil flow channels, so that the oil exploitation efficiency is effectively improved; the porous ceramic microspheres with certain porosity can also be used as a catalyst carrier for chemical catalysis. Compared with porous carriers made of other materials, the porous ceramic microsphere carrier has the remarkable advantages of good acid and alkali corrosion resistance, stable chemical performance, convenience in recovery, recyclability and the like; in addition, the ceramic microspheres can be used as reinforcing fillers in plastic, rubber and nylon products, so that the filling is more uniform.
At present, there are many methods for preparing ceramic microspheres. The principle of balling is mainly divided into three categories. The first type is a method for forming balls by mechanical force, such as extrusion, friction, collision, and the like, and mainly comprises an extrusion forming-ball rolling method (such as pellet forming by a pellet mill), a ball rolling method (such as ball forming by a sugar coating machine), a powder scattering and shot blasting method, and the like. However, although such a method of balling based on mechanical force has a simple process and high production efficiency, the roundness and size uniformity of the balling are poor, and it is difficult to obtain microspheres having a size of less than 500 μm. More importantly, as the size of the microspheres decreases, their shape is difficult to control;
the second method is based on the principle of surface tension to perform balling, such as freeze solidification, sol-gel, thermal curing, etc. The invention patent with application number CN2016101924487 discloses a preparation method of inorganic microspheres and the inorganic microspheres prepared thereby and application thereof, wherein gelatin is used as a microsphere template, the temperature and the diameter of the spheres are controlled, the inorganic/gelatin composite microspheres are prepared in a freezing solidification mode at-6-4 ℃, and finally the gelatin is removed by calcination to obtain the inorganic microspheres; the invention patent with the application number of CN2012102314080 discloses a novel preparation method of ceramic microspheres, which is characterized in that reactant raw materials, a dispersing agent and water are mechanically stirred or ball-milled to prepare uniform suspension slurry with good dispersibility. And then the slurry is dripped into hydrophobic powder with circular grooves carved in advance through a dispersing device, and the hydrophobic powder is contracted into microspheres under the action of surface tension. Finally, drying and sintering to obtain ceramic microspheres; the invention patent CN200610113783X discloses a method and device for preparing ceramic microspheres by gel casting, which comprises vibrating a stable slurry with a certain solid content into droplets, dispersing the droplets into an oily medium with a certain temperature, allowing the droplets to form spheres under the action of interfacial tension, polymerizing polymer monomers in the droplets to cause gelation reaction, and curing the spheres. And then the ceramic microspheres with high yield and meeting the design requirements are finally obtained through the processes of washing, drying, roasting, sintering and the like. It should be noted that such methods are more complicated and, due to the lower solids content, the cracking and roundness of the spheres are affected due to the greater shrinkage on drying and firing. More importantly, the raw materials such as the organic monomer, the cross-linking agent and the like have certain toxicity or are expensive, so the popularization is poor in the aspects of cost and environmental friendliness.
The third method is to prepare ceramic microspheres based on a microsphere template. The invention patent with the application number of CN2013103155211 discloses a hollow ceramic microsphere and a preparation method thereof, wherein polystyrene microspheres are sulfonated and dispersed in a mixed solution of ethanol and butyl phthalate, then the polystyrene microspheres coated with a ceramic precursor are obtained through hydrothermal treatment, and finally TiO solid microspheres are obtained through high-temperature calcination2A hollow ceramic microsphere with a core-shell structure coated with SiC. The main problems of this method are that not only is the cost of the organic template expensive and is disadvantageous to the cost control, but also it is difficult to prepare the millimeter-sized ceramic microspheres with large size by this method.
In summary, most of the existing preparation methods can produce ceramic microspheres meeting different requirements, but it is difficult to meet the requirements of performance, efficiency, economy and environmental protection at the same time. Therefore, there is a need to find a new process that is efficient, cost effective and environmentally friendly.
Disclosure of Invention
The invention aims to solve the problems pointed out in the background art and the defects in the prior art and aims to provide a high-porosity porous ceramic microsphere and a preparation method thereof.
In order to achieve the above object, the inventors of the present invention have developed a porous ceramic microsphere with high porosity through a large number of experimental studies, wherein the porous ceramic microsphere contains multi-level pores of micropores, mesopores and macropores, the particle size of the porous ceramic microsphere is 200 to 1000 μm, and the porosity is 65 to 90%.
Another object of the present invention is to provide a method for preparing the above porous ceramic microspheres with high porosity, the method comprising the steps of:
(1) mixing ceramic powder, a pore-forming agent and oleic acid in proportion, and performing ball milling to obtain a uniform mixture, wherein the weight ratio of the total weight of the ceramic powder and the pore-forming agent to the oleic acid is 100 (0-1);
(2) mixing the mixture prepared in the step (1) with paraffin according to a proportion, and then uniformly stirring at the temperature of 80-120 ℃ to prepare wax slurry, wherein the weight ratio of the mixture to the paraffin is 100: (10-100);
(3) continuously heating the wax slurry prepared in the step (2) to 120-155 ℃, and then dropwise dripping the wax slurry into a low-temperature liquid medium by using a syringe needle to solidify into balls to prepare solidified microspheres;
(4) carrying out high-temperature dewaxing treatment on the solidified microspheres prepared in the step (3) by adopting a burial method to obtain bisque-fired ceramic microspheres;
(5) and (4) calcining the bisque-fired ceramic microspheres prepared in the step (4) at a high temperature to prepare the porous ceramic microspheres.
Further, the temperature of the low-temperature liquid medium in the step (3) in the technical scheme is 25-60 ℃.
Furthermore, in the step (4) of the technical scheme, the temperature of the burning dewaxing is 900-1300 ℃, and the dewaxing treatment time is 30-120 min.
Further, in the step (5) of the technical scheme, the high-temperature calcination temperature is 1100-1600 ℃, and the calcination time is 60-180 min.
Further, the weight ratio of the ceramic powder and the pore-forming agent in the step (1) in the technical scheme is (75-100): (25-0).
Further, the ceramic powder in step (1) of the technical scheme is one or more of metal oxide, metal carbide, metal nitride and alpha-tricalcium phosphate.
Further, in the above technical scheme, the pore-forming agent in step (1) may be any one or more of carbon powder, graphite powder, acetylene black, and starch.
Further, the fineness of the mixture in the step (1) in the technical scheme is smaller than 100 meshes.
Further, the liquid medium in step (3) in the above technical solution may be any one of water, silicone oil, olive oil, and inorganic salt solution.
Further, in the above technical solution, the component of the buried powder adopted in the burying method in step (4) needs to be the same as the raw material component of the ceramic microsphere, and may be any one of metal oxide, metal carbide, and metal nitride.
The invention is based on the principle that flowable wax slurries are agglomerated into spheres in a second phase liquid medium under the action of surface tension and are solidified because the temperature of the liquid medium is below the melting point of the paraffin wax. In addition, the porosity of the final product porous ceramic microspheres can be adjusted by adjusting the dosage and the ratio of the ceramic powder to the pore-forming agent.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) the preparation method adopts a dry ball milling process, and the ball dropping process can be carried out in an oily medium, so the preparation method can avoid the deterioration of the moisture-sensitive powder during the formation of the microspheres, and is particularly suitable for preparing the water-sensitive inorganic microspheres (such as a-tricalcium phosphate, magnesium oxide and the like).
(2) The preparation method has simple process and low cost, does not adopt any toxic organic solvent, is an economic and environment-friendly green preparation method, and is beneficial to industrial production;
(3) the preparation method has good reproducibility, and can obtain inorganic microspheres with various particle sizes ranging from micron to millimeter levels by adjusting the size of the needle head according to needs, the particle size range of the porous ceramic microspheres prepared by the method is 200-1000 mu m, and the porosity can reach 90%.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the high porosity porous ceramic microspheres of the present invention;
fig. 2 (a) and (b) are Scanning Electron Microscope (SEM) images of the surface and cross-section of the porous ceramic microsphere prepared in example 1 of the present invention, respectively.
Detailed Description
The technical solution of the present invention is further explained in detail by the following specific examples and the accompanying drawings. The following embodiments are merely exemplary of the present invention, which is not intended to limit the present invention in any way, and those skilled in the art may modify the present invention in many ways by applying the teachings set forth above to equivalent embodiments with equivalent modifications. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Example 1
The preparation method of the high-porosity porous alumina ceramic microspheres of the embodiment comprises the following steps:
(1) according to the weight ratio of 90: 10: 0.5 weighing alumina (Al) respectively2O3) Uniformly mixing ceramic powder, carbon powder and oleic acid, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 15, and then uniformly stirring at the temperature of 120 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 130 ℃, and then dropwise adding the wax slurry into water of 40 ℃ by using a No. 6 syringe needle to solidify into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into alumina powder, placing the solidified microspheres in a muffle furnace at normal temperature, heating to 900 ℃ at a heating rate of 1 ℃/min, removing wax, keeping the temperature for 30min, and cooling to room temperature to obtain bisque-fired alumina ceramic microspheres;
(5) and (3) putting the bisque-fired alumina ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1100 ℃ at a heating rate of 5 ℃/min, then preserving heat for 60min, and cooling to room temperature to prepare the alumina porous ceramic microspheres.
Fig. 2 (a) and (b) are Scanning Electron Microscope (SEM) images of the surface and cross section of the porous ceramic microsphere prepared in this example, and it can be seen from the images that the alumina porous ceramic microsphere prepared in this example contains multi-level pores of micropores, mesopores, and macropores, the particle size of the prepared alumina porous ceramic microsphere is about 400 μm, and the porosity is as high as 83%.
Example 2
The preparation method of the high-porosity porous zirconia ceramic microspheres of the embodiment comprises the following steps:
(1) according to the weight ratio of 95: 5 weighing zirconia (ZrO)2) Uniformly mixing ceramic powder and acetylene black, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 10, and then uniformly stirring at the temperature of 120 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 155 ℃, and then dropwise adding the wax slurry into water at 25 ℃ by using a No. 6 syringe needle to solidify into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into zirconia powder, placing the zirconium powder in a muffle furnace at normal temperature, heating to 1150 ℃ at a heating rate of 1 ℃/min, removing wax, keeping the temperature for 30min, and cooling to room temperature to obtain bisque-fired zirconia ceramic microspheres;
(5) and (3) putting the bisque-fired zirconia ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1450 ℃ at the heating rate of 5 ℃/min, then preserving heat for 60min, and cooling to room temperature to prepare the zirconia porous ceramic microspheres.
The zirconia porous ceramic microspheres prepared by the embodiment contain multi-level pores of micropores, mesopores and macropores, the particle size of the prepared zirconia porous ceramic microspheres is about 450 micrometers, and the porosity is 65%.
Example 3
The preparation method of the high-porosity porous magnesia ceramic microspheres of the embodiment comprises the following steps:
(1) according to the weight ratio of 75: 25: 1, respectively weighing magnesium oxide (MgO) ceramic powder, starch and oleic acid, uniformly mixing the magnesium oxide ceramic powder, the starch and the oleic acid, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 40, and then uniformly stirring at the temperature of 95 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 135 ℃, and then dropwise dripping the wax slurry into 35 ℃ silicone oil by using a No. 5 syringe needle to be solidified into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into magnesia powder, placing the magnesia powder in a muffle furnace at normal temperature, heating to 950 ℃ at the heating rate of 1 ℃/min to remove wax, preserving heat for 30min, and cooling to room temperature to obtain the calcined magnesia ceramic microspheres;
(5) and (3) putting the calcined magnesia ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1250 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 120min, and cooling to room temperature to prepare the magnesia porous ceramic microspheres.
The magnesium oxide porous ceramic microspheres prepared by the embodiment contain multi-level pores of micropores, mesopores and macropores, the particle size of the prepared magnesium oxide porous ceramic microspheres is about 320 mu m, and the porosity is as high as 90%.
Example 4
The preparation method of the high-porosity porous α -tricalcium phosphate ceramic microspheres of this example includes the following steps:
(1) according to the weight ratio of 90: 10: 1, respectively weighing alpha-tricalcium phosphate (alpha-TCP) ceramic powder, graphite powder and beeswax, uniformly mixing the alpha-tricalcium phosphate (alpha-TCP) ceramic powder, the graphite powder and the beeswax, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 100, and then uniformly stirring at the temperature of 80 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 120 ℃, and then dropwise dripping the wax slurry into olive oil at 25 ℃ by using a No. 15 syringe needle to solidify into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into alpha-tricalcium phosphate powder, placing the alpha-tricalcium phosphate powder in a muffle furnace at normal temperature, heating to 900 ℃ at a heating rate of 1 ℃/min to remove wax, keeping the temperature for 60min, and cooling to room temperature to obtain bisque-fired alpha-tricalcium phosphate ceramic microspheres;
(5) and (3) putting the bisque-fired alpha-tricalcium phosphate ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1250 ℃ at the heating rate of 5 ℃/min, then preserving heat for 60min, and cooling to room temperature to prepare the alpha-tricalcium phosphate porous ceramic microspheres.
The α -tricalcium phosphate porous ceramic microspheres prepared in this example contain micropores, mesopores, and macroporous multi-stage pores, and the particle size of the prepared α -tricalcium phosphate porous ceramic microspheres is about 200 μm, and the porosity is 68%.
Example 5
The preparation method of the porous silicon carbide ceramic microspheres with high porosity of the embodiment comprises the following steps:
(1) according to the weight ratio of 90: 10: 0.2 respectively weighing silicon carbide (SiC) ceramic powder, carbon powder and beeswax, uniformly mixing the silicon carbide (SiC) ceramic powder, the carbon powder and the beeswax, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 25, and then uniformly stirring at the temperature of 90 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 140 ℃, and then dropwise adding the wax slurry into water at 60 ℃ by using a No. 6 syringe needle to solidify into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into silicon carbide powder, placing the silicon carbide powder in a muffle furnace at normal temperature, heating to 1300 ℃ at the heating rate of 1 ℃/min for de-waxing, preserving heat for 120min, and cooling to room temperature to obtain bisque-fired silicon carbide ceramic microspheres;
(5) and (3) putting the bisque-fired silicon carbide ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1600 ℃ at a heating rate of 5 ℃/min, then preserving heat for 180min, and cooling to room temperature to prepare the silicon carbide porous ceramic microspheres.
The silicon carbide porous ceramic microspheres prepared by the embodiment contain multi-level pores of micropores, mesopores and macropores, the particle size of the prepared silicon carbide porous ceramic microspheres is about 350 μm, and the porosity is 74%.
Example 6
The preparation method of the high-porosity porous zirconia ceramic microspheres of the embodiment comprises the following steps:
(1) according to the weight ratio of 100: 0.5 weighing zirconia (ZrO)2) Uniformly mixing ceramic powder and oleic acid, and screening the mixture through a 100-mesh sieve after ball milling to obtain a mixture;
(2) mixing the mixture prepared in the step (1) with paraffin according to a ratio of 100: 12, and then uniformly stirring at the temperature of 120 ℃ to prepare wax slurry;
(3) continuously heating the wax slurry prepared in the step (2) to 155 ℃, and then directly dripping the wax slurry into water with the temperature of 25 ℃ drop by adopting an injector to solidify into balls to prepare solidified microspheres;
(4) embedding the solidified microspheres prepared in the step (3) into zirconia powder, placing the zirconium powder in a muffle furnace at normal temperature, heating to 1150 ℃ at a heating rate of 1 ℃/min, removing wax, keeping the temperature for 30min, and cooling to room temperature to obtain bisque-fired zirconia ceramic microspheres;
(5) and (3) putting the bisque-fired zirconia ceramic microspheres prepared in the step (4) into a muffle furnace at normal temperature, heating to 1450 ℃ at the heating rate of 5 ℃/min, then preserving heat for 60min, and cooling to room temperature to prepare the zirconia porous ceramic microspheres.
The zirconia porous ceramic microspheres prepared by the embodiment contain multi-level pores of micropores, mesopores and macropores, the particle size of the prepared zirconia porous ceramic microspheres is about 1000 microns, and the porosity is 72%.
Claims (7)
1. A high porosity porous ceramic microsphere, characterized in that: the porous ceramic microspheres contain microporous, mesoporous and macroporous multilevel pores, the particle size of the porous ceramic microspheres is 200-1000 mu m, and the porosity is 65-90%;
wherein: the high-porosity porous ceramic microspheres are prepared by the following method, comprising the following steps:
(1) mixing ceramic powder, a pore-forming agent and oleic acid in proportion, and performing ball milling to obtain a uniform mixture, wherein the weight ratio of the total weight of the ceramic powder and the pore-forming agent to the oleic acid is 100 (0-1);
(2) mixing the mixture prepared in the step (1) with paraffin according to a proportion, and then uniformly stirring at the temperature of 80-120 ℃ to prepare wax slurry, wherein the weight ratio of the mixture to the paraffin is 100: (10-100);
(3) continuously heating the wax slurry prepared in the step (2) to 120-155 ℃, and then dropwise dripping the wax slurry into a low-temperature liquid medium by using a syringe needle to solidify into balls to prepare solidified microspheres;
(4) carrying out high-temperature dewaxing treatment on the solidified microspheres prepared in the step (3) by adopting a burial method to obtain bisque-fired ceramic microspheres; the temperature of the burning dewaxing is 900-1300 ℃, and the dewaxing treatment time is 30-120 min;
(5) calcining the bisque-fired ceramic microspheres prepared in the step (4) at high temperature to prepare the porous ceramic microspheres; the high-temperature calcination temperature is 1100-1600 ℃, and the calcination time is 60-180 min.
2. The high porosity porous ceramic microspheres of claim 1, wherein: the temperature of the low-temperature liquid medium in the step (3) is 25-60 ℃.
3. The high porosity porous ceramic microspheres of claim 1, wherein: the weight ratio of the ceramic powder and the pore-forming agent in the step (1) is (75-100): (25-0).
4. The high-porosity porous ceramic microspheres according to any one of claims 1 to 3, wherein: the ceramic powder in the step (1) is one or more of metal oxide, metal carbide, metal nitride and alpha-tricalcium phosphate.
5. The high-porosity porous ceramic microspheres according to any one of claims 1 to 3, wherein: the pore-forming agent in the step (1) can be any one or more of carbon powder, graphite powder, acetylene black and starch.
6. The high-porosity porous ceramic microspheres according to any one of claims 1 to 3, wherein: in the technical scheme, the fineness of the mixture in the step (1) is less than 100 meshes.
7. The high-porosity porous ceramic microspheres according to any one of claims 1 to 3, wherein: the liquid medium in the step (3) is any one of water, silicone oil, olive oil and inorganic salt solution.
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| CN106542643B (en) * | 2015-09-18 | 2020-07-07 | 北京航空航天大学 | Method for treating deep sea spilled oil by using high-efficiency pressure-philic oil-reducing microbial inoculum with porous alumina as carrier |
| CN109529111A (en) * | 2018-12-12 | 2019-03-29 | 上海摩漾生物科技有限公司 | High porosity porous nano hydroxyapatite micro-sphere and preparation method thereof |
| CN111484351A (en) * | 2019-12-31 | 2020-08-04 | 新兴远建（天津）新材料科技有限公司 | Preparation method and application of lightweight porous ceramic hollow microspheres |
| CN114074933B (en) * | 2020-08-18 | 2023-04-18 | 中山职业技术学院 | Preparation method of high-hydration beta-tricalcium phosphate for 3D printing |
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