阅读说明：本技术 整体有序-局部无序多孔陶瓷及其制备方法 (Wholly ordered-partially disordered porous ceramic and preparation method thereof ) 是由 赵国瑞 付超 王恩哥 陈秀娟 战斗 朱凯 于 2020-12-30 设计创作，主要内容包括：本申请涉及多孔材料领域,涉及一种整体有序-局部无序多孔陶瓷及其制备方法。该方法包括以粘接有有机粘接材料的陶瓷粉末为原料,按照预设的路径进行打印构筑,得到包含多个有序孔的多孔材料；然后,将打印得到的多孔材料中的有机粘接材料去除,并在多孔材料中留下无序孔,得到多孔陶瓷材料；将多孔陶瓷材料进行烧结。按照预设的路径进行打印构筑,使得整个多孔陶瓷内部的孔按照预设的有序路径进行排列,从而实现整体有序的效果。然后将多孔材料中的有机粘接材料去除后,原来的有机粘接材料所在的位置成为新的孔。由于有机粘接材料在多孔材料中的位置是无序的,因此能够使得多孔陶瓷中的局部出现无序孔,进而获得整体有序-局部无序的多孔陶瓷。(The application relates to the field of porous materials, in particular to a wholly ordered-partially disordered porous ceramic and a preparation method thereof. The method comprises the steps of taking ceramic powder bonded with an organic bonding material as a raw material, and printing and constructing according to a preset path to obtain a porous material containing a plurality of ordered pores; then, removing the organic bonding material in the printed porous material, and leaving disordered holes in the porous material to obtain a porous ceramic material; sintering the porous ceramic material. Printing and constructing according to a preset path, so that the holes in the whole porous ceramic are arranged according to a preset ordered path, and the effect of integral ordering is realized. And then removing the organic bonding material in the porous material, wherein the position of the original organic bonding material becomes a new hole. Because the position of the organic bonding material in the porous material is disordered, disordered holes can be formed in the porous ceramic locally, and the integrally ordered-locally disordered porous ceramic is obtained.)

1. A method for preparing a wholly ordered-partially disordered porous ceramic, comprising:

printing and constructing ceramic powder bonded with an organic bonding material according to a preset path to obtain a porous material containing a plurality of ordered pores;

then, removing the organic bonding material in the printed porous material, and leaving disordered holes in the porous material to obtain a porous ceramic material;

sintering the porous ceramic material.

2. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 1,

the preset path is obtained by adopting three-dimensional modeling software to design the porous material structure;

optionally, the overall shape of the porous material comprises: any one of a cube, a regular dodecahedron, a regular tetrahedron or a cylinder;

optionally, the shape of the ordered pore is selected from square pores.

3. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 2,

the pore size of the ordered pores is within the range of 10 mu m-10 mm.

4. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 1,

the printing construction is that under the condition of heating, the organic bonding material in the raw materials is melted to obtain ceramic slurry, and the ceramic slurry is used for printing.

5. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 4,

the heating temperature is 120-300 ℃.

6. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 1,

the raw materials are prepared according to the following steps:

uniformly mixing the ceramic powder and the organic bonding material under the heating condition to bond the organic bonding material and the ceramic powder together, and then crushing;

optionally, the particle size reduction of the feedstock is in the range of 0.1-5 mm;

alternatively, the heating temperature is 120-.

7. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 6,

the particle size range of the ceramic powder is 50 nm-10 mu m.

8. The method for producing a wholly ordered-partially disordered porous ceramic according to claim 6,

according to the volume ratio, the ceramic powder accounts for 35-70% of the raw materials, and the organic bonding material accounts for 30-65%;

optionally, the ceramic powder comprises: at least one of zirconia, alumina, silicon carbide, silicon nitride, zirconium boride or titanium aluminum carbon;

optionally, the organic bonding material includes, by volume: 1-3% of surfactant, 34-65% of macromolecular large framework material, 3-8% of plasticizer and 25-55% of lubricant;

optionally, the surfactant is selected from stearic acid;

optionally, the macromolecular large framework material comprises one or two of polyethylene and polypropylene; optionally, when the macromolecular large framework material simultaneously comprises the polyethylene and the polypropylene, the volume ratio of the polyethylene to the organic bonding material is 15-35%, and the volume ratio of the polypropylene to the organic bonding material is 15-30%;

optionally, the plasticizer is selected from polyethylene glycol;

optionally, the lubricant is selected from paraffin.

9. The method for producing a wholly ordered-partially disordered porous ceramic according to any one of claims 1 to 8,

the step of removing the organic bonding material in the printed porous material comprises:

and carrying out microwave heating treatment on the porous material.

10. A bulk ordered-partially disordered porous ceramic, characterized in that the interior of the porous ceramic comprises a plurality of ordered pores and a plurality of disordered pores;

optionally, the ordered pore size ranges from 10 μm to 10 mm; the disordered hole size range is 50 nm-300 nm;

optionally, the porosity of the porous ceramic is in the range of 20% to 90%.

Technical Field

The application relates to the field of porous materials, in particular to a wholly ordered-partially disordered porous ceramic and a preparation method thereof.

Background

Various methods for preparing porous ceramics are reported in the prior publication, including a foam template method, a mold forming method, a pore-forming agent method and a photocuring 3D printing method.

The foam template method mainly comprises the steps of coating ceramic slurry containing powder on an organic foam template with a porous structure, drying and then burning off the organic foam template to obtain porous ceramic;

a mould forming method, which mainly comprises the steps of granulating ceramic powder, a sintering aid and the like, filling a granulated material into a mould, obtaining a formed blank by adopting a pressure forming process, putting the formed blank into an atmosphere furnace, and sintering in the atmosphere to obtain porous ceramic;

the pore-forming agent method mainly comprises the steps of mixing ceramic powder with a pore-forming agent, and removing the pore-forming agent by a sintering or dissolving method to obtain the porous ceramic.

The photocuring 3D printing method mainly comprises the steps of taking ceramic powder and photosensitive resin as main starting raw materials, and manufacturing porous ceramic through laser selective solidification.

However, the porous ceramics prepared by the foam template method, the mold forming method and the pore-forming agent method are all disordered structures, and the pore structures are all randomly distributed and cannot be designed. The porous ceramic prepared by the photocuring 3D printing method cannot realize the porous ceramic with an overall ordered and local disordered structure.

Disclosure of Invention

An object of the embodiments of the present application is to provide an integrally ordered-partially disordered porous ceramic and a method for preparing the same.

In a first aspect, the present application provides a method for preparing a globally ordered-locally disordered porous ceramic, comprising:

printing and constructing ceramic powder bonded with an organic bonding material according to a preset path to obtain a porous material containing a plurality of ordered pores;

then, removing the organic bonding material in the printed porous material, and leaving disordered holes in the porous material to obtain a porous ceramic material;

sintering the porous ceramic material.

The method can be used for printing and constructing according to a preset path, and can obtain the porous material containing a plurality of ordered holes, so that the holes in the whole porous ceramic are arranged according to the preset ordered path, and the integral ordered effect is realized. And then removing the organic bonding material in the porous material containing the plurality of ordered pores, wherein the position of the original organic bonding material becomes a new pore. Because the position of the organic bonding material in the porous material is disordered, disordered holes can be formed in the porous ceramic locally, and the integrally ordered-locally disordered porous ceramic is obtained.

In other embodiments of the present application, the preset path is obtained by performing a porous material structure design using three-dimensional modeling software;

optionally, the overall shape of the porous material comprises: any one of a cube, a regular dodecahedron, a regular tetrahedron or a cylinder;

optionally, the shape of the ordered pores is selected to be square.

In other embodiments of the present application, the pore size dimension of the ordered pores is in the range of 10 μm to 10 mm.

In another embodiment of the present application, the printing is performed by heating the organic binder in the raw material to melt the organic binder to obtain a ceramic paste, and printing the ceramic paste.

In other embodiments of the present application, the heating temperature is 120-300 ℃.

In other embodiments of the present application, the above starting materials are prepared by the following steps:

uniformly mixing ceramic powder and an organic bonding material under a heating condition to bond the organic bonding material and the ceramic powder together, and then crushing;

optionally, the particle size reduction of the feedstock is in the range of 0.1-5 mm;

alternatively, the heating temperature is 120-.

In other embodiments of the present application, the ceramic powder has a particle size ranging from 50nm to 10 μm.

In other embodiments of the present application, the raw materials include, by volume, 35% to 70% of ceramic powder and 30% to 65% of an organic binder;

optionally, the ceramic powder comprises: at least one of zirconia, alumina, silicon carbide, silicon nitride, zirconium boride or titanium aluminum carbon;

optionally, the organic bonding material includes, in terms of volume ratio: 1-3% of surfactant, 34-65% of macromolecular large framework material, 3-8% of plasticizer and 25-55% of lubricant;

alternatively, the surfactant is selected from stearic acid;

optionally, the macromolecular large framework material comprises one or two of polyethylene and polypropylene; optionally, when the macromolecular large framework material simultaneously comprises polyethylene and polypropylene, the volume ratio of the polyethylene to the organic bonding material is 15-35%, and the volume ratio of the polypropylene to the organic bonding material is 15-30%;

alternatively, the plasticizer is selected from polyethylene glycol;

optionally, the lubricant is selected from paraffin.

In another embodiment of the present application, the step of removing the organic bonding material from the printed porous material includes:

and (3) subjecting the porous material to microwave heating treatment.

In a second aspect, the present application provides a globally ordered-locally disordered porous ceramic comprising a plurality of ordered pores and a plurality of disordered pores inside;

optionally, the ordered pore size ranges from 10 μm to 10 mm; the disordered pore size range is 50 nm-300 nm;

optionally, the porosity of the porous ceramic is in the range of 20% to 90%.

The porous ceramic has an overall ordered-local disordered structure, and is wide in porosity distribution range and designable range.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

FIG. 1 is a macroscopic picture of a globally ordered-locally disordered porous ceramic provided in example 1 of the present application;

fig. 2 is a scanning electron microscope image of locally disordered pores of the globally ordered-locally disordered porous ceramic provided in example 1 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments.

Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.

The embodiment of the application provides a preparation method of wholly ordered-locally disordered porous ceramic, which comprises the following steps:

and step S1, printing and constructing according to a preset path by using the ceramic powder bonded with the organic bonding material as a raw material to obtain the porous material containing a plurality of ordered pores.

Further, in some embodiments of the present application, the above-mentioned starting materials are prepared by the following steps:

the ceramic powder and the organic bonding material are mixed and stirred to be uniform under the heating condition, so that the organic bonding material and the ceramic powder are bonded together. Then the materials with larger grain diameter which are bonded together are crushed into granular raw materials with the grain diameter within the range of 0.1-5 mm.

Furthermore, the particle size of the raw material is 0.1-5 mm.

Further alternatively, the particle size of the feedstock is in the range of 0.2-4.9 mm.

Further alternatively, the particle size of the feedstock is in the range of 0.5-4.0 mm.

Illustratively, the particle size of the above raw material is 0.8mm, 1.0mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, or 3.5 mm.

Further optionally, the heating temperature for mixing the ceramic powder and the organic bonding material under heating is in a range of 120 to 300 ℃.

Further optionally, the heating temperature for mixing the ceramic powder and the organic bonding material under heating is 130 to 290 ℃.

Further alternatively, the heating temperature for mixing the ceramic powder and the organic binder under heating is 140 to 280 ℃.

Illustratively, the heating temperature for mixing the ceramic powder and the organic binder under heating is 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 220 ℃ or 250 ℃.

Further, the ceramic powder described above includes: at least one of zirconia, alumina, silicon carbide, silicon nitride, zirconium boride or titanium aluminum carbon.

Illustratively, in some embodiments of the present application, the ceramic powder is one of zirconia, alumina, silicon carbide, silicon nitride, zirconium boride, or titanium aluminum carbon.

Illustratively, in some embodiments of the present application, the ceramic powder described above is zirconia and alumina.

Illustratively, in some embodiments of the present application, the ceramic powder is zirconia, alumina, silicon carbide, silicon nitride, zirconium boride, and titanium aluminum carbon.

Further, the particle size of the ceramic powder is in the range of 50nm to 10 μm.

Further alternatively, the ceramic powder has a particle size in the range of 60nm to 9 μm.

Further alternatively, the ceramic powder has a particle size in the range of 70nm to 8 μm.

Illustratively, the particle size of the above-mentioned ceramic powder is 70nm, 100nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm.

Furthermore, according to the volume ratio, the ceramic powder in the raw material is 35-70%; 30 to 65 percent of organic bonding material.

Further optionally, the ceramic powder in the raw materials accounts for 36-69% by volume ratio; 31 to 64 percent of organic bonding material.

Further optionally, the ceramic powder in the raw materials accounts for 36-69% by volume ratio; 32 to 63 percent of organic bonding material.

Illustratively, the ceramic powder content in the raw material is 40% by volume; 60% of organic bonding material. Or, according to the volume ratio, the ceramic powder in the raw materials is 45 percent; 55% of organic bonding material. Or, according to the volume ratio, the ceramic powder in the raw material is 50 percent; 50% of organic bonding material. Or, according to the volume ratio, the ceramic powder in the raw material is 60 percent; 40% of organic bonding material.

Further, the organic bonding material includes, in terms of volume ratio: 1 to 3 percent of surfactant, 34 to 65 percent of macromolecular large framework material, 3 to 8 percent of plasticizer and 25 to 55 percent of lubricant.

Further optionally, the organic bonding material comprises, by volume: 1.1 to 2.9 percent of surfactant, 35 to 64 percent of macromolecular large framework material, 3.1 to 7.9 percent of plasticizer and 26 to 54 percent of lubricant.

Further optionally, the organic bonding material comprises, by volume: 1.2 to 2.8 percent of surfactant, 40 to 55 percent of macromolecular large framework material, 3.2 to 7.8 percent of plasticizer and 28 to 53 percent of lubricant.

Further alternatively, in some embodiments herein, the surfactant is stearic acid.

Further optionally, in some embodiments of the present application, the macromolecular macroskeletal material includes one or both of polyethylene and polypropylene; optionally, when the macromolecular large framework material simultaneously comprises polyethylene and polypropylene, the volume ratio of the polyethylene to the organic bonding material is 15-35%, and the volume ratio of the polypropylene to the organic bonding material is 15-30%.

Further optionally, when the macromolecular large framework material simultaneously comprises polyethylene and polypropylene, the volume ratio of the polyethylene to the organic bonding material is 16-34%, and the volume ratio of the polypropylene to the organic bonding material is 16-31%. The high-molecular large framework material simultaneously comprises polyethylene and polypropylene, and the two materials have larger and smaller molecular weights, so that a synergistic effect can be achieved when the materials exist simultaneously, the bonding effect is improved, and the forming uniformity of the ceramic powder and the organic bonding material is improved.

Further optionally, in some embodiments herein, the plasticizer is selected from polyethylene glycol.

Further optionally, in some embodiments of the present application, the lubricant is selected from paraffin wax.

Further, in some embodiments of the present application, the step of constructing a print according to the preset path includes:

and (4) adopting three-dimensional modeling software to design the porous material structure to obtain a preset path.

Further, when the porous material structure is designed by using three-dimensional modeling software, the overall shape of the entire porous ceramic may be designed to be a regular shape, for example, a cube, a regular dodecahedron, a regular tetrahedron, a cylinder, or the like.

Further, when the porous material structure is designed by adopting three-dimensional modeling software, the shape of the ordered pores in the porous ceramic with the regular shape can be selected to be designed into square pores and the like.

Furthermore, the pore size of the ordered pores is designed to be within the range of 10 μm to 10 mm.

Further optionally, the pore size of the ordered pores is designed to be in the range of 11 μm to 9 mm.

Further optionally, the pore size of the ordered pores is designed to be in the range of 12 μm to 8 mm.

Illustratively, the pore size of the ordered pores is dimensioned to be 50 μm, 100 μm, 500 μm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, or the like.

Further, the step of constructing a print according to the predetermined path includes:

under the condition of heating, the organic bonding material in the raw materials is melted to obtain ceramic slurry, and the ceramic slurry is used for printing.

Further optionally, the heating temperature of the above heating conditions is within the range of 120-300 ℃.

Further optionally, the heating temperature of the above heating conditions is in the range of 150 ℃ and 280 ℃.

Further optionally, the heating temperature of the above heating conditions is within the range of 180-250 ℃.

Illustratively, the heating temperature of the above-mentioned heating conditions is 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃.

In some embodiments of the present application, the printing construction according to the preset path is to introduce the prepared granular raw material into a bin of a device (e.g., a 3D printing device), transport the granular raw material to a sample construction mechanism (e.g., a nozzle of the 3D printing device) through a feeding system of the device, heat the construction mechanism at a temperature of 120-.

And step S2, removing the organic bonding material in the printed porous material to form a plurality of disordered holes on the porous material locally, thereby obtaining the porous ceramic material.

Further, the step of removing the organic bonding material from the printed porous material includes:

and (3) carrying out microwave heating treatment on the porous material to remove the organic bonding material.

By carrying out microwave heating treatment on the porous material, the organic material in the prepared porous material can be removed, and disordered holes are left in the porous material, so that the disordered holes are locally formed in the porous material.

Further, in other alternative embodiments of the present application, other heating methods may be used to remove the organic bonding material.

Further, in some embodiments of the present invention, the microwave treatment time is 10 to 30 minutes.

Further optionally, in some embodiments of the present application, the microwave treatment time is 15 to 25 minutes.

Illustratively, in some embodiments of the present application, the microwave treatment is performed for 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, or 25 minutes.

And step S3, sintering the porous ceramic material.

Sintering according to the sintering temperature required by the ceramic material. The sintering process can adopt the conventional sintering process of the ceramic material corresponding to the field.

The porous ceramic material is sintered to obtain the wholly ordered-partially disordered porous ceramic.

The porosity of the wholly ordered-partially disordered porous ceramic prepared by the method is within the range of 20-90%.

Some embodiments of the present application also provide a globally ordered-locally disordered porous ceramic that can be prepared using the method for preparing the globally ordered-locally disordered porous ceramic provided by the foregoing embodiments.

Further, the porous ceramic contains a plurality of ordered pores and a plurality of disordered pores therein.

Furthermore, the ordered pore size range of the porous ceramic is 10 mu m-10 mm; the disordered pore size range is 50 nm-300 nm.

Further, the porosity of the porous ceramic is in the range of 20% to 90%.

Further optionally, the porosity of the porous ceramic is in the range of 21% to 89%.

Further optionally, the porosity of the porous ceramic is in the range of 22% to 88%.

Illustratively, the porosity of the porous ceramic is 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%.

The features and properties of the present application are described in further detail below with reference to examples:

example 1

The overall ordered-local disordered porous ceramic is prepared according to the following steps:

80g of zirconia with the particle size of 3 mu m, 8g of paraffin, 6g of polyethylene, 3.5g of polypropylene, 2g of polyethylene glycol and 0.5g of stearic acid, heating, mixing and stirring at 160 ℃ until the mixture is uniform, and then crushing to obtain a granular raw material with the particle size of 2 mm. And (3) carrying out structural design on the porous material by adopting three-dimensional modeling software, wherein the aperture of the ordered hole is 2mm, and the shape of the porous material is a cubic structure. Then the prepared zirconia granular raw material is led into a storage bin of printing equipment, then the granular material is conveyed to a sample construction mechanism through a feeding system, then the construction mechanism is heated to 160 ℃, the zirconia granular raw material is fed and melted, the raw material flows out of the construction mechanism, and the porous ceramic structure with ordered pore structure is obtained by printing according to a designed model. And (3) carrying out microwave treatment on the porous ceramic structure for 20 minutes, removing the organic adhesive, and sintering the ceramic structure to obtain the wholly ordered-locally disordered porous ceramic.

The macroscopic picture of the prepared integrally ordered-partially disordered porous ceramic is shown in the attached figure 1 of the specification; the local disordered holes of the wholly ordered-local disordered porous ceramic are observed by adopting a scanning electron microscope, and the result is shown in the attached figure 2 of the specification.

As can be seen from FIG. 1, the porous ceramic is integrally formed into a cubic structure, and has a plurality of ordered square holes therein. As can be seen from fig. 2, a plurality of disordered pores exist in the microstructure of the prepared porous ceramic, thereby illustrating that the prepared porous ceramic has an overall ordered, locally disordered porous structure.

Example 2

The preparation method of the wholly ordered-partially disordered porous ceramic is the same as that of example 1, and the differences are in raw material composition and porous structure design and specifically comprise the following steps:

78.2g of alumina with the particle size of 5 mu m, 9.5g of paraffin, 5.5g of polyethylene, 4.5g of polypropylene, 1.8g of polyethylene glycol and 0.5g of stearic acid are heated, mixed and stirred at 160 ℃ until the mixture is uniform, and then crushed to obtain a granular raw material with the particle size of 1 mm. And (3) carrying out structural design on the porous material by adopting three-dimensional modeling software, wherein the aperture of the ordered pores is 1mm, and the shape of the porous material is a regular dodecahedron structure.

Example 3

The preparation method of the wholly ordered-partially disordered porous ceramic is the same as that of example 1, and the differences are in raw material composition and porous structure design and specifically comprise the following steps:

75.5g of silicon nitride with the particle size of 5 mu m, 10g of paraffin, 7.5g of polyethylene, 4g of polypropylene, 2g of polyethylene glycol and 1g of stearic acid, heating, mixing and stirring at 160 ℃ until the mixture is uniform, and then crushing to obtain a granular raw material with the particle size of 2 mm. And (3) carrying out structural design on the porous material by adopting three-dimensional modeling software, wherein the aperture of the ordered pores is 3mm, and the porous material is in a regular tetrahedron structure.

The porous ceramics prepared in examples 2 and 3 also have a globally ordered, locally disordered structure similar to that of example 1.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.