CN110451990B - Method for preparing metal oxide textured ceramic material by rapid sintering at normal temperature - Google Patents

Method for preparing metal oxide textured ceramic material by rapid sintering at normal temperature Download PDF

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CN110451990B
CN110451990B CN201910841234.1A CN201910841234A CN110451990B CN 110451990 B CN110451990 B CN 110451990B CN 201910841234 A CN201910841234 A CN 201910841234A CN 110451990 B CN110451990 B CN 110451990B
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metal oxide
blank
powder
textured ceramic
preparing
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CN110451990A (en
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李焕勇
张春辉
黄欢欢
王乾
唐琦
罗发
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Shaanxi Zhihangyu Armor New Materials Co ltd
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Northwestern Polytechnical University
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Abstract

The invention relates to a method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature, which is a preparation method for directly and rapidly sintering the metal oxide textured ceramic or oxide solid solution textured ceramic or composite oxide textured ceramic at normal temperature by combining a current thermal effect and a direct current electric field orientation effect without a high-temperature heating furnace. Compared with the existing texture ceramic sintering technology, the method can realize densification sintering and texture formation of various oxide ceramic materials without high-temperature furnace equipment or preheating samples, has the characteristics of short sintering time, high efficiency, small hardware investment, high energy utilization rate, wide application range, simple process, good energy-saving effect and low cost, and can realize the densification sintering and texture formation of various oxide ceramic materials. Is suitable for preparing oxide texture ceramics on a large scale and has wide application prospect.

Description

Method for preparing metal oxide textured ceramic material by rapid sintering at normal temperature
Technical Field
The invention belongs to the technical field of materials, relates to a method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature, and particularly relates to a method for preparing various metal oxide textured ceramics or oxide solid solution textured ceramics or composite oxide textured ceramics by direct rapid sintering at normal temperature by adopting a direct current thermal effect without a heating furnace.
Background
Oxide ceramic materials can be used as structural or functional ceramic materials and generally have a number of excellent physical and chemical properties such as: high chemical stability, high melting point, high temperature resistance, oxidation resistance, corrosion resistance, wear resistance, high-temperature strength, excellent mechanical and mechanical properties and the like, and has wide application in the fields of engineering technology and high technology. The microscopic crystal grains of the oxide ceramic grow along a certain direction with preferred orientation to form the textured ceramic, and the textured ceramic can greatly improve or fully exert the physical effect related to the anisotropy of the crystal in the material, and is a novel functional or structural material with special performance and promising prospect.
At present, the preparation technology of oxide texture ceramic materials mostly adopts tape casting, a reaction template seed crystal epitaxial growth method, hot forging orientation treatment at high temperature, a temperature gradient auxiliary molten salt method, or the technologies of placing a ceramic blank in a high temperature furnace for sintering and simultaneously applying an electric field and a magnetic field, or melt directional solidification, high-temperature mechanical extrusion and the like, wherein the technologies all need to place a sample in the high temperature furnace or add the sample to the high temperature in advance, then physical fields such as temperature gradient, mechanical field, electric field, magnetic field and the like are applied to complete sintering, the sintering and texturing processes need high temperature furnace equipment, and the technical defects of large equipment investment, long sintering time, high energy consumption, low energy utilization rate, high cost and the like exist.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature, which solves the defects of the prior art. The method for preparing various metal oxide textured ceramics or oxide solid solution textured ceramics or composite oxide textured ceramics by direct current electric effect and direct current electric field combination at normal temperature without a high-temperature sintering furnace. The method solves the defects of large hardware investment, high-temperature furnace equipment for sintering, long sintering time, high energy consumption, low energy utilization rate and high cost in the preparation of various oxide textured ceramic materials at present.
Technical scheme
A method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature is characterized by comprising the following steps:
step 1, weighing oxide nano powder: uniformly mixing one or more metal oxide nano-powders with the granularity of 1 nm-500 nm to obtain mixed oxide nano-powder, and weighing the total mass of the mixed oxide nano-powder;
the metal oxide nano powder comprises: an alkali metal oxide, an alkaline earth metal oxide, a transition metal oxide, or a rare earth metal oxide;
When the prepared unit metal oxide textured ceramic is alkaline earth metal oxide textured ceramic, selecting alkaline earth metal oxide nano powder as a raw material;
when the prepared unit metal oxide textured ceramic is transition metal oxide textured ceramic, selecting transition metal oxide nano powder as a raw material;
when the prepared unit metal oxide textured ceramic is rare earth oxide textured ceramic, selecting rare earth metal oxide nano powder as a raw material;
when the oxide solid solution texture ceramic is prepared, selecting one or more nano-powders of the alkaline earth metal oxides, the transition metal oxides or the rare earth metal oxides listed above which can form a solid solution with one or more alkali metal oxides as a raw material, or selecting several nano-powders of the metal oxides which can form a solid solution as a raw material;
when the composite metal oxide textured ceramic material is prepared, more than two kinds of alkali metal oxide nano-powder are selected as raw materials, or several kinds of metal oxide nano-powder are selected as raw materials;
step 2, preparation of a water-soluble metal inorganic salt saturated solution: dissolving one or more water-soluble metal salts in distilled water at 4-60 deg.C, stirring with magnetic stirrer, adding hydrochloric acid or nitric acid to adjust pH value of the salt generated by hydrolysis until the solution is clear, and making into saturated solution of inorganic salt;
When water-soluble metal inorganic salt is selected, the valence of the cation of the inorganic salt is inconsistent with the valence of the cation of the oxide with the largest content in the ingredients;
step 3, preparing an oxide nano powder precursor and forming a wet blank:
adding a metal inorganic salt saturated solution into the mixed oxide nano powder, adding distilled water until the water content is 50-90%, stirring the water-containing oxide mixed powder until the mixed powder is uniform, standing and aging for 0.5-24 hours, and then airing the wet oxide mixed powder at the temperature of 20-100 ℃ until the water content is 3-30% to obtain a metal oxide precursor; then the prepared metal oxide precursor is put into a mould, and the pressure of 0.5MPa to 50MPa is applied to shape the precursor to prepare a wet blank
The total mass of the water-soluble metal inorganic salt accounts for 0.5-30 wt% of the total mass of the metal oxide nano powder;
step 4, direct-current sintering texturing of the oxide textured ceramic blank:
placing the formed wet blank between two electrodes connected with a direct current power supply at 4-60 ℃, enabling the positive and negative electrodes to be in close contact with the blank, switching on the power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to enable the current intensity applied to the two ends of the blank to be between 0.1A/cm 2～20A/cm2Heating and sintering the oxide green body under current, and electrifying for 3-30 min to obtain an oxide textured ceramic material with certain density;
the electrode material is made of a metal material with a melting point higher than 1800 ℃, or an alloy material with a melting point higher than 1800 ℃ or a graphite material.
The alkali metal oxide is: li2O、Na2O、K2O、Rb2O、Cs2O。
The alkaline earth metal oxide: BeO, MgO, CaO, SrO and BaO.
The transition metal oxide includes: divalent transition metal oxide: ZnO, CuO, CdO, FeO, NiO, CoO, MnO or PbO; trivalent transition metal oxide: al (Al)2O3、Fe2O3、B2O3、V2O3、Cr2O3、In2O3、Sc2O3Or Ga2O3(ii) a Tetravalent transition metal oxide: ZrO (ZrO)2、TiO2、SiO2、GaO2、GeO2、HfO2、TaO2、VO2、MnO2Or SnO2(ii) a Pentavalent and hexavalent transition metal oxides: nb2O5、V2O5、Ta2O5Or WO3(ii) a Mixed-valence transition metal oxide: fe3O4、Mn3O4Or Co3O4。
The rare earth metal oxide: y is2O3、Sc2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、Er2O3、EuO、Pm2O3、Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3Or Lu2O3。
The water-soluble metal inorganic salt includes: alkali metal halides: AX, a ═ Li, Na, K, Rb, Cs, X ═ F, Cl, Br, I; or alkali metal sulfate: a. the2SO4, a ═ Li, Na, K, Rb, Cs; or an alkali metal carbonate: a. the2CO3A ═ Li, Na, K, Rb, Cs; or an alkali metal nitrate: ANO3A ═ Li, Na, K, Rb, Cs; or an alkaline earth metal halide: BX2B ═ Mg, Ca, Sr, Ba, X ═ F, Cl, Br, I; or a zinc salt: ZnX 2，X＝F、Cl、Br、I；ZnSO4、ZnNO3(ii) a Or iron salt: FeCl3、Fe2(SO4)3、Fe(NO3)3(ii) a Or an indium salt: InCl3，In2(SO4)3，In(NO3)3(ii) a Or a bismuth salt: BiCl3、Bi(NO3)3(ii) a Or an aluminum salt: AlCl3、Al2(SO4)3、Al(NO3)3。
The water-soluble metal inorganic salt contains crystal water or adsorbed water.
The electrode is a flat plate electrode, wherein tiny circular through holes are uniformly distributed on the flat plate electrode, the diameter of each through hole is 1-5 mm, and the distribution density of the through holes is 0.5-1/cm2。
Advantageous effects
The invention provides a method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature, which is a preparation method for directly and rapidly sintering the metal oxide textured ceramic, oxide solid solution textured ceramic or composite oxide textured ceramic at normal temperature by combining a current thermal effect and a direct current electric field orientation effect without a high-temperature heating furnace. Compared with the existing texture ceramic sintering technology, the method can realize densification sintering and texture formation of various oxide ceramic materials without high-temperature furnace equipment or preheating samples, has the characteristics of short sintering time, high efficiency, small hardware investment, high energy utilization rate, wide application range, simple process, good energy-saving effect and low cost. Is suitable for preparing oxide texture ceramics on a large scale and has wide application prospect.
Detailed Description
The invention will now be further described with reference to the following examples:
example 1: furnace-free rapid preparation of MgO textured ceramic material at 20 DEG C
Step 1, weighing MgO superfine powder: taking 25.00 g of MgO superfine powder with the granularity of 1 nm-20 nm.
Step 2, preparation of saturated sodium chloride solution: analytically pure sodium chloride 1.79 g is weighed, and at 20 ℃, the weighed sodium chloride is added into 5.0mL of distilled water and stirred uniformly by a magnetic stirrer until the solution is clear, so as to prepare a saturated solution of the sodium chloride at 20 ℃.
Step 3, preparation of MgO superfine powder precursor and wet blank forming: injecting the saturated sodium chloride solution prepared in the step 2 into MgO nano powder, adding 15.0mL of distilled water, stirring the MgO nano powder to be uniform, standing and aging for 24 hours, and drying MgO at 40 ℃ until the water content is 13% to obtain an MgO precursor; then the prepared MgO precursor is put into a die, and pressure of 40MPa is applied to shape the precursor, so that an MgO wet blank with the diameter of phi 30mm and the thickness of 20mm is prepared.
Step 4, direct current sintering texturing of the MgO textured ceramic blank: placing the MgO wet blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with two end faces of the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 1mm, and the distribution density of the through holes is 0.5/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 100A so that the current intensity applied to two ends of the blank is 14.14A/cm2Heating and sintering the MgO blank under current, electrifying for 6min to obtain the edge [111 ] with the density of 93.5 percent]A cubic MgO texture ceramic material with high preferred orientation in the direction.
Example 2: furnace-free rapid preparation of MgO textured ceramic material at 20 DEG C
Step 1, weighing MgO superfine powder: 30.00 g of MgO superfine powder with the granularity of 5-50 nm is taken.
Step 2, preparation of saturated sodium sulfate solution: 0.93 g of analytical grade sodium sulfate powder was weighed, sodium sulfate was added to 5.0mL of distilled water at 20 ℃ and stirred uniformly with a magnetic stirrer until the solution was clear, making a saturated solution of sodium sulfate at 20 ℃.
Step 3, preparation of MgO superfine powder precursor and wet blank forming: injecting the saturated sodium sulfate solution prepared in the step 2 into MgO, adding 15.0mL of distilled water, stirring the MgO powder to be uniform, standing and aging for 20 hours, and drying the MgO at 42 ℃ until the water content is 10% to obtain an MgO powder precursor; then the prepared MgO precursor is put into a die, and pressure is applied for 30MPa, so that the precursor is molded to prepare an MgO wet blank with the diameter phi of 40mm and the thickness of 20 mm.
Step 4, direct current sintering texturing of the MgO textured ceramic blank: placing the MgO wet blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with two end faces of the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 90A so that the current intensity applied to two ends of the blank is 7.16A/cm2Heating and sintering the MgO blank under current, electrifying for 9min to obtain the edge [111 ] with the density of 84 percent]A cubic MgO textured ceramic material with direction and high preferred orientation.
Example 3: BaO textured ceramic material prepared rapidly at 35 ℃ without furnace
Step 1, weighing BaO superfine powder: 35.00 g of BaO superfine powder with the granularity of 10-100 nm is taken.
Step 2, preparing a potassium chloride saturated solution, an aluminum sulfate saturated solution and a ferric nitrate saturated solution respectively: respectively weighing 0.39 g of analytically pure potassium chloride powder, 0.43 g of analytically pure aluminum sulfate powder and 1.66 g of analytically pure ferric nitrate powder, and adding the weighed potassium chloride into 1.0mL of distilled water at 35 ℃ to prepare a potassium chloride saturated solution; dissolving the weighed aluminum sulfate in 1.0mL of distilled water, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and uniformly stirring the solution by using a magnetic stirrer to prepare an aluminum sulfate saturated solution at the temperature of 35 ℃; the ferric nitrate is dissolved in 1.0mL of distilled water, 1.0mol/L hydrochloric acid is added to adjust the pH value to 3 until the solution is clear, and the solution is stirred uniformly by a magnetic stirrer to prepare a saturated ferric nitrate solution at the temperature of 35 ℃.
Step 3, preparation of BaO superfine powder precursor and wet blank forming: respectively and completely injecting the saturated solutions prepared in the step 2 into BaO, adding 16.0mL of distilled water, stirring BaO powder to be uniform, standing and aging for 22 hours, and then drying BaO at 80 ℃ until the water content is 3% to obtain a BaO powder precursor; and then putting the prepared BaO precursor into a mould, and applying pressure of 2MPa to form the precursor to prepare a BaO wet blank body with the diameter of phi 30mm and the thickness of 22 mm.
Step 4, direct current sintering texturing of the BaO textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 35 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 2mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 85A so that the current intensity applied to two ends of the blank is 12.03A/cm2Heating and sintering the BaO blank under current, electrifying for 10min to obtain a rim [100 ] with a density of 90.2%]The cubic BaO texture ceramic material with the direction highly preferred orientation.
Example 4: non-furnace rapid preparation of ZnO texture ceramic material at 30 DEG C
Step 1, weighing ZnO ultrafine powder: 40.00 g of ZnO superfine powder with the granularity of 5-50 nm is taken.
Step 2, preparation of saturated potassium chloride solution: 1.86 g of analytically pure potassium chloride powder was weighed, added to 5.0mL of distilled water at 30 ℃ and stirred uniformly with a magnetic stirrer until the solution was clear, to prepare a saturated solution of potassium chloride at 30 ℃.
Step 3, preparing ZnO superfine powder precursor and forming a wet blank: injecting the potassium chloride saturated solution prepared in the step 2 into ZnO, adding 20.0mL of distilled water, stirring ZnO powder to be uniform, standing and aging for 19 hours, and drying ZnO at 60 ℃ until the water content is 3% to obtain a ZnO powder precursor; and then putting the prepared ZnO precursor into a mold, and applying pressure of 0.5MPa to mold the precursor to prepare a ZnO wet blank with the diameter of phi 40mm and the thickness of 20 mm.
Step 4, direct current sintering texturing of the ZnO textured ceramic blank: placing the blank obtained in the step (3) at 30 ℃ into two graphite electrodes connected with a direct current power supplyWherein the area of the electrode covers the upper surface and the lower surface of the green body, micro round through holes are uniformly distributed on the upper flat plate electrode, the diameter of the through holes is phi 3mm, and the distribution density of the through holes is 1/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 95A so that the current intensity applied to two ends of the blank is 7.56A/cm2Heating and sintering the ZnO green body under current, electrifying for 10min to obtain the product with density of 97.2% and density of [ 0001%]ZnO textured ceramic material with wurtzite structure with direction and height preferred orientation.
Example 5: non-furnace rapid preparation of ZnO textured ceramic material at 30 DEG C
Step 1, weighing ZnO superfine powder: 20.00 g of ZnO superfine powder with the granularity of 10-100 nm is taken.
Step 2, preparation of saturated solution of sodium nitrate: 0.87 g of analytically pure sodium nitrate powder is weighed, added into 1.0mL of distilled water at 20 ℃, and stirred uniformly by a magnetic stirrer until the solution is clear, so as to prepare a saturated solution of sodium nitrate at 20 ℃.
Step 3, preparing ZnO superfine powder precursor and forming a wet blank: injecting the saturated solution of sodium nitrate prepared in the step 2 into ZnO, adding 10.0mL of distilled water, stirring ZnO powder to be uniform, standing and aging for 24 hours, and drying ZnO at 40 ℃ until the water content is 20% to obtain a ZnO powder precursor; and then putting the prepared ZnO precursor into a mold, and applying pressure of 0.5MPa to mold the precursor to prepare a ZnO wet blank with the diameter of phi 20mm and the thickness of 20 mm.
Step 4, direct current sintering texturing of the ZnO textured ceramic blank: placing the blank obtained in the step 3 between two molybdenum electrodes connected with a direct current power supply at 30 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 60A so that the current intensity applied to two ends of the blank is 19.10A/cm2ZnO green body in the field of electronicsHeating and sintering under flowing down, and electrifying for 6min to obtain a binder [0001 ] with density of 96.5%]ZnO textured ceramic material with wurtzite structure with direction and height preferred orientation.
Example 6: furnace-free rapid preparation of alpha-Al at 30 DEG C2O3Textured ceramic material
Step 1 alpha-Al2O3Weighing the superfine powder: taking alpha-Al with the particle size of 1-30 nm2O320.00 g of superfine powder.
Step 2, preparation of a saturated calcium chloride solution: weighing 1.00 g of analytically pure calcium chloride powder, adding calcium chloride into 1.0mL of distilled water at 30 ℃, and uniformly stirring by using a magnetic stirrer until the solution is clear to prepare a saturated solution of calcium chloride at 30 ℃.
Step 3 alpha-Al2O3Preparing an ultrafine powder precursor and forming a wet blank: injecting the calcium chloride saturated solution prepared in the step 2 into Al2O3In (1), 10.0mL of distilled water was added thereto, and Al was stirred2O3The powder is uniform, placed and aged for 24 hours, and then Al is added at 50 DEG C2O3Drying to water content of 30% to obtain Al2O3A powder precursor; then the prepared Al is added2O3Putting the precursor into a mold, applying pressure of 35MPa to mold the precursor, and preparing Al with the diameter of phi 30mm and the thickness of 20mm2O3And (5) wetting the blank.
Step 4 alpha-Al2O3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 30 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 5mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 35A so that the current intensity applied to two ends of the blank is 5A/cm2，Al2O3Heating and sintering the blank under current, electrifying for 30min to obtain a binder [0001 ] with density of 97.5%]Preferred direction and height Oriented alpha-Al2O3Textured ceramic materials.
Example 7: non-furnace rapid preparation of alpha-Al at 20 DEG C2O3Textured ceramic material
Step 1 alpha-Al2O3Weighing the superfine powder: taking Al with the particle size of 5-50 nm2O320.00 g of superfine powder.
Step 2, preparation of a barium chloride saturated solution: 0.90 g of analytically pure barium chloride powder is weighed, and at the temperature of 20 ℃, the barium chloride is added into 2.5mL of distilled water and stirred uniformly by a magnetic stirrer until the solution is clear, so that a saturated solution of the barium chloride at the temperature of 20 ℃ is prepared.
Step 3 alpha-Al2O3Preparing an ultrafine powder precursor and forming a wet blank: injecting the barium chloride saturated solution prepared in the step 2 into Al2O3In (1), 10.0mL of distilled water was added thereto, and Al was stirred2O3The powder is uniform, placed and aged for 22 hours, and then Al is added at 38 DEG C2O3Drying to water content of 18% to obtain Al2O3A powder precursor; then the prepared Al is added2O3Putting the precursor into a mold, applying pressure of 35MPa to mold the precursor, and preparing Al with the diameter of phi 30mm and the thickness of 20mm2O3And (5) wetting the blank.
Step 4 alpha-Al2O3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step 3 between two molybdenum alloy electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 4mm, and the distribution density of the through holes is 0.5/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 80A so that the current intensity applied to two ends of the blank is 11.32A/cm2，Al2O3Heating and sintering the blank under current, electrifying for 10min to obtain a binder [0001 ] with density of 84%]Highly oriented Al2O3Textured ceramic materials.
Example 8: furnace-free rapid preparation of alpha-Fe at 30 DEG C2O3Textured ceramic material
Step 1 alpha-Fe2O3Weighing the superfine powder: taking alpha-Fe with the particle size of 10-300 nm2O335.00 g of superfine powder.
Step 2, preparing saturated solutions of zinc sulfate, lithium nitrate, sodium chloride and barium chloride respectively: weighing 0.50 g of analytically pure zinc sulfate powder, 0.97 g of analytically pure lithium nitrate powder, 0.36 g of analytically pure sodium chloride powder and 0.25 g of analytically pure barium chloride powder, adding the weighed zinc sulfate powder into 0.7mL of distilled water at 30 ℃, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clarified, and uniformly stirring by using a magnetic stirrer to prepare an aluminum sulfate saturated solution at 30 ℃; adding weighed lithium nitrate powder into 0.7mL of distilled water, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and uniformly stirring by using a magnetic stirrer to prepare a lithium nitrate saturated solution at the temperature of 30 ℃; adding weighed sodium chloride powder into 0.7mL of distilled water, and uniformly stirring by using a magnetic stirrer to prepare a sodium chloride saturated solution at the temperature of 30 ℃; the weighed barium chloride powder was added to 0.7mL of distilled water, and stirred uniformly with a magnetic stirrer to prepare a saturated solution of barium chloride at 30 ℃.
Step 3 alpha-Fe2O3Preparing an ultrafine powder precursor and forming a wet blank: respectively injecting the saturated solution prepared in the step 2 into Fe2O3To the solution, 18.0mL of distilled water was added and Fe was stirred2O3The powder is homogenized, placed and aged for 12 hours, and then Fe is added at the temperature of 39 DEG C2O3Drying to water content of 18% to obtain Fe2O3A powder precursor; then the prepared Fe2O3Putting the precursor into a mold, applying pressure of 40MPa to mold the precursor, and preparing Fe with the diameter of phi 30mm and the thickness of 20mm2O3And (5) wetting the blank.
Step 4 alpha-Fe2O3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 30 ℃, and enabling the anode and the cathode to be connected with the blankClosely contacting, wherein the electrode area covers the upper and lower surfaces of the blank, micro round through holes are uniformly distributed on the upper flat electrode, the diameter of the through holes is phi 1mm, and the distribution density of the through holes is 0.6/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 3.6A so that the current intensity applied to two ends of the blank is 0.5A/cm2，Fe2O3Heating and sintering the blank under current, electrifying for 30min to obtain a binder [0001 ] with density of 96.7%]alpha-Fe of highly preferred orientation 2O3Textured ceramic materials.
Example 9: 30 ℃ furnace-free rapid preparation of TiO2Textured ceramic material
Step 1 rutile TiO2Weighing the superfine powder: taking rutile-structured TiO with the granularity of 10-100 nm250.00 g of superfine powder.
Step 2, preparation of aluminum chloride saturated solution: weighing 1.41 g of analytically pure aluminum chloride powder, adding the aluminum chloride into 3.0mL of distilled water, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and preparing a saturated solution of the aluminum chloride at the temperature of 30 ℃.
Step 3TiO2Preparing an ultrafine powder precursor and forming a wet blank: injecting all the aluminum chloride saturated solution prepared in the step 2 into TiO2In (1), 25.0mL of distilled water was added and the TiO was stirred2The powder is homogenized, placed and aged for 22 hours, and then TiO is put at 45 DEG C2Drying to water content of 18% to obtain TiO2A powder precursor; then the prepared TiO is mixed2Putting the precursor into a mold, applying pressure of 43MPa to mold the precursor, and preparing the TiO with the diameter of phi 40mm and the thickness of 20mm2And (5) wetting the blank.
Step 4 rutile TiO2Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 30 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 110A so that the current intensity applied to two ends of the blank is 8.75A/cm2，TiO2Heating and sintering the ceramic blank under current, electrifying for 10min to obtain a ceramic blank with a density of 92 percent and a [001 ] edge]Rutile TiO with highly preferred orientation2Textured ceramic materials.
Example 10: no-furnace rapid preparation of rutile TiO at 20 DEG C2Textured ceramic material
Step 1 rutile TiO2Weighing the superfine powder: taking rutile TiO with the granularity of 10-100 nm220.00 g of superfine powder.
Step 2, preparation of saturated ferric chloride solution: 0.92 g of analytically pure iron chloride powder is weighed, at 20 ℃, the iron chloride is added into 1.0mL of distilled water, the mixture is stirred uniformly by a magnetic stirrer, 1.0mol/L hydrochloric acid is added to adjust the pH value to 3 until the solution is clear, and a saturated solution of the iron chloride at 20 ℃ is prepared.
Step 3TiO2Preparing an ultrafine powder precursor and forming a wet blank: injecting the ferric chloride saturated solution prepared in the step 2 into TiO2In (1), 10.0mL of distilled water was added and the TiO was stirred2The powder is homogenized, placed and aged for 22 hours, and then TiO is put into the mixture at the temperature of 20 DEG C2Drying to water content of 16% to obtain TiO2A powder precursor; then the prepared TiO is mixed 2Putting the precursor into a mould, applying pressure of 39MPa to form the precursor, and preparing the TiO with the diameter of phi 30mm and the thickness of 15mm2And (5) wetting the blank.
Step 4TiO2Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 40A so that the current intensity applied to two ends of the blank is 5.7A/cm2，TiO2Heating and sintering the ceramic blank under current, electrifying for 15min to obtain a bead [001 ] with the density of 92.3%]Rutile TiO with highly preferred orientation2Textured ceramic materials.
Example 11: rapid preparation of alpha-MnO at 30 ℃ without furnace2Textured ceramic material
Step 1 alpha-MnO2Weighing the superfine powder: taking alpha-MnO with the particle size of 20-200 nm227.00 g of superfine powder.
Step 2, preparing saturated solutions of potassium nitrate, lithium sulfate and ferric chloride respectively: weighing 0.45 g of analytically pure potassium nitrate powder, 0.34 g of analytically pure lithium sulfate powder and 1.07 g of analytically pure iron chloride powder, adding the weighed potassium nitrate powder into 5.0mL of distilled water at the temperature of 30 ℃, and uniformly stirring by using a magnetic stirrer to prepare a potassium nitrate saturated solution at the temperature of 30 ℃; adding weighed lithium sulfate powder into 5.0mL of distilled water, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and uniformly stirring by using a magnetic stirrer to prepare a lithium sulfate saturated solution at the temperature of 30 ℃; the weighed ferric chloride powder is added into 5.0mL of distilled water, 1.0mol/L hydrochloric acid is added to adjust the pH value to 3 until the solution is clear, and the solution is stirred uniformly by a magnetic stirrer to prepare a saturated ferric chloride solution at the temperature of 30 ℃.
Step 3 alpha-MnO2Preparing an ultrafine powder precursor and forming a wet blank: respectively and completely injecting the saturated solution prepared in the step 2 into MnO2Adding 15.0mL of distilled water and stirring the MnO2The powder is uniform, placed and aged for 21 hours, and then MnO is added at 46 DEG C2Drying to a water content of 16% to obtain MnO2A powder precursor; then the MnO prepared2Putting the precursor into a mold, applying pressure of 41MPa to mold the precursor, and preparing MnO with the diameter of phi 30mm and the thickness of 15mm2And (5) wetting the blank.
Step 4 alpha-MnO2Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two molybdenum alloy electrodes connected with a direct current power supply at 30 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, and micro-electrodes are uniformly distributed on a flat plate electrode at the upper endSmall round through holes with diameter phi of 1mm and distribution density of 0.5 through holes/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 45A so that the current intensity applied to two ends of the blank is 6.4A/cm2，MnO2Heating and sintering the ceramic blank under current, electrifying for 18min to obtain a ceramic blank with density of 93.8 percent and density of [0001 ] ]alpha-MnO of highly preferred orientation2Textured ceramic materials.
Example 12: non-furnace rapid preparation of B-Nb at 4 DEG C2O5Textured ceramic material
Step 1Nb2O5Weighing the superfine powder: taking B-Nb with the granularity of 20-100 nm2O520.00 g of superfine powder.
Step 2, preparation of saturated sodium chloride solution: weighing 1.06 g of analytically pure sodium chloride powder, adding sodium chloride into 3.0mL of distilled water at 4 ℃, and uniformly stirring by using a magnetic stirrer until the solution is clear to prepare a saturated solution of sodium chloride at 4 ℃.
Step 3Nb2O5Preparing an ultrafine powder precursor and forming a wet blank: injecting the saturated solution of sodium chloride prepared in the step 2 into the Nb2O5In (1), 10.0mL of distilled water was added and Nb was stirred2O5The powder is uniform, placed and aged for 21 hours, and then Nb is added at 45 DEG C2O5Drying to water content of 16% to obtain Nb2O5A powder precursor; then the prepared Nb is2O5Putting the precursor into a mould, applying pressure of 33MPa to shape the precursor, and preparing the Nb with the diameter of phi 30mm and the thickness of 15mm2O5And (5) wetting the blank.
Step 4B-Nb2O5Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step 3 between two graphite electrodes connected with a direct current power supply at 4 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm 2. Power on and power off regulatorThe working state is a constant current mode, the current limiting value is adjusted to be 70A, and the current intensity applied to the two ends of the blank is enabled to be 9.8A/cm2，Nb2O5Heating and sintering the ceramic blank under current, electrifying for 8min to obtain a rim [110 ] with density of 97.5%]Highly directionally oriented B-Nb2O5Textured ceramic materials.
Example 13: non-furnace rapid preparation of B-Nb at 20 DEG C2O5Textured ceramic material
Step 1Nb2O5Weighing the superfine powder: taking B-Nb with the granularity of 30-300 nm2O525.00 g of superfine powder.
Step 2, preparation of zinc chloride saturated solution: 1.98 g of analytically pure zinc chloride powder is weighed, added into 0.5mL of distilled water at the temperature of 20 ℃, stirred uniformly by a magnetic stirrer, added with hydrochloric acid to adjust the pH value to 3 until the solution is clear, and prepared into a saturated solution of zinc chloride at the temperature of 20 ℃.
Step 3Nb2O5Preparing an ultrafine powder precursor and forming a wet blank: injecting the saturated solution of zinc chloride prepared in the step 2 into Nb2O5In (1), 15.0mL of distilled water was added and Nb was stirred2O5The powder is uniform, placed and aged for 23 hours, and then Nb is added at 36 DEG C2O5Drying to water content of 15% to obtain Nb2O5A powder precursor; then the prepared Nb is2O5The precursor is put into a mould, and pressure of 42MPa is applied to shape the precursor, so as to prepare Nb with the diameter of phi 30mm and the thickness of 16mm 2O5And (5) wet blank.
Step 4B-Nb2O5Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 50A so as to applyThe current intensity applied to both ends of the green body was 7.1A/cm2，Nb2O5Heating and sintering the ceramic blank under current, electrifying for 18min to obtain the edge [110 ] with the density of 95.6 percent]Highly directionally oriented B-Nb2O5Textured ceramic materials.
Example 14: rapid preparation of WO at 30 ℃ without furnace3Textured ceramic material
Step 1WO3Weighing the superfine powder: taking WO with the particle size of 50-500 nm340.00 g of superfine powder.
Step 2, preparing saturated solutions of potassium chloride, zinc nitrate and aluminum sulfate respectively: weighing 0.37 g of analytically pure potassium chloride powder, 1.38 g of analytically pure zinc nitrate powder and 0.40 g of analytically pure aluminum sulfate powder, adding the weighed potassium chloride powder into 1.0mL of distilled water at 30 ℃, and uniformly stirring by using a magnetic stirrer to prepare a potassium chloride saturated solution at 30 ℃; adding weighed zinc nitrate powder into 1.0mL of distilled water, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and uniformly stirring by using a magnetic stirrer to prepare a zinc nitrate saturated solution at the temperature of 30 ℃; adding weighed aluminum sulfate powder into 1.0mL of distilled water, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and uniformly stirring by using a magnetic stirrer to prepare an aluminum sulfate saturated solution at the temperature of 30 ℃.
Step 3WO3Preparing an ultrafine powder precursor and forming a wet blank: respectively and totally injecting the saturated solutions prepared in the step 2 into WO3In (1), 20mL of distilled water was added thereto, and the WO was stirred3The powder is homogenized, left to age for 23 hours, and then the WO is put at 37 DEG C3Drying to a water content of 15% to obtain WO3A powder precursor; then the obtained WO is added3Putting the precursor into a mould, applying pressure of 40MPa to form the precursor, and preparing the WO with the diameter of phi 30mm and the thickness of 16mm3And (5) wetting the blank.
Step 4WO3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 30 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the blankThe lower two surfaces and the upper flat electrode are uniformly distributed with micro round through holes with the diameter phi of 1mm and the distribution density of 0.5 through holes/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 20A so that the current intensity applied to two ends of the blank is 2.9A/cm2，WO3Heating and sintering the ceramic blank under current, electrifying for 25min to obtain the edge [110 ] with the density of 95.9%]WO with highly preferred orientation 3Textured ceramic materials.
Example 15: non-furnace rapid preparation of Fe at 20 DEG C3O4Textured ceramic material
Step 1Fe3O4Weighing the superfine powder: taking Fe with the particle size of 1-20 nm3O440.00 g of superfine powder.
Step 2, preparation of a potassium nitrate saturated solution: 1.58 g of analytically pure potassium nitrate powder is weighed, added into 5.0mL of distilled water at 20 ℃, and uniformly stirred by a magnetic stirrer until the solution is clear, so as to prepare a saturated solution of potassium nitrate at 20 ℃.
Step 3Fe3O4Preparing an ultrafine powder precursor and forming a wet blank: fully injecting the saturated potassium nitrate solution prepared in the step 2 into Fe3O4In (1), 20.0mL of distilled water was added thereto, and Fe was stirred3O4The powder is homogenized, placed and aged for 0.5 hour, and then Fe is added at 37 DEG C3O4Drying to water content of 15% to obtain Fe3O4A powder precursor; then the prepared Fe3O4Putting the precursor into a mold, applying pressure of 41MPa to mold the precursor, and preparing Fe with the diameter of phi 30mm and the thickness of 25mm3O4And (5) wetting the blank.
Step 4Fe3O4Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 3mm, and the distribution density of the through holes is 0.5/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 0.7A so that the current intensity applied to two ends of the blank is 0.1A/cm2，Fe3O4Heating and sintering the ceramic blank under current, electrifying for 30min to obtain the edge [100 ] with the density of 88.4 percent]Highly oriented Fe3O4Textured ceramic materials.
Example 16: non-furnace rapid preparation of Fe at 60 DEG C3O4Textured ceramic material
Step 1Fe3O4Weighing the superfine powder: taking Fe with the particle size of 1-20 nm3O440.00 g of superfine powder.
Step 2, preparation of sodium bromide saturated solution: 1.18 g of analytically pure sodium bromide powder is weighed, lithium chloride is added into 1.0mL of distilled water at 60 ℃, and the mixture is stirred uniformly by a magnetic stirrer and clarified to prepare a saturated solution of sodium bromide at 60 ℃.
Step 3Fe3O4Preparing an ultrafine powder precursor and forming a wet blank: injecting the saturated sodium bromide solution prepared in the step 2 into Fe3O4In (1), 20.0mL of distilled water was added thereto, and Fe was stirred3O4The powder is homogenized, placed and aged for 2 hours, and then Fe is added at 60 DEG C3O4Drying to water content of 20% to obtain Fe3O4A powder precursor; then the prepared Fe3O4Putting the precursor into a mould, applying pressure of 35MPa to form the precursor, and preparing Fe with the diameter of phi 30mm and the thickness of 30mm 3O4And (5) wetting the blank.
Step 4Fe3O4Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two molybdenum electrodes connected with a direct current power supply at 60 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on the power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 9A so as to applyThe current intensity applied to both ends of the green body was 1.28A/cm2，Fe3O4Heating and sintering the ceramic blank under current, electrifying for 21min to obtain the edge [100 ] with the density of 93.2%]Highly directionally oriented Fe3O4Textured ceramic materials.
Example 17: rapid preparation of Y at 20 ℃ without furnace2O3Textured ceramic material
Step 1Y2O3Weighing the superfine powder: taking Y with the particle size of 10-100 nm2O330.00 g of superfine powder.
Step 2, preparation of a barium chloride saturated solution: 0.72 g of analytically pure barium chloride powder is weighed, at the temperature of 20 ℃, the barium chloride is added into 2.0mL of distilled water, and the mixture is stirred uniformly by a magnetic stirrer until the solution is clear, so that a saturated solution of the barium chloride at the temperature of 20 ℃ is prepared.
Step 3Y2O3Preparing a precursor of the superfine powder and forming a wet blank: injecting the barium chloride saturated solution prepared in the step 2 into Y2O3In (1), 20.0mL of distilled water was added and Y was stirred2O3The powder is homogenized, placed and aged for 2 hours, and then Y is put into the solution at the temperature of 48 DEG C2O3Drying to water content of 18% to obtain Y2O3A powder precursor; then the prepared Y2O3Putting the precursor into a mold, applying pressure of 40MPa to mold the precursor, and making into Y with diameter of phi 30mm and thickness of 20mm2O3And (5) wetting the blank.
Step 4Y2O3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two zirconium-titanium-molybdenum alloy electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 2mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 71A so that the current intensity applied to two ends of the blank is 10A/cm2，Y2O3Ceramic blankThe body is sintered under current and electrified for 10min to obtain a rim (100) with the density of 95.8 percent]Cube Y with highly preferred orientation 2O3Textured ceramic materials.
Example 18: rapid preparation of Y at 40 ℃ without furnace2O3Textured ceramic material
Step 1Y2O3Weighing the superfine powder: taking Y with the particle size of 10-100 nm2O335.00 g of superfine powder.
Step 2, preparing saturated solutions of sodium chloride and potassium sulfate respectively: weighing 1.08 g of analytically pure sodium chloride powder and 0.39 g of analytically pure potassium sulfate powder, adding the weighed sodium chloride powder into 3.0mL of distilled water at 40 ℃, and uniformly stirring by using a magnetic stirrer to prepare a sodium chloride saturated solution at 30 ℃; the weighed potassium sulfate powder is added into 3.0mL of distilled water, and is stirred uniformly by a magnetic stirrer to prepare a saturated solution of potassium sulfate at the temperature of 30 ℃.
Step 3Y2O3Preparing an ultrafine powder precursor and forming a wet blank: respectively injecting the saturated solutions prepared in the step 2 into Y2O3In (1), 18.0mL of distilled water was added, and Y was stirred2O3The powder is homogenized, placed and aged for 24 hours, and then Y is put at 38 DEG C2O3Drying to water content of 12% to obtain Y2O3A powder precursor; then the prepared Y2O3Putting the precursor into a mold, applying pressure of 36MPa to mold the precursor, and making into Y with diameter of phi 30mm and thickness of 25mm2O3And (5) wetting the blank.
Step 4Y2O3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 40 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 3mm, and the distribution density of the through holes is 0.5/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 141A so as to apply the current to the blankThe current intensity at both ends is 20A/cm2，Y2O3Heating and sintering the ceramic blank under current, electrifying for 4min to obtain a ceramic blank with a density of 94.3 percent and a border of 100]Cube Y with highly preferred orientation2O3Textured ceramic materials.
Example 19: non-furnace fast spinel (MgO. Al) at 20 DEG C2O3) Textured ceramic material
Step 1MgO and Al2O3Weighing the superfine powder: weighing 20.00 g of MgO superfine powder with the particle size of 10-100 nm and 7.91 g of alumina superfine powder with the particle size of 5-50 nm, and uniformly mixing the two powders together.
Step 2, preparation of saturated sodium chloride solution: 0.72 g of analytically pure sodium chloride powder is weighed, and at 20 ℃, sodium chloride is added into 2.0mL of distilled water and stirred uniformly by a magnetic stirrer until the solution is clear, so as to prepare a saturated solution of sodium chloride at 20 ℃.
Step 3 MgO. Al2O3Preparing an ultrafine powder precursor and forming a wet blank: injecting the saturated sodium chloride solution prepared in the step 2 into the mixed powder, adding 10.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 12 hours, and drying the mixed powder at 39 ℃ until the water content is 14% to obtain a mixed powder precursor; then the prepared MgO-Al 2O3Putting the precursor into a mold, applying pressure of 40MPa to form the precursor, and preparing MgO-Al with the diameter of phi 30mm and the thickness of 25mm2O3And (5) wet blank.
Step 4 MgO. Al2O3D, direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 80A so that the current intensity applied to two ends of the blank is 11.4A/cm2，MgO·Al2O3Heating and sintering the ceramic blank under current, electrifying for 9min to obtain a ceramic blank with a density of 94.2 percent and a rim [111 ]]MgO-Al with highly preferred orientation2O3Textured ceramic materials.
Example 20: non-furnace fast preparation of spinel (MgO. Al) at 20 DEG C2O3) Textured ceramic material
Step 1MgO and Al2O3Weighing the superfine powder: weighing 20.00 g of MgO superfine powder with the particle size of 55nm and 7.91 g of alumina superfine powder with the particle size of 40nm, and uniformly mixing the two powders together;
Step 2, preparation of a potassium bromide saturated solution: 0.65 g of analytically pure potassium bromide powder is weighed, added into 1.0mL of distilled water at 20 ℃, and stirred uniformly by a magnetic stirrer until the solution is clear, so as to prepare a saturated solution of potassium bromide at 20 ℃.
Step 3 MgO. Al2O3Preparing a precursor of the superfine powder and forming a wet blank: injecting the saturated potassium bromide solution prepared in the step 2 into the mixed powder, adding 15.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 22 hours, and drying the mixed powder at 45 ℃ until the water content is 16% to obtain a mixed powder precursor; then the prepared MgO-Al2O3Putting the precursor into a mold, applying pressure of 50MPa to mold the precursor, and preparing MgO. Al with diameter of phi 30mm and thickness of 20mm2O3And (5) wetting the blank.
Step 4 MgO. Al2O3Direct current sintering texturing of the textured ceramic blank: placing the green body obtained in the step (3) between two electric molybdenum electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the green body, wherein the area of the electrodes covers the upper surface and the lower surface of the green body, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of the through holes is phi 1mm, and the distribution density of the through holes is 0.8/cm 2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 49A so that the current intensity applied to two ends of the blank is 7A/cm2，MgO·Al2O3Heating and burning ceramic body under currentFinally, electrifying for 15min to obtain a rim [111 ] with the density of 95.8 percent]MgO-Al with highly preferred orientation in direction2O3Textured ceramic materials.
Example 21: non-furnace rapid BaTiO preparation at 20 DEG C3Textured ceramic material
Step 1BaO and TiO2Weighing the superfine powder: weighing 30.00 g of BaO superfine powder with the particle size of 20-200 nm and 15.63 g of titanium oxide superfine powder with the particle size of 10-100 nm, and uniformly mixing the powders together.
Step 2, preparation of a saturated ferric nitrate solution: weighing 1.38 g of analytically pure grade ferric nitrate powder, adding ferric nitrate into 1.0mL of distilled water at 20 ℃, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L nitric acid to adjust the pH value to 3 until the solution is clear, and preparing a saturated solution of ferric nitrate at 20 ℃.
Step 3BaTiO3Preparing an ultrafine powder precursor and forming a wet blank: injecting the ferric nitrate saturated solution prepared in the step 2 into the mixed powder, adding 25.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 22 hours, and then adding BaTiO at 45 DEG C 3Drying until the water content is 15% to obtain a mixed powder precursor; then the prepared BaTiO is added3Putting the precursor into a mould, applying pressure of 46MPa to form the precursor, and preparing the BaTiO with the diameter of phi 30mm and the thickness of 25mm3And (5) wetting the blank.
Step 4BaTiO3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is phi 2mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 60A so that the current intensity applied to two ends of the blank is 8.6A/cm2，BaTiO3Heating and sintering the ceramic blank under current, electrifying for 10min to obtain a bead [001 ] with density of 96.9%]BaTiO of perovskite structure with direction highly preferred orientation3Textured ceramic materials.
Example 22: non-furnace rapid BaTiO preparation at 20 DEG C3Textured ceramic material
Step 1BaO and TiO2Weighing the superfine powder: weighing 60.00 g of BaO superfine powder with the particle size of 20-200 nm and 31.27 g of titanium oxide superfine powder with the particle size of 10-100 nm, and uniformly mixing the powders together.
Step 2, preparing saturated solutions of lithium chloride, potassium sulfate and aluminum nitrate respectively: weighing 0.84 g of analytically pure lithium chloride powder, 0.11 g of analytically pure potassium sulfate powder and 0.74 g of analytically pure aluminum nitrate powder, adding the weighed lithium chloride powder into 1.0mL of distilled water at the temperature of 20 ℃, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and preparing a lithium chloride saturated solution at the temperature of 20 ℃; adding weighed potassium sulfate powder into 1.0mL of distilled water, and uniformly stirring by using a magnetic stirrer until the solution is clear to prepare a saturated potassium sulfate solution at the temperature of 20 ℃; adding weighed aluminum nitrate powder into 1.0mL of distilled water, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L nitric acid, adjusting the pH value to 3 until the solution is clear, and preparing an aluminum nitrate saturated solution at the temperature of 20 ℃.
Step 3BaTiO3Preparing a precursor of the superfine powder and forming a wet blank: respectively and completely injecting the saturated solutions prepared in the step 2 into the mixed powder, adding 50.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 21 hours, and drying the mixed powder at 46 ℃ until the water content is 14% to obtain a mixed powder precursor; then the prepared BaTiO is added 3The precursor is put into a mould, and pressure of 42MPa is applied to shape the precursor to prepare BaTiO with the diameter of phi 30mm and the thickness of 25mm3And (5) wet blank.
Step 4BaTiO3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 1/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 50A so that the current intensity applied to two ends of the blank is 7.64A/cm2，BaTiO3Heating and sintering the ceramic blank under current, electrifying for 12min to obtain a bead [001 ] with the density of 92.2%]BaTiO of perovskite structure with direction highly preferred orientation3Textured ceramic materials.
Example 23: non-furnace fast preparation of LiNbO at 20 DEG C3Textured ceramic material
Step 1Li2O and Nb2O5Weighing the superfine powder: weighing 5.06 g of lithium oxide superfine powder with the granularity of 50-500 nm and 45.00 g of niobium oxide superfine powder with the granularity of 20-200 nm, and uniformly mixing the two powders together.
Step 2, preparing saturated solutions of zinc chloride, ferric sulfate and aluminum nitrate respectively: weighing 1.98 g of analytically pure zinc chloride powder, 2.2 g of analytically pure ferric sulfate powder and 0.37 g of analytically pure aluminum nitrate powder, adding the weighed zinc chloride powder into 0.5mL of distilled water at 20 ℃, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and preparing a zinc chloride saturated solution at 20 ℃; adding weighed ferric sulfate powder into 0.5mL of distilled water, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L hydrochloric acid to adjust the pH value to 3 until the solution is clear, and preparing a ferric sulfate saturated solution at the temperature of 20 ℃; adding weighed aluminum nitrate powder into 0.5mL of distilled water, uniformly stirring by using a magnetic stirrer, adding 1.0mol/L nitric acid to adjust the pH value to 3 until the solution is clear, and preparing an aluminum nitrate saturated solution at the temperature of 20 ℃.
Step 3LiNbO3Preparing a precursor of the superfine powder and forming a wet blank: respectively and completely injecting the saturated solutions prepared in the step 2 into the mixed powder, adding 30.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 21 hours, and drying the mixed powder at 48 ℃ until the water content is 13% to obtain a mixed powder precursor; then the prepared LiNbO 3Putting the precursor into a mould, applying pressure of 32MPa to form the precursor, and preparing the LiNbO with the diameter of phi 30mm and the thickness of 25mm3And (5) wet blank.
Step 4LiNbO3Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step (3) between two graphite electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 30A so that the current intensity applied to two ends of the blank is 4.2A/cm2，LiNbO3Heating and sintering the ceramic blank under current, electrifying for 7min to obtain the edge [001 ] with the density of 91.8%]LiNbO of ilmenite-type structure with highly preferred orientation3Textured ceramic materials.
Example 24: furnace-free rapid preparation of lanthanum zirconate (La) at 20 DEG C2Zr2O7) Textured ceramic material
Step 1La2O3And ZrO2Weighing the superfine powder: weighing 33.05 g of lanthanum oxide superfine powder with the particle size of 10-100 nm and 25.00 g of zirconium oxide superfine powder with the particle size of 10-100 nm, and uniformly mixing the two powders together.
Step 2, preparation of lithium chloride saturated solution: 1.67 g of analytically pure lithium chloride powder was weighed, and lithium chloride was added to 2.0mL of distilled water at 20 ℃ and stirred uniformly with a magnetic stirrer to prepare a saturated solution of lithium chloride at 20 ℃.
Step 3La2Zr2O7Preparing an ultrafine powder precursor and forming a wet blank: injecting the lithium chloride saturated solution prepared in the step 2 into the mixed powder, adding 30.0mL of distilled water, stirring the mixed powder to be uniform, standing and aging for 12 hours, and drying the mixed powder at 45 ℃ until the water content is 16% to obtain a mixed powder precursor; then the prepared La is added2Zr2O7Putting the precursor into a mold, applying pressure of 48MPa to mold the precursor, and preparing La with the diameter of phi 30mm and the thickness of 25mm2Zr2O7And (5) wet blank.
Step 4La2Zr2O7Direct current sintering texturing of the textured ceramic blank: placing the blank obtained in the step 3 between two molybdenum electrodes connected with a direct current power supply at 20 ℃, and enabling the positive electrode and the negative electrode to be in close contact with the blank, wherein the area of the electrodes covers the upper surface and the lower surface of the blank, micro round through holes are uniformly distributed on a flat plate electrode at the upper end, the diameter of each through hole is 1mm, and the distribution density of the through holes is 0.5/cm2. Switching on a power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to be 30A so that the current intensity applied to two ends of the blank is 4.3A/cm 2，La2Zr2O7The ceramic blank is sintered under current for 15min to obtain a ceramic edge (100) with a density of 94.8%]Highly directionally preferentially oriented cubic La2Zr2O7Textured ceramic materials.

Claims (7)

1. A method for preparing a metal oxide textured ceramic material by rapid sintering at normal temperature is characterized by comprising the following steps:
step 1, weighing oxide nano powder: uniformly mixing one or more metal oxide nano-powders with the granularity of 1-500 nm to obtain mixed oxide nano-powders, and weighing the total mass of the mixed powders;
the metal oxide nano powder comprises: an alkali metal oxide, an alkaline earth metal oxide, a transition metal oxide, or a rare earth metal oxide;
when the prepared unit metal oxide textured ceramic is alkaline earth metal oxide textured ceramic, selecting the alkaline earth metal oxide nano powder as a raw material;
when the prepared unit metal oxide textured ceramic is transition metal oxide textured ceramic, selecting the transition metal oxide nano powder as a raw material;
when the prepared unit metal oxide textured ceramic is rare earth oxide textured ceramic, selecting the rare earth metal oxide nano powder as a raw material;
When the prepared unit metal oxide textured ceramic is oxide solid solution textured ceramic, more than two kinds of metal oxide nano powder capable of forming solid solution are selected as raw materials;
when the prepared unit metal oxide textured ceramic is composite metal oxide textured ceramic, more than two kinds of metal oxide nano powder are selected as raw materials;
step 2, preparation of a water-soluble metal inorganic salt saturated solution: dissolving one or more of water-soluble metal inorganic salts in distilled water at 4-60 ℃, and uniformly stirring by using a magnetic stirrer; if the hydrolysis generates precipitated salt, adding hydrochloric acid or nitric acid to adjust the pH value until the solution is clear, and preparing saturated solution of inorganic salt; if the water-soluble metal inorganic salt is completely dissolved, directly preparing a saturated solution of the inorganic salt;
when water-soluble metal inorganic salt is selected, the valence of the cation of the inorganic salt is inconsistent with the valence of the cation of the metal oxide with the largest content in the ingredients;
step 3, preparing an oxide nano powder precursor and forming a wet blank:
adding the water-soluble metal inorganic salt saturated solution into mixed oxide nano powder, adding distilled water until the water content is 50-90%, stirring the water-containing oxide mixed powder until the mixture is uniform, standing and aging for 0.5-24 hours, and then airing the wet oxide mixed powder at the temperature of 20-100 ℃ until the water content is 3-30% to obtain a metal oxide precursor; then putting the prepared metal oxide precursor into a mould, and applying pressure of 0.5-50 MPa to form the precursor to prepare a wet blank;
The total mass of the water-soluble metal inorganic salt accounts for 0.5-30 wt% of the total mass of the metal oxide nano powder;
step 4, direct-current sintering texturing of the oxide textured ceramic blank:
placing the formed wet blank between two electrodes connected with a direct current power supply at 4-60 ℃, enabling the positive and negative electrodes to be in close contact with the blank, switching on the power supply, adjusting the working state of the power supply to be in a constant current mode, and adjusting the current limiting value to enable the current intensity applied to the two ends of the blank to be between 0.1A/cm2～20A/cm2Heating and sintering the blank under current, and electrifying for 3-30 min to obtain an oxide textured ceramic material with certain density;
the two electrodes are made of metal materials or graphite materials with the melting point higher than 1800 ℃;
the two electrodes are flat plate electrodes, wherein tiny circular through holes are uniformly distributed on the flat plate electrodes, the diameter of each through hole is 1-5 mm, and the distribution density of the through holes is 0.5-1/cm2。
2. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the alkali metal oxide is: li2O、Na2O、K2O、Rb2O or Cs2O。
3. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the alkaline earth metal oxide is: BeO, MgO, CaO, SrO or BaO.
4. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the transition metal oxide includes:
divalent transition metal oxide: ZnO, CuO, CdO, FeO, NiO, CoO or MnO; or
Trivalent transition metal oxide: fe2O3、V2O3、Cr2O3Or Sc2O3(ii) a Or
Tetravalent transition metal oxide: ZrO (ZrO)2、TiO2、HfO2、TaO2、VO2Or MnO2(ii) a Or
Pentavalent and hexavalent transition metal oxides: nb2O5、V2O5、Ta2O5Or WO3(ii) a Or
Mixed-valence transition metal oxide: fe3O4、Mn3O4Or Co3O4。
5. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the rare earth metal oxide is: y is2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、Er2O3、EuO、Pm2O3、Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3Or Lu2O3。
6. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the water-soluble metal inorganic salt includes:
alkali metal halides: AX, a ═ Li, Na, K, Rb, or Cs, X ═ F, Cl, Br, or I; or
Alkali metal sulfate: a. the2SO4, a ═ Li, Na, K, Rb, or Cs; or
Alkali metal carbonates: a. the2CO3A ═ Li, Na, K, Rb, or Cs; or
Alkali metal nitrates: ANO3A ═ Li, Na, K, Rb, or Cs; or
Alkaline earth metal halide: BX2B ═ Mg, Ca, Sr or Ba, X ═ F, Cl, Br or I; or
Zinc salt: ZnSO4、ZnNO3Or ZnX2X ═ F, Cl, Br or I; or
Iron salt: FeCl3、Fe2(SO4)3Or Fe (NO)3)3(ii) a Or
Indium salt: InCl3，In2(SO4)3Or In (NO)3)3(ii) a Or
Bismuth salt: BiCl3Or Bi (NO)3)3(ii) a Or
Aluminum salt: AlCl3、Al2(SO4)3Or Al (NO)3)3。
7. The method for preparing the metal oxide textured ceramic material by rapid sintering at normal temperature according to claim 1, which is characterized in that: the water-soluble metal inorganic salt contains crystal water or adsorbed water.
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