CN110451990A - A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature - Google Patents

A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature Download PDF

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CN110451990A
CN110451990A CN201910841234.1A CN201910841234A CN110451990A CN 110451990 A CN110451990 A CN 110451990A CN 201910841234 A CN201910841234 A CN 201910841234A CN 110451990 A CN110451990 A CN 110451990A
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oxide
powder
metal oxide
green body
ceramic
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CN110451990B (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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Northwest University of Technology
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Abstract

The present invention relates to the methods that Fast Sintering under a kind of room temperature prepares metal oxide texture ceramic material, without combining the preparation method of direct Fast Sintering metal oxide textured ceramic or oxide solid solution textured ceramic or composite oxides textured ceramic under high-temperature heater, room temperature with DC electric field directionality effect using heating effect of current.Compared with existing textured ceramic sintering technology, the invention is not necessarily to high temperature furnace apparatus, without prior heating sample, the densification sintering and texture that all kinds of oxide ceramic materials can be realized are formed, short high-efficient, the hardware investment of sintering time is small, energy utilization rate is high, has the characteristics that widely applicable, simple process, energy-saving effect are good, at low cost.It is suitable for large scale preparation oxide textured ceramic, has broad application prospects.

Description

A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature
Technical field
The invention belongs to field of material technology, it is related to Fast Sintering under a kind of room temperature and prepares metal oxide textured ceramic material The method of material, and in particular to one kind is various without being prepared under heating furnace, room temperature using the direct Fast Sintering of DC current fuel factor The preparation method of metal oxide textured ceramic or oxide solid solution textured ceramic or composite oxides textured ceramic.
Background technique
Oxide ceramic material may be used as structural ceramics or ceramic material, generally have many excellent physics and chemistry Performance is such as: chemical stability height, fusing point height, high temperature resistant, resistance to oxidation, corrosion-resistant, wear-resisting, elevated temperature strength is high, mechanical and mechanical property The excellent equal common features of energy, have a wide range of applications in engineering technology and high-tech area.The microcosmic crystal grain edge of oxide ceramics Textured ceramic is formed after the growth of a direction preferred orientation, textured ceramic can greatly improve or give full play to crystal in material Anisotropy associated by physical effect, be one kind have specific characteristics can, up-and-coming new function or structural material.
Currently, the technology of preparing of oxide texture ceramic material mostly uses tape casting, reaction template seed crystal epitaxial growth Orientation process is hot-forged under method, high temperature, temperature gradient assists molten-salt growth method, or ceramic body is placed in while be sintered in high temperature furnace Apply technologies, these technologies such as mechanics extruding under electric field magnetic field or melt directional solidification, high temperature to be required to sample being placed in height After adding to high temperature in warm furnace or in advance, then by applying temperature gradient, mechanics field, electric field, the physical fields such as magnetic field are completed to be sintered, Sintering and texturing process need high temperature furnace apparatus, that there are equipment investments is big, sintering time is long, energy consumption is high, energy utilization rate is low, The technological deficiencies such as at high cost.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that Fast Sintering prepares metal oxide under a kind of room temperature The method of texture ceramic material solves the deficiency or defect of existing oxide textured ceramic technology of preparing.Without high temperature sintering Various metal oxide texture potteries are prepared in conjunction with direct Fast Sintering is carried out using DC potential effect and DC electric field under furnace, room temperature The method of porcelain or oxide solid solution textured ceramic or composite oxides textured ceramic.Solve each type oxide texture pottery at present In ceramic material preparation, hardware investment is big, sintering needs high temperature furnace apparatus, sintering time is long, energy consumption is high, energy utilization rate is low, at This high defect.
Technical solution
A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature, it is characterised in that step is such as Under:
The weighing of step 1, nm-class oxide powder: one or several kinds of metals by granularity between 1nm~500nm aoxidize Object nano-powder is uniformly mixed to get mixed oxide nanoparticle powder and weighs mixed powder gross mass；
The metallic oxide nano powder includes: alkali metal oxide, alkaline earth oxide, transition metal oxide Or rare-earth oxide；
When the unit metal oxide textured ceramic of preparation is alkaline earth oxide textured ceramic, alkaline-earth metal is chosen Nm-class oxide powder is as raw material；
When the unit metal oxide textured ceramic of preparation is transition metal oxide textured ceramic, transition metal is chosen Nm-class oxide powder is as raw material；
When the unit metal oxide textured ceramic of preparation is rare earth oxide textured ceramic, rare earth metal oxidation is chosen Object nano-powder is as raw material；
When the oxide solid solution textured ceramic of preparation, one or more of selection and alkali metal oxide can be formed One of above-mentioned listed alkaline earth oxide, transition metal oxide or the rare-earth oxide of solid solution nano-powder As raw material, or several metallic oxide nano powders for forming solid solution are chosen as raw material；
When the metal composite oxide texture ceramic material of preparation, two or more alkali metal oxide nano-powders are chosen As raw material, or several metallic oxide nano powders are chosen as raw material；
The preparation of the inorganic salt saturated solution of step 2, water-soluble metal: at 4 DEG C~60 DEG C, by the one of water-soluble metal salt Kind is several, is dissolved in, the salt that for hydrolyze generation precipitates uniform with magnetic stirrer after distilled water, addition hydrochloric acid respectively Or the saturated solution of inorganic salts is made until solution is clarified in nitre acid for adjusting pH value；
When selecting water-soluble metal inorganic salts, the cation of inorganic salts should be with the cation of the most oxides of content in ingredient Chemical valence it is inconsistent；
Step 3, the modulation of nm-class oxide powder presoma and wet blank forming:
By metal inorganic salt saturated solution be added mixed oxide nanoparticle powder in, and add distilled water to water content 50~ 90%, stirring hydrous oxide mixed powder to uniform, placement ageing 0.5~24 hour, then at a temperature of 20 DEG C~100 DEG C It is 3%~30% that wet oxide mixed powder, which is dried to water content, obtains metal oxide precursor；It then will be made Metal oxide precursor is put into mold, and wet base is made so that forerunner is body formed in the pressure for applying 0.5MPa~50MPa Body
The gross mass of the water-soluble metal inorganic salts account for the 0.5wt% of metallic oxide nano powder gross mass~ 30wt%；
The direct current sintering texturing of step 4, oxide textured ceramic green body:
At 4 DEG C~60 DEG C, molding wet green body is placed between two electrodes for being connected with DC power supply, and is made just Cathode and green body are in close contact, and open power supply, and adjustment power work state is constant current mode, current limitation value are adjusted, so that applying The current strength at green body both ends is added between 0.1A/cm2~20A/cm2, oxide green body issues thermal sintering in electric current, is powered 3min~30min obtains the oxide texture ceramic material with certain consistency；
Metal material or fusing point of the electrode material using fusing point higher than 1800 DEG C are higher than 1800 DEG C of alloy material Or graphite material.
The alkali metal oxide are as follows: Li2O、Na2O、K2O、Rb2O、Cs2O。
The alkaline earth oxide: BeO, MgO, CaO, SrO, BaO.
The transition metal oxide includes: divalent transition metal oxide: ZnO, CuO, CdO, FeO, NiO, CoO, MnO Or PbO；Trivalent transition metal oxide: Al2O3、Fe2O3、B2O3、V2O3、Cr2O3、In2O3、Sc2O3Or Ga2O3；Tetravalent transition gold Belong to oxide: ZrO2、TiO2、SiO2、GaO2、GeO2、HfO2、TaO2、VO2、MnO2Or SnO2；Pentavalent and sexavalence oxo transition metal Compound: Nb2O5、V2O5、Ta2O5Or WO3；Mixed valence transition metal oxide: Fe3O4、Mn3O4Or Co3O4。
The rare-earth oxide: Y2O3、Sc2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、Er2O3、EuO、Pm2O3、 Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3Or Lu2O3。
The water-soluble metal inorganic salts include: alkali halide: AX, A=Li, Na, K, Rb, Cs, X=F, Cl, Br, I；Or alkali metal sulfates: A2SO4, A=Li, Na, K, Rb, Cs；Or alkali carbonate: A2CO3, A=Li, Na, K, Rb, Cs； Or alkali nitrates: ANO3, A=Li, Na, K, Rb, Cs；Or alkaline-earth halide: BX2, B=Mg, Ca, Sr, Ba, X =F, Cl, Br, I；Or zinc salt: ZnX2, X=F, Cl, Br, I；ZnSO4、ZnNO3；Or molysite: FeCl3、Fe2(SO4)3、Fe (NO3)3；Or indium salts: InCl3, In2(SO4)3, In (NO3)3；Or bismuth salt: BiCl3、Bi(NO3)3；Or aluminium salt: AlCl3、 Al2(SO4)3、Al(NO3)3。
The water-soluble metal inorganic salts contain the crystallization water or absorption water.
The electrode is plate electrode, and small round tube hole, through-hole diameter Φ 1mm are wherein evenly distributed on plate electrode ~5mm, 0.5~1/cm of through-hole distribution density2。
Beneficial effect
The method that Fast Sintering prepares metal oxide texture ceramic material under a kind of room temperature proposed by the present invention, without height Direct Fast Sintering metal oxide is combined with DC electric field directionality effect using heating effect of current under warm heating furnace, room temperature to knit The preparation method of structure ceramic or oxide solid solution textured ceramic or composite oxides textured ceramic.It is burnt with existing textured ceramic Knot technology is compared, which is not necessarily to high temperature furnace apparatus, and without prior heating sample, all kinds of oxide ceramic materials can be realized Densification sintering and texture formed, short high-efficient, the hardware investment of sintering time is small, energy utilization rate is high, have it is widely applicable, Good, the at low cost feature of simple process, energy-saving effect.It is suitable for large scale preparation oxide textured ceramic, there is wide answer Use prospect.
Specific embodiment
Now in conjunction with embodiment, the invention will be further described:
MgO texture ceramic material is quickly prepared at 1:20 DEG C of embodiment without furnace
The weighing of step 1MgO superfine powder: take granularity between 25.00 grams of MgO superfine powder of 1nm~20nm.
The preparation of step 2 sodium chloride saturated solution: pure 1.79 grams of grade sodium chloride of analysis are weighed, at 20 DEG C, by alleged chlorine Change sodium to be added in 5.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of sodium chloride at 20 DEG C is made And solution.
The modulation of step 3MgO superfine powder presoma and wet blank forming: the sodium chloride saturated solution that step 2 is prepared All in injection MgO nano-powder, and MgO nano-powder is stirred to uniform, placement ageing 24 after adding the distilled water of 15.0mL Hour, it is then at 40 DEG C that MgO is dry to water content 13%, obtain MgO presoma；Then made MgO presoma is put Enter in mold, apply pressure 40MPa, so that forerunner is body formed, the wet green body of MgO that diameter is Φ 30mm, thickness 20mm is made.
The direct current of step 4MgO textured ceramic green body is sintered texturing: at 20 DEG C, the wet base of the MgO that step 3 is obtained Body is placed between two graphite electrodes for being connected with DC power supply, and two end faces of positive and negative anodes and green body are in close contact, Middle electrode area size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter on the plate electrode of upper end Φ 1mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, adjusts current limitation Value is 100A, so that the current strength for being applied to green body both ends is 14.14A/cm2, MgO green body issues thermal sintering in electric current, logical Electric 6min, obtaining consistency is 93.5%, edge [111] direction height preferred orientation cube MgO texture ceramic material.
MgO texture ceramic material is quickly prepared at 2:20 DEG C of embodiment without furnace
The weighing of step 1MgO superfine powder: take granularity between 30.00 grams of MgO superfine powder of 5~50nm.
The preparation of step 2 sodium sulphate saturated solution: 0.93 gram of pure grade sodium sulphate powder of analysis is weighed, at 20 DEG C, by sulphur Sour sodium is added in 5.0mL distilled water, uniform with magnetic stirrer, until solution is clarified, the full of sodium sulphate at 20 DEG C is made And solution.
The modulation of step 3MgO superfine powder presoma and wet blank forming: the sodium sulphate saturated solution that step 2 is prepared All in injection MgO, and MgO powder is stirred to uniform, placement ageing 20 hours, then 42 after adding the distilled water of 15.0mL It is at DEG C that MgO is dry to water content 10%, obtain MgO powder presoma；Then made MgO presoma is put into mold, Apply pressure 30MPa, so that forerunner is body formed, the wet green body of MgO that diameter is Φ 40mm, thickness 20mm is made.
The direct current of step 4MgO textured ceramic green body is sintered texturing: at 20 DEG C, the wet base of the MgO that step 3 is obtained Body is placed between two graphite electrodes for being connected with DC power supply, and two end faces of positive and negative anodes and green body are in close contact, Middle electrode area size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter on the plate electrode of upper end Φ 1mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, adjusts current limitation Value is 90A, so that the current strength for being applied to green body both ends is 7.16A/cm2, MgO green body issues thermal sintering in electric current, is powered 9min, obtaining consistency is 84%, edge [111] direction height preferred orientation cube MgO texture ceramic material.
BaO texture ceramic material is quickly prepared at 3:35 DEG C of embodiment without furnace
The weighing of step 1BaO superfine powder: take granularity between 35.00 grams of BaO superfine powder of 10~100nm.
Step 2 prepares saturated potassium chloride solution, aluminum sulfate saturated solution and ferric nitrate saturated solution respectively: weighing respectively The pure grade potassium chloride powder of 0.39 gram of analysis, the pure grade aluminum sulfate powder of 0.43 analysis and 1.66 grams of pure grade nitric acid iron powder bodies of analysis, In At 35 DEG C, above-mentioned alleged potassium chloride is added in 1.0mL distilled water, saturated potassium chloride solution is made；Alleged aluminum sulfate is dissolved in In 1.0mL distilled water, and be added 1.0mol/L hydrochloric acid adjust pH=3 to solution clarify, it is uniform with magnetic stirrer, be made Aluminum sulfate saturated solution at 35 DEG C；Alleged ferric nitrate is dissolved in 1.0mL distilled water, and 1.0mol/L salt acid for adjusting pH is added =3 to solution clarify, it is uniform with magnetic stirrer, the ferric nitrate saturated solution at 35 DEG C is made.
The modulation of step 3BaO superfine powder presoma and wet blank forming: the saturated solution difference that step 2 is prepared is complete Portion is injected in BaO, and stirs BaO powder to uniform, placement ageing 22 hours, then at 80 DEG C after adding the distilled water of 16.0mL It is lower that BaO is dry to water content 3%, obtain BaO powder presoma；Then made BaO presoma is put into mold, is applied The wet green body of BaO that diameter is Φ 30mm, thickness 22mm is made so that forerunner is body formed in pressure 2MPa.
The direct current of step 4BaO textured ceramic green body is sintered texturing: at 35 DEG C, the green body that step 3 is obtained is placed in It is connected between two graphite electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area size Green body upper and lower surfaces are covered, small round tube hole, through-hole diameter Φ 2mm, through-hole distribution are evenly distributed on the plate electrode of upper end 0.5/cm of density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 85A, so that applying The current strength for being added in green body both ends is 12.03A/cm2, BaO green body issues thermal sintering in electric current, and energization 10min obtains densification Degree is 90.2%, edge [100] direction height preferred orientation cube BaO texture ceramic material.
ZnO texture ceramic material is quickly prepared at 4:30 DEG C of embodiment without furnace
The weighing of step 1ZnO superfine powder: take granularity between 40.00 grams of ultrafine ZnO powder of 5~50nm.
The preparation of step 2 saturated potassium chloride solution: 1.86 grams of pure grade potassium chloride powders of analysis are weighed, at 30 DEG C, by chlorine Change potassium to be added in 5.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of potassium chloride at 30 DEG C is made And solution.
The modulation of step 3ZnO superfine powder presoma and wet blank forming: the saturated potassium chloride solution that step 2 is prepared All in injection ZnO, and ZnO powder is stirred to uniform, placement ageing 19 hours, then 60 after adding the distilled water of 20.0mL It is at DEG C that ZnO is dry to water content 3%, obtain ZnO powder presoma；Then made ZnO precursor is put into mold, is applied The wet green body of ZnO that diameter is Φ 40mm, thickness 20mm is made so that forerunner is body formed in plus-pressure 0.5MPa.
The direct current of step 4ZnO textured ceramic green body is sintered texturing: at 30 DEG C, the green body that step 3 is obtained is placed in It is connected between two graphite electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area size Green body upper and lower surfaces are covered, small round tube hole, through-hole diameter Φ 3mm, through-hole distribution are evenly distributed on the plate electrode of upper end 1/cm of density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 95A, so that applying Current strength at green body both ends is 7.56A/cm2, ZnO green body issues thermal sintering in electric current, and energization 10min obtains consistency The ZnO texture ceramic material of wurtzite structure for 97.2%, along [0001] direction height preferred orientation.
ZnO texture ceramic material is quickly prepared at 5:30 DEG C of embodiment without furnace
The weighing of step 1ZnO superfine powder: take granularity between 20.00 grams of ultrafine ZnO powder of 10~100nm.
The preparation of step 2 sodium nitrate saturated solution: 0.87 gram of pure grade sodium nitrate powder of analysis is weighed, at 20 DEG C, by nitre Sour sodium is added in 1.0mL distilled water, uniform with magnetic stirrer, until solution is clarified, the full of sodium nitrate at 20 DEG C is made And solution.
The modulation of step 3ZnO superfine powder presoma and wet blank forming: the sodium nitrate saturated solution that step 2 is prepared All in injection ZnO, and ZnO powder is stirred to uniform, placement ageing 24 hours, then 40 after adding the distilled water of 10.0mL It is at DEG C that ZnO is dry to water content 20%, obtain ZnO powder presoma；Then made ZnO precursor is put into mold, Apply pressure 0.5MPa, so that forerunner is body formed, the wet green body of ZnO that diameter is Φ 20mm, thickness 20mm is made.
The direct current of step 4ZnO textured ceramic green body is sintered texturing: at 30 DEG C, the green body that step 3 is obtained is placed in It is connected between two molybdenum electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area size is covered Lid green body upper and lower surfaces, are evenly distributed with small round tube hole on the plate electrode of upper end, through-hole diameter Φ 1mm, and through-hole distribution is close Spend 0.5/cm2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 60A, so that applying Current strength at green body both ends is 19.10A/cm2, ZnO green body issues thermal sintering in electric current, and energization 6min obtains consistency The ZnO texture ceramic material of wurtzite structure for 96.5%, along [0001] direction height preferred orientation.
α-Al is quickly prepared at 6:30 DEG C of embodiment without furnace2O3Texture ceramic material
Step 1 α-Al2O3The weighing of superfine powder: α-Al of the granularity between 1~30nm is taken2O320.00 grams of superfine powder.
The preparation of step 2 calcium chloride saturated solution: 1.00 grams of pure grade calcium chloride powders of analysis are weighed, at 30 DEG C, by chlorine Change calcium to be added in 1.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of calcium chloride at 30 DEG C is made And solution.
Step 3 α-Al2O3The modulation of superfine powder presoma and wet blank forming: the calcium chloride saturation that step 2 is prepared is molten Liquid all injects Al2O3In, and Al is stirred after adding the distilled water of 10.0mL2O3Powder places ageing 24 hours, so to uniform Afterwards by Al at 50 DEG C2O3Drying obtains Al to water content 30%2O3Powder presoma；Then by made Al2O3Presoma is put Enter in mold, apply pressure 35MPa, so that forerunner is body formed, the Al that diameter is Φ 30mm, thickness 20mm is made2O3Wet green body.
Step 4 α-Al2O3The direct current of textured ceramic green body is sintered texturing: at 30 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 5mm, through-hole on the plate electrode of upper end 0.5/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 35A, is made The current strength that green body both ends must be applied to is 5A/cm2, Al2O3Green body issues thermal sintering in electric current, and energization 30min is caused Density is 97.5%, edge [0001] direction height preferred orientation α-Al2O3Texture ceramic material.
α-Al is quickly prepared at 7:20 DEG C of embodiment without furnace2O3Texture ceramic material
Step 1 α-Al2O3The weighing of superfine powder: Al of the granularity between 5~50nm is taken2O320.00 grams of superfine powder.
The preparation of step 2 barium chloride saturated solution: 0.90 gram of pure grade barium chloride powder of analysis is weighed, at 20 DEG C, by chlorine Change barium to be added in 2.5mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of barium chloride at 20 DEG C is made And solution.
Step 3 α-Al2O3The modulation of superfine powder presoma and wet blank forming: the barium chloride saturation that step 2 is prepared is molten Liquid all injects Al2O3In, and Al is stirred after adding the distilled water of 10.0mL2O3Powder places ageing 22 hours, so to uniform Afterwards by Al at 38 DEG C2O3Drying obtains Al to water content 18%2O3Powder presoma；Then by made Al2O3Presoma is put Enter in mold, apply pressure 35MPa, so that forerunner is body formed, the Al that diameter is Φ 30mm, thickness 20mm is made2O3Wet green body.
Step 4 α-Al2O3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two molybdenum alloy electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode surface Product size covers green body upper and lower surfaces, and small round tube hole is evenly distributed on the plate electrode of upper end, and through-hole diameter Φ 4mm leads to 0.5/cm of pore size distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 80A, So that the current strength for being applied to green body both ends is 11.32A/cm2, Al2O3Green body issues thermal sintering in electric current, energization 10min, Obtaining consistency is 84%, edge [0001] direction height preferred orientation Al2O3Texture ceramic material.
α-Fe is quickly prepared at 8:30 DEG C of embodiment without furnace2O3Texture ceramic material
Step 1 α-Fe2O3The weighing of superfine powder: α-Fe of the granularity between 10~300nm is taken2O3Superfine powder 35.00 Gram.
Step 2 prepares the saturated solution of zinc sulfate, lithium nitrate, sodium chloride and barium chloride respectively: it is pure to weigh 0.50 gram of analysis Level zinc sulfate powder, the pure grade nitric acid powder for lithium of 0.97 gram of analysis, 0.36 gram of pure grade sodium chloride powder of analysis and 0.25 gram of analysis are pure Grade barium chloride powder the zinc sulfate powder of weighing is added in 0.7mL distilled water, and 1.0mol/L hydrochloric acid is added at 30 DEG C Adjust pH=3 to solution clarify, it is uniform with magnetic stirrer, the aluminum sulfate saturated solution at 30 DEG C is made；By weighing Nitric acid powder for lithium is added in 0.7mL distilled water, and 1.0mol/L hydrochloric acid is added and adjusts pH=3 to solution clarification, uses magnetic agitation Device stirs evenly, and the lithium nitrate saturated solution at 30 DEG C is made；The sodium chloride powder of weighing is added in 0.7mL distilled water, is used Magnetic stirrer is uniform, and the sodium chloride saturated solution at 30 DEG C is made；0.7mL distillation is added in the barium chloride powder of weighing It is uniform with magnetic stirrer in water, the barium chloride saturated solution at 30 DEG C is made.
Step 3 α-Fe2O3The modulation of superfine powder presoma and wet blank forming: the saturated solution that step 2 is prepared is distinguished All injection Fe2O3In, and Fe is stirred after adding the distilled water of 18.0mL2O3Powder places ageing 12 hours, then to uniform By Fe at 39 DEG C2O3Drying obtains Fe to water content 18%2O3Powder presoma；Then by made Fe2O3Presoma is put into In mold, apply pressure 40MPa, so that forerunner is body formed, the Fe that diameter is Φ 30mm, thickness 20mm is made2O3Wet green body.
Step 4 α-Fe2O3The direct current of textured ceramic green body is sintered texturing: at 30 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole on the plate electrode of upper end 0.6/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 3.6A, is made The current strength that green body both ends must be applied to is 0.5A/cm2, Fe2O3Green body issues thermal sintering in electric current, and energization 30min is obtained Consistency is 96.7%, edge [0001] direction height preferred orientation α-Fe2O3Texture ceramic material.
9:30 DEG C of embodiment quickly prepares TiO without furnace2Texture ceramic material
Step 1 rutile TiO2The weighing of superfine powder: take granularity between the TiO of the rutile structure of 10~100nm2It is super 50.00 grams of fine powder.
The preparation of step 2 aluminium chloride saturated solution: 1.41 grams of pure grade aluminium chloride powders of analysis are weighed, aluminium chloride is added Uniform with magnetic stirrer in 3.0mL distilled water, the hydrochloric acid tune pH=3 that 1.0mol/L is added is clarified to solution, is made 30 The saturated solution of aluminium chloride at DEG C.
Step 3TiO2The modulation of superfine powder presoma and wet blank forming: the aluminium chloride saturated solution that step 2 is prepared All injection TiO2In, and TiO is stirred after adding the distilled water of 25.0mL2Powder places ageing 22 hours, then exists to uniform By TiO at 45 DEG C2Drying obtains TiO to water content 18%2Powder presoma；Then by made TiO2Presoma is put into mold In, apply pressure 43MPa, so that forerunner is body formed, the TiO that diameter is Φ 40mm, thickness 20mm is made2Wet green body.
Step 4 rutile TiO2The direct current of textured ceramic green body is sintered texturing: at 30 DEG C, step 3 being obtained Green body is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole on the plate electrode of upper end, through-hole diameter Φ 1mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, adjusts current limitation value and is 110A, so that the current strength for being applied to green body both ends is 8.75A/cm2, TiO2Ceramic body issues thermal sintering in electric current, is powered 10min, obtaining consistency is 92%, edge [001] direction height preferred orientation rutile TiO2Texture ceramic material.
Rutile TiO is quickly prepared at 10:20 DEG C of embodiment without furnace2Texture ceramic material
Step 1 rutile TiO2The weighing of superfine powder: rutile structure TiO of the granularity between 10~100nm is taken2It is ultra-fine 20.00 grams of powder.
The preparation of step 2 iron chloride saturated solution: 0.92 gram of pure grade chlorination iron powder body of analysis is weighed, at 20 DEG C, by chlorine Change iron to be added in 1.0mL distilled water, uniform with magnetic stirrer, addition 1.0mol/L hydrochloric acid tune pH=3 to solution is clarified, The saturated solution of iron chloride at 20 DEG C is made.
Step 3TiO2The modulation of superfine powder presoma and wet blank forming: the iron chloride saturated solution that step 2 is prepared All injection TiO2In, and TiO is stirred after adding the distilled water of 10.0mL2Powder places ageing 22 hours, then exists to uniform By TiO at 20 DEG C2Drying obtains TiO to water content 16%2Powder presoma；Then by made TiO2Presoma is put into mold In, apply pressure 39MPa, so that forerunner is body formed, the TiO that diameter is Φ 30mm, thickness 15mm is made2Wet green body.
Step 4TiO2The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, the green body that step 3 is obtained is set Between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode area is big Small covering green body upper and lower surfaces are evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole point on the plate electrode of upper end 0.5/cm of cloth density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 40A, so that The current strength for being applied to green body both ends is 5.7A/cm2, TiO2Ceramic body issues thermal sintering in electric current, and energization 15min is obtained Consistency is 92.3%, edge [001] direction height preferred orientation rutile TiO2Texture ceramic material.
α-MnO is quickly prepared at 11:30 DEG C of embodiment without furnace2Texture ceramic material
Step 1 α-MnO2The weighing of superfine powder: α-MnO of the granularity between 20~200nm is taken227.00 grams of superfine powder.
Step 2 prepares the saturated solution of potassium nitrate, lithium sulfate and iron chloride respectively: weighing 0.45 gram of pure grade potassium nitrate of analysis Powder takes the pure grade sulfuric acid powder for lithium of 0.34 gram of analysis and takes 1.07 grams of pure grade chlorination iron powder bodies of analysis, at 30 DEG C, by weighing Potassium nitrate powder is added in 5.0mL distilled water, uniform with magnetic stirrer, and the potassium nitrate saturated solution at 30 DEG C is made； The sulfuric acid powder for lithium of weighing is added in 5.0mL distilled water, and 1.0mol/L hydrochloric acid is added and adjusts pH=3 to solution clarification, is used Magnetic stirrer is uniform, and the lithium sulfate saturated solution at 30 DEG C is made；5.0mL distillation is added in the chlorination iron powder body of weighing In water, and be added 1.0mol/L hydrochloric acid adjust pH=3 to solution clarify, it is uniform with magnetic stirrer, be made at 30 DEG C Iron chloride saturated solution.
Step 3 α-MnO2The modulation of superfine powder presoma and wet blank forming: the saturated solution that step 2 is prepared is distinguished All injection MnO2In, and MnO is stirred after adding the distilled water of 15.0mL2Powder places ageing 21 hours, then exists to uniform By MnO at 46 DEG C2Drying obtains MnO to water content 16%2Powder presoma；Then by made MnO2Presoma is put into mold In, apply pressure 41MPa, so that forerunner is body formed, the MnO that diameter is Φ 30mm, thickness 15mm is made2Wet green body.
Step 4 α-MnO2The direct current of textured ceramic green body is sintered texturing: at 30 DEG C, green body that step 3 is obtained It is placed between two molybdenum alloy electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode surface Product size covers green body upper and lower surfaces, and small round tube hole is evenly distributed on the plate electrode of upper end, and through-hole diameter Φ 1mm leads to 0.5/cm of pore size distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 45A, So that the current strength for being applied to green body both ends is 6.4A/cm2, MnO2Ceramic body issues thermal sintering in electric current, energization 18min, Obtaining consistency is 93.8%, edge [0001] direction height preferred orientation α-MnO2Texture ceramic material.
B-Nb is quickly prepared without furnace at 12:4 DEG C of embodiment2O5Texture ceramic material
Step 1Nb2O5The weighing of superfine powder: B-Nb of the granularity between 20~100nm is taken2O520.00 grams of superfine powder.
The preparation of step 2 sodium chloride saturated solution: 1.06 grams of pure grade sodium chloride powders of analysis are weighed, at 4 DEG C, by chlorination Sodium is added in 3.0mL distilled water, uniform with magnetic stirrer, until solution is clarified, the saturation that sodium chloride at 4 DEG C is made is molten Liquid.
Step 3Nb2O5The modulation of superfine powder presoma and wet blank forming: the sodium chloride saturated solution that step 2 is prepared All injection Nb2O5In, and Nb is stirred after adding the distilled water of 10.0mL2O5Powder places ageing 21 hours, then to uniform By Nb at 45 DEG C2O5Drying obtains Nb to water content 16%2O5Powder presoma；Then by made Nb2O5Presoma is put into In mold, apply pressure 33MPa, so that forerunner is body formed, the Nb that diameter is Φ 30mm, thickness 15mm is made2O5Wet green body.
Step 4B-Nb2O5The direct current of textured ceramic green body is sintered texturing: at 4 DEG C, the green body that step 3 is obtained is set Between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode area is big Small covering green body upper and lower surfaces are evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole point on the plate electrode of upper end 0.5/cm of cloth density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 70A, so that The current strength for being applied to green body both ends is 9.8A/cm2, Nb2O5Ceramic body issues thermal sintering in electric current, and energization 8min is obtained Consistency is 97.5%, edge [110] direction height preferred orientation B-Nb2O5Texture ceramic material.
B-Nb is quickly prepared without furnace at 13:20 DEG C of embodiment2O5Texture ceramic material
Step 1Nb2O5The weighing of superfine powder: B-Nb of the granularity between 30~300nm is taken2O525.00 grams of superfine powder.
The preparation of step 2 zinc chloride saturated solution: 1.98 grams of pure grade zinc chloride powders of analysis are weighed, at 20 DEG C, by chlorine Change zinc to be added in 0.5mL distilled water, it is uniform with magnetic stirrer, hydrochloric acid tune pH=3 is added and is clarified to solution, is made 20 DEG C The saturated solution of lower zinc chloride.
Step 3Nb2O5The modulation of superfine powder presoma and wet blank forming: the zinc chloride saturated solution that step 2 is prepared All injection Nb2O5In, and Nb is stirred after adding the distilled water of 15.0mL2O5Powder places ageing 23 hours, then to uniform By Nb at 36 DEG C2O5Drying obtains Nb to water content 15%2O5Powder presoma；Then by made Nb2O5Presoma is put into In mold, apply pressure 42MPa, so that forerunner is body formed, the Nb that diameter is Φ 30mm, thickness 16mm is made2O5Wet green body.
Step 4B-Nb2O5The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole on the plate electrode of upper end 0.5/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 50A, is made The current strength that green body both ends must be applied to is 7.1A/cm2, Nb2O5Ceramic body issues thermal sintering in electric current, energization 18min, Obtaining consistency is 95.6%, edge [110] direction height preferred orientation B-Nb2O5Texture ceramic material.
WO is quickly prepared without furnace at 14:30 DEG C of embodiment3Texture ceramic material
Step 1WO3The weighing of superfine powder: WO of the granularity between 50~500nm is taken340.00 grams of superfine powder.
Step 2 prepares the saturated solution of potassium chloride, zinc nitrate and aluminum sulfate respectively: weighing 0.37 gram of pure grade potassium chloride of analysis Powder takes the pure grade zinc nitrate powder of 1.38 grams of analyses and takes 0.40 gram of pure grade aluminum sulfate powder of analysis, at 30 DEG C, by weighing Potassium chloride powder is added in 1.0mL distilled water, uniform with magnetic stirrer, and the saturated potassium chloride solution at 30 DEG C is made； The zinc nitrate powder of weighing is added in 1.0mL distilled water, and 1.0mol/L hydrochloric acid is added and adjusts pH=3 to solution clarification, is used Magnetic stirrer is uniform, and the zinc nitrate saturated solution at 30 DEG C is made；1.0mL distillation is added in the aluminum sulfate powder of weighing In water, and be added 1.0mol/L hydrochloric acid adjust pH=3 to solution clarify, it is uniform with magnetic stirrer, be made at 30 DEG C Aluminum sulfate saturated solution.
Step 3WO3The modulation of superfine powder presoma and wet blank forming: the saturated solution difference that step 2 is prepared is complete WO is injected in portion3In, and WO is stirred after adding the distilled water of 20mL3Powder places ageing 23 hours, then at 37 DEG C to uniform By WO3Drying obtains WO to water content 15%3Powder presoma；Then by made WO3Presoma is put into mold, applies pressure The WO that diameter is Φ 30mm, thickness 16mm is made so that forerunner is body formed in power 40MPa3Wet green body.
Step 4WO3The direct current of textured ceramic green body is sintered texturing: at 30 DEG C, the green body that step 3 is obtained is placed in It is connected between two graphite electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area size Green body upper and lower surfaces are covered, small round tube hole, through-hole diameter Φ 1mm, through-hole distribution are evenly distributed on the plate electrode of upper end 0.5/cm of density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 20A, so that applying The current strength for being added in green body both ends is 2.9A/cm2, WO3Ceramic body issues thermal sintering in electric current, and energization 25min is caused Density is 95.9%, edge [110] direction height preferred orientation WO3Texture ceramic material.
Fe is quickly prepared without furnace at 15:20 DEG C of embodiment3O4Texture ceramic material
Step 1Fe3O4The weighing of superfine powder: Fe of the granularity between 1~20nm is taken3O440.00 grams of superfine powder.
The preparation of step 2 potassium nitrate saturated solution: 1.58 grams of pure grade potassium nitrate powders of analysis are weighed, at 20 DEG C, by nitre Sour potassium is added in 5.0mL distilled water, uniform with magnetic stirrer, until solution is clarified, the full of potassium nitrate at 20 DEG C is made And solution.
Step 3Fe3O4The modulation of superfine powder presoma and wet blank forming: the potassium nitrate saturated solution that step 2 is prepared All injection Fe3O4In, and Fe is stirred after adding the distilled water of 20.0mL3O4Powder places ageing 0.5 hour, then to uniform By Fe at 37 DEG C3O4Drying obtains Fe to water content 15%3O4Powder presoma；Then by made Fe3O4Presoma is put into In mold, apply pressure 41MPa, so that forerunner is body formed, the Fe that diameter is Φ 30mm, thickness 25mm is made3O4Wet green body.
Step 4Fe3O4The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, the green body that step 3 is obtained is set Between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode area is big Small covering green body upper and lower surfaces are evenly distributed with small round tube hole, through-hole diameter Φ 3mm, through-hole point on the plate electrode of upper end 0.5/cm of cloth density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 0.7A, so that The current strength for being applied to green body both ends is 0.1A/cm2, Fe3O4Ceramic body issues thermal sintering in electric current, and energization 30min is obtained It is 88.4%, edge [100] direction height preferred orientation Fe to consistency3O4Texture ceramic material.
Fe is quickly prepared without furnace at 16:60 DEG C of embodiment3O4Texture ceramic material
Step 1Fe3O4The weighing of superfine powder: Fe of the granularity between 1~20nm is taken3O440.00 grams of superfine powder.
The preparation of step 2 sodium bromide saturated solution: 1.18 grams of pure grade sodium bromide powders of analysis are weighed, at 60 DEG C, by chlorine Change lithium to be added in 1.0mL distilled water, is uniformly clarified with magnetic stirrer, the saturated solution of sodium bromide at 60 DEG C is made.
Step 3Fe3O4The modulation of superfine powder presoma and wet blank forming: the sodium bromide saturated solution that step 2 is prepared All injection Fe3O4In, and Fe is stirred after adding the distilled water of 20.0mL3O4Powder places ageing 2 hours, then exists to uniform By Fe at 60 DEG C3O4Drying obtains Fe to water content 20%3O4Powder presoma；Then by made Fe3O4Presoma is put into mould In tool, apply pressure 35MPa, so that forerunner is body formed, the Fe that diameter is Φ 30mm, thickness 30mm is made3O4Wet green body.
Step 4Fe3O4The direct current of textured ceramic green body is sintered texturing: at 60 DEG C, the green body that step 3 is obtained is set Between two molybdenum electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode area size Green body upper and lower surfaces are covered, small round tube hole, through-hole diameter Φ 1mm, through-hole distribution are evenly distributed on the plate electrode of upper end 0.5/cm of density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 9A, so that applying Current strength at green body both ends is 1.28A/cm2, Fe3O4Ceramic body issues thermal sintering in electric current, and energization 21min is caused Density is 93.2%, edge [100] direction height preferred orientation Fe3O4Texture ceramic material.
Y is quickly prepared without furnace at 17:20 DEG C of embodiment2O3Texture ceramic material
Step 1Y2O3The weighing of superfine powder: Y of the granularity between 10~100nm is taken2O330.00 grams of superfine powder.
The preparation of step 2 barium chloride saturated solution: 0.72 gram of pure grade barium chloride powder of analysis is weighed, at 20 DEG C, by chlorine Change barium to be added in 2.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of barium chloride at 20 DEG C is made And solution.
Step 3Y2O3The modulation of superfine powder presoma and wet blank forming: the barium chloride saturated solution that step 2 is prepared All injection Y2O3In, and Y is stirred after adding the distilled water of 20.0mL2O3Powder places ageing 2 hours, then 48 to uniform By Y at DEG C2O3Drying obtains Y to water content 18%2O3Powder presoma；Then by made Y2O3Presoma is put into mold, Apply pressure 40MPa, so that forerunner is body formed, the Y that diameter is Φ 30mm, thickness 20mm is made2O3Wet green body.
Step 4Y2O3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, the green body that step 3 is obtained is placed in It is connected between two zirconium titanium maxter alloy electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode surface Product size covers green body upper and lower surfaces, and small round tube hole is evenly distributed on the plate electrode of upper end, and through-hole diameter Φ 2mm leads to 0.5/cm of pore size distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 71A, So that the current strength for being applied to green body both ends is 10A/cm2, Y2O3Ceramic body issues thermal sintering in electric current, energization 10min, Obtaining consistency is 95.8%, edge [100] direction height preferred orientation cube Y2O3Texture ceramic material.
Y is quickly prepared without furnace at 18:40 DEG C of embodiment2O3Texture ceramic material
Step 1Y2O3The weighing of superfine powder: Y of the granularity between 10~100nm is taken2O335.00 grams of superfine powder.
Step 2 prepares the saturated solution of sodium chloride and potassium sulfate respectively: weigh 1.08 grams of pure grade sodium chloride powders of analysis and Take 0.39 gram of pure grade potassium sulfate powder of analysis that the sodium chloride powder of weighing is added in 3.0mL distilled water, uses magnetic at 40 DEG C Power blender stirs evenly, and the sodium chloride saturated solution at 30 DEG C is made；3.0mL distilled water is added in the potassium sulfate powder of weighing In, it is uniform with magnetic stirrer, the potassium sulfate saturated solution at 30 DEG C is made.
Step 3Y2O3The modulation of superfine powder presoma and wet blank forming: the saturated solution difference that step 2 is prepared is complete Y is injected in portion2O3In, and Y is stirred after adding the distilled water of 18.0mL2O3Powder places ageing 24 hours, then 38 to uniform By Y at DEG C2O3Drying obtains Y to water content 12%2O3Powder presoma；Then by made Y2O3Presoma is put into mold, Apply pressure 36MPa, so that forerunner is body formed, the Y that diameter is Φ 30mm, thickness 25mm is made2O3Wet green body.
Step 4Y2O3The direct current of textured ceramic green body is sintered texturing: at 40 DEG C, the green body that step 3 is obtained is placed in It is connected between two graphite electrodes of DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area size Green body upper and lower surfaces are covered, small round tube hole, through-hole diameter Φ 3mm, through-hole distribution are evenly distributed on the plate electrode of upper end 0.5/cm of density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 141A, so that applying The current strength for being added in green body both ends is 20A/cm2, Y2O3Ceramic body issues thermal sintering in electric current, and energization 4min obtains densification Degree 94.3%, edge [100] direction height preferred orientation cube Y2O3Texture ceramic material.
Without the quick spinelle (MgOAl of furnace at 19:20 DEG C of embodiment2O3) texture ceramic material
Step 1MgO and Al2O3The weighing of superfine powder: weigh 20.00 gram particle degree between 10~100nm MgO it is ultra-fine Powder and 7.91 gram particle degree are homogenously mixed together between the superfine powder of the aluminium oxide of 5~50nm.
The preparation of step 2 sodium chloride saturated solution: 0.72 gram of pure grade sodium chloride powder of analysis is weighed, at 20 DEG C, by chlorine Change sodium to be added in 2.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of sodium chloride at 20 DEG C is made And solution.
Step 3MgOAl2O3The modulation of superfine powder presoma and wet blank forming: the sodium chloride that step 2 is prepared is satisfied Powder is stirred to uniform, placement ageing 12 in solution all injection mixed powder, and after adding the distilled water of 10.0mL Hour, it is then at 39 DEG C that mixed powder is dry to water content 14%, obtain mixed powder presoma；It then will be made MgO·Al2O3Presoma is put into mold, applies pressure 40MPa, so that forerunner is body formed, it is Φ 30mm, thickness that diameter, which is made, The MgOAl of 25mm2O3Wet green body.
Step 4MgOAl2O3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, base that step 3 is obtained Body is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode surface Product size covers green body upper and lower surfaces, and small round tube hole is evenly distributed on the plate electrode of upper end, and through-hole diameter Φ 1mm leads to 0.5/cm of pore size distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 80A, So that the current strength for being applied to green body both ends is 11.4A/cm2, MgOAl2O3Ceramic body issues thermal sintering in electric current, leads to Electric 9min, obtaining consistency is 94.2%, edge [111] direction height preferred orientation MgOAl2O3Texture ceramic material.
Spinelle (MgOAl is quickly prepared at 20:20 DEG C of embodiment without furnace2O3) texture ceramic material
Step 1MgO and Al2O3The weighing of superfine powder: weigh 20.00 gram particle degree between the MgO of 55nm superfine powder and 7.91 gram particle degree are homogenously mixed together between the superfine powder of the aluminium oxide of 40nm；
The preparation of step 2 potassium bromide saturated solution: 0.65 gram of pure grade potassium bromide powder of analysis is weighed, at 20 DEG C, by bromine Change potassium to be added in 1.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of potassium bromide at 20 DEG C is made And solution.
Step 3MgOAl2O3The modulation of superfine powder presoma and wet blank forming: the potassium bromide that step 2 is prepared is satisfied Powder is stirred to uniform, placement ageing 22 in solution all injection mixed powder, and after adding the distilled water of 15.0mL Hour, it is then at 45 DEG C that mixed powder is dry to water content 16%, obtain mixed powder presoma；It then will be made MgO·Al2O3Presoma is put into mold, applies pressure 50MPa, so that forerunner is body formed, it is Φ 30mm, thickness that diameter, which is made, The MgOAl of 20mm2O3Wet green body.
Step 4MgOAl2O3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, base that step 3 is obtained Body is placed between two electric molybdenum poles for being connected with DC power supply, and positive and negative anodes and green body are in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole on the plate electrode of upper end 0.8/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 49A, is made The current strength that green body both ends must be applied to is 7A/cm2, MgOAl2O3Ceramic body issues thermal sintering in electric current, is powered 15min, obtaining consistency is 95.8%, edge [111] direction height preferred orientation MgOAl2O3Texture ceramic material.
BaTiO is quickly prepared without furnace at 21:20 DEG C of embodiment3Texture ceramic material
Step 1BaO and TiO2The weighing of superfine powder: weigh 30.00 gram particle degree between 20~200nm BaO it is ultra-fine It powder and takes 15.63 gram particle degree between the superfine powder of the titanium oxide of 10~100nm, is homogenously mixed together.
The preparation of step 2 ferric nitrate saturated solution: 1.38 grams of pure grade nitric acid iron powder bodies of analysis are weighed, at 20 DEG C, by nitre Sour iron is added in 1.0mL distilled water, uniform with magnetic stirrer, and addition 1.0mol/L nitric acid tune pH=3 to solution is clarified, The saturated solution of ferric nitrate at 20 DEG C is made.
Step 3BaTiO3The modulation of superfine powder presoma and wet blank forming: the ferric nitrate saturation that step 2 is prepared is molten Liquid is all in injection mixed powders, and adds and be stirred powder after the distilled water of 25.0mL to uniform, places ageing 22 hours, Then by BaTiO at 45 DEG C3Drying obtains mixed powder presoma to water content 15%；Then by made BaTiO3Forerunner Body is put into mold, applies pressure 46MPa, so that forerunner is body formed, the BaTiO that diameter is Φ 30mm, thickness 25mm is made3It is wet Green body.
Step 4BaTiO3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 2mm, through-hole on the plate electrode of upper end 0.5/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 60A, is made The current strength that green body both ends must be applied to is 8.6A/cm2, BaTiO3Ceramic body issues thermal sintering in electric current, energization 10min, Obtain consistency be 96.9%, along [001] direction height preferred orientation perovskite structure BaTiO3Texture ceramic material.
BaTiO is quickly prepared without furnace at 22:20 DEG C of embodiment3Texture ceramic material
Step 1BaO and TiO2The weighing of superfine powder: weigh 60.00 gram particle degree between 20~200nm BaO it is ultra-fine It powder and takes 31.27 gram particle degree between the superfine powder of the titanium oxide of 10~100nm, is homogenously mixed together.
Step 2 prepares the saturated solution of lithium chloride, potassium sulfate and aluminum nitrate respectively: weighing 0.84 gram of pure grade lithium chloride of analysis Powder, the pure grade potassium sulfate powder of 0.11 gram of analysis and 0.74 gram of pure grade aluminum nitrate powder of analysis, at 20 DEG C, by the chlorination of weighing Powder for lithium is added in 1.0mL distilled water, uniform with magnetic stirrer, and 1.0mol/L hydrochloric acid tune pH=3 is added until solution Clarification, is made the lithium chloride saturated solution at 20 DEG C；The potassium sulfate powder of weighing is added in 1.0mL distilled water, is stirred with magnetic force It mixes device to stir evenly, until solution is clarified, the potassium sulfate saturated solution at 20 DEG C is made；The aluminum nitrate powder of weighing is added It is uniform with magnetic stirrer in 1.0mL distilled water, 1.0mol/L nitric acid tune pH=3 is added until solution clarification, is made 20 Aluminum nitrate saturated solution at DEG C.
Step 3BaTiO3The modulation of superfine powder presoma and wet blank forming: the saturated solution that step 2 is prepared is distinguished It all in injection mixed powders, and adds and is stirred powder after the distilled water of 50.0mL to uniform, place ageing 21 hours, so It is at 46 DEG C that mixed powder is dry to water content 14% afterwards, obtain mixed powder presoma；Then by made BaTiO3Before It drives body to be put into mold, applies pressure 42MPa, so that forerunner is body formed, the BaTiO that diameter is Φ 30mm, thickness 25mm is made3 Wet green body.
Step 4BaTiO3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole on the plate electrode of upper end 1/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 50A, so that The current strength for being applied to green body both ends is 7.64A/cm2, BaTiO3Ceramic body issues thermal sintering in electric current, energization 12min, Obtain consistency be 92.2%, along [001] direction height preferred orientation perovskite structure BaTiO3Texture ceramic material.
LiNbO is quickly prepared without furnace at 23:20 DEG C of embodiment3Texture ceramic material
Step 1Li2O and Nb2O5The weighing of superfine powder: weigh 5.06 gram particle degree between 50~500nm lithia it is super It fine powder and takes 45.00 gram particle degree between the superfine powder of the niobium oxide of 20~200nm, is homogenously mixed together.
Step 2 prepares the saturated solution of zinc chloride, ferric sulfate and aluminum nitrate respectively: weighing 1.98 grams of pure grade zinc chloride of analysis Powder, the pure grade sulfuric acid iron powder body of 2.2 grams of analyses and 0.37 gram of pure grade aluminum nitrate powder of analysis, at 20 DEG C, by the chlorination of weighing Zinc powder body is added in 0.5mL distilled water, uniform with magnetic stirrer, and 1.0mol/L hydrochloric acid tune pH=3 is added until solution Clarification, is made the zinc chloride saturated solution at 20 DEG C；The sulfuric acid iron powder body of weighing is added in 0.5mL distilled water, is stirred with magnetic force It mixes device to stir evenly, 1.0mol/L hydrochloric acid tune pH=3 is added until solution clarification, is made the ferric sulfate saturated solution at 20 DEG C； The aluminum nitrate powder of weighing is added in 0.5mL distilled water, it is uniform with magnetic stirrer, 1.0mol/L nitric acid tune pH is added =3 until solution clarification, is made the aluminum nitrate saturated solution at 20 DEG C.
Step 3LiNbO3The modulation of superfine powder presoma and wet blank forming: the saturated solution that step 2 is prepared is distinguished It all in injection mixed powders, and adds and is stirred powder after the distilled water of 30.0mL to uniform, place ageing 21 hours, so It is at 48 DEG C that mixed powder is dry to water content 13% afterwards, obtain mixed powder presoma；Then by made LiNbO3Before It drives body to be put into mold, applies pressure 32MPa, so that forerunner is body formed, the LiNbO that diameter is Φ 30mm, thickness 25mm is made3 Wet green body.
Step 4LiNbO3The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two graphite electrodes for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area Size covers green body upper and lower surfaces, is evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole on the plate electrode of upper end 0.5/cm of distribution density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 30A, is made The current strength that green body both ends must be applied to is 4.2A/cm2, LiNbO3Ceramic body issues thermal sintering in electric current, energization 7min, Obtain consistency be 91.8%, along [001] direction height preferred orientation ilmenite type structure LiNbO3Textured ceramic material Material.
Zirconic acid lanthanum (La is quickly prepared at 24:20 DEG C of embodiment without furnace2Zr2O7) texture ceramic material
Step 1La2O3And ZrO2The weighing of superfine powder: the lanthana of 33.05 gram particle degree between 10~100nm is weighed Superfine powder and 25.00 gram particle degree are homogenously mixed together between the superfine powder of the zirconium oxide of 10~100nm.
The preparation of step 2 lithium chloride saturated solution: 1.67 grams of pure grade chlorination powder for lithium of analysis are weighed, at 20 DEG C, by chlorine Change lithium to be added in 2.0mL distilled water, it is uniform with magnetic stirrer, the saturated solution of lithium chloride at 20 DEG C is made.
Step 3La2Zr2O7The modulation of superfine powder presoma and wet blank forming: the lithium chloride that step 2 is prepared is saturated Solution is all in injection mixed powders, and adds and be stirred powder after the distilled water of 30.0mL to uniform, and it is small to place ageing 12 When, it is then at 45 DEG C that mixed powder is dry to water content 16%, obtain mixed powder presoma；It then will be made La2Zr2O7Presoma is put into mold, applies pressure 48MPa, so that forerunner is body formed, it is Φ 30mm, thickness that diameter, which is made, The La of 25mm2Zr2O7Wet green body.
Step 4La2Zr2O7The direct current of textured ceramic green body is sintered texturing: at 20 DEG C, green body that step 3 is obtained It is placed between two electric molybdenum poles for being connected with DC power supply, and positive and negative anodes and green body is in close contact, wherein electrode area is big Small covering green body upper and lower surfaces are evenly distributed with small round tube hole, through-hole diameter Φ 1mm, through-hole point on the plate electrode of upper end 0.5/cm of cloth density2.Power supply is opened, adjustment power work state is constant current mode, and adjusting current limitation value is 30A, so that The current strength for being applied to green body both ends is 4.3A/cm2, La2Zr2O7Ceramic body issues thermal sintering in electric current, energization 15min, Obtaining consistency is 94.8%, edge [100] direction height preferred orientation cube La2Zr2O7Texture ceramic material.

Claims (8)

1. a kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature, it is characterised in that steps are as follows:
The weighing of step 1, nm-class oxide powder: one or several kinds of metal oxides by granularity between 1nm~500nm are received Rice flour body is uniformly mixed to get mixed oxide nanoparticle powder and weighs mixed powder gross mass；
The metallic oxide nano powder includes: alkali metal oxide, alkaline earth oxide, transition metal oxide or dilute Soil metal oxide；
When the unit metal oxide textured ceramic of preparation is alkaline earth oxide textured ceramic, alkaline-earth metal oxide is chosen Object nano-powder is as raw material；
When the unit metal oxide textured ceramic of preparation is transition metal oxide textured ceramic, transiting metal oxidation is chosen Object nano-powder is as raw material；
When the unit metal oxide textured ceramic of preparation is rare earth oxide textured ceramic, chooses rare-earth oxide and receive Rice flour body is as raw material；
When the oxide solid solution textured ceramic of preparation, one or more of selection and alkali metal oxide can form solid solution The nano-powder conduct of one of above-mentioned listed alkaline earth oxide, transition metal oxide or the rare-earth oxide of body Raw material, or several metallic oxide nano powders for forming solid solution are chosen as raw material；
When the metal composite oxide texture ceramic material of preparation, two or more alkali metal oxide nano-powder conducts are chosen Raw material, or several metallic oxide nano powders are chosen as raw material；
The preparation of the inorganic salt saturated solution of step 2, water-soluble metal: at 4 DEG C~60 DEG C, by one kind of water-soluble metal salt or Person is several, is dissolved in respectively uniform with magnetic stirrer after distilled water, and the salt of precipitating is generated for hydrolysis, be added hydrochloric acid or The saturated solution of inorganic salts is made until solution is clarified in nitre acid for adjusting pH value；
When selecting water-soluble metal inorganic salts, the cation of inorganic salts should be with the change of the cation of the most oxides of content in ingredient Conjunction valence is inconsistent；
Step 3, the modulation of nm-class oxide powder presoma and wet blank forming:
Metal inorganic salt saturated solution is added in mixed oxide nanoparticle powder, and adds distilled water to water content 50~90%, Stirring hydrous oxide mixed powder, then will be wet at a temperature of 20 DEG C~100 DEG C to uniform, placement ageing 0.5~24 hour Oxide mixed powder dry to water content be 3%~30%, obtain metal oxide precursor；Then by made metal Oxide precursor is put into mold, and wet green body is made so that forerunner is body formed in the pressure for applying 0.5MPa~50MPa
The gross mass of the water-soluble metal inorganic salts accounts for 0.5wt%~30wt% of metallic oxide nano powder gross mass；
The direct current sintering texturing of step 4, oxide textured ceramic green body:
At 4 DEG C~60 DEG C, molding wet green body is placed between two electrodes for being connected with DC power supply, and make positive and negative anodes It is in close contact with green body, opens power supply, adjustment power work state is constant current mode, current limitation value is adjusted, so that being applied to The current strength at green body both ends is between 0.1A/cm2~20A/cm2, oxide green body issues thermal sintering in electric current, and energization 3min~ 30min obtains the oxide texture ceramic material with certain consistency；
The electrode material using fusing point higher than 1800 DEG C metal material or fusing point higher than 1800 DEG C alloy material or Graphite material.
2. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature It is: the alkali metal oxide are as follows: Li2O、Na2O、K2O、Rb2O、Cs2O。
3. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature It is: the alkaline earth oxide: BeO, MgO, CaO, SrO, BaO.
4. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature Be: the transition metal oxide includes: divalent transition metal oxide: ZnO, CuO, CdO, FeO, NiO, CoO, MnO or PbO；Trivalent transition metal oxide: Al2O3、Fe2O3、B2O3、V2O3、Cr2O3、In2O3、Sc2O3Or Ga2O3；Tetravalent transition metal Oxide: ZrO2、TiO2、SiO2、GaO2、GeO2、HfO2、TaO2、VO2、MnO2Or SnO2；Pentavalent and sexavalence transiting metal oxidation Object: Nb2O5、V2O5、Ta2O5Or WO3；Mixed valence transition metal oxide: Fe3O4、Mn3O4Or Co3O4。
5. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature It is: the rare-earth oxide: Y2O3、Sc2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、Er2O3、EuO、Pm2O3、 Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3Or Lu2O3。
6. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature Be: the water-soluble metal inorganic salts include: alkali halide: AX, A=Li, Na, K, Rb, Cs, X=F, Cl, Br, I； Or alkali metal sulfates: A2SO4, A=Li, Na, K, Rb, Cs；Or alkali carbonate: A2CO3, A=Li, Na, K, Rb, Cs；Or Person's alkali nitrates: ANO3, A=Li, Na, K, Rb, Cs；Or alkaline-earth halide: BX2, B=Mg, Ca, Sr, Ba, X= F,Cl,Br,I；Or zinc salt: ZnX2, X=F, Cl, Br, I；ZnSO4、ZnNO3；Or molysite: FeCl3、Fe2(SO4)3、Fe (NO3)3；Or indium salts: InCl3, In2(SO4)3, In (NO3)3；Or bismuth salt: BiCl3、Bi(NO3)3；Or aluminium salt: AlCl3、 Al2(SO4)3、Al(NO3)3。
7. the method that Fast Sintering prepares metal oxide texture ceramic material under room temperature according to claim 1, feature Be: the water-soluble metal inorganic salts contain the crystallization water or absorption water.
8. quickly preparing the method for building block under room temperature without furnace according to claim 1, it is characterised in that: the electrode is Plate electrode is wherein evenly distributed with small round tube hole, through-hole diameter Φ 1mm~5mm, through-hole distribution density on plate electrode 0.5~1/cm2。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423224A (en) * 2020-04-17 2020-07-17 汪平南 Red interior line ceramic material, ceramic product, preparation method and application thereof
CN111925206A (en) * 2020-07-01 2020-11-13 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN114538925A (en) * 2022-01-25 2022-05-27 北京科技大学 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850725A (en) * 2006-05-23 2006-10-25 青岛大学 Method for preparing polycrystal texture ceramic material
CN105957958A (en) * 2016-05-04 2016-09-21 中国工程物理研究院流体物理研究所 La2Ti2O7 or solid solution material application in high temperature piezoelectric transducer and prepared transducer
CN106247797A (en) * 2016-06-29 2016-12-21 佛山市盈通黑金碳材料股份有限公司 Re-crystallized silicon carbide kiln and preparation method thereof
CN108383522A (en) * 2018-03-29 2018-08-10 长安大学 A kind of low temperature Fast Sintering prepares the method and piezoelectric ceramics of PZT piezoelectric ceramics
CN108558398A (en) * 2018-05-08 2018-09-21 北京科技大学 A kind of method of pulsed discharge room temperature flash sintering nano ceramic material
CN109734445A (en) * 2019-03-06 2019-05-10 武汉理工大学 A kind of electric field-assisted flash sintering method of Ultra-fine Grained hafnium oxide ceramics

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850725A (en) * 2006-05-23 2006-10-25 青岛大学 Method for preparing polycrystal texture ceramic material
CN105957958A (en) * 2016-05-04 2016-09-21 中国工程物理研究院流体物理研究所 La2Ti2O7 or solid solution material application in high temperature piezoelectric transducer and prepared transducer
CN106247797A (en) * 2016-06-29 2016-12-21 佛山市盈通黑金碳材料股份有限公司 Re-crystallized silicon carbide kiln and preparation method thereof
CN108383522A (en) * 2018-03-29 2018-08-10 长安大学 A kind of low temperature Fast Sintering prepares the method and piezoelectric ceramics of PZT piezoelectric ceramics
CN108558398A (en) * 2018-05-08 2018-09-21 北京科技大学 A kind of method of pulsed discharge room temperature flash sintering nano ceramic material
CN109734445A (en) * 2019-03-06 2019-05-10 武汉理工大学 A kind of electric field-assisted flash sintering method of Ultra-fine Grained hafnium oxide ceramics

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423224A (en) * 2020-04-17 2020-07-17 汪平南 Red interior line ceramic material, ceramic product, preparation method and application thereof
CN111925206A (en) * 2020-07-01 2020-11-13 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN111925206B (en) * 2020-07-01 2022-05-03 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN114538925A (en) * 2022-01-25 2022-05-27 北京科技大学 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic
CN114538925B (en) * 2022-01-25 2023-01-31 北京科技大学 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic

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