CN110498399A - The method that composite oxide of metal powder is prepared using heating effect of current direct sintering under no furnace room temperature - Google Patents

The method that composite oxide of metal powder is prepared using heating effect of current direct sintering under no furnace room temperature Download PDF

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CN110498399A
CN110498399A CN201910841473.7A CN201910841473A CN110498399A CN 110498399 A CN110498399 A CN 110498399A CN 201910841473 A CN201910841473 A CN 201910841473A CN 110498399 A CN110498399 A CN 110498399A
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powder
metal
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composite oxide
alkali
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李焕勇
王乾
张春辉
黄欢欢
唐琦
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Northwest University of Technology
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Abstract

The present invention relates to a kind of methods for using heating effect of current direct sintering to prepare composite oxide of metal powder under no furnace room temperature, compared with existing composite oxide of metal technology of preparing, the invention is without expensive high temperature furnace apparatus, without prior heating sample, the preparation of various composite oxide of metal powders can be realized at room temperature, firing preparation time is short, high-efficient, hardware investment 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 composite oxide of metal powder body material, has broad application prospects.

Description

Composite oxide of metal powder is prepared using heating effect of current direct sintering under no furnace room temperature The method of body
Technical field
The invention belongs to field of material technology, it is related under a kind of no furnace room temperature using heating effect of current direct sintering preparation gold Belong to the method for composite oxide powder, and in particular to one kind is without directly reacting fast using heating effect of current under heating furnace, room temperature The method that speed prepares composite oxide of metal powder body material.
Background technique
Composite oxide of metal is usually is formed a kind of polynary by two or more metal oxides are compound or reaction Complex oxide.Composite oxide of metal generally than contain only a kind of unit metal oxide of metallic element possess it is richer Crystal structure and property.The crystal structure types of different metal composite oxides are more, such as the composite oxides of perovskite structure: BaTiO3、FeYO3、SrFeO3、LaCrO3、CaZrO3Deng scheelite type composite oxides: CaCrO4、BaCrO4Deng spinel-type Structure: MgAl2O4、MnFe2O4Deng pyrochlore type structure composite oxides: La2Zr2O7、Sm2InNbO7、Sm2Sn1.8Mn0.2O7Deng, Fluorite type composite oxides Ce2Sn2O7Etc.；Composite oxide of metal has good as important a kind of inorganic functional material Electric conductivity, photocatalytic, oxygen diffusivity, gas sensing property, electromagnetic property, giant magnetoresistance performance, electrical conductance and catalytic activity etc., In The fields such as information, the energy, electronics, metallurgy, aerospace, chemical industry, biology and medicine have broad application prospects.Metal composite oxidation Object can also be divided into whole more multiple than composite oxides and non-stoichiometric according to the stoichiometric ratio of metallic element in composition and nonmetalloid Oxide is closed, wherein non-stoichiometric composite oxides such as La1-xSrxCrO3、La2Ni1-xCuO4-δ、LiNixCoyMn1-x-yO2(0<x< 0.5,0 < y < 0.5) etc.；Compound transition metal oxide, rare earth can be divided into according to the different metal composite oxides of chemical composition Composite oxides or transition metal-rare earth composite oxides etc..
Currently, the technology of preparing of existing composite oxide of metal powder mainly has chemical precipitation method, high temperature and pressure synthesis The technologies of preparing such as method, infusion process, microemulsion method, freeze-drying, solid reaction process, hydrothermal synthesis method, high temperature microwave method, these Technology the high requirements on the equipment is heated, and that there are equipment investments is big, sintering time is long, energy consumption is high, energy utilization rate The technological deficiencies such as low, 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 propose it is direct using heating effect of current under a kind of no furnace room temperature The method that sintering prepares composite oxide of metal powder solves in all kinds of composite oxide of metal powder preparations at present, and hardware is thrown Enter defect big, that preparation time is long, energy consumption is high, energy utilization rate is low, at high cost, the technology is small with hardware investment, technique is simple Single quick, energy conservation and feature at low cost.
Technical solution
A method of composite oxide of metal powder being prepared using heating effect of current direct sintering under no furnace room temperature, it is special Sign is that steps are as follows:
The weighing of step 1, material powder: metal-oxide powder, metal hydroxide with granularity for 5nm~2000 μm Object, metal carbonate powder, metal nitrate powder, metal sulfate powder or five class powder of metal organic acid salt powder are made For raw material, two or more metal compound powders are chosen according to the composition for the metal target composite oxides to be synthesized, are claimed The powder of weighing is homogenously mixed together to obtain mixed powder raw material, and obtains mixed powder by the quality for measuring each material powder Gross mass；
The metal-oxide powder includes: alkali metal oxide, alkaline earth oxide, transition metal oxide or dilute Soil metal oxide；
The metal hydroxides includes: alkali metal hydroxide, alkaline earth metal hydroxide or transition metal element Hydroxide；
The metal carbonate powder includes: the carbonic acid of alkali carbonate, alkaline earth metal carbonate, transition metal element The carbonate or subcarbonate of salt, thulium；
The metal nitrate powder includes: the nitric acid of alkali nitrates, alkaline earth nitrate, transition metal element The nitrate of salt or thulium；
The metal sulfate powder includes: the sulfuric acid of alkali metal sulfates, alkali earth metal sulfate, transition metal element The sulfate or subsulfate of salt or subsulfate, thulium；
The metal organic acid salt powder includes: existing for alkali metal element, alkali earth metal or transition metal element The powder of acylate；
It further include the alkali formula oxysalt or acid that corresponding to all kinds of metal oxyacid salts and can be stabilized Oxysalt；
The preparation of step 2, water-soluble metal salt saturated solution: at 4 DEG C~50 DEG C, one kind of soluble metallic salt is weighed Or it is several, it is uniform with magnetic stirrer after being dissolved in distilled water respectively, the metal salt of precipitating is generated for hydrolysis, is added The saturated solution of one or several kinds of soluble metallic salts is made until solution is clarified in hydrochloric acid or nitre acid for adjusting pH value；
The water-soluble metal salt is with the crystallization water or adsorbs water, or without the crystallization water；
Wherein in the selection of water-soluble metal salt, the cation of water-soluble metal salt should be with one in selected material powder The chemical valence of the cation of kind or several compounds is different；
Step 3, powder pre-burning are body formed:
One or several kinds of soluble metal salt saturated solutions are separately added into mixed powder raw material, and add distilled water tune To water content 30~90%, aqueous mixed powder raw material is stirred to uniform, then by wet mixing at a temperature of 20 DEG C~100 DEG C It is 3%~20% that powder material, which is dried to water content,；Then made wet material powder is put into mold, applies pressure Wet powder pre-burning body is made so that wet material powder forms in 0.1MPa~30MPa；
The gross mass of the water-soluble metal salt accounts for 0.5wt%~30wt% of mixed powder total mass of raw material；
The DC/AC electric treatment of step 4, powder pre-burning body:
At 4~50 DEG C, wet powder pre-burning body molding in step 3 is placed in and is connected with DC power supply or alternating current Between two electrodes in source, and two electrodes and green body are in close contact, open power supply, adjustment power work state is constant current mould Formula adjusts current limitation value, so that being applied to the current strength at green body both ends between 0.1A/cm2~30A/cm2, green body is in electric current Lower fever generates high temperature, and energization 0.2min~25min obtains the metallic composite oxides material of bulk multi-hole；
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；
Step 5, composite oxide of metal are processed at powder: the metallic composite oxides material that electric current sintering in step 4 is gone out Smashing and grinding processing is carried out to get the varigrained powder body material of corresponding composite oxide of metal is arrived.
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 alkali metal hydroxide, alkali carbonate, alkali nitrates, alkali metal sulfates, alkali metal are organic Alkali metal element in the powder of hydrochlorate is Li, Na, K, Rb, Cs.
The alkaline earth metal hydroxide, alkaline earth metal carbonate, alkaline earth nitrate, alkali earth metal sulfate, alkali Alkaline-earth metal in the powder of earth metal acylate are as follows: Be, Mg, Ca, Sr, Ba.
The hydroxide of the transition metal element, the carbonate of transition metal element, transition metal element nitrate, Transition metal element in the sulfate or subsulfate of transition metal element or the powder of acylate are as follows: aluminium Al, zinc Zn, iron Fe, copper Cu, manganese Mn, nickel, cobalt Co, indium In, chromium Cr, tin Sn, antimony Sb, bismuth Bi, zirconium Zr.
The carbonate or subcarbonate of the thulium, the nitrate of thulium, rare earth metal The sulfate or the thulium in subsulfate of element are as follows: yttrium Y, scandium Sc, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, erbium Er, europium Eu, promethium Pm, samarium Sm, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, thulium Tm, ytterbium Yb, lutetium Lu.
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
Composite oxide of metal powder is prepared using heating effect of current direct sintering under a kind of no furnace room temperature proposed by the present invention The method of body, compared with existing composite oxide of metal technology of preparing, the invention is without expensive high temperature furnace apparatus, without thing Sample is first heated, can be realized the preparation of various composite oxide of metal powders at room temperature, firing preparation time is short, efficiency Height, hardware investment 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 suitble to In large scale preparation composite oxide of metal powder body material, have broad application prospects.
Specific embodiment
Now in conjunction with embodiment, the invention will be further described:
Magnesium aluminate spinel (MgOAl is quickly prepared at 1:4 DEG C of embodiment without furnace2O3) powder
Step 1MgCO3And Al2O3The weighing of powder: according to spinelle (MgOAl2O3) composition, weigh 42.00 respectively Gram particle degree between 50~500nm magnesium carbonate powder and 7.91 gram particle degree between the aluminium oxide of 5~50nm nano-powder, by two Person is homogenously mixed together, and obtains 49.91 grams of mixture of magnesium carbonate powder and nanometer alumina powder.
The preparation of step 2 water-soluble metal salt saturated solution: 0.5 gram of NaCO is weighed respectively3With 0.5 gram of KCl, at 4 DEG C, It is dissolved in 7.0ml and 2.0ml distilled water respectively, it is uniform with magnetic stirrer, NaCO is obtained respectively3It is molten with the saturation of KCl Liquid.
Step 3 powder pre-burning is body formed: by the made NaCO of step 23Step 1 is all added respectively with the saturated solution of KCl In weighed magnesium carbonate and aluminium oxide mixed powder raw material, and distilled water is added to be adjusted to water content 90%, stirs aqueous mixed powder Wet mixed powder material dry to water content is at 50 °C then 20% to uniform by body raw material.It then will be made Wet material powder be put into mold, apply pressure 0.1MPa, so that wet material powder form, diameter be made as Φ The wet powder pre-burning body of 30mm, thickness 24mm.
The AC process of step 4 powder pre-burning body: at 4 DEG C, the powder pre-burning body that step 3 obtains is horizontally placed at company It is connected between two graphite electrodes of AC power source, and two electrodes and powder pre-burning body is in close contact, wherein upper end plate Diameter of phi 6mm round tube hole 3 is evenly distributed on electrode.Power supply is opened, adjustment power work state is constant current mode, adjusts electricity Ductility limit flow valuve is 120A, so that the current strength for being applied to green body both ends is 16.98A/cm2, green body issues thermal sintering in electric current, Energization 5min, obtains that there are the MgOAl of a large amount of holes2O3Bulk material.
Step 5 composite oxide of metal is at powder working process: by MgOAl obtained in step 42O3Bulk material uses Planetary ball mill carries out crushing grinding, grinds 1h, obtains 2~6 μm of granularity of MgOAl2O3Powder.
Mullite (3Al is quickly prepared at 2:25 DEG C of embodiment without furnace2O3·2SiO2) powder
Step 1 aluminum nitrate (Al (NO3)3) and silica (SiO2) powder weighing: according to mullite (3Al2O3· 2SiO2) composition, weigh 37.59 gram particle degree between the superfine powder of the aluminum nitrate of 5~50nm and 14.76 gram particle degree between 5~ The silicon dioxide ultrafine powder body of 50nm, is homogenously mixed together, and the mixed powder 52.36 of aluminum nitrate and silica is obtained Gram.
The preparation of step 2 water-soluble metal salt saturated solution: 1.05 grams of LiCl are weighed respectively and are dissolved in 1.7ml at 25 DEG C In distilled water, the hydrochloric acid tune pH=3 that 1.0mol/L is added is clarified to solution, and uniform with magnetic stirrer, acquisition is clear LiCl saturated solution.
Step 3 powder pre-burning is body formed: the weighed powder of step 1 is all added in the made LiCl saturated solution of step 2 In body raw material, and distilled water is added to be adjusted to water content 30%, stirs aqueous mixed powder raw material to uniform, then at a temperature of 25 DEG C It is 10% by wet mixed powder material dry to water content.Then made wet material powder is put into mold, is applied The powder pre-burning body that diameter is Φ 30mm, thickness 21mm is made so that wet material powder forms in pressure 1MPa.
The AC process of step 4 powder pre-burning body: at 25 DEG C, the powder pre-burning body that step 3 obtains is horizontally placed at It is connected between two plate graphite electrodes of AC power source, diameter of phi 1mm circle is wherein evenly distributed on the plate electrode of upper end Through-hole, 7, and two electrodes and green body are in close contact.Power supply is opened, adjustment power work state is constant current mode, is adjusted Current limitation value is 212A, so that the current strength for being applied to green body both ends is 30A/cm2, green body issues thermal sintering in electric current, Energization 0.2min obtains porous 3Al2O3·2SiO2Block materials.
Step 5 mullite (3Al2O3·2SiO2) at powder working process: by 3Al obtained in step 42O3·2SiO2Block Material carries out crushing grinding using automatic agate grinder, and grinding 0.5h obtains granularity between 1~5 μm of mullite 3Al2O3· 2SiO2Powder.
Mullite (3Al is quickly prepared at 3:40 DEG C of embodiment without furnace2O3·2SiO2) powder
Step 1Al2(SO4)3And SiO2The weighing of powder: the aluminum sulfate of 30.00 gram particle degree between 100~500nm is weighed Superfine powder and 3.51 gram particle degree are homogenously mixed together between the superfine powder of the silica of 5~100nm, obtain sulphur 33.51 grams of mixed powder of sour aluminium and silica.
The preparation of step 2 water-soluble metal salt saturated solution: 2.68 grams of CaCl are weighed2, at 40 DEG C, it is dissolved in 2.7ml steaming It in distilled water, stirs evenly, obtains clear CaCl2Solution.
Step 3 powder pre-burning is body formed: by the CaCl that step 2 is made2It is former that the weighed powder of step 1 is all added in solution In material, and distilled water is added to be adjusted to water content 30%, stirs aqueous mixed powder raw material to uniform, it then will be wet at a temperature of 40 DEG C Mixed powder material dry to water content be 5%.Then made wet material powder is put into cylindrical die, is applied The powder pre-burning body that diameter is Φ 30mm, thickness 20mm is made so that wet material powder forms in pressure 5MPa.
The AC process of step 4 powder pre-burning body: at 40 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two graphite electrodes of AC power source, diameter of phi 2mm round tube hole, through-hole are wherein evenly distributed on the plate electrode of upper end 1/cm of distribution density2, and two electrodes and green body are in close contact, power supply is opened, adjustment power work state is constant current mould Formula, adjustment power work state are constant current mode, and adjusting current limitation value is 42.4A, so that being applied to the electric current at green body both ends Intensity is 6.0A/cm2, green body issues thermal sintering in electric current, and energization 10min obtains 3Al2O3·2SiO2Block materials.
Step 5 mullite (3Al2O3·2SiO2) at powder working process: by 3Al fluffy obtained in step 42O3· 2SiO2Block materials using planetary ball mill carry out crushing grinding, grinding 1.5h can be obtained granularity between 1~4 μm not come Stone 3Al2O3·2SiO2Powder.
BaTiO is quickly prepared without furnace at 4:20 DEG C of embodiment3Powder
Step 1BaCO3And TiO2The weighing of powder: 38.63 gram particle degree are weighed between the powder of the barium carbonate of 90~300nm With take 15.63 gram particle degree to be homogenously mixed together between the superfine powder of the titanium oxide of 10~100nm.
The preparation of step 2 water-soluble metal salt saturated solution: 3.72 grams of pure grade potassium chloride powders of analysis are weighed, at 20 DEG C Under, potassium chloride is added in 10.0mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, chlorine at 20 DEG C is made Change the saturated solution of potassium.
Step 3 powder pre-burning is body formed: it is weighed that step 1 is all added in the made saturated potassium chloride solution of step 2 In powder material, and distilled water is added to be adjusted to water content 60%, stirs aqueous mixed powder raw material to uniform, then in 40 DEG C of temperature It is lower by wet mixed powder material dry to water content be 3%.Then made wet material powder is put into cylindrical die In, apply pressure 30MPa, the green body that diameter is Φ 30mm, thickness 25mm is made.
The current processing of step 4 powder pre-burning body: at 20 DEG C, the green body that step 2 is obtained, which is placed in, is connected with direct current Between two molybdenum alloy electrodes in source, and two electrodes and green body are in close contact, are wherein uniformly distributed on the plate electrode of upper end There are diameter of phi 2mm round tube hole, 0.5/cm of through-hole distribution density2, power supply is opened, adjustment power work state is constant current mode, Adjusting current limitation value is 120A, so that the current strength for being applied to green body both ends is 16.98A/cm2, green body issues in electric current Thermal sintering, energization 3min obtain the BaTiO containing a large amount of holes3Bulk material.
Step 5 is at powder working process: by BaTiO obtained in step 43Bulk material is crushed using planetary ball mill Grinding grinds 20h, obtains granularity between 1~2 μm of BaTiO3Powder.
BaTiO is quickly prepared without furnace at 5:20 DEG C of embodiment3Powder
Step 1BaSO4And TiO2The weighing of powder: weighing granularity between 40.00 grams of barium sulfate powder of 100~500nm, With granularity between 13.73 grams of superfine powder of the titanium dioxide of 10~100nm, it is homogenously mixed together.
The preparation of step 2 water-soluble metal salt saturated solution: weighing 3.55 grams of sodium nitrate powder, will be alleged at 20 DEG C Sodium nitrate powder is added in 4.0mL distilled water, is uniformly clarified to solution with magnetic stirrer, the sodium nitrate at 20 DEG C is made Saturated solution.
Step 3 powder pre-burning is body formed: weighed powder material is all added in the made sodium nitrate solution of step 2 In, and distilled water is added to be adjusted to water content 70%, stirs aqueous mixed powder raw material to uniform, it then will be wet at a temperature of 80 DEG C Mixed powder material dry to water content is 5%.Then made wet material powder is put into cylindrical die, applies pressure The wet pre-burning body that diameter is Φ 30mm, thickness 23mm is made in power 0.1MPa.
The current processing of step 4 pre-burning body: at 20 DEG C, wet pre-burning body is placed in two zirconium titaniums for being connected with DC power supply Between molybdenum alloy electrode, and two electrodes and green body are in close contact, are wherein evenly distributed with diameter of phi 2mm's in upper end electrode Round tube hole, 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 12A, so that the current strength for being applied to green body both ends is 1.7A/cm2, green body issues thermal sintering in electric current, is powered 20min obtains the BaTiO containing a large amount of cavities3Bulk material.
Step 5 is at powder working process: by BaTiO obtained in step 43Bulk material is carried out using electronic agate grinder Crushing grinding grinds 10h, obtains granularity between 1~3 μm of BaTiO3Powder.
LiNbO is quickly prepared without furnace at 6:20 DEG C of embodiment3Powder
Step 1Li2O and Nb2O5The weighing of powder: weighing granularity between 4.9 grams of oxidation powder for lithium of 100~600nm, then Granularity is weighed between 45.00 grams of superfine powder of the niobium oxide of 20~200nm, is homogenously mixed together.
The preparation of step 2 water-soluble metal salt saturated solution: weighing 0.25 gram of carbonic acid powder for lithium, will be alleged at 20 DEG C Carbonic acid powder for lithium is added in 18.8mL distilled water, and the hydrochloric acid tune pH=3 that 1.0mol/L is added is clarified to solution, uses magnetic stirring apparatus It stirs evenly, the lithium carbonate saturated solution at 20 DEG C is made.
Step 3 powder pre-burning is body formed: weighed powder material is all added in the made Lithium carbonate solution of step 2 In, and it is adjusted to water content 85%, stirs aqueous mixed powder raw material to uniform, then by wet mixed powder at a temperature of 30 DEG C Material dry to water content is 10%.Then made wet material powder is put into cylindrical die, applies pressure The green body that diameter is Φ 40mm, thickness 18mm is made in 9.5MPa.
The current processing of step 4 pre-burning body: at 20 DEG C, wet pre-burning body is placed in two zirconium titaniums for being connected with DC power supply Between molybdenum alloy electrode, and two electrodes and green body are in close contact, are wherein evenly distributed with diameter of phi 1mm's in upper end electrode Round tube hole, 1/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, adjusts current limitation value For 90A, so that the current strength for being applied to pre-burning body both ends is 7.16A/cm2, pre-burning body issues thermal sintering in electric current, is powered 9.0min obtains the LiNbO containing a large amount of holes3Bulk material.
Step 5 is at powder working process: by BaTiO obtained in step 43Bulk material is carried out using electronic agate grinder Crushing grinding grinds 2h, obtains granularity between 3~7 μm of LiNbO3Powder.
BaZr is quickly prepared without furnace at 7:40 DEG C of embodiment0.1Ce0.7Y0.1Yb0.1O3Powder
Step 1BaSO4、ZrO2、CeO2、Y2(CO3)3And Yb2O3The weighing of powder: weigh 30.46 gram particle degree between 100~ The powder of the barium sulfate of 400nm, 1.61 gram particle degree between the superfine powder of the zirconium oxide of 20~100nm, 15.72 gram particle degree between The superfine powder of the cerium oxide of 10~100nm, 4.67 gram particle degree between the yttrium carbonate of 50~300nm powder and 5.14 gram particle degree Between the superfine powder of the ytterbium oxide of 20~200nm, it is homogenously mixed together.
The preparation of step 2 water-soluble metal salt saturated solution: the pure grade barium chloride powder of 0.41 gram of analysis is weighed respectively, is taken 1.02 grams are analyzed pure grade sodium nitrate powders and take 0.34 gram of pure grade sulfuric acid powder for lithium of analysis, at 40 DEG C, by the barium chloride of weighing Powder is added in 1.0mL distilled water, and the hydrochloric acid tune pH=3 of 1.0mol/L is added and clarifies to solution, equal with magnetic stirrer It is even, the barium chloride saturated solution at 40 DEG C is made；The sodium nitrate powder of weighing is added in 1.0mL distilled water, magnetic agitation is used Device stirs evenly, and the sodium nitrate saturated solution at 40 DEG C is made；The sulfuric acid powder for lithium of weighing is added in 1.0mL distilled water, is added The hydrochloric acid tune pH=3 for entering 1.0mol/L is clarified to solution, is uniformly clarified, is made at 40 DEG C to solution with magnetic stirrer Lithium sulfate saturated solution.
Step 3 powder pre-burning is body formed: the weighed powder of step 1 is all added in 3 kinds of made saturated solutions of step 2 In raw material, and distilled water is added and is adjusted to water content 45%, stirs aqueous mixed powder raw material to uniform, then at a temperature of 60 DEG C It is 15% by wet mixed powder material dry to water content.Then made wet material powder is put into cylindrical die In, apply pressure 20MPa, the green body that diameter is Φ 30mm, thickness 25mm is made.
The current processing of step 4 pre-burning body: at 40 DEG C, wet pre-burning body is placed in two zirconium titaniums for being connected with DC power supply Between molybdenum alloy electrode, and two electrodes and green body are in close contact, are wherein evenly distributed with diameter of phi 4mm's in upper end electrode Round tube hole, 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 130A, so that the current strength for being applied to green body both ends is 18.39A/cm2, green body issues thermal sintering in electric current, is powered 2.0min obtains the BaZr containing a large amount of holes0.1Ce0.7Y0.1Yb0.1O3Bulk material.
Step 5 is at powder working process: by BaZr obtained in step 40.1Ce0.7Y0.1Yb0.1O3Bulk material is using electronic Agate grinder carries out crushing grinding, grinds 1h, obtains granularity between 3~9 μm of BaZr0.1Ce0.7Y0.1Yb0.1O3Powder.
Lanthanum Chromite (LaCrO is quickly prepared at 8:4 DEG C of embodiment without furnace3) powder
Step 1La2(CO3)3And Cr2(SO4)3The weighing of powder: 34.00 gram particle degree are weighed between the carbonic acid of 200~600nm It the powder of lanthanum and takes 18.42 gram particle degree between the powder of the chromium sulfate of 300~800nm, is homogenously mixed together.
The preparation of step 2 water-soluble metal salt saturated solution: the pure grade bluestone powder of 2.52 grams of analyses is weighed respectively, is taken The copper sulphate powder of weighing is added in 17.0mL distilled water at 4 DEG C for 2.7 grams of pure grade sodium bicarbonate powders of analysis, is added The hydrochloric acid tune pH=3 of 1.0mol/L is clarified to solution, and uniform with magnetic stirrer, the copper sulphate saturation being made at 4 DEG C is molten Liquid；The sodium bicarbonate powder of weighing is added in 36.0mL distilled water, it is uniform with magnetic stirrer, the carbon at 4 DEG C is made Sour hydrogen sodium saturated solution.
Step 3 powder pre-burning is body formed: the weighed powder of step 1 is all added in 2 kinds of made saturated solutions of step 2 In raw material, and distilled water is added and is adjusted to water content 75%, stirs aqueous mixed powder raw material to uniform, then at 50 °C It is 12% by wet mixed powder material dry to water content.Then made wet material powder is put into cylindrical die In, apply pressure 30MPa, the green body that diameter is Φ 30mm, thickness 22mm is made.
The current processing of step 4 pre-burning body: at 4 DEG C, wet pre-burning body is placed in two zirconium titaniums for being connected with AC power source Between molybdenum alloy electrode, and two electrodes and green body are in close contact, are wherein evenly distributed with diameter of phi 2mm's in upper end electrode Round tube hole, 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 60A, so that the current strength for being applied to green body both ends is 8.5A/cm2, green body issues thermal sintering in electric current, energization 6min, Obtain the LaCrO containing a large amount of holes3Bulk material.
Step 5 is at powder working process: by LaCrO obtained in step 43Bulk material is crushed using planetary ball mill Granularity can be obtained between 0.8~1.2 μm of LaCrO in grinding, grinding 15h3Powder.
Zirconic acid lanthanum (La is quickly prepared at 9:25 DEG C of embodiment without furnace2Zr2O7) powder
Step 1La2(CO3)3And ZrO2The weighing of powder: the lanthanum carbonate of 37.51 gram particle degree between 100~500nm is weighed Powder and 25.00 gram particle degree are homogenously mixed together between the powder of the zirconium oxide of 50~200nm.
The preparation of step 2 water-soluble metal salt saturated solution: 3.75 grams of pure grade Ba (NO of analysis are weighed3)2Powder, in 20 DEG C Under, lithium chloride is added in 94.0mL distilled water, is uniformly clarified with magnetic stirrer, Ba (NO at 25 DEG C is made3)2It is full And solution.
Step 3La2Zr2O7Powder pre-burning is body formed: the Ba (NO that step 2 is prepared3)2Saturated solution all injects mixed powder In body, and it is modulated into water content 70%, stirs aqueous mixed powder to uniform, it is then at 45 DEG C that mixed powder is dry to containing Water 9%；Then made wet powder is put into mold, made wet material powder is then put into cylindrical die In, apply pressure 10MPa, the La that diameter is Φ 30mm, thickness 25mm is made2Zr2O7Wet powder pre-burning body.
The current processing of step 4 pre-burning body: at 25 DEG C, wet pre-burning body is placed in two zirconium titaniums for being connected with AC power source Between molybdenum alloy electrode, and two electrodes and green body are in close contact, are wherein evenly distributed with diameter of phi 3mm's in upper end electrode Round tube hole, 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 120A, so that the current strength for being applied to green body both ends is 16.98A/cm2, pre-burning body issues thermal sintering in electric current, is powered 1.2min obtains the La containing a large amount of holes2Zr2O7Bulk material.
Step 5 is at powder working process: by La obtained in step 42Zr2O7Bulk material is carried out brokenly using planetary ball mill Breakdown mill, grinding 5h obtain granularity between 0.8~1.2 μm of La2Zr2O7Powder.
MnFe is quickly prepared without furnace at 10:50 DEG C of embodiment2O4Powder
Step 1MnSO4With Fe (NO)3The weighing of powder: the manganese sulfate of 20.00 gram particle degree between 100~400nm is weighed Powder and 8.75 gram particle degree are homogenously mixed together between the powder of the ferric nitrate of 50~200nm.
Step 2 prepares the saturated solution of potassium chloride and zinc sulfate respectively: weigh 0.98 gram of pure grade potassium chloride powder of analysis and Take 0.75 gram of pure level zinc sulfate powder of analysis that the potassium chloride powder of weighing is added in 1.2mL distilled water, uses magnetic at 50 DEG C Power blender stirs evenly, and the saturated potassium chloride solution at 50 DEG C is made；1.0mL distilled water is added in the zinc sulfate powder of weighing In, the hydrochloric acid tune pH=3 of 1.0mol/L is added and clarifies to solution, it is uniform with magnetic stirrer, the sulfuric acid at 50 DEG C is made Zincification solution.
Step 3 powder pre-burning is body formed: the saturated potassium chloride solution and zinc sulfate saturated solution that step 2 is prepared all are infused Enter in mixed powder, and distilled water is added and is modulated into water content 60%, stirs aqueous mixed powder to uniform, then at 50 DEG C Mixed powder is dry to water content 3%；Then made wet powder is put into mold, then by made wet raw material Powder is put into cylindrical die, applies pressure 20MPa, and the wet pre-burning body that diameter is Φ 30mm, thickness 19mm is made.
The AC process of the wet pre-burning body of step 4: at 50 DEG C, the wet pre-burning body that step 3 is obtained, which is placed in, is connected with friendship Between two graphite electrodes in galvanic electricity source, and two electrodes and green body are in close contact, are wherein evenly distributed in upper end electrode The round tube hole of diameter of phi 3mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, Adjusting current limitation value is 100A, so that the current strength for being applied to pre-burning body both ends is 14.15A/cm2, green body is under electric current Fever sintering, energization 4min obtain the MnFe containing hole2O4Bulk material.
Step 5 is at powder working process: by MnFe obtained in step 42O4Bulk material is crushed using planetary ball mill Granularity can be obtained between 0.5~1.0 μm of MnFe in grinding, grinding 20h2O4Powder.
MnFe is quickly prepared without furnace at 11:20 DEG C of embodiment2O4Powder
Step 1MnSO4And Fe2(SO4)3The weighing of powder: 10.00 gram particle degree are weighed between the manganese sulfate of 100~400nm Powder and 26.49 gram particle degree between the powder of the ferric sulfate iron of 50~200nm, be homogenously mixed together.
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
Step 3 powder pre-burning is body formed: raw material alleged by the sodium sulphate saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 50%, stir aqueous mixed powder to uniform, it then will mixing at 60 DEG C Then made wet powder is put into mold to water content 15%, applies pressure 30MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 20mm.
The AC process of the wet pre-burning body of step 3: at 20 DEG C, the wet pre-burning body that step 3 is obtained is horizontally placed at connection Have between two graphite electrodes of AC power source, and two end faces in two poles and green body are in close contact, wherein upper end graphite The round tube hole of diameter of phi 3mm, 1/cm of through-hole distribution density are evenly distributed on electrode2.Power supply is opened, power work shape is adjusted State is constant current mode, adjusts current limitation value 50A, so that the current strength for being applied to pre-burning body both ends is 7.2A/cm2, pre-burning Body issues thermal sintering in electric current, and energization 11min obtains the MnFe containing hole2O4Bulk material.
Step 5 is at powder working process: by MnFe obtained in step 42O4Bulk material is crushed using planetary ball mill Grinding, grinding 10h obtain granularity between 1.3~1.9 μm of MnFe2O4Powder.
ZnCo is quickly prepared without furnace at 12:10 DEG C of embodiment2O4Powder
Step 1Zn (CH3COO)2With Co (CH3COO)3The weighing of powder: 20.00 gram particle degree are weighed between 1000~2000 μ The powder of the zinc acetate of m and 38.69 gram particle degree are homogenously mixed together between the powder of 500~1000 μm of cobalt acetate.
The preparation of step 2 saturated potassium chloride solution: 4.7 grams of pure grade potassium chloride powders of analysis are weighed, at 10 DEG C, by chlorination Potassium is added in 14.9mL distilled water, uniform with magnetic stirrer, until solution is clarified, the saturation of potassium chloride at 10 DEG C is made Solution.
Step 3 powder pre-burning is body formed: raw material alleged by the saturated potassium chloride solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 72%, stir aqueous mixed powder to uniform, then will be mixed at 100 DEG C Powder drying is closed to water content 20%, then made wet powder is put into mold, applies pressure 4MPa, it is Φ that diameter, which is made, The wet powder pre-burning body of 30mm, thickness 23mm.
The AC process of step 4 powder pre-burning body: at 10 DEG C, the green body that step 3 is obtained, which is placed in, is connected with exchange Between two graphite electrodes of power supply, and two electrodes and green body are in close contact, are wherein uniformly distributed on the graphite electrode of upper end There are the round tube hole of diameter of phi 5mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 110A, so that the current strength for being applied to green body both ends is 15.56A/cm2, green body is under electric current Fever sintering, energization 3min obtain ZnCo2O4Porous block material.
Step 5 is at powder working process: by ZnCo obtained in step 42O4Porous block material is carried out using planetary ball mill Crushing grinding, grinding 6h obtain granularity between 1.3~1.9 μm of ZnCo2O4Powder.
CaTiO is quickly prepared without furnace at 13:40 DEG C of embodiment3Powder
Step 1CaCO3And TiO2The weighing of powder: weigh 19.61 gram particle degree between 10~50 μm of calcium carbonate powder and It takes 15.63 gram particle degree between the powder of the titanium oxide of 500~1000nm, is homogenously mixed together.
The preparation of step 2 sodium acetate saturated solution: 7.0 grams of pure grade sodium acetate powders of analysis are weighed, at 40 DEG C, by acetic acid Sodium is added in 17.0mL distilled water, uniform with magnetic stirrer, until solution is clarified, the saturation of sodium acetate at 40 DEG C is made Solution.
Step 3 powder pre-burning is body formed: raw material alleged by the sodium acetate saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 50%, stir aqueous mixed powder to uniform, it then will mixing at 40 DEG C Then made wet powder is put into mold to water content 10%, applies pressure 30MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 19mm.
The AC process of step 4 powder pre-burning body: at 40 DEG C, the green body that step 3 is obtained, which is placed in, is connected with exchange Between two graphite electrodes of power supply, and two electrodes and green body are in close contact, are wherein uniformly distributed on the graphite electrode of upper end There are the round tube hole of diameter of phi 2mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 120A, so that the current strength for being applied to green body both ends is 17A/cm2, green body issues in electric current Thermal sintering, energization 7min obtain porous C aTiO3Bulk material.
Step 5 is at powder working process: by porous C aTiO obtained in step 43Bulk material using electronic agate mortar into Row crushing grinding, grinding 2h obtain granularity between 1.1~2.9 μm of CaTiO3Powder.
ZnSnO is quickly prepared without furnace at 14:25 DEG C of embodiment3Powder
Step 1ZnCO3And SnSO4The weighing of powder: weigh 20.00 gram particle degree between 1~3 μm of zinc carbonate powder and 34.4 gram particle degree are homogenously mixed together between the powder of 5~10 μm of stannous sulfate.
The preparation of step 2 sodium nitrate saturated solution: 4.9 grams of pure grade sodium nitrate powders of analysis are weighed, at 25 DEG C, by nitric acid Sodium is added in 5.7mL distilled water, uniform with magnetic stirrer, until solution is clarified, the saturation of sodium nitrate at 25 DEG C is made Solution.
Step 3 powder pre-burning is body formed: raw material alleged by the sodium nitrate saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 90%, stir aqueous mixed powder to uniform, it then will mixing at 25 DEG C Then made wet powder is put into mold to water content 5%, applies pressure 12MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 21mm.
The AC process of step 4 powder pre-burning body: at 25 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two graphite electrodes of DC power supply, and two electrodes and green body are in close contact, wherein on the graphite electrode of upper end The even round tube hole that diameter of phi 1mm is distributed with, 1/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current Mode, adjusting current limitation value are 24A, so that the current strength for being applied to green body both ends is 3.5A/cm2, green body is under electric current Fever sintering, energization 10min obtain porous ZnSnO3Bulk material.
Step 5 is at powder working process: by porous ZnSnO obtained in step 43Bulk material using electronic agate mortar into Row crushing grinding, grinding 1h obtain granularity between 2~6 μm of ZnSnO3Powder.
LaFeO is quickly prepared without furnace at 15:50 DEG C of embodiment3Powder
Step 1La2(CO3)3And Fe2(SO4)3The weighing of powder: 30.00 gram particle degree are weighed between the carbonic acid of 200~600nm It the powder of lanthanum and takes 26.20 gram particle degree between the powder of the ferric sulfate of 300~700nm, is homogenously mixed together.
The preparation of step 2 saturated potassium chloride solution: 2.81 grams of pure grade potassium chloride powders of analysis are weighed, at 50 DEG C, by chlorine Change potassium to be added in 7.4mL distilled water, it is uniform with magnetic stirrer, until solution is clarified, the full of potassium chloride at 50 DEG C is made And solution.
Step 3 powder pre-burning is body formed: raw material alleged by the saturated potassium chloride solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 60%, stir aqueous mixed powder to uniform, it then will mixing at 50 DEG C Then made wet powder is put into mold to water content 10%, applies pressure 19MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 19mm.
The Direct current treatment of step 4 powder pre-burning body: at 25 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two graphite electrodes of DC power supply, and two electrodes and green body are in close contact, wherein on the graphite electrode of upper end The even round tube hole that diameter of phi 5mm is distributed with, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is perseverance Stream mode, adjusting current limitation value are 24A, so that the current strength for being applied to green body both ends is 3.5A/cm2, green body is in electric current Thermal sintering is issued, energization 12min obtains porous LaFeO3Bulk material.
Step 5 is at powder working process: by porous LaFeO obtained in step 43Bulk material using electronic agate mortar into Row crushing grinding, grinding 0.5h obtain granularity between 7~12 μm of LaFeO3Powder.
Mg is quickly prepared without furnace at 16:20 DEG C of embodiment2TiO4Powder
Step 1MgCO3And TiO2The weighing of powder: 30.00 gram particle degree are weighed between the powder of the magnesium carbonate of 100~500nm With take 14.29 gram particle degree to be homogenously mixed together between the powder of the titanium dioxide of 10~100nm.
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.
Step 3 powder pre-burning is body formed: raw material alleged by the sodium chloride saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 80%, stir aqueous mixed powder to uniform, it then will mixing at 20 DEG C Then made wet powder is put into mold to water content 11%, applies pressure 30MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 22mm.
The Direct current treatment of step 4 powder pre-burning body: at 20 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two tungsten electrodes of DC power supply, and two electrodes and green body are in close contact, is wherein uniformly distributed in upper end electrode There are the round tube hole of diameter of phi 2mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 100A, so that the current strength for being applied to green body both ends is 14.15A/cm2, green body is under electric current Fever sintering, energization 3min obtain porous Mg2TiO4Bulk material.
Step 5 is at powder working process: by porous Mg obtained in step 42TiO4Bulk material using electronic agate mortar into Row crushing grinding, grinding 0.5h obtain granularity between 6~15 μm of Mg2TiO4Powder.
CaWO is quickly prepared without furnace at 17:40 DEG C of embodiment4Powder
Step 1CaCO3And WO3The weighing of powder: weigh 5.00 gram particle degree between the calcium carbonate of 100~500nm powder and It takes 34.80 gram particle degree between the powder of the tungsten oxide of 10~100nm, is homogenously mixed together.
The preparation of step 2 lithium chloride saturated solution: 0.28 gram of pure grade chlorination powder for lithium of analysis is weighed, at 40 DEG C, by chlorine Change lithium to be added in 0.4mL distilled water, the hydrochloric acid tune pH=3 of 1.0mol/L is added and clarifies to solution, it is equal with magnetic stirrer It is even, the saturated solution of lithium chloride at 50 DEG C is made.
Step 3 powder pre-burning is body formed: raw material alleged by the lithium chloride saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 80%, stir aqueous mixed powder to uniform, it then will mixing at 50 DEG C Then made wet powder is put into mold to water content 5%, applies pressure 30MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 17mm.
The Direct current treatment of step 4 powder pre-burning body: at 40 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two tungsten electrodes of DC power supply, and two electrodes and green body are in close contact, is wherein uniformly distributed in upper end electrode There are the round tube hole of diameter of phi 1mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 120A, so that the current strength for being applied to green body both ends is 16.98A/cm2, green body is under electric current Fever sintering, energization 3min obtain porous CaWO4Bulk material.
Step 5 is at powder working process: by porous C aWO obtained in step 44Bulk material using electronic agate mortar into Row crushing grinding, grinding 0.5h obtain granularity between 7~18 μm of CaWO4Powder.
BaWO is quickly prepared without furnace at 18:4 DEG C of embodiment4Powder
Step 1BaSO4And WO3The weighing of powder: 20.00 gram particle degree are weighed between the powder of the barium sulfate of 100~500nm With take 19.91 gram particle degree to be homogenously mixed together between the powder of the tungsten oxide of 10~100nm.
The preparation of step 2 lithium chloride saturated solution: 0.32 gram of pure grade chlorination powder for lithium of analysis is weighed, at 4 DEG C, by chlorination Lithium is added in 0.8mL distilled water, is uniformly clarified to solution with magnetic stirrer, the saturated solution of lithium chloride at 4 DEG C is made.
Step 3 powder pre-burning is body formed: raw material alleged by the lithium chloride saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 80%, stir aqueous mixed powder to uniform, it then will mixing at 50 DEG C Then made wet powder is put into mold to water content 6%, applies pressure 20MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 16mm.
The Direct current treatment of step 4 powder pre-burning body: at 4 DEG C, the powder pre-burning body that step 3 obtains is placed in and is connected with Between two tungsten electrodes of DC power supply, and two electrodes and green body are in close contact, are wherein evenly distributed in upper end electrode The round tube hole of diameter of phi 1mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mode, Adjusting current limitation value is 12A, so that the current strength for being applied to green body both ends is 1.7A/cm2, green body generates heat burning under electric current Knot, energization 25min obtain porous CaWO4Bulk material.
Step 5 is at powder working process: by porous C aWO obtained in step 44Bulk material using electronic agate mortar into Row crushing grinding, grinding 2h obtain granularity between 5~15 μm of CaWO4Powder.
CaMoO is quickly prepared without furnace at 19:25 DEG C of embodiment4Powder
Step 1CaCO3And MoO3The weighing of powder: 20.00 gram particle degree are weighed between the powder of the calcium carbonate of 100~500nm With take 28.80 gram particle degree to be homogenously mixed together between the powder of the molybdenum oxide of 10~100nm.
The preparation of step 2 sodium nitrate saturated solution: 0.95 gram of pure grade sodium nitrate powder of analysis is weighed, at 25 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 25 DEG C is made And solution.
Step 3 powder pre-burning is body formed: raw material alleged by the sodium nitrate saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 80%, stir aqueous mixed powder to uniform, it then will mixing at 25 DEG C Then made wet powder is put into mold to water content 10%, applies pressure 12MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 21mm.
The Direct current treatment of step 4 powder pre-burning body: at 25 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two graphite electrodes of DC power supply, and two electrodes and green body are in close contact, wherein uniformly divides in upper end electrode It is furnished with the round tube hole of diameter of phi 3mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 24A, so that the current strength for being applied to green body both ends is 3.5A/cm2, green body issues in electric current Thermal sintering, energization 20min obtain porous CaMoO4Bulk material.
Step 5 is at powder working process: by porous C aMoO obtained in step 44Bulk material using electronic agate mortar into Row crushing grinding, grinding 10h obtain granularity between 1~2 μm of CaMoO4Powder.
PbMoO is quickly prepared without furnace at 20:10 DEG C of embodiment4Powder
Step 1PbSO4And MoO3The weighing of powder: 30.00 gram particle degree are weighed between the powder of the lead sulfate of 100~400nm With take 14.26 gram particle degree to be homogenously mixed together between the powder of the molybdenum oxide of 10~100nm.
The preparation of step 2 potassium nitrate saturated solution: 0.20 gram of pure grade potassium nitrate powder of analysis is weighed, at 10 DEG C, by nitre Sour potassium is added in 1.6mL distilled water, uniform with magnetic stirrer, until solution is clarified, the full of potassium nitrate at 10 DEG C is made And solution.
Step 3 powder pre-burning is body formed: raw material alleged by the potassium nitrate saturated solution whole injection step 1 that step 2 is prepared It in powder, and adds distilled water and is modulated into water content 70%, stir aqueous mixed powder to uniform, it then will mixing at 65 DEG C Then made wet powder is put into mold to water content 13%, applies pressure 15MPa, it is Φ that diameter, which is made, by powder drying The wet powder pre-burning body of 30mm, thickness 20mm.
The AC process of step 4 powder pre-burning body: at 10 DEG C, the powder pre-burning body that step 3 obtains is placed in connection Have between two graphite electrodes of AC power source, and two electrodes and green body are in close contact, wherein uniformly divides in upper end electrode It is furnished with the round tube hole of diameter of phi 2mm, 0.5/cm of through-hole distribution density2.Power supply is opened, adjustment power work state is constant current mould Formula, adjusting current limitation value are 48A, so that the current strength for being applied to green body both ends is 7.1A/cm2, green body issues in electric current Thermal sintering, energization 12min obtain porous PbMoO4Bulk material.
Step 5 is at powder working process: by porous PbMoO obtained in step 44Bulk material using electronic agate mortar into Row crushing grinding, grinding 20h obtain granularity between 0.7~1.2 μm of PbMoO4Powder.
In the present invention, in the material powder, metal oxide-type raw material is related to the powder of following 8 small type oxides:
1. alkali metal oxide: Li2O、Na2O、K2O、Rb2O、Cs2O；
2. alkaline earth oxide: BeO, MgO, CaO, SrO, BaO；
3. divalent transition metal oxide: ZnO, CuO, CdO, FeO, NiO, CoO, MnO, PbO etc.；
4. trivalent transition metal oxide: Al2O3、Fe2O3、B2O3、V2O3、Cr2O3、In2O3、Sc2O3、Ga2O3Deng；
5. tetravalent transition metal oxide: ZrO2、TiO2、SiO2、GaO2、GeO2、HfO2、TaO2、VO2、MnO2、SnO2、 PbO2Deng；
6. pentavalent and sexavalence transition metal oxide: Nb2O5、V2O5、Ta2O5、WO3Deng；
7. mixed valence transition metal oxide: Fe3O4、Mn3O4、Co3O4；
8. rare-earth oxide: Y2O3、Sc2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、Er2O3、EuO、Pm2O3、 Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3、Lu2O3Deng；
It further illustrates,
In the material powder, metal hydroxides class raw material is related to the powder of following 3 small hydroxides:
1. alkali metal hydroxide: AOH, A=Li, Na, K, Rb, Cs；
2. alkaline earth metal hydroxide: B (OH)2, B=Be, Mg, Ca, Sr, Ba；
3. the hydroxide of some transition metal elements: including aluminium (Al), zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), The transition metal elements such as nickel (Ni), cobalt (Co), indium (In), chromium (Cr), tin (Sn), antimony (Sb), bismuth (Bi), zirconium (Zr) and can be steady Fixed existing hydroxide.
In the material powder, metal carbonate salt raw material is related to the powder of following 4 class carbonate:
1. alkali carbonate: A2CO3, A=Li, Na, K, Rb, Cs；
2. alkaline earth metal carbonate: BCO3, B=Be, Mg, Ca, Sr, Ba；
3. the carbonate of some transition metal elements: aluminium (Al), zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), nickel (Ni), The transition metal elements such as cobalt (Co), indium (In), chromium (Cr), tin (Sn), antimony (Sb), bismuth (Bi), zirconium (Zr) are stabilized Carbonate.
4. the carbonate or subcarbonate of some thuliums: including yttrium (Y), scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), erbium (Er), europium (Eu), promethium (Pm), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), thulium (Tm), the carbonate of the thuliums such as ytterbium (Yb), lutetium (Lu)；
In the material powder, metal nitrate powder material is related to the powder of following metal nitrate:
1. alkali nitrates (ANO3, A=Li, Na, K, Rb, Cs)；
2. alkaline earth nitrate (B (NO3)2, B=Be, Mg, Ca, Sr, Ba)；
3. the nitrate of some transition metal elements: including aluminium (Al), zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), nickel (Ni), the nitre of the transition metal elements such as cobalt (Co), indium (In), tin (Sn), antimony (Sb), bismuth (Bi), zirconium (Zr) being stabilized Hydrochlorate.
4. the nitrate of some thuliums: including yttrium (Y), scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), erbium (Er), europium (Eu), promethium (Pm), samarium (Sm), gadolinium (Gd), terbium (Tb, dysprosium (Dy), holmium (Ho), thulium (Tm), ytterbium (Yb), lutetium (Lu)。
The metal sulfate salt powder material is related to following sulfate or subsulfate powder:
1. alkali metal sulfates: A2SO4, A=Li, Na, K, Rb, Cs；
2. alkali earth metal sulfate: BSO4, B=Mg, Ca, Sr, Ba；
3. the sulfate or subsulfate of some transition metal elements: including aluminium (Al), zinc (Zn), iron (Fe), copper (Cu), the transition metal elements such as manganese (Mn), nickel (Ni), cobalt (Co), indium (In), tin (Sn), antimony (Sb), bismuth (Bi), zirconium (Zr) Low price water soluble sulfate.
4. the sulfate or subsulfate of some thuliums: including yttrium (Y), scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), erbium (Er), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb, dysprosium (Dy), holmium (Ho), thulium (Tm), ytterbium (Yb), lutetium (Lu).
The metal organic acid salt powder is related to the powder of the acylate of following metallic element: alkali metal element (packet Include Li, Na, K, Rb, Cs), alkali earth metal (including Mg, Ca, Sr, Ba), some transition metal elements (include: aluminium (Al), Zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), nickel (Ni), cobalt (Co), indium (In), tin (Sn), antimony (Sb), bismuth (Bi), zirconium (Zr)) The acylate of equal elements being stabilized, such as acetate, oxalates.
It further illustrates:
The physical form of the material powder is crystalline state or amorphous state or amorphous state.
Corresponding to all kinds of metal oxyacid salts and the alkali formula oxysalt or acid oxyacid that can be stabilized Salt also can be used as raw material.

Claims (10)

1. a kind of method for preparing composite oxide of metal powder using heating effect of current direct sintering under no furnace room temperature, feature It is that steps are as follows:
The weighing of step 1, material powder: being the metal-oxide powder, metal hydroxides, gold of 5nm~2000 μm with granularity Belong to carbonate powder, metal nitrate powder, metal sulfate powder or five class powder of metal organic acid salt powder as former Material chooses two or more metal compound powders according to the composition for the metal target composite oxides to be synthesized, and weighs each The powder of weighing is homogenously mixed together to obtain mixed powder raw material by the quality of material powder, and obtains the total matter of mixed powder Amount；
The metal-oxide powder includes: alkali metal oxide, alkaline earth oxide, transition metal oxide or rare earth gold Belong to oxide；
The metal hydroxides includes: the hydrogen-oxygen of alkali metal hydroxide, alkaline earth metal hydroxide or transition metal element Compound；
The metal carbonate powder include: alkali carbonate, alkaline earth metal carbonate, transition metal element carbonate, The carbonate or subcarbonate of thulium；
The metal nitrate powder include: alkali nitrates, alkaline earth nitrate, transition metal element nitrate or The nitrate of thulium；
The metal sulfate powder include: alkali metal sulfates, alkali earth metal sulfate, transition metal element sulfate or The sulfate or subsulfate of person's subsulfate, thulium；
The metal organic acid salt powder includes: organic existing for alkali metal element, alkali earth metal or transition metal element The powder of hydrochlorate；
It further include that the alkali formula oxysalt or acid that corresponding to all kinds of metal oxyacid salts and can be stabilized are oxygen-containing Hydrochlorate；
The preparation of step 2, water-soluble metal salt saturated solution: at 4 DEG C~50 DEG C, weigh soluble metallic salt one kind or It is several, it is uniform with magnetic stirrer after being dissolved in distilled water respectively, the metal salt of precipitating is generated for hydrolysis, and hydrochloric acid is added Or the saturated solution of one or several kinds of soluble metallic salts is made until solution is clarified in nitre acid for adjusting pH value；
The water-soluble metal salt is with the crystallization water or adsorbs water, or without the crystallization water；
Wherein in the selection of water-soluble metal salt, the cation of water-soluble metal salt should with one of selected material powder or The chemical valence of the cation of several compounds of person is different；
Step 3, powder pre-burning are body formed:
One or several kinds of soluble metal salt saturated solutions are separately added into mixed powder raw material, and distilled water is added to be adjusted to contain Water 30~90% stirs aqueous mixed powder raw material to uniform, then by wet mixed powder at a temperature of 20 DEG C~100 DEG C Material dry to water content is 3%~20%；Then made wet material powder is put into mold, applies pressure 0.1MPa Wet powder pre-burning body is made so that wet material powder forms in~30MPa；
The gross mass of the water-soluble metal salt accounts for 0.5wt%~30wt% of mixed powder total mass of raw material；
The DC/AC electric treatment of step 4, powder pre-burning body:
At 4~50 DEG C, wet powder pre-burning body molding in step 3 is placed in and is connected with DC power supply or AC power source Between two electrodes, and two electrodes and green body being in close contact, 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 between 0.1A/cm2~30A/cm2, green body is under electric current Fever generates high temperature, and energization 0.2min~25min obtains the metallic composite oxides material of bulk multi-hole；
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；
Step 5, composite oxide of metal are processed at powder: the metallic composite oxides material that electric current sintering in step 4 is gone out carries out Smashing and grinding processing is to get the varigrained powder body material for arriving corresponding composite oxide of metal.
2. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the alkali metal oxide are as follows: Li2O、Na2O、K2O、Rb2O、Cs2O。
3. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the alkaline earth oxide: BeO, MgO, CaO, SrO, BaO.
4. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: 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 transition metal oxide: Nb2O5、V2O5、Ta2O5Or WO3；Mixed valence transition metal oxide: Fe3O4、Mn3O4Or Co3O4。
5. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the rare-earth oxide: Y2O3、Sc2O3、La2O3、Ce2O3、CeO2、Pr2O3、Nd2O3、 Er2O3、EuO、Pm2O3、Eu2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Tm2O3、Yb2O3Or Lu2O3。
6. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the alkali metal hydroxide, alkali carbonate, alkali nitrates, alkali metal sulfates, Alkali metal element in the powder of alkali metal acylate is Li, Na, K, Rb, Cs.
7. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the alkaline earth metal hydroxide, alkaline earth metal carbonate, alkaline earth nitrate, alkaline-earth metal Sulfate, alkaline-earth metal acylate powder in alkaline-earth metal are as follows: Be, Mg, Ca, Sr, Ba.
8. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the hydroxide of the transition metal element, the carbonate of transition metal element, transition metal member Transition metal element in the powder of the nitrate of element, the sulfate of transition metal element or subsulfate or acylate Are as follows: aluminium Al, zinc Zn, iron Fe, copper Cu, manganese Mn, nickel, cobalt Co, indium In, chromium Cr, tin Sn, antimony Sb, bismuth Bi, zirconium Zr.
9. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder Method, it is characterised in that: the nitric acid of the carbonate or subcarbonate of the thulium, thulium Salt, the sulfate of thulium or the thulium in subsulfate are as follows: yttrium Y, scandium Sc, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, erbium Er, europium Eu, promethium Pm, samarium Sm, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, thulium Tm, ytterbium Yb, lutetium Lu.
10. according to claim 1 without under furnace room temperature use heating effect of current direct sintering prepare composite oxide of metal powder The method of body, it is characterised in that: the electrode is plate electrode, and small round tube hole is wherein evenly distributed on plate electrode, Through-hole diameter Φ 1mm~5mm, 0.5~1/cm of through-hole distribution density2。
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* Cited by examiner, † Cited by third party
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CN111733337A (en) * 2020-07-06 2020-10-02 攀钢集团研究院有限公司 Method for preparing vanadium oxide by reducing vanadium solution
CN111848184A (en) * 2020-07-30 2020-10-30 武汉理工大学 High-aluminum-content magnesia-alumina spinel transparent ceramic powder and preparation method thereof
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

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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

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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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111733337A (en) * 2020-07-06 2020-10-02 攀钢集团研究院有限公司 Method for preparing vanadium oxide by reducing vanadium solution
CN111848184A (en) * 2020-07-30 2020-10-30 武汉理工大学 High-aluminum-content magnesia-alumina spinel transparent ceramic powder and preparation method thereof
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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