CN106673645B - A kind of preparation method of the multiferroic complex phase ceramic of mosaic texture - Google Patents
A kind of preparation method of the multiferroic complex phase ceramic of mosaic texture Download PDFInfo
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Abstract
A kind of preparation method of the multiferroic complex phase ceramic of mosaic texture, is related to a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture.The present invention is to solve the technical issues of current complex phase multi-iron material is higher by the leakage current of multiple orders of magnitude than single phase multi-iron material.The present invention: one, Sol A is prepared；Two, sol B is prepared；Three, solution C is prepared；Four, colloidal sol D is prepared；Five, colloidal sol E is prepared；Six, mixed sols F is prepared；Seven, it dries；Eight, it calcines；Nine, it grinds；Ten, it is granulated；11, tabletting；12, dumping；13, it is sintered.Advantages of the present invention: the present invention can get the multiferroic complex phase ceramic with mosaic texture, and leakage current is less than 0-3,1-3,2-2 type multiferroic complex phase ceramic.The present invention is applied to preparation multiferroic complex phase ceramic.
Description
Technical field
The present invention relates to a kind of preparation methods of the multiferroic complex phase ceramic of mosaic texture.
Background technique
Multi-iron material refers to while at least with two kinds of performance in ferromagnetism, ferroelectricity or ferroelasticity and with coupling effect
Functional material.In application multi-iron material, it can property is coupled using it, it can also be using only certain property therein
Matter, therefore it is using very extensive, is related to the multiple fields such as microwave, storage, logical device.
It is divided according to composition, multi-iron material can be divided into single phase multi-iron material and complex phase multi-iron material, single-phase more iron materials
Expect that performance is poor, cannot still put into practical application, and complex phase multi-iron material is taken seriously because its is magneto-electric coupled functional.
For complex phase multi-iron material (by taking ferroelectricity, ferromagnetism two-phase are compound as an example), current two alternate composite squares
Formula has 0-3 (particle-block) type, 1-3 (cylinder-block) type and 2-2 (stratiform-stratiform) type, and different complex methods generates not
Same magneto-electric coupled performance, but three kinds of complex methods can not all solve electrical leakage problems: and ferromagnetic phase is present in the grain boundaries of ferroelectric phase,
Cause the leakage current that multiple orders of magnitude are higher by than single phase multi-iron material.
Summary of the invention
The present invention is that the electric leakage of multiple orders of magnitude is higher by solve current complex phase multi-iron material than single phase multi-iron material
The technical issues of stream, and a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture is provided.
A kind of preparation method of the multiferroic complex phase ceramic of mosaic texture of the invention carries out according to the following steps:
One, it prepares Sol A: bismuth salt is uniformly mixed with acetic acid, be 100r/min~300r/min, heating in stirring rate
Power be 300W~500W and heating temperature be 70 DEG C~100 DEG C under conditions of heating stirring to bismuth salt be completely dissolved, obtain bismuth
The acetic acid solution of salt naturally cools to 40 DEG C~50 DEG C, and solvent a is added, and is then 100r/min~300r/ in stirring rate
10min~15min is stirred under conditions of min, obtains Sol A；
Bismuth salt described in step 1 is bismuth subnitrate or bismuth acetate；
The amount of the substance of bismuth salt described in step 1 and the volume ratio of acetic acid are 1mmol:(1.5mL~2.5mL)；
Solvent a described in step 1 is ethylene glycol or ethylene glycol monomethyl ether；
The volume ratio of solvent a and acetic acid described in step 1 is 1:(1~5)；
Two, prepare sol B: metal salt a is uniformly mixed with acetic acid, stirring rate be 100r/min~300r/min with
Stirring is completely dissolved to metal salt a under conditions of room temperature, obtains the acetic acid solution of metal salt a, and solvent b is added, is then stirring
Rate stirs 10min~15min under conditions of being 100r/min~300r/min, obtains sol B；
Metal salt a described in step 2 is sodium salt or sylvite；
The amount of the substance of metal salt a and the volume ratio of acetic acid described in step 2 are 1mmol:(0.4mL~0.8mL)；
Solvent b described in step 2 is identical as solvent a described in step 1；
The volume ratio of solvent b and acetic acid described in step 2 is 1:(1~5)；
Three, it prepares solution C: butyl titanate is uniformly mixed with solvent c, be 100r/min~300r/ in stirring rate
Stirring obtains solution c to solution clear under conditions of min；
Solvent c described in step 3 is identical as solvent a described in step 1；
The amount of the substance of butyl titanate described in step 3 and the volume ratio of solvent c be 1mmol:(0.1mL~
0.4mL)；
Four, according to chemical formula A0.5Bi0.5TiO3In each metallic element stoichiometric ratio by Sol A, sol B and solution
C is uniformly mixed, and is stirred 10min~15min at room temperature with the stirring rate of 100r/min~300r/min, is obtained colloidal sol D；Institute
The chemical formula A stated0.5Bi0.5TiO3Middle A is sodium or potassium；
Five, it prepares colloidal sol E: metal salt b uniformly being mixed with ferric nitrate, acetic acid is then added, be 100r/ in stirring rate
Min~300r/min, heating power be 100W~300W and heating temperature be 50 DEG C~70 DEG C under conditions of heating stirring to gold
Belong to salt b to be completely dissolved with ferric nitrate, naturally cool to 40 DEG C~50 DEG C, solvent d is added, stirring rate for 100r/min~
10min~15min is stirred under conditions of 300r/min, obtains colloidal sol E；
Metal salt b described in step 5 is cobalt salt or nickel salt；
The ratio of the amount of the substance of iron is 1:2 in metallic element and ferric nitrate in metal salt b described in step 5；
The amount of the substance of metal salt b and the volume ratio of acetic acid described in step 5 are 1mmol:(1mL~5mL)；
Solvent d described in step 5 is identical as solvent a described in step 1；
The volume ratio of solvent d and acetic acid described in step 5 is 1:(2~5)；
Six, mixed sols F is prepared: according to chemical formula aA0.5Bi0.5TiO3-bBFe2O4In each metallic element chemistry meter
Colloidal sol D and colloidal sol E is sufficiently mixed by amount ratio, at room temperature with the stirring rate of 100r/min~300r/min stir 10min~
15min obtains mixed sols F；The aA0.5Bi0.5TiO3-bBFe2O4In 0.5≤a≤0.95, a+b=1, A be sodium or potassium,
B is cobalt or nickel；
Seven, it dries: mixed sols F obtained in step 6 is placed in dustfree environment, be 25 DEG C~50 DEG C in temperature
Under conditions of keep the temperature for 24 hours~168h, obtain mixing xerogel；
Eight, calcine: will mixing xerogel obtained in step 7 with 1 DEG C/min~5 DEG C/min heating rate from room temperature
Be warming up to 100 DEG C~200 DEG C, temperature be 100 DEG C~200 DEG C under conditions of keep the temperature 30min~1h, then with 5 DEG C/min~
The heating rate of 15 DEG C/min is warming up to 350 DEG C~450 DEG C from 100 DEG C~200 DEG C, the condition for being 350 DEG C~450 DEG C in temperature
Lower heat preservation 1h~2h, then 600 DEG C~900 DEG C are warming up to from 350 DEG C~450 DEG C with 5 DEG C/min~15 DEG C/min heating rate,
1h~2h is kept the temperature under conditions of temperature is 600 DEG C~900 DEG C, then furnace cooling obtains ceramic powder；
Nine, it grinds: ceramic powder obtained in step 7 being placed in mortar and is ground, then cross 100 mesh~160 mesh
Sieve, 100 mesh~160 meshes powder can be crossed by collecting；
Ten, be granulated: polyvinyl alcohol is uniformly mixed with deionized water, stirring rate be 100r/min~300r/min,
Heating power be 100W~300W and temperature be 50 DEG C~100 DEG C under conditions of carry out heating stirring it is completely molten to polyvinyl alcohol
Solution, obtains polyvinyl alcohol water solution；100 mesh~160 meshes powder will can be crossed obtained in step 9 and polyvinyl alcohol is water-soluble
Liquid is added in mortar, and being ground to mixture from pasty substances becomes uniformed powder；
The mass concentration of polyvinyl alcohol is 5% in the polyvinyl alcohol water solution；
The mass ratio of 100 mesh~160 meshes powder can be crossed obtained in the polyvinyl alcohol water solution and step 9
For 0.4:1；
11, tabletting: uniformed powder obtained in step 10 is placed in mold, in the condition that pressure is 6MPa~8MPa
Lower pressure maintaining 1min~3min, is pressed as block；
12, dumping: by block obtained in step 11 with 0.5 DEG C/min~1.5 DEG C/min heating rate from room
Temperature is warming up to 500 DEG C~600 DEG C, and 30min~2h, furnace cooling to room are kept the temperature under conditions of temperature is 500 DEG C~600 DEG C
Temperature obtains the ceramic green block without polyvinyl alcohol；
13, it is sintered: under oxygen atmosphere, 100 mesh~160 meshes powder can be crossed obtained in step 9 by step
Ceramic green block obtained in 12 without polyvinyl alcohol embeds, with 5 DEG C/min~10 DEG C/min under oxygen atmosphere
Heating rate is from room temperature to 1000 DEG C~1200 DEG C, under oxygen atmosphere and under conditions of temperature is 1000 DEG C~1200 DEG C
30min~2h is kept the temperature, then room temperature is cooled to the furnace under oxygen atmosphere, obtains ferroelectric phase A0.5Bi0.5TiO3In inlay it is ferromagnetic
Phase BFe2O4Multiferroic complex phase ceramic block；A is sodium or potassium, and B is cobalt or nickel.
Advantages of the present invention:
One, in the multiferroic complex phase ceramic prepared by the present invention with mosaic texture, ferromagnetic phase is embedded in ferroelectric phase, compared with
It appears on ferroelectric phase crystal boundary or is not present in less on ferroelectric phase crystal boundary, leakage current is less than congruent other methods system
Standby ceramic block；
Two, the sol-gel process process stabilizing that the present invention uses, the performance of product are uniform；
Three, the sol-gel process that mid-early stage of the invention uses takes low temperature drying, and the required energy is few, the calcining in later period
It is lower than with sintering process temperature and uses other methods, can effectively reduces energy waste；
The present invention can get the multiferroic complex phase ceramic with mosaic texture, and it is more that leakage current is less than 0-3,1-3,2-2 type
Iron complex phase ceramic.
Detailed description of the invention
Fig. 1 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block
Body amplifies 7000 times of scanning electron microscope secondary electron image；
Fig. 2 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block
Body amplifies 7000 times of scanning electron microscope backscattered electron image；
Fig. 3 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block
The XRD diagram of body；
Fig. 4 is the hysteresis loop figure of mosaic texture multiferroic composite ceramics；
Fig. 5 is the ferroelectric hysteresis loop figure of mosaic texture multiferroic composite ceramics.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture, tool
Body carries out according to the following steps:
One, it prepares Sol A: bismuth salt is uniformly mixed with acetic acid, be 100r/min~300r/min, heating in stirring rate
Power be 300W~500W and heating temperature be 70 DEG C~100 DEG C under conditions of heating stirring to bismuth salt be completely dissolved, obtain bismuth
The acetic acid solution of salt naturally cools to 40 DEG C~50 DEG C, and solvent a is added, and is then 100r/min~300r/ in stirring rate
10min~15min is stirred under conditions of min, obtains Sol A；
Bismuth salt described in step 1 is bismuth subnitrate or bismuth acetate；
The amount of the substance of bismuth salt described in step 1 and the volume ratio of acetic acid are 1mmol:(1.5mL~2.5mL)；
Solvent a described in step 1 is ethylene glycol or ethylene glycol monomethyl ether；
The volume ratio of solvent a and acetic acid described in step 1 is 1:(1~5)；
Two, prepare sol B: metal salt a is uniformly mixed with acetic acid, stirring rate be 100r/min~300r/min with
Stirring is completely dissolved to metal salt a under conditions of room temperature, obtains the acetic acid solution of metal salt a, and solvent b is added, is then stirring
Rate stirs 10min~15min under conditions of being 100r/min~300r/min, obtains sol B；
Metal salt a described in step 2 is sodium salt or sylvite；
The amount of the substance of metal salt a and the volume ratio of acetic acid described in step 2 are 1mmol:(0.4mL~0.8mL)；
Solvent b described in step 2 is identical as solvent a described in step 1；
The volume ratio of solvent b and acetic acid described in step 2 is 1:(1~5)；
Three, it prepares solution C: butyl titanate is uniformly mixed with solvent c, be 100r/min~300r/ in stirring rate
Stirring obtains solution c to solution clear under conditions of min；
Solvent c described in step 3 is identical as solvent a described in step 1；
The amount of the substance of butyl titanate described in step 3 and the volume ratio of solvent c be 1mmol:(0.1mL~
0.4mL)；
Four, according to chemical formula A0.5Bi0.5TiO3In each metallic element stoichiometric ratio by Sol A, sol B and solution
C is uniformly mixed, and is stirred 10min~15min at room temperature with the stirring rate of 100r/min~300r/min, is obtained colloidal sol D；Institute
The chemical formula A stated0.5Bi0.5TiO3Middle A is sodium or potassium；
Five, it prepares colloidal sol E: metal salt b uniformly being mixed with ferric nitrate, acetic acid is then added, be 100r/ in stirring rate
Min~300r/min, heating power be 100W~300W and heating temperature be 50 DEG C~70 DEG C under conditions of heating stirring to gold
Belong to salt b to be completely dissolved with ferric nitrate, naturally cool to 40 DEG C~50 DEG C, solvent d is added, stirring rate for 100r/min~
10min~15min is stirred under conditions of 300r/min, obtains colloidal sol E；
Metal salt b described in step 5 is cobalt salt or nickel salt；
The ratio of the amount of the substance of iron is 1:2 in metallic element and ferric nitrate in metal salt b described in step 5；
The amount of the substance of metal salt b and the volume ratio of acetic acid described in step 5 are 1mmol:(1mL~5mL)；
Solvent d described in step 5 is identical as solvent a described in step 1；
The volume ratio of solvent d and acetic acid described in step 5 is 1:(2~5)；
Six, mixed sols F is prepared: according to chemical formula aA0.5Bi0.5TiO3-bBFe2O4In each metallic element chemistry meter
Colloidal sol D and colloidal sol E is sufficiently mixed by amount ratio, at room temperature with the stirring rate of 100r/min~300r/min stir 10min~
15min obtains mixed sols F；The aA0.5Bi0.5TiO3-bBFe2O4In 0.5≤a≤0.95, a+b=1, A be sodium or potassium,
B is cobalt or nickel；
Seven, it dries: mixed sols F obtained in step 6 is placed in dustfree environment, be 25 DEG C~50 DEG C in temperature
Under conditions of keep the temperature for 24 hours~168h, obtain mixing xerogel；
Eight, calcine: will mixing xerogel obtained in step 7 with 1 DEG C/min~5 DEG C/min heating rate from room temperature
Be warming up to 100 DEG C~200 DEG C, temperature be 100 DEG C~200 DEG C under conditions of keep the temperature 30min~1h, then with 5 DEG C/min~
The heating rate of 15 DEG C/min is warming up to 350 DEG C~450 DEG C from 100 DEG C~200 DEG C, the condition for being 350 DEG C~450 DEG C in temperature
Lower heat preservation 1h~2h, then 600 DEG C~900 DEG C are warming up to from 350 DEG C~450 DEG C with 5 DEG C/min~15 DEG C/min heating rate,
1h~2h is kept the temperature under conditions of temperature is 600 DEG C~900 DEG C, then furnace cooling obtains ceramic powder；
Nine, it grinds: ceramic powder obtained in step 7 being placed in mortar and is ground, then cross 100 mesh~160 mesh
Sieve, 100 mesh~160 meshes powder can be crossed by collecting；
Ten, be granulated: polyvinyl alcohol is uniformly mixed with deionized water, stirring rate be 100r/min~300r/min,
Heating power be 100W~300W and temperature be 50 DEG C~100 DEG C under conditions of carry out heating stirring it is completely molten to polyvinyl alcohol
Solution, obtains polyvinyl alcohol water solution；100 mesh~160 meshes powder will can be crossed obtained in step 9 and polyvinyl alcohol is water-soluble
Liquid is added in mortar, and being ground to mixture from pasty substances becomes uniformed powder；
The mass concentration of polyvinyl alcohol is 5% in the polyvinyl alcohol water solution；
The mass ratio of 100 mesh~160 meshes powder can be crossed obtained in the polyvinyl alcohol water solution and step 9
For 0.4:1；
11, tabletting: uniformed powder obtained in step 10 is placed in mold, in the condition that pressure is 6MPa~8MPa
Lower pressure maintaining 1min~3min, is pressed as block；
12, dumping: by block obtained in step 11 with 0.5 DEG C/min~1.5 DEG C/min heating rate from room
Temperature is warming up to 500 DEG C~600 DEG C, and 30min~2h, furnace cooling to room are kept the temperature under conditions of temperature is 500 DEG C~600 DEG C
Temperature obtains the ceramic green block without polyvinyl alcohol；
13, it is sintered: under oxygen atmosphere, 100 mesh~160 meshes powder can be crossed obtained in step 9 by step
Ceramic green block obtained in 12 without polyvinyl alcohol embeds, with 5 DEG C/min~10 DEG C/min under oxygen atmosphere
Heating rate is from room temperature to 1000 DEG C~1200 DEG C, under oxygen atmosphere and under conditions of temperature is 1000 DEG C~1200 DEG C
30min~2h is kept the temperature, then room temperature is cooled to the furnace under oxygen atmosphere, obtains ferroelectric phase A0.5Bi0.5TiO3In inlay it is ferromagnetic
Phase BFe2O4Multiferroic complex phase ceramic block；A is sodium or potassium, and B is cobalt or nickel.
Heating power 300W~500W used in present embodiment step 1 is higher than 100W~300W's in step 5
The reason is that bismuth salt is more difficult to dissolve, and heating time too long is easy to cause bismuth salt to decompose or other reactions.
By mixing xerogel obtained in step 7 with 1 DEG C/min~5 DEG C/min heating in present embodiment step 8
Rate is to react organic matter sufficiently simultaneously in this temperature 30min~1h from room temperature to 100 DEG C~200 DEG C
So that the gas in product is sufficiently volatilized prevents from gas from taking away powder causing the loss of product and the change of stoichiometric ratio；Then with
The heating rate of 5 DEG C/min~15 DEG C/min rises to 350 DEG C~450 DEG C, and in this temperature 1h~2h be in order to enable
BFe2O4It crystallizes first；600 DEG C~900 DEG C are risen to 5 DEG C/min~15 DEG C/min heating rate again, and in this temperature
The purpose of 1h~2h is so that A0.5Bi0.5TiO3It crystallizes and by BFe2O4It inlays wherein.
Grinding purpose in present embodiment step 9 is to refine and screen powder, provides convenience for subsequent granulation.
The effect of polyvinyl alcohol is binder in present embodiment step 10, and carrying out mixed grinding using polyvinyl alcohol can be with
Obtain that shape is consistent, the tiny powder with size distribution gradient.
The purpose being sintered in present embodiment step 13 is so that ceramic green block densifies.
Specific embodiment 2: present embodiment is unlike specific embodiment one: sodium described in step 2
Salt is sodium acetate or sodium nitrate.It is other same as the specific embodiment one.
Specific embodiment 3: present embodiment is unlike specific embodiment one: potassium described in step 2
Salt is potassium acetate or potassium nitrate.It is other same as the specific embodiment one.
Specific embodiment 4: present embodiment is unlike specific embodiment one: described in step 5
Cobalt salt is cobalt nitrate or cobalt acetate.It is other same as the specific embodiment one.
Specific embodiment 5: present embodiment is unlike specific embodiment one: described in step 5
Nickel salt is nickel nitrate or nickel acetate.It is other same as the specific embodiment one.
Effect of the invention is verified by following tests:
Test one: this test is a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture, specifically presses following step
Suddenly it carries out:
One, prepare Sol A: bismuth salt is uniformly mixed with acetic acid, stirring rate be 200r/min, heating power 300W
Heating stirring to bismuth salt is completely dissolved under conditions of being 100 DEG C with heating temperature, is obtained the acetic acid solution of bismuth salt, is naturally cooled to
50 DEG C, solvent a is added, then stirs 15min under conditions of stirring rate is 200r/min, obtains Sol A；
Bismuth salt described in step 1 is bismuth subnitrate；
The amount of the substance of bismuth salt described in step 1 and the volume ratio of acetic acid are 1mmol:2mL；
Solvent a described in step 1 is ethylene glycol；
The volume ratio of solvent a and acetic acid described in step 1 is 1:2；
Two, it prepares sol B: metal salt a is uniformly mixed with acetic acid, in the condition that stirring rate is 200r/min and room temperature
Lower stirring is completely dissolved to metal salt a, obtains the acetic acid solution of metal salt a, and solvent b is added, and is then 200r/ in stirring rate
15min is stirred under conditions of min, obtains sol B；
Metal salt a described in step 2 is sodium salt；
The amount of the substance of metal salt a and the volume ratio of acetic acid described in step 2 are 1mmol:0.5mL；
Solvent b described in step 2 is identical as solvent a described in step 1；
The volume ratio of solvent b and acetic acid described in step 2 is 1:1；
Three, it prepares solution C: butyl titanate is uniformly mixed with solvent c, under conditions of stirring rate is 200r/min
Stirring obtains solution c to solution clear；
Solvent c described in step 3 is identical as solvent a described in step 1；
The amount of the substance of butyl titanate described in step 3 and the volume ratio of solvent c are 1mmol:0.3mL；
Four, according to chemical formula A0.5Bi0.5TiO3In each metallic element stoichiometric ratio by Sol A, sol B and solution
C is uniformly mixed, and is stirred 15min at room temperature with the stirring rate of 200r/min, is obtained colloidal sol D；The chemical formula
A0.5Bi0.5TiO3Middle A is sodium；
Five, it prepares colloidal sol E: metal salt b uniformly being mixed with ferric nitrate, acetic acid is then added, be 200r/ in stirring rate
Min, heating power be 100W and heating temperature be 50 DEG C under conditions of heating stirring be completely dissolved to metal salt b and ferric nitrate,
50 DEG C are naturally cooled to, solvent d is added, 15min is stirred under conditions of stirring rate is 200r/min, obtains colloidal sol E；
Metal salt b described in step 5 is cobalt salt；
The ratio of the amount of the substance of iron is 1:2 in metallic element and ferric nitrate in metal salt b described in step 5；
The amount of the substance of metal salt b and the volume ratio of acetic acid described in step 5 are 1mmol:1mL；
Solvent d described in step 5 is identical as solvent a described in step 1；
The volume ratio of solvent d and acetic acid described in step 5 is 1:2；
Six, mixed sols F is prepared: according to chemical formula aA0.5Bi0.5TiO3-bBFe2O4In each metallic element chemistry meter
Colloidal sol D and colloidal sol E is sufficiently mixed by amount ratio, is stirred 15min at room temperature with the stirring rate of 200r/min, is obtained mixed sols
F；The aA0.5Bi0.5TiO3-bBFe2O4Middle a=0.95, b=0.05, A are sodium, and B is cobalt；
Seven, it dries: mixed sols F obtained in step 6 is placed in dustfree environment, the condition for being 40 DEG C in temperature
Lower heat preservation 96h obtains mixing xerogel；
Eight, calcine: will mixing xerogel obtained in step 7 with the heating rate of 1 DEG C/min from room temperature to 150
DEG C, 1h is kept the temperature under conditions of temperature is 150 DEG C, then 350 DEG C are warming up to from 150 DEG C with the heating rate of 5 DEG C/min, in temperature
Degree keeps the temperature 1h under conditions of being 350 DEG C, then is warming up to 700 DEG C from 350 DEG C with the heating rate of 5 DEG C/min, is 700 DEG C in temperature
Under conditions of keep the temperature 1h, then furnace cooling obtains ceramic powder；
Nine, it grinds: ceramic powder obtained in step 7 being placed in mortar and is ground, then cross 160 meshes, collect
The powder of 160 meshes can be crossed；
Ten, it is granulated: polyvinyl alcohol is uniformly mixed with deionized water, stirring rate is 200r/min, heating power is
100W and temperature carry out heating stirring to polyvinyl alcohol under conditions of being 50 DEG C and are completely dissolved, and obtain polyvinyl alcohol water solution；It will
The powder of 160 meshes can be crossed obtained in step 9 and polyvinyl alcohol water solution is added in mortar, be ground to mixture by paste
Shape substance becomes uniformed powder；
The mass concentration of polyvinyl alcohol is 5% in the polyvinyl alcohol water solution；
The mass ratio that the powder of 160 meshes can be crossed obtained in the polyvinyl alcohol water solution and step 9 is 0.4:1；
11, tabletting: uniformed powder obtained in step 10 is placed in mold, pressure maintaining under conditions of pressure is 6MPa
1min presses as block；
12, dumping: by block obtained in step 11 with the heating rate of 1 DEG C/min from room temperature to 500 DEG C,
1h is kept the temperature under conditions of temperature is 500 DEG C, furnace cooling to room temperature obtains the ceramic green block without polyvinyl alcohol；
13, be sintered: under oxygen atmosphere, the powder that 160 meshes can be crossed obtained in step 9 will be in step 12
The obtained ceramic green block embedding without polyvinyl alcohol, with the heating rate of 5 DEG C/min from room temperature liter under oxygen atmosphere
Temperature keeps the temperature 50min under oxygen atmosphere and under conditions of temperature is 1150 DEG C to 1150 DEG C, then cold with furnace under oxygen atmosphere
But to room temperature, ferroelectric phase A is obtained0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block；A is sodium, and B is
Cobalt.
Sodium salt described in step 1 is sodium acetate；Cobalt salt described in step 5 is cobalt nitrate.
Fig. 1 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block
Body amplifies 7000 times of scanning electron microscope secondary electron image, and Fig. 2 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3-In
Inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block amplify 7000 times of scanning electron microscope backscattered electron image,
The same area is shown in Fig. 1 and Fig. 2.
Fig. 1 is demonstrated by the grain morphology of mosaic texture multiferroic composite ceramics, altogether there are two types of crystal grain, i.e., cubic shape with it is isometric
Shape.
Fig. 2 is demonstrated by the component distributing of mosaic texture multiferroic composite ceramics, and altogether there are two types of the crystal grain of color, i.e. light color is brilliant
Grain and dark crystal grain, CoFe in two kinds of crystal grain2O4Content it is different.By taking light crystal grain as an example, ferromagnetic phase CoFe2O4It is embedded in
Ferroelectric phase Na0.5Bi0.5TiO3In, dark-shaded can be seen in crystal grain central part, and have dark CoFe2O4Crystal grain is inlayed
Wherein, these dark colors CoFe2O4The diameter of crystal grain is 500nm~2 μm.
Fig. 3 is to test an obtained ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4Multiferroic complex phase ceramic block
The XRD diagram of body, ▼ are Na0.5Bi0.5TiO3, ● it is CoFe2O4, compared using standard card (card number 46-0001,03-0864)
Discovery gains are mutually required Na really afterwards0.5Bi0.5TiO3And CoFe2O4, and the intensity of diffraction maximum also complies with the content of two-phase
Ratio.
The ferroelectric phase A that test one is obtained using vibrating specimen magnetometer (VSM)0.5Bi0.5TiO3In inlay ferromagnetic phase
BFe2O4Multiferroic complex phase ceramic block carry out magnetism testing, as shown in figure 4, Fig. 4 is mosaic texture multiferroic composite ceramics
Hysteresis loop figure, wherein saturation magnetization be 18.8emu/g, according to CoFe2O4Shared actual volume is converted into
The magnetism of 46.3emu/g, mosaic texture multiferroic composite ceramics are good.
The ferroelectric phase A that test one is obtained using ferroelectricity test macro0.5Bi0.5TiO3In inlay ferromagnetic phase BFe2O4It is more
Iron complex phase ceramic block carries out ferroelectric properties test, as shown in figure 5, Fig. 5 is the electric hysteresis of mosaic texture multiferroic composite ceramics
Loop line figure, the electric field strength of curve 1 are 100KV/cm, and the electric field strength of curve 2 is 120KV/cm, and the electric field strength of curve 3 is
140KV/cm, the electric field strength of curve 4 are 160KV/cm, and wherein remanent polarization is 38.2 (μ C/cm2), mosaic texture is more
The ferroelectric hysteresis loop rectangular degree of iron composite ceramics is high, and leakage current is small, surveys leakage current 10-6(Amps/cm2) order of magnitude.
Claims (5)
1. a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture, it is characterised in that the multiferroic complex phase of mosaic texture is made pottery
The preparation method of porcelain carries out according to the following steps:
One, it prepares Sol A: bismuth salt is uniformly mixed with acetic acid, be 100r/min~300r/min, heating power in stirring rate
Heating stirring to bismuth salt is completely dissolved under conditions of being 70 DEG C~100 DEG C for 300W~500W and heating temperature, obtains bismuth salt
Acetic acid solution naturally cools to 40 DEG C~50 DEG C, and solvent a is added, and is then 100r/min~300r/min's in stirring rate
Under the conditions of stir 10min~15min, obtain Sol A；
Bismuth salt described in step 1 is bismuth subnitrate or bismuth acetate；
The amount of the substance of bismuth salt described in step 1 and the volume ratio of acetic acid are 1mmol:(1.5mL~2.5mL)；
Solvent a described in step 1 is ethylene glycol or ethylene glycol monomethyl ether；
The volume ratio of solvent a and acetic acid described in step 1 is 1:(1~5)；
Two, it prepares sol B: metal salt a is uniformly mixed with acetic acid, be 100r/min~300r/min and room temperature in stirring rate
Under conditions of stir and be completely dissolved to metal salt a, obtain the acetic acid solution of metal salt a, solvent b be added, then in stirring rate
To stir 10min~15min under conditions of 100r/min~300r/min, sol B is obtained；
Metal salt a described in step 2 is sodium salt or sylvite；
The amount of the substance of metal salt a and the volume ratio of acetic acid described in step 2 are 1mmol:(0.4mL~0.8mL)；
Solvent b described in step 2 is identical as solvent a described in step 1；
The volume ratio of solvent b and acetic acid described in step 2 is 1:(1~5)；
Three, it prepares solution C: butyl titanate is uniformly mixed with solvent c, be 100r/min~300r/min's in stirring rate
Under the conditions of stirring to solution clear, obtain solution c；
Solvent c described in step 3 is identical as solvent a described in step 1；
The amount of the substance of butyl titanate described in step 3 and the volume ratio of solvent c are 1mmol:(0.1mL~0.4mL)；
Four, according to chemical formula A0.5Bi0.5TiO3In each metallic element stoichiometric ratio Sol A, sol B and solution C is uniform
Mixing stirs 10min~15min at room temperature with the stirring rate of 100r/min~300r/min, obtains colloidal sol D；Described
Chemical formula A0.5Bi0.5TiO3Middle A is sodium or potassium；
Five, it prepares colloidal sol E: metal salt b uniformly being mixed with ferric nitrate, acetic acid is then added, be 100r/min in stirring rate
~300r/min, heating power be 100W~300W and heating temperature be 50 DEG C~70 DEG C under conditions of heating stirring to metal salt
B is completely dissolved with ferric nitrate, naturally cools to 40 DEG C~50 DEG C, and solvent d is added, and is 100r/min~300r/ in stirring rate
10min~15min is stirred under conditions of min, obtains colloidal sol E；
Metal salt b described in step 5 is cobalt salt or nickel salt；
The ratio of the amount of the substance of iron is 1:2 in metallic element and ferric nitrate in metal salt b described in step 5；
The amount of the substance of metal salt b and the volume ratio of acetic acid described in step 5 are 1mmol:(1mL~5mL)；
Solvent d described in step 5 is identical as solvent a described in step 1；
The volume ratio of solvent d and acetic acid described in step 5 is 1:(2~5)；
Six, mixed sols F is prepared: according to chemical formula aA0.5Bi0.5TiO3-bBFe2O4In each metallic element stoichiometric ratio
Colloidal sol D and colloidal sol E are sufficiently mixed, at room temperature with the stirring rate of 100r/min~300r/min stirring 10min~
15min obtains mixed sols F；The aA0.5Bi0.5TiO3-bBFe2O4In 0.5≤a≤0.95, a+b=1, A be sodium or potassium,
B is cobalt or nickel；
Seven, it dries: mixed sols F obtained in step 6 is placed in dustfree environment, the item for being 25 DEG C~50 DEG C in temperature
For 24 hours~168h is kept the temperature under part, obtains mixing xerogel；
Eight, calcine: will mixing xerogel obtained in step 7 with 1 DEG C/min~5 DEG C/min heating rate from room temperature
To 100 DEG C~200 DEG C, temperature be 100 DEG C~200 DEG C under conditions of keep the temperature 30min~1h, then with 5 DEG C/min~15 DEG C/
The heating rate of min is warming up to 350 DEG C~450 DEG C from 100 DEG C~200 DEG C, protects under conditions of temperature is 350 DEG C~450 DEG C
Warm 1h~2h, then 600 DEG C~900 DEG C are warming up to from 350 DEG C~450 DEG C with 5 DEG C/min~15 DEG C/min heating rate, in temperature
Degree keeps the temperature 1h~2h under conditions of being 600 DEG C~900 DEG C, and then furnace cooling obtains ceramic powder；
Nine, it grinds: ceramic powder obtained in step 7 being placed in mortar and is ground, then cross 100 mesh~160 meshes,
100 mesh~160 meshes powder can be crossed by collecting；
Ten, it is granulated: polyvinyl alcohol is uniformly mixed with deionized water, be 100r/min~300r/min, heating in stirring rate
Power be 100W~300W and temperature be 50 DEG C~100 DEG C under conditions of carry out heating stirring to polyvinyl alcohol be completely dissolved, obtain
To polyvinyl alcohol water solution；100 mesh~160 meshes powder will can be crossed obtained in step 9 and polyvinyl alcohol water solution is added to
In mortar, being ground to mixture from pasty substances becomes uniformed powder；
The mass concentration of polyvinyl alcohol is 5% in the polyvinyl alcohol water solution；
Obtained in the polyvinyl alcohol water solution and step 9 can cross 100 mesh~160 meshes powder mass ratio be
0.4:1；
11, tabletting: uniformed powder obtained in step 10 is placed in mold, is protected under conditions of pressure is 6MPa~8MPa
1min~3min is pressed, is pressed as block；
12, dumping: by block obtained in step 11 with 0.5 DEG C/min~1.5 DEG C/min heating rate from room temperature liter
Temperature keeps the temperature 30min~2h to 500 DEG C~600 DEG C under conditions of temperature is 500 DEG C~600 DEG C, and furnace cooling to room temperature obtains
To the ceramic green block for being free of polyvinyl alcohol；
13, it is sintered: under oxygen atmosphere, 100 mesh~160 meshes powder can be crossed obtained in step 9 by step 12
Obtained in without polyvinyl alcohol ceramic green block embed, with 5 DEG C/min~10 DEG C/min heating under oxygen atmosphere
Rate is kept the temperature under oxygen atmosphere and under conditions of temperature is 1000 DEG C~1200 DEG C from room temperature to 1000 DEG C~1200 DEG C
Then 30min~2h cools to room temperature with the furnace under oxygen atmosphere, obtain ferroelectric phase A0.5Bi0.5TiO3In inlay ferromagnetic phase
BFe2O4Multiferroic complex phase ceramic block；A is sodium or potassium, and B is cobalt or nickel.
2. a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture according to claim 1, it is characterised in that step
Sodium salt described in rapid two is sodium acetate or sodium nitrate.
3. a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture according to claim 1, it is characterised in that step
Sylvite described in rapid two is potassium acetate or potassium nitrate.
4. a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture according to claim 1, it is characterised in that step
Cobalt salt described in rapid five is cobalt nitrate or cobalt acetate.
5. a kind of preparation method of the multiferroic complex phase ceramic of mosaic texture according to claim 1, it is characterised in that step
Nickel salt described in rapid five is nickel nitrate or nickel acetate.
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| CN1919783A (en) * | 2006-09-20 | 2007-02-28 | 浙江大学 | Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic |
| CN103588474A (en) * | 2013-11-15 | 2014-02-19 | 哈尔滨工业大学 | Preparation method of magneto-electricity composite ceramic with coating structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919783A (en) * | 2006-09-20 | 2007-02-28 | 浙江大学 | Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic |
| CN103588474A (en) * | 2013-11-15 | 2014-02-19 | 哈尔滨工业大学 | Preparation method of magneto-electricity composite ceramic with coating structure |
Non-Patent Citations (1)
| Title |
|---|
| Effect of magnetic CoFe2O4 component on sintering densification process of Bi3.15Nd0.85Ti3O12 ceramics;Hongjun Zhang el al.;《Journal of the European Ceramic Society》;20161222;第37卷(第5期);第2115-2122页 |
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