CN106588032A - Ceramic material as well as preparation method and piezoelectric ceramic thereof - Google Patents
Ceramic material as well as preparation method and piezoelectric ceramic thereof Download PDFInfo
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Abstract
The invention provides a ceramic material as well as a preparation method and piezoelectric ceramic thereof and belongs to the technical field of materials. The preparation method of the ceramic material comprises the following steps: performing electrophoretic deposition on a suspension made of template grains to obtain a green body, and sintering the green body. The green body made by the electrophoretic deposition is higher in degree of orientation, and the sintered green body is more compact in structure, higher in compactness and better in texture degree. Meanwhile, the bonding strength among template grain particles is enhanced in the sintering process, so that the mechanical strength of the ceramic material is improved. The piezoelectric ceramic provided by the invention is also prepared by the ceramic material through polarization and is high in sensitivity.
Description
Technical field
The present invention relates to field of material technology, and more particularly to a kind of ceramic material and preparation method thereof, piezoelectric ceramics.
Background technology
Piezoelectric ceramics is a kind of functional ceramic material that can mutually convert electric energy and mechanical energy.The material is in dispatch from foreign news agency
Can produce strain under field action, and the positive and negative charge center of material internal occurs relative displacement under mechanical force, so as to
The two poles of the earth of material produce opposite charges.Piezoelectric ceramics is usually ferroelectric, can be disappeared near Curie temperature piezoelectricity.For need
Will be in the piezoelectric ceramics of hot environment work, it is desirable to which it has higher Curie temperature.
The piezoelectric ceramics of superelevation Curie temperature (550 DEG C～950 DEG C) is may be made with after the polarization of bismuth laminate ceramic.Cause
This, the preparation of bismuth laminate ceramic has very important impact to the performance of the piezoelectric ceramics of its later stage preparation.But bismuth stratiform
The current complicated process of preparation of ceramic material, and simple shape, the ceramic material of rule can only be obtained.
The content of the invention
It is an object of the invention to provide a kind of preparation method of ceramic material, the preparation method being capable of simple and direct efficient life
Produce the ceramic material of arbitrary shape.
Another object of the present invention is to provide a kind of ceramic material, it is obtained using above-mentioned preparation method, the ceramic material
The textured structure of material is more preferable, with preferable anisotropy.
Present invention also offers a kind of piezoelectric ceramics, is obtained by above-mentioned ceramic material by polarizer.
The present invention solves its technical problem and employs the following technical solutions to realize.
The present invention proposes a kind of preparation method of ceramic material, and it includes：The suspension made by template grains is carried out
Electrophoretic deposition obtains green compact, and green compact are sintered.
The present invention proposes a kind of ceramic material, is obtained using above-mentioned preparation method.
The present invention proposes a kind of piezoelectric ceramics, is obtained by polarizer by above-mentioned ceramic material.
Ceramic material of the embodiment of the present invention and preparation method thereof, the beneficial effect of piezoelectric ceramics are：Using what is prepared
Template grains are simultaneously made into suspension, are adsorbed onto what template grains were oriented on conductive material by electrophoretic deposition, and formation takes
To the higher green compact of degree.Green compact are sintered again, make that the structure of green compact is more compact, consistency is higher, and texturing degree is more
It is good.Meanwhile, sintering process causes the solvent that green compact are contained within and other impurities composition effectively to be removed, template grains
Interparticle bond strength strengthens, and ceramic material mechanical strength is improved.Because the ceramic material possesses preferable anisotropy, because
This, the piezoelectric ceramics prepared by the ceramic material meets piezoelectric ceramics field for piezoelectric ceramics should possess wanting for high sensitivity
Ask.
Description of the drawings
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can be with according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the structural representation of the electrophoretic deposition set that the embodiment of the present invention 1 is provided；
Fig. 2 is the scanning electron microscope diagram of the ceramic material surfaces prepared in the embodiment of the present invention 1；
Fig. 3 is the X-ray diffraction of the ceramic material and commercial non-textured ceramic material prepared in the embodiment of the present invention 1
Figure；
Fig. 4 is the structural representation of the electrophoretic deposition set that the embodiment of the present invention 2 is provided；
Fig. 5 is the scanning electron microscope diagram of the ceramic material surfaces prepared in the embodiment of the present invention 2；
Fig. 6 is the X-ray diffraction of the ceramic material and commercial non-textured ceramic material prepared in the embodiment of the present invention 2
Figure；
Fig. 7 is the structural representation of the electrophoretic deposition set that the embodiment of the present invention 3 is provided；
Fig. 8 is the scanning electron microscope diagram of the ceramic material surfaces prepared in the embodiment of the present invention 3；
Fig. 9 is the X-ray diffraction of the ceramic material and commercial non-textured ceramic material prepared in the embodiment of the present invention 3
Figure；
Figure 10 is the structural representation of the electrophoretic deposition set that the embodiment of the present invention 4 is provided；
Figure 11 is the scanning electron microscope diagram of the ceramic material surfaces prepared in the embodiment of the present invention 4；
Figure 12 is the X-ray diffraction of the ceramic material and commercial non-textured ceramic material prepared in the embodiment of the present invention 4
Figure.
Icon：100- electrophoretic deposition sets；102- first electrodes；104- second electrodes；106- template grains；200- electrophoresis
Precipitation equipment；202- first electrodes；204- second electrodes；206- template grains；300- electrophoretic deposition sets；302- first is electric
Pole；304- second electrodes；306- template grains；400- electrophoretic deposition sets；402- first electrodes；404- second electrodes；406-
Template grains.
Specific embodiment
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can pass through the conventional product that commercially available purchase is obtained
Product." parallel " mentioned in embodiment, does not imply that absolute parallel, can there is appropriate inclination.
Ceramic material of the embodiment of the present invention and preparation method thereof, piezoelectric ceramics are specifically described below.
A kind of preparation method of ceramic material, comprises the following steps：
The suspension made by template grains is carried out into electrophoretic deposition and obtains green compact, green compact are sintered.
Further, template grains can be lamellar.The template grains of lamellar have higher orientation, its pressure for preparing
Electroceramics has more preferable textured structure, and intergranular combination is more tight, the mechanical performance and electrical property of piezoelectric ceramics compared with
It is good.Certainly the template grains of other shapes also be can select, such as it is spherical.But contact area is less between spherical template grains, because
This lamination effect is not as good as lamellar template grains.Interparticle cohesion of the spherical template grains in ceramic material is less, causes
The bad mechanical property of ceramic material.
Further, above-mentioned ceramic material has bismuth laminated.Bismuth laminated ceramic material has higher Curie
The advantages of temperature, fatigue resistance are good, leakage current is little, is usually used in high temperature, high frequency, high pressure occasion.
Further, above-mentioned template grains have formula (Bi2O2)2+(Am-1BmO3m+1)2-, 2≤m≤5, m is integer, A, B
Metal ion is, and template grains are made by the following method：
To be 1 according to mass ratio:2～2:The metal chlorination salt of 1 mixing is incubated with raw material at a temperature of 800～1100 DEG C
1～5 hour.
Metal chlorination salt fusing point is below 800 DEG C.Metal chlorination salt can be chlorine of any one fusing point below 800 DEG C
Salt dissolving, such as KCl or NaCl；Can also be the mixture of any several chlorates, such as NaCl and MnCl2。
Raw material is included according to formula (Bi2O2)2+(Am-1BmO3m+1)2-Stoichiometric proportion mixing Bi oxide or salt, A
The oxide or salt of element and the oxide or salt of B element.
For example, as m=2, A is Co+4, B is Ti+4, formula is Bi2CoTi2O9, now raw material can select Bi2O3、TiO2
And CoCO3, and it is passed through a certain amount of oxygen in insulation.As m=3, A is Bi+3, B is Ti+4, formula is Bi4Ti3O12, now
Raw material can select Bi2O3And TiO2.As m=3, it is also an option that A is Zr+3, B is Co+4, formula is Bi2Zr2Co3O12, now
Raw material can select Bi2O3、Zr2O3With Co (CO3)2.During m=4, A is Cr+4, B be Nb+3, formula is Bi2Cr3Nb4O15, now raw material
Optional Cr (NO3)4、Bi2O3And Nb2O3.During m=5, A is Nb+5, B be V+2, formula is Bi2Nb4V5O18, now raw material is optional
Use Nb2O5、Bi2O3And VO.Certainly A, B can also adopt same metal ion species, such as m=2, A, B are Ti+4, lead to
Formula is Bi2Ti3O9, now raw material can select Bi2O3And TiO2。
It is 1 according to mass ratio by metal chlorination salt and raw material to obtain particle diameter distribution template grains evenly:2～
2:After 1 mixing, first add a little solvent in mixed metal chlorination salt and raw material and it is sufficiently ground, is dried
Afterwards, then be placed at a temperature of 800～1100 DEG C be incubated 1～5 hour.Wherein solvent is from insoluble raw material, metal chlorination salt
Solvent, such as ethanol, acetone etc..
800～1100 DEG C of insulating process is the high temperature solid state reaction process of raw material, should ensure that metal chlorate is in
Molten condition, also to ensure generate template grains at such a temperature can stable existence, be not in decomposing phenomenon.Using molten
(middle finger of the present invention adopts the metal chlorination salt of molten condition as the reaction medium of template grains to salt method.) can significantly reduce
Synthesis temperature and shortening response time, can more easily control the shape and size of powder granule.It is to pass through in the present embodiment
The ratio of control raw material and metal chlorination salt, with the template grains that ensure to prepare as lamellar and degree of grain alignment height.In addition,
In the course of reaction of molten-salt growth method and subsequent cleaning process, can easier elimination impurity, form high-purity product,
So typically high-power piezoelectric ceramic is prepared using molten-salt growth method.
Further, the preparation method of suspension includes：
Template grains are dispersed in solvent, solvent includes alcoholic solution.Alcoholic solution includes methanol, ethanol, propanol, isopropanol
In one or more of aqueous solution.If only with distilled water as solvent, distilled water will generate gas under the voltage of very little
Body discharges at electrode, so as to the base substrate compactness extent for causing green compact is reduced.
Wherein, template grains dispersion in a solvent can adopt at least one in mechanical dispersion, addition chemical dispersant
Dispersing mode.Dispersant includes at least one in mineral acid, organic acid.Mineral acid includes hydrochloric acid and/or nitric acid；Organic acid bag
Include one or more in acetic acid, polyacrylic acid, phosphate ester.Mechanical dispersion includes ultrasonic disperse.
In order to ensure the carrying out of electrophoretic deposition, it is necessary to template grains are made into suspension, therefore insoluble template may be selected
The alcoholic solution of crystal grain is used as solvent.In order to the displacement of template grains is more orderly in electrophoretic deposition process, lamination is more regular,
Need to be disperseed template grains with dispersant.Organic acid by wrapping up template grains, make it is mutually isolated between template grains, and can
Stable existence；Mineral acid is by the repulsive interaction of electric charge by template grains stable existence.Ultrasonic disperse pair can be selected to add
The suspension for entering dispersant is further processed, and makes the dispersion of template grains in suspension evenly, stably.
Further, the method that suspension carries out electrophoretic deposition is included：
First electrode and second electrode are arranged in a vertical direction, first electrode is big relative to the height on ground in vertical direction
Template grains is deposited to first electrode by electrophoresis relative to the height on ground in vertical direction in second electrode, given birth to
Base.
For example, first electrode and second electrode are positioned in the beaker for filling suspension, and first electrode is apart from beaker
The vertical dimension of bottom is 10 centimetres, and second electrode is 7 centimetres apart from the vertical dimension of beaker bottom.Because first electrode is
The top of two electrodes, therefore, when template grains are on displacement to first electrode, need the weight for overcoming template grains itself
Power.Ensure that the template grains in first electrode are to deposit to first electrode by the effect of electric field, make between template grains
Combination it is tightr, in order, be conducive to the densification in later stage.
The method of sintering green compact includes：Heating green compact are put to 900 DEG C～1200 DEG C and are incubated 0.5～5 hour.Sintering process
It is able to for green compact to form densification, textured ceramics.Intergranular adhesion is strengthened by high temperature sintering, pottery is improved
The mechanical performance of porcelain, obtains textured ceramics.The green compact that electrophoresis is obtained are attached in first electrode.If the ceramic later stage needs
Conductive material is done, then can be sintered together with first electrode when sintering green compact.If ceramics need not be used for conduction material by the later stage
Material, then can take off first electrode from green compact, then green compact are sintered.For simplicity, the reality that the present invention is provided
Apply in example is to sinter green compact together with electrode.
A kind of ceramic material, is obtained using method made above.The ceramic material has excellent anisotropic, texturing
Structure is obvious.By controlling reaction mass ratio in template grains preparation process, the template grains of synthesizing flaky give later stage ceramics
Preferably texturing provides prerequisite.The shape of change first electrode can also be passed through, green compact of different shapes are obtained, and then
Obtain ceramic material of different shapes.
A kind of piezoelectric ceramics, is obtained by above-mentioned ceramic material by polarizer.Because above-mentioned ceramic material possesses excellent each
The item opposite sex, therefore the piezoelectric ceramics piezoelectric susceptibility for preparing is preferably, can be applied to the higher field of various piezoelectric susceptibilities requirement
Institute, such as sonar.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of ceramic material of offer and preparation method thereof is originally provided.The preparation method of the present embodiment ceramic material is as follows：
(1) according to chemical formula Bi4Ti3O12, with Bi2O3、TiO2For reactant, Bi is weighed2O393.2g、TiO224g mixing,
Grinding, mean diameter is controlled below 2 microns, to obtain raw material.With KCl and NaCl as metal chlorination salt, wherein KCl is weighed
78.1g, NaCl weigh 156.3g.In adding raw materials into metal chlorination salt, ethanol 10ml is added.Through grinding, it is dried, is placed in and adds
In hot stove, temperature setting is 1100 DEG C (synthesis temperature), is incubated 2 hours, clean with distilled water after cooling, sucking filtration, must after drying
To Bi4Ti3O12Lamellar template grains 106 (refer to Fig. 1).Zeta potential test is carried out to template grains 106, its surface is determined
It is charge.Test indicate that template grains 106 are negatively charged in the present embodiment.
(2) template grains 106 are mixed with propanol 500ml, hydrochloric acid 500ml, the ultrasonic disperse through 2 hours obtains more steady
Fixed suspension.
(3) refer to Fig. 1.The present embodiment provides a kind of electrophoretic deposition set 100, electric as first from conductive material platinum
Pole 102, graphite adopts rectangular laminated structure as second electrode 104, first electrode 102.First electrode 102 is electric with second
Pole 104 adopts arranged in parallel one on the other in suspension, and spacing is 30 millimeters.First electrode 102 and second electrode 104 it
Between apply 100 volts of voltage.Wherein, first electrode 102 makees positive pole；Second electrode 104 makees negative pole.Green compact thickness as needed
Select the electrophoretic deposition time.The green compact thickness needed in the present embodiment is 1 centimetre, 60 minutes electrophoretic deposition time.
(4) above-mentioned green compact are placed in high temperature furnace and are sintered, 1120 DEG C of temperature is incubated 3 hours, obtains the ceramic material of cuboid
Material.
The scope of material microscopic appearance can be observed using scanning electron microscope, projection Electronic Speculum etc., to ceramic material surfaces
Observed.The embodiment of the present invention is observed ceramic material using MIRA3LM field emission scanning electron microscopes.Using
RigakuX x ray diffractometer xs carry out the detection of crystal structure to ceramic material.Fig. 2 is the scanning of the present embodiment ceramic material surfaces
Electron microscope picture.From figure 2 it can be seen that ceramic material texturing degree is preferably, compactness extent preferably, but is present fraction of
Space.Under 1100 DEG C of synthesis temperature, the size of template grains 106 is larger, causes the hole of ceramic material more；Higher conjunction
It is likely to cause the volatilization of part of atoms into temperature, equally has hole appearance, causes consistency to reduce.Fig. 3 is to implement this
Ceramic material and commercial untextured Bi prepared by example4Ti3O12Ceramic material carries out X-ray diffraction test result comparison diagram.
As can be seen from Figure 3 004,006,008,0014 peak intensity is remarkably reinforced, and 111,117,200 peak intensity substantially weakens, explanation
Preferably, crystal is presented and aligned the texturing degree of the present embodiment ceramics.
Embodiment 2
A kind of ceramic material of offer and preparation method thereof is originally provided.The preparation method of the present embodiment ceramic material is as follows：
(1) according to chemical formula Bi2Zr2Co3O12, with Bi2O3、Zr2O3、Co(CO3)2For reactant, Bi is weighed2O346.6g、
Zr2O323g、Co(CO3)217.9g, mixing, grinding, mean diameter is controlled in 3 microns, obtains raw material.With KCl and
LiCl is metal chlorination salt, and wherein KCl weighs 14.6g, LiCl and weighs 29.2g.In adding raw materials into metal chlorination salt, third is added
Ketone 9ml.Through grinding, it is dried, in being placed in heating furnace, temperature setting is 900 DEG C (synthesis temperature), is incubated 3 hours, is used after cooling
Bi is obtained after distilled water cleaning, sucking filtration, drying2Zr2Co3O12Lamellar template grains 206 (refer to Fig. 4).To template grains 206
Potential test is carried out, the charge of its surface is determined.The positively charged of template grains 206 is test indicate that in the present embodiment.
(2) by template grains 206 and ethanol 300ml, methanol 200ml, nitric acid 200ml, acetic acid 250ml, phosphate ester 150ml
Mixing, the ultrasonic disperse through 3 hours obtains more stable suspension.
(3) refer to Fig. 4.The present embodiment provides a kind of electrophoretic deposition set 200, electric as first from conductive material palladium
Pole 202, platinum adopts laminated structure similar to Example 1 as second electrode 204, first electrode 202.First electrode 202 with
Second electrode 204 is arranged in parallel using the first from left right side in suspension, and spacing is 20 millimeters.It is electric with second in first electrode 202
Apply 80 volts of voltage between pole 204.Wherein, first electrode 202 makees negative pole；Second electrode 204 makees positive pole.Life as needed
Base thickness selects the electrophoretic deposition time.The green compact thickness needed in the present embodiment is 1.5 centimetres, 120 minutes electrophoretic deposition time.
(4) above-mentioned green compact are placed in high temperature furnace and are sintered, 1200 DEG C of temperature is incubated 4 hours, obtains and the structure of embodiment 1
Similar ceramic material.
Fig. 5 is the scanning electron microscope diagram of the present embodiment ceramic material surfaces.From figure 5 it can be seen that ceramic material
Preferably, compactness extent is preferable, but similar to situation in embodiment 1, and surface yet suffers from a small amount of hole for texturing degree.But
The hole of ceramic material is little in the ceramic material surfaces void ratio embodiment 1 of the present embodiment, and is substantially not present completely exposed
Hole.Under 900 DEG C of synthesis temperature, the size that the size of template grains 206 is compared in embodiment 1 has reduced, and causes ceramics
The hole of material is reduced；Compactness extent increases compared with the ceramic material in embodiment 1.Fig. 6 is by pottery manufactured in the present embodiment
Ceramic material and commercial untextured Bi2Zr2Co3O12Ceramic material carries out X-ray diffraction test result comparison diagram.Can from Fig. 6
To find out that 004,006,008,0014 peak intensity is remarkably reinforced, 111,117,200 peak intensity substantially weakens, and illustrates that the present embodiment is made pottery
Preferably, crystal is presented and aligned the texturing degree of porcelain.But compare with embodiment 1 as can be seen that the peak intensity of the present embodiment increases
Strong degree and peak intensity weaken and be below embodiment 1, and the texturing degree and crystal for illustrating the present embodiment aligns degree
It is low than embodiment 1.Because in the preparation process of template grains 206, the synthesis temperature of template grains 206 is improved and can cause mould
Becoming large-sized for lath grain 206, laterally increases with the ratio of radial direction, is conducive to the oriented growth of texturing and crystal.
Embodiment 3
A kind of ceramic material of offer and preparation method thereof is originally provided.The preparation method of the present embodiment ceramic material is as follows：
(1) according to chemical formula Bi2CoTi2O9, with Bi2O3、CoCO3、TiO2For reactant, Bi is weighed2O346.6g、
CoCO311.9g、TiO28.0g, mixing, grinding, mean diameter is controlled in 1 microns, obtains raw material.With NaCl and MnCl2
For metal chlorination salt, wherein MnCl2Weigh 33.3g, NaCl and weigh 33.2g.In adding raw materials into metal chlorination salt, acetone is added
10ml, ethanol 5ml.Through grinding, it is dried, in being placed in the heating furnace of logical oxygen.Temperature setting is 800 DEG C (synthesis temperature), is protected
Temperature 5 hours, is cleaned with distilled water after cooling, sucking filtration, obtains Bi after drying2Zr2Co3O12Lamellar template grains 306 (refer to figure
7).Potential test is carried out to template grains 306, the charge of its surface is determined.Template grains are test indicate that in the present embodiment
306 positively chargeds.
(2) by template grains 306 and methanol 200ml, isopropanol 300ml, ethanol 800ml, mix, it is super through 4 hours
Sound dispersion obtains more stable suspension.
(3) refer to Fig. 7.The present embodiment provides a kind of electrophoretic deposition set 300, from conductive material graphite as first
Electrode 302, silver adopts S type structures as second electrode 304, first electrode 302.First electrode 302 is with second electrode 304 outstanding
Adopt arranged in parallel one on the other in supernatant liquid, spacing is 30 millimeters.Apply 100 between first electrode 302 and second electrode 304
The voltage of volt.Wherein, first electrode 302 makees negative pole；Second electrode 304 makees positive pole.Green compact thickness as needed selects electrophoresis
Sedimentation time.The green compact thickness needed in the present embodiment is 2.5 centimetres, 150 minutes electrophoretic deposition time.
(4) above-mentioned green compact are placed in high temperature furnace and are sintered, 900 DEG C of temperature is incubated 5 hours, obtains S type ceramic materials.
Fig. 8 is the scanning electron microscope diagram of the present embodiment ceramic material surfaces.As can be seen from Figure 8, ceramic material
Preferably, compactness extent is preferable, but similar to situation in embodiment 2, and surface yet suffers from a small amount of hole for texturing degree.But
The hole of ceramic material is little in the ceramic material surfaces void ratio embodiment 2 of the present embodiment, and hole quantity is less.At 800 DEG C
Synthesis temperature under, the size that the size of template grains 306 is compared in embodiment 2 has reduced, and the hole for causing ceramic material subtracts
It is few；Compactness extent increases compared with the ceramic material in embodiment 2.Fig. 9 be by ceramic material manufactured in the present embodiment with it is commercial
Untextured Bi2CoTi2O9Ceramic material carries out X-ray diffraction test result comparison diagram.As can be seen from Figure 9 004,
006th, 008,0014 peak intensity is remarkably reinforced, and 111,117,200 peak intensity weakens, and illustrates the texturing degree of the present embodiment ceramics
Preferably, crystal exists and aligns.But compare with embodiment 1 as can be seen that the peak intensity of the present embodiment strengthens degree and peak intensity subtracts
It is weak to be below embodiment 1, illustrate the present embodiment texturing degree and crystal to align degree low than embodiment 1.
Its reason is also that synthesis temperature has an impact to the size of template grains 306, and oriented growth of the size of template grains 306 to crystal
All have a certain impact with texturing.
Embodiment 4
A kind of ceramic material of offer and preparation method thereof is originally provided.The preparation method of the present embodiment ceramic material is as follows：
(1) according to chemical formula Pb3MnNb2O9, with PbO, K2MnO4、Nb2O3For reactant, weigh PbO22.3g,
K2MnO419.7g、Nb2O323.4g, mixing, grinding, mean diameter is controlled in 2 microns, obtains raw material.With CaCl2As
Metal chlorination salt, wherein CaCl2Weigh 54.5g.In adding raw materials into metal chlorination salt, then it is mixed thing and is placed in heating furnace
In, temperature setting is 1000 DEG C (synthesis temperature), is incubated 1 hour, is cleaned with distilled water after cooling, sucking filtration, is obtained after drying
Pb3MnNb2O9Spherical template grains 406 (refer to Figure 10).Potential test is carried out to template grains 406, the electricity on its surface is determined
Lotus property.Test indicate that template grains 406 are negatively charged in the present embodiment.
(2) by template grains 406 and methanol 200ml, isopropanol 150ml, ethanol 100ml, propanol 150ml, acetic acid
200ml, polyacrylic acid 250ml, phosphate ester 250ml mixing, obtain stable suspension.
(3) refer to Figure 10.The present embodiment provides a kind of electrophoretic deposition set 400, from conductive material platinum as first
Electrode 402, platinum adopts circular platform type structure as second electrode 404, first electrode 402.First electrode 402 and second electrode 404
Arranged in parallel using the tilting shown in Figure 10 in suspension, spacing is 5 millimeters.In first electrode 402 and second electrode
Apply 10 volts of voltage between 404.Wherein, first electrode 402 makees positive pole；Second electrode 404 makees negative pole.Green compact as needed
Thickness selects the electrophoretic deposition time.The green compact thickness needed in the present embodiment is 0.2 centimetre, 3 minutes electrophoretic deposition time.
(4) above-mentioned green compact are placed in high temperature furnace and are sintered, 1000 DEG C of temperature is incubated 0.5 hour, obtain circular platform type ceramics material
Material.
Figure 11 is the scanning electron microscope diagram of the present embodiment ceramic material surfaces.It can be seen from fig. 11 that ceramic material
Preferably, compactness extent is preferable, but surface yet suffers from the larger hole in aperture for material texturing degree.The template grains of the present embodiment
406 for spherical, and embodiment 1～3 is lamellar, therefore lamination of the template grains 406 of the present embodiment in electrophoretic deposition process
Effect is more slightly worse than embodiment 1～3, and the compactness extent of the ceramic material for finally obtaining, texturing degree are also relatively poor.
Figure 12 is by ceramic material manufactured in the present embodiment and commercial untextured Pb3MnNb2O9Ceramic material carries out X
X ray diffraction test result comparison diagram.As can be seen from Figure 6 004,006,008,111,117,200,0014 peak intensity is obvious
Strengthen, illustrate the texturing degree of the present embodiment ceramics preferably, crystal presence is aligned.With commercial untextured ceramics
Material is compared, and preferably, crystal habit is also more regular for ceramic material anisotropy manufactured in the present embodiment.
The ceramic material that embodiment 1～4 is provided can be prepared into piezoelectric ceramics by polarization.Although leaded ceramics are comprehensive
Better performances, but it is poisonous because of its, and present research is directed generally to lead-free ceramicses and prepares piezoelectric ceramics.The embodiment of the present invention is provided
The piezoelectric ceramics that is prepared into of ceramic material, because it possesses excellent anisotropy, therefore, it is possible to be applied to every field, including
Higher place is required to piezoelectric susceptibility.And the higher ceramics of texturing degree, its comprehensive mechanical performance is also preferable, more
Facilitate the machine-shaping in later stage.
Embodiments described above is a part of embodiment of the invention, rather than the embodiment of whole.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of ceramic material, it is characterised in that comprise the following steps：
The suspension made by template grains is carried out into electrophoretic deposition and obtains green compact, the green compact are sintered.
2. the preparation method of ceramic material according to claim 1, it is characterised in that the template grains are lamellar.
3. the preparation method of ceramic material according to claim 2, it is characterised in that the ceramic material has bismuth stratiform
Structure.
4. the preparation method of ceramic material according to claim 3, it is characterised in that the template grains have formula
(Bi2O2)2+(Am-1BmO3m+1)2-, 2≤m≤5, m is integer, and A, B are metal ion, and the template grains by with lower section
Method is made：
To be 1 according to mass ratio:2～2:The metal chlorination salt of 1 mixing is incubated 1～5 with raw material at a temperature of 800～1100 DEG C
Hour；
The metal chlorination salt fusing point is below 800 DEG C；
The raw material is included according to the formula (Bi2O2)2+(Am-1BmO3m+1)2-Stoichiometric proportion mixing Bi oxide or
The oxide or salt of salt, the oxide of element A or salt and B element.
5. the preparation method of ceramic material according to claim 1, it is characterised in that the preparation method bag of the suspension
Include：
The template grains are dispersed in solvent, the solvent includes alcoholic solution.
6. the preparation method of ceramic material according to claim 5, it is characterised in that the alcoholic solution includes methanol, second
The aqueous solution of one or more in alcohol, propanol, isopropanol.
7. the preparation method of the ceramic material according to any one of claim 1～6, it is characterised in that to the suspension
Carrying out the method for electrophoretic deposition includes：
Be arranged in a vertical direction first electrode and second electrode, the first electrode the vertical direction relative to ground height
Degree is more than the second electrode in the vertical direction relative to the height on the ground, makes the template grains sink by electrophoresis
Product is to the first electrode.
8. the preparation method of ceramic material according to claim 1, it is characterised in that the method bag of the sintering green compact
Include：
The green compact are heated to 900 DEG C～1200 DEG C and 0.5～5 hour is incubated.
9. a kind of ceramic material, it is characterised in that the ceramic material is by the ceramic material as described in any one of claim 1～8
The preparation method of material is obtained.
10. a kind of piezoelectric ceramics, it is characterised in that obtained by polarizer by ceramic material as claimed in claim 9.
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| CN108752010A (en) * | 2018-07-18 | 2018-11-06 | 广东工业大学 | Piezoelectric ceramic, preparation method thereof and 3D printing piezoelectric ceramic device |
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