CN109437895A - A kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics - Google Patents
A kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics Download PDFInfo
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Abstract
The invention discloses a kind of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics preparation method, stoichiometric equation is (Pb97Ba3)(0.75(ZrxTi100‑x)+0.25(Mg1/3Nb2/3))O3+0.1wt%Fe2O3, wherein x=45.0~47.0.The present invention is based on lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics, using traditional solid reaction process, the ratio of Zr/Ti is adjusted to improve electric property, improve its displacement under electric field strength driving, piezoceramic material prepared by the present invention is mainly used in piezoelectric transformer, filter, energy converter, the especially fields such as piezoelectric actuator can provide effective solution for the application of micro- positioning, valve control, vibration damping and sound emission etc..Piezoelectric ceramic process made from solid reaction process is simple, can be effectively reduced cost.
Description
Technical field
The present invention relates to the preparation of piezoelectric ceramics more particularly to a kind of preparations of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics
Method.
Background technique
Piezoelectric material is the functional material for realizing that the one kind mutually converted between electric energy and mechanical energy is important.Piezoelectric ceramics is most
It is found before more than 100 year by scientist, by constantly studying and exploring, piezoceramic material is in national defense construction, boat
The high-technology fields such as empty space flight, biological medicine, Ocean Surveying have a wide range of applications.Main application has: piezoelectric transformer,
Piezoelectric ultrasonic transducer, oscillator, sensor, piezoelectric actuator etc..
Along with nowadays scientific and technical fast development, either daily life demand or industrial production demand, all
To the various performances of piezoelectric ceramics, more stringent requirements are proposed.More and more fields require piezoelectric ceramics to have higher piezoelectricity
Constant and dielectric constant, in addition to this, in certain special applications, other than high piezoelectric constant and dielectric constant, also to pressure
Electroceramics proposes other requirements.Such as in big displacement quantity actuator using upper, in addition to require piezoelectric ceramics piezoelectric constant and
Other than dielectric constant is higher, also require it that there are the performances such as biggish displacement under electric field driven.
In numerous piezoceramic materials, lead zirconate titanate (PZT) piezoelectric ceramics is most commonly used piezoelectric material, niobium magnesium
Lead plumbate (PMN) piezoelectric ceramics is most commonly used electrostriction material.It is various in electricity in order to adapt to the market demand to become increasingly abundant
Driving lower new material and new process with larger displacement amount in field just constantly developed by researcher.Piezoelectric actuator is by answering
The characteristic that deformation occurs (elongation or contraction) of the application voltage possessed by piezoelectric ceramics can be micro- positioning, valve control, vibration damping
And the application such as sound emission provides effective solution.Piezoelectric actuator has linear, reproducible, response fastly and stability is strong
The features such as, it is accurate electric drive displacement device, there is the extensive market demand.It makes pottery by the ternary system piezoelectric of representative of PMN-PZT
Porcelain has more superior performance, can adjust constituent significantly to improve its comprehensive performance.Lead based relaxor type composite calcium
For perovskite like structure PMN-PZT piezoceramic material due to having the characteristics that Diffuse phase transition, electrostriction effect is larger, can be used for making
Make big displacement quantity actuator.Therefore, because PMN-PZT piezoelectric ceramics has high dielectric, high-voltage electricity and has under electric field driven
There are the performances such as biggish displacement to have become the research hotspot of domestic and international researcher at present.
Summary of the invention
The purpose of the present invention is improving lead zirconate titanate-displacement of the lead magnesio-niobate piezoelectric ceramics under electric field driven, pass through
It adjusts Zr/Ti ratio and improves electric property, a kind of lead zirconate titanate that can have preferable electric property-lead magnesio-niobate system pressure is provided
Electroceramics.
The present invention selects lead zirconate titanate-lead magnesio-niobate piezoelectric material, by some in terms of formula adjustment, preparation process
Research, to obtain with excellent piezoelectric constant, dielectric constant and under electric field driven with property such as biggish displacements
The piezoelectric material of energy, to realize its application on big displacement quantity actuator.
The invention is realized by the following technical scheme: a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics,
It is characterized in that, which has following steps:
(1), ingredient
By raw material Pb3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O, by following metering-type:
(Pb97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/3Nb2/3))O3+0.1wt%Fe2O3It is mixed, x=45.0 in formula~
47.0, it is put into ball grinder after mixing；Ball-milling medium is deionized water and agate ball, agate ball: material: the weight ratio of deionized water
For 1.0:(0.4~0.8): 0.6；Mixture is respectively put into drying in oven again, is then placed in grinding in mortar, respectively mistake
Sieve.
(2), it synthesizes
Be respectively put into the powder after sieving in step (1) in crucible, be compacted, cover, sealing, in synthetic furnace in 850~
950 DEG C of synthesis, keep the temperature 2~4h, naturally cool to room temperature, come out of the stove.
(3), secondary ball milling
The synthesis powder of step (2) is put into ball mill grinding in ball grinder, then the powder after ball milling is put into drying in oven, so
After be ground up, sieved.
(4), tabletting
By the powder after step (3) sieving, into powder, addition deionized water, which is fully ground, is granulated, with electric tablet machine pressure
It at column, then is smashed to pieces, uses electric tablet machine and isostatic pressing machine compression moulding for blank after being ground up, sieved.
(5), dumping
The blank of step (4) is put into Muffle furnace, after being warming up to 500~600 DEG C with the rate of 2~5 DEG C/min, with furnace nature
It is cooled to room temperature.
(6), it is sintered
Blank after step (5) dumping is put into and is added in crucible and material prepared with the powder of system carries out burying burning, with 5~
The heating rate of 8 DEG C/min is warming up to 1180~1260 DEG C of sintering, keeps the temperature 1~3h, and with furnace cooled to room temperature, zirconium titanium is made
Lead plumbate-lead magnesio-niobate piezoelectric ceramics.
(7), electrode and surface treatment are applied
Lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics upper and lower surfaces that step (6) obtains are polished to a thickness of 1~
Then 1.2mm coats silver electrode in upper and lower surface in the way of silk-screen printing, be warming up to the heating rate of 5~8 DEG C/min
700~850 DEG C of silver ink firings keep the temperature 10~15min；It is put into silicone oil after cooling taking-up, under the conditions of 140~170 DEG C, uses high pressure
Polarization platform polarizes under DC electric field, obtains final lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics.
Raw material Pb of the present invention3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O,
For the chemical pure raw material of commercially available quality purity >=99%.
In the step (1) of the present invention, the metering-type (Pb of raw material97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/ 3Nb2/3))O3+0.1wt%Fe2O3, wherein x=46.0.
In the step (1) of the present invention, preferred agate ball: material: the weight ratio of deionized water is 1.0:0.8:0.6.
In step (1) of the present invention and step (3), Ball-milling Time 8h, ball milling unit frequency is 33.5Hz.
In step (2) of the present invention, preferred synthesis temperature is 900 DEG C, soaking time 3h.
In step (4) of the present invention, the pressure using isostatic pressing machine compression moulding is 300MPa, the blank of compression moulding
For the cylindric blank of diameter 20mm, 1 ~ 1.5mm of thickness.
In step (5) of the present invention, preferred heating rate is 2 DEG C/min, and temperature rises to 500 DEG C.
In step (6) of the present invention, preferred heating rate is 5 DEG C/min, and sintering temperature is 1240 DEG C, soaking time
For 2h.
In step (7) of the present invention, potsherd is after polishing with a thickness of 1mm；When silver ink firing preferred heating rate be 5 DEG C/
Min, temperature are 800 DEG C, soaking time 15min；It is polarized using high voltage polarization platform, DC electric field Polarization field strength is
4300V/mm, polarization time 30min, poling temperature are 160 DEG C.
The beneficial effects of the present invention are: with (Pb97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/3Nb2/3))O3+0.1wt%
Fe2O3Based on piezoelectric ceramics, adjusted using traditional solid reaction process by the adjustment and improvement of composition of raw materials and technique
The ratio of Zr/Ti improves electric property, improves displacement of the piezoelectric ceramics under electric field driven, has obtained a kind of comprehensive
Can preferable piezoelectric ceramics, wherein permittivity εr=3000, piezoelectric constant d33Under the driving of=637pC/N, 750V/mm electric field strength
Displacement be 6.58 μm.Piezoceramic material prepared by the present invention is mainly used in piezoelectric transformer, filter, energy conversion
The fields such as device, especially piezoelectric actuator can be provided with for the application of micro- positioning, valve control, vibration damping and sound emission etc.
The solution of effect.It is simple using piezoelectric ceramic process made from solid reaction process, it can be effectively reduced cost.
Detailed description of the invention
Fig. 1 is permittivity ε of the inventionrMap；
Fig. 2 is piezoelectric constant d of the invention33Map；
Fig. 3 is displacement map of the invention.
Specific embodiment
The invention will be further described with reference to embodiments:
The raw material Pb that the present invention uses3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O is
Commercially available chemistry pure raw material (purity >=99%).
It is of the invention the preparation method is as follows:
(1), ingredient
By raw material Pb3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O, by following metering-type:
(Pb97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/3Nb2/3))O3+0.1wt%Fe2O3It is mixed, wherein x=46.0 in formula.
In formula, from left to right 97,3,0.75, x, 100-x, 0.25,1/3,2/3,3 be raw material mole percent level,
0.1wt% is Fe2O3Additive amount account for the mass percents of other raw material weighing gross masses (metering-type illustrated above be in piezoelectric ceramics
It is general in industry).By taking gross mass 400.4g powder as an example, Pb is weighed3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3With
(MgCO3)4Mg(OH)2•5H2The quality of O is respectively 266.073g, 7.141g, 39.019g, 51.282g, 26.721g, 0.400g
And 9.764g.
It is put into ball grinder after mixing；Ball-milling medium is deionized water and agate ball, ball: material: the weight ratio of deionized water
It is 1.0:0.8:0.6, Ball-milling Time 8h, ball milling unit frequency is 33.5Hz；Mixture is respectively put into baking oven in 110 again
DEG C drying, is then placed in grinding in mortar, crosses 40 meshes respectively.
(2), it synthesizes
It is respectively put into the powder after sieving in step (1) in crucible, is compacted, cover, sealing is closed in synthetic furnace in 900 DEG C
At heat preservation 3h naturally cools to room temperature, comes out of the stove.
(3), secondary ball milling
The synthesis powder of step (2) is put into ball mill grinding in ball grinder, Ball-milling Time 8h, ball milling unit frequency is 33.5Hz；
The powder after ball milling is put into baking oven again and is dried in 110 DEG C, then grinding, the sieving of 40 mesh.
(4), tabletting
By the powder after step (3) sieving, into powder, addition deionized water, which is fully ground, is granulated, with electric tablet machine pressure
It at column, then is smashed to pieces, uses electric tablet machine and isostatic pressing machine compression moulding for blank after being ground up, sieved；The static pressure such as use
The pressure of machine compression moulding is 300MPa, and the blank of compression moulding is the cylindric blank of diameter 20mm, thickness 1.5mm.
(5), dumping
The blank of step (4) is put into Muffle furnace, heating rate is 2 DEG C/min, naturally cold with furnace after temperature rises to 500 DEG C
But to room temperature.
(6), it is sintered
It puts the blank after step (5) dumping into crucible addition and material prepared to carry out burying burning with the powder of system, heat up
Rate is 5 DEG C/min, and sintering temperature is 1240 DEG C, soaking time 2h；With furnace cooled to room temperature, lead zirconate titanate-is made
Lead magnesio-niobate piezoelectric ceramics.
(7), electrode and surface treatment are applied
Lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics upper and lower surfaces that step (6) obtains are polished, potsherd is thick after polishing
Degree is 1mm；Then silver electrode is coated in the way of silk-screen printing in upper and lower surface, heating rate is 5 DEG C/min, temperature when silver ink firing
Degree is 800 DEG C, soaking time 15min；It is put into silicone oil after cooling taking-up, is polarized using high voltage polarization platform, direct current
Polarization field strength is 4300V/mm, polarization time 30min, and poling temperature is 160 DEG C to get arriving final lead zirconate titanate-niobium
Magnesium lead plumbate piezoelectric ceramics.
(8), piezoelectric property is tested
It is quiet using PV90A type impedance analyzer, ZJ-6A type standard in being stored at room temperature for 24 hours by the piezoelectric ceramics after step (7) polarization
State d33/d31Measuring instrument and DGS-6C type inductance amesdial test its εr、d33With the performances such as displacement.
Specific embodiment is as follows:
X=45.0, sintering temperature are 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, are denoted as embodiment 1-1,1- respectively
2,1-3,1-4,1-5；
X=45.5, sintering temperature are 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, are denoted as embodiment 2-1,2- respectively
2,2-3,2-4,2-5；
X=46.0, sintering temperature are 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, are denoted as embodiment 3-1,3- respectively
2,3-3,3-4,3-5；
X=46.5, sintering temperature are 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, are denoted as embodiment 4-1,4- respectively
2,4-3,4-4,4-5；
X=47.0, sintering temperature are 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, are denoted as embodiment 5-1,5- respectively
2、5-3、5-4、5-5。
The piezoelectric property and all-round property testing result of above-described embodiment are listed in table 1, and embodiment 3-4 is in different electric field strengths
Displacement result under driving is listed in table 2.
Table 1
Table 2
| Electric field strength (V/mm) | Displacement (μm) |
| 50 | 0.27 |
| 100 | 0.64 |
| 150 | 1.05 |
| 200 | 1.51 |
| 250 | 2.00 |
| 300 | 2.43 |
| 350 | 2.93 |
| 400 | 3.47 |
| 450 | 3.97 |
| 500 | 4.45 |
| 550 | 4.95 |
| 600 | 5.38 |
| 650 | 5.86 |
| 700 | 6.23 |
| 750 | 6.58 |
Embodiment 3-4 is most preferred embodiment, as x=46.0, when sintering temperature is 1240 DEG C, and εr=3000, d33=637pC/N,
Displacement under the driving of 750V/mm electric field strength is 6.58 μm.
Fig. 1 shows the increase with sintering temperature, and becoming for first increases and then decreases is presented in the corresponding dielectric constant of each ingredient
Gesture, this is because when sintering temperature is lower, the defects of ceramics sample grain growth is insufficient, stomata, is more, and compactness is poor；
When sintering temperature is excessively high, some abnormal grain growths cause ceramics sample internal flaw to increase.Under same sintering temperature,
With the increase of Zr content, the trend of first increases and then decreases is presented in dielectric constant.When Zr content is 46.0mol%, sintering temperature is
At 1240 DEG C, the dielectric constant of ceramics sample is maximum.
Fig. 2 shows for lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics, with the raising of sintering temperature, the pressure of ceramics sample
Electrically first increase and reduces afterwards.When sintering temperature is 1240 DEG C, and Zr content is 46.0mol%, ceramics sample has optimal piezoelectricity
Performance, piezoelectric coefficient d33=637pC/N illustrates that it is attached to be in quasi- homotype phase boundary for lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics at this time
Closely, piezoelectric property is best.Research shows that: there are the quasi- homotypes that rhombohedral-tetragonal phase coexists in lead zirconate titanate-lead magnesio-niobate ceramics
Phase boundary, at quasi- homotype phase boundary, the different two-phase energy of crystal structure plays pendulum, the small energy variation of system
It will lead to two alternate transformations, crystals can generate more defect in transition process, be conducive to electricdomain and make in external electric field
Steering under, so that maximum occur in the electric properties such as piezoelectric constant, dielectric constant.
Fig. 3 shows the increase with driving electric field intensity, and the displacement of ceramics sample increases, when driving electric field intensity is
When 750V/mm, the displacement of ceramics sample is up to 6.58 μm.
Claims (10)
1. a kind of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics preparation method, which is characterized in that the preparation method has as follows
Step:
(1), ingredient
By raw material Pb3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O, by following metering-type:
(Pb97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/3Nb2/3))O3+0.1wt%Fe2O3It is mixed, x=45.0 in formula~
47.0, it is put into ball grinder after mixing；Ball-milling medium is deionized water and agate ball, agate ball: material: the weight ratio of deionized water
For 1.0:(0.4~0.8): 0.6；Mixture is respectively put into drying in oven again, is then placed in grinding in mortar, respectively mistake
Sieve；
(2), it synthesizes
Be respectively put into the powder after sieving in step (1) in crucible, be compacted, cover, sealing, in synthetic furnace in 850~
950 DEG C of synthesis, keep the temperature 2~4h, naturally cool to room temperature, come out of the stove；
(3), secondary ball milling
The synthesis powder of step (2) is put into ball mill grinding in ball grinder, then the powder after ball milling is put into drying in oven, so
After be ground up, sieved；
(4), tabletting
By the powder after step (3) sieving, into powder, addition deionized water, which is fully ground, is granulated, with electric tablet machine pressure
It at column, then is smashed to pieces, uses electric tablet machine and isostatic pressing machine compression moulding for blank after being ground up, sieved；
(5), dumping
The blank of step (4) is put into Muffle furnace, after being warming up to 500~600 DEG C with the rate of 2~5 DEG C/min, with furnace nature
It is cooled to room temperature；
(6), it is sintered
Blank after step (5) dumping is put into and is added in crucible and material prepared with the powder of system carries out burying burning, with 5~
The heating rate of 8 DEG C/min is warming up to 1180~1260 DEG C of sintering, keeps the temperature 1~3h, and with furnace cooled to room temperature, zirconium titanium is made
Lead plumbate-lead magnesio-niobate piezoelectric ceramics；
(7), electrode and surface treatment are applied
Lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics upper and lower surfaces that step (6) obtains are polished to a thickness of 1~
Then 1.2mm coats silver electrode in upper and lower surface in the way of silk-screen printing, be warming up to the heating rate of 5~8 DEG C/min
700~850 DEG C of silver ink firings keep the temperature 10~15min；It is put into silicone oil after cooling taking-up, under the conditions of 140~170 DEG C, uses high pressure
Polarization platform polarizes under DC electric field, obtains final lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics.
2. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
The raw material Pb3O4、BaCO3、TiO2、ZrO2、Nb2O5、Fe2O3(MgCO3)4Mg(OH)2•5H2O is that commercially available quality is pure
The chemical pure raw material of degree >=99%.
3. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (1), the metering-type (Pb of raw material97Ba3)(0.75(ZrxTi100-x)+0.25(Mg1/3Nb2/3))O3+0.1wt%
Fe2O3, wherein x=46.0.
4. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (1), preferred agate ball: material: the weight ratio of deionized water is 1.0:0.8:0.6.
5. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (1) and step (3), Ball-milling Time 8h, ball milling unit frequency is 33.5Hz.
6. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (2), preferred synthesis temperature is 900 DEG C, soaking time 3h.
7. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (4), the pressure using isostatic pressing machine compression moulding is 300MPa, and the blank of compression moulding is diameter 20mm, thickness
Spend the cylindric blank of 1~1.5mm.
8. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (5), preferred heating rate is 2 DEG C/min, and temperature rises to 500 DEG C.
9. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (6), preferred heating rate is 5 DEG C/min, and sintering temperature is 1240 DEG C, soaking time 2h.
10. a kind of preparation method of lead zirconate titanate-lead magnesio-niobate piezoelectric ceramics according to claim 1, which is characterized in that
In the step (7), potsherd is after polishing with a thickness of 1mm；Preferred heating rate is 5 DEG C/min, temperature 800 when silver ink firing
DEG C, soaking time 15min；It is polarized using high voltage polarization platform, DC electric field Polarization field strength is 4300V/mm, polarization time
For 30min, poling temperature is 160 DEG C.
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