CN104016674B - A kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof - Google Patents
A kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof Download PDFInfo
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Abstract
A kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof, the component general formula of described pottery is (Ba
1-xca
x) (Ti
1-ym
y) O
3, wherein, 0<x≤0.3,0<y≤0.3, M is Sn or Hf, its preparation process comprise batching, batch mixing, drying, Microwave synthesize, granulation, shaping, binder removal, microwave sintering, by silver, polarization etc.The present invention is by optimizing ceramic component and preparation technology, and the piezoelectric ceramic density prepared is high, piezoelectric property is excellent, compared with traditional ceramics preparation technology, when keep identical or more high tension performance, substantially reduce manufacturing cycle, saved electric energy.
Description
Technical field
The invention belongs to environmentally friendly ceramic material field, specifically a kind of barium titanate-based lead-free piezoelectric ceramic and preparation method thereof.
Background technology
Piezoelectric ceramic is a class widely used new and high technology material in electron trade.But prevailing is in the market lead zirconate titanate Pb (Zr, Ti) O
3(PZT) base piezoelectric ceramic, in PZT, Pb content is up to more than 60wt. %, in its preparation, uses and all can work the mischief to human body health and living environment thereof in waste procedures.Therefore development environment leadless piezoelectric ceramics that is friendly, excellent performance is urgent, to have an important social effect problem.
In leadless piezoelectric ceramics system, barium titanate-based lead-free piezoelectric ceramic be a kind of research and development comparatively early, piezoceramic material that performance is more stable.Through the unremitting effort of scientific research personnel, its piezoelectric property obtains and increases substantially, and is the lead-free piezoceramic material that current uniquely energy and PZT base ceramic phase match in excellence or beauty.But there is with barium titanate based ceramic prepared by traditional ceramics technique the shortcoming that sintering temperature is high, sintering time long, piezoelectric property is lower, add the densification sintering temperature that sintering aid can reduce pottery, but greatly can damage other performance of pottery, and sintering temperature reduction is very limited.
Microwave sintering is a kind of energy-efficient sintering method, has following characteristics compared with sintering with conventional solid: (1) rate of heat addition is fast, and temperature retention time is short; (2) microwave energy directly penetrates the sample of certain depth, heats at different depth simultaneously, does not need diabatic process, avoids the abnormal growth of ceramic crystalline grain in sintering process, can prepare the ceramic material of uniform crystal particles distribution at a lower temperature; (3) by regulating the power output of microwave, can make the heating state of sample that inertialess occurs immediately and changing, be convenient to automatically control and continued operation; (4) thermal inertia of microwave sintering is little, and energy fast cooling after terminating, heat utilization rate is high.The pure barium titanate piezoelectric ceramics constant that the people such as Japanese scholars Hirofumi Takahashi utilize microwave sintering process to prepare
d 33=350 pC/N, electromechanical coupling factor
k p=36%; And the pottery of the same recipe prepared by conventional sintering technique is the highest
d 33=220 pC/N,
k p =28%, they are summed up as higher density and less crystallite dimension (Japanese Journal of Applied Physics, 2006,45(1) the reason that piezoelectric property improves: 30-32).It is reported A position Ca
2+with B position Sn
4+barium titanate based ceramic Ba (Sn, the Ti) O of doping vario-property
3-(Ba, Ca) TiO
3there is excellent piezoelectric property (APPLIED PHYSICS LETTERS, 2013,103,072905; J. Am. Ceram. Soc., 2013,96 [1] 241 – 245; J. Am. Ceram .Soc., 2011,94 [12] 4131 – 4134), but the performance of this type of pottery prepared with microwave sintering process have not been reported.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of barium titanate-based lead-free piezoelectric ceramic, can be quick, efficient, energy-conservation prepare piezoelectric property excellence, mechanical quality is good, and density is high, the barium titanate-based lead-free piezoelectric ceramic that temperature stability is good.
The present invention is the technical scheme solving the problems of the technologies described above employing: a kind of barium titanate-based lead-free piezoelectric ceramic, and the component general formula of described pottery is (Ba
1-
x ca
x ) (Ti
1-
y m
y ) O
3, wherein, 0<
x≤ 0.3,0<
y≤ 0.3, and M is Sn or Hf.
A preparation method for barium titanate-based lead-free piezoelectric ceramic, comprises the following steps:
Step one, be the ratio of 1-x:x:1-y:y according to the molar ratio of Ba, Ca, Ti and M tetra-kinds of elements, by BaCO
3, CaCO
3, TiO
2mix with the compound proportioning of doped chemical M, wherein 0<
x≤ 0.3,0<
y≤ 0.3, then Wet blend-milling 4 ~ 8h, take out the drying box inner drying 8-12h being positioned over 100 DEG C after wet-milling;
The compound of described doped chemical M is SnO
2or HfO
2;
Step 2, dried for step one material is put into microwave oven, material is incubated 5-60 min after being warming up to 1100-1200 DEG C, obtains barium titanate based ceramic powder, for subsequent use;
Step 3, ceramic powder step 2 obtained carry out secondary wet-milling 4-6 h, take out the drying box inner drying 8-12h being placed in 100 DEG C after wet-milling;
Step 4, in the dried material of step 3, add the polyvinyl alcohol of its quality 5%, after stirring, cross 60-80 object sieve and carry out granulation, afterwards the particle made is put into mould, under the pressure of 200MPa, be pressed into base substrate;
Step 5, base substrate obtained for step 4 is put into temperature programmed control box type furnace, rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60min afterwards and carry out binder removal process, be then cooled to room temperature;
Step 6, the base substrate after step 5 binder removal is put into microwave oven, material is incubated the sintering that 30-60 min carries out base substrate after being warming up to 1100-1300 DEG C, be cooled to room temperature afterwards;
One deck silver slurry is brushed again after step 7, the billet surface sanding and polishing that step 6 sintered, then, put into temperature programmed control box type furnace, at 550 DEG C of temperature, be incubated 30 min carry out roasting silver, afterwards, it is 20-30 DEG C that base substrate after roasting silver is put into temperature, and dielectric strength is polarize in the silicone oil of 3-5 kV/mm, namely completes preparation.
Described step one and step 3 all adopt planetary ball mill to carry out wet-milling to material.
In the wet-milling process of described step one and step 3, the wet grinding media of employing comprises absolute ethyl alcohol and zirconia ball, and treats that the mass ratio of wet-milling siccative, absolute ethyl alcohol and zirconia ball is: 1:1:2, and the rotating speed of planetary ball mill is 250-300 r/min.
Warming machine in described step 2 and step 6 in microwave oven is made as: the heating rate between room temperature to 1000 DEG C is 20 DEG C/min; 1000 DEG C of heating rates to the intensification upper limit are 15 DEG C/min.
In described step 4, the base substrate of compacting is disc-shaped structure, and blank diameter is 10mm, and thickness is 1.5mm.
Described BaCO
3, CaCO
3, TiO
2, SnO
2and HfO
2be chemically pure reagent.
Beneficial effect of the present invention:
Barium titanate-based lead-free piezoelectric ceramic prepared by the present invention has higher piezoelectric constant, preferably mechanical performance quality and splendid temperature stability, the technique of method own is simple, stable, by microwave sintering synthesis of barium titanate based ceramic powder body, prepare ceramics sample, make that synthesis and sintering temperature reduce, time shorten, greatly reduce the manufacturing cycle of barium titanate-based lead-free piezoelectric ceramic, be conducive to suitability for industrialized production.Meanwhile, the pottery that microwave sintering obtains, crystallite dimension reduces, and density is high, and be conducive to the raising of piezoelectric property, finished product has clear superiority, and application prospect is very wide.
Embodiment
Following embodiment is only described in further detail the present invention.
A kind of barium titanate-based lead-free piezoelectric ceramic, according to (Ba
1-
x ca
x ) (Ti
1-
y m
y ) O
3(M is Sn, Hf etc.) (0<
x≤ 0.3; 0<
y≤ 0.3) stoichiometric proportion carries out accurate weighing batching, ball mill mixing, dry, and Microwave synthesize ceramic powder is compressing, microwave sintering.Its preparation process comprise batching, batch mixing, drying, Microwave synthesize, granulation, shaping, binder removal, microwave sintering, by steps such as silver, polarization.Advantage of the present invention is, when keep identical or more high tension performance, make the manufacturing cycle of barium titanate based ceramic shorten 4-6 h; Each energy savings 20-30 degree electricity.
The technical process that microwave sintering of the present invention prepares barium titanate based ceramic is:
(1) raw material is pressed chemical formula (Ba
1-
x ca
x ) (Ti
1-
y m
y ) O
3(M is Zr, Sn, Hf etc.) (0<
x≤ 0.3; 0<
y≤ 0.3) metering ratio is prepared burden, and by the material planetary ball mill ball milling 4-8 h prepared, is placed on by the slurry mixed in drying box and obtains dry powder after 100 DEG C of oven dry 8-12h;
(2) step (1) gained dry powder is put into microwave oven, be warming up to 1100-1200 DEG C, insulation 5-60 min, synthesis of barium titanate based ceramic powder body;
(3) the barium titanate based ceramic powder synthesized carries out secondary ball milling, and Ball-milling Time is 4-6 h.Again the slurry of milled is placed in drying box, carries out drying at 100 DEG C of insulation 8-12h;
(4) using adding the polyvinyl alcohol (PVA) of 5wt.% in step (3) gained ceramic powder as binding agent, stir, with the granulation of 60-80 object sieve aperture.Powder after granulation is put into mould, under 200MPa, is pressed into the disc-shaped biscuit of Ф 10 × 1.5mm with Manual tablet pressing machine;
(5) biscuit that step (4) suppresses is put into temperature programmed control box type furnace, rise to 650 DEG C with the heating rate of 10 DEG C/min, insulation 60min carries out binder removal, is then cooled to room temperature;
(6) ceramics sample after step (5) binder removal is placed in microwave agglomerating furnace, at 1100-1300 DEG C of temperature, is incubated the sintering that 30-60 min carries out ceramics sample.
(7) ceramics sample sintered grinds two smooth planes on 300 order sand paper, and two planes are evenly coated silver slurry, is heated to 550 DEG C of insulation 30 min roasting silver in temperature programmed control box type furnace.Ceramics sample after roasting silver is put into silicone oil and is polarized, and poling temperature is 20-30 DEG C; Polarizing voltage is 3-5 kV/mm; Polarization time is 10-30 min.The ceramics sample polarized carries out the test of electric property.
Described technique (1) and (3) middle ball-milling medium are absolute ethyl alcohol and zirconia ball, and the mass ratio of raw material, absolute ethyl alcohol and zirconia ball is: 1:1:2, and drum's speed of rotation is 250-300 r/min.
Described technique (2) and (6) middle microwave sintering warming machine are made as: the heating rates before 1000 DEG C are 20 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.
The present invention is raw materials used is chemical pure BaCO
3, CaCO
3, TiO
2, ZrO
2, SnO
2, HfO
2.
Embodiment 1:
With chemical pure BaCO
3, CaCO
3, TiO
2, ZrO
2for raw material, get
x=0.01,
y=0.05, according to chemical formula (Ba
0.99ca
0.01) (Ti
0.95zr
0.05) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 r/min, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 60 min at 1100 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1100 DEG C of insulation 60min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 280 | 42 | 116 | 4520 | 90.4 | 8.4 | 102 |
Embodiment 2:
With chemical pure BaCO
3, CaCO
3, TiO
2, ZrO
2for raw material, get
x=0.05,
y=0.05 according to chemical formula (Ba
0.95ca
0.05) (Ti
0.95zr
0.05) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 300 r/min, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 30 min at 1150 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 6 h, and rotating speed is 250 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1200 DEG C of insulation 30min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 335 | 44 | 145 | 4860 | 94.2 | 10.6 | 105 |
Embodiment 3:
With chemical pure BaCO
3, CaCO
3, TiO
2, ZrO
2for raw material, get
x=0.2,
y=0.05 according to chemical formula (Ba
0.8ca
0.2) (Ti
0.95zr
0.05) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 r/min, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 30 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 5 h, and rotating speed is 270 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1200 DEG C of insulation 45 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 396 | 46 | 110 | 4785 | 96.5 | 10.5 | 108 |
Embodiment 4:
With chemical pure BaCO
3, CaCO
3, TiO
2, ZrO
2for raw material, get
x=0.2,
y=0.1 according to chemical formula (Ba
0.8ca
0.2) (Ti
0.9zr
0.1) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 6 h, rotating speed is 250 r/min, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 30 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 250 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1250 DEG C of insulation 50 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 425 | 48 | 120 | 4716 | 93.7 | 12.5 | 103 |
Embodiment 5:
With chemical pure BaCO
3, CaCO
3, TiO
2, SnO
2for raw material, get
x=0.05,
y=0.1 according to chemical formula (Ba
0.95ca
0.05) (Ti
0.9sn
0.1) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 50 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1300 DEG C of insulation 45 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 521 | 46.5 | 115 | 4695 | 96.8 | 10.8 | 65 |
Embodiment 6:
With chemical pure BaCO
3, CaCO
3, TiO
2, SnO
2for raw material, get
x=0.05,
y=0.2 according to chemical formula (Ba
0.95ca
0.05) (Ti
0.8sn
0.2) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip dries 10 h at 100 DEG C.After drying, powder is incubated 30 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip dries 12 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1250 DEG C of insulation 50 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 387 | 26 | 96 | 2572 | 91.4 | 11.7 | 69 |
Embodiment 7:
With chemical pure BaCO
3, CaCO
3, TiO
2, HfO
2for raw material, get
x=0.05,
y=0.1 according to chemical formula (Ba
0.95ca
0.05) (Ti
0.8hf
0.1) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip dries 8 h at 100 DEG C.After drying, powder is incubated 30 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip dries 10 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1300 DEG C of insulation 50 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil, at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 438 | 43 | 106 | 3782 | 88.4 | 12.4 | 78 |
Embodiment 8:
With chemical pure BaCO
3, CaCO
3, TiO
2, SnO
2for raw material, get
x=0.3,
y=0.3 according to chemical formula (Ba
0.7ca
0.3) (Ti
0.7sn
0.3) O
3prepare burden, using absolute ethyl alcohol as ball-milling medium, with planetary ball mill batch mixing 8 h, rotating speed is 300 rpm, and slip dries 12h at 100 DEG C.After drying, powder is incubated 40 min at 1200 DEG C, synthesis of barium titanate based ceramic powder body in microwave oven.The ceramic powder of synthesis carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip dries 8 h at 100 DEG C.The polyvinyl alcohol (PVA) of 5wt.% is added in powder, compressing under 200MPa.First use conventional sintering method to rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60 min and carry out binder removal, be cooled to room temperature.And then by microwave sintering method at 1300 DEG C of insulation 50 min, the heating rate before 1000 DEG C is 25 DEG C/min; 1000 DEG C of later heating rates are 15 DEG C/min.Upper and lower two surfaces of burned ceramics sample are parallel to be polished and evenly coats silver slurry afterwards, puts into box type furnace, at 550 DEG C, is incubated 30min, carry out roasting silver-colored.Roast silver-colored potsherd and put into silicone oil, at 25 DEG C, under 3 kV/mm voltages, keep 20 min to polarize, after static 24 h, carry out electrical performance testing.Result is as follows:
| d 33(pC/N) | k p(%) | Q m | ε r | ρ r(%) | P r(μC/cm 2) | T c(℃) |
| 489 | 47 | 104 | 4528 | 95.4 | 11.2 | 102 |
Claims (3)
1. a preparation method for barium titanate-based lead-free piezoelectric ceramic, the component general formula of this pottery is (Ba
1-
x ca
x ) (Ti
1-
y m
y ) O
3, in formula, 0<
x≤ 0.3,0<
y≤ 0.3, and M is Sn or Hf; It is characterized in that, the preparation method of described pottery comprises the following steps:
Step one, be the ratio of 1-x:x:1-y:y according to the molar ratio of Ba, Ca, Ti and M tetra-kinds of elements, by BaCO
3, CaCO
3, TiO
2mix with the compound proportioning of doped chemical M, wherein 0<
x≤ 0.3,0<
y≤ 0.3, then Wet blend-milling 4 ~ 8h, take out the drying box inner drying 8-12h being positioned over 100 DEG C after wet-milling;
The compound of described doped chemical M is SnO
2or HfO
2;
Step 2, dried for step one material is put into microwave oven, material is incubated 5-60 min after being warming up to 1100-1200 DEG C, obtains barium titanate based ceramic powder, for subsequent use;
Step 3, ceramic powder step 2 obtained carry out secondary wet-milling 4-6 h, take out the drying box inner drying 8-12h being placed in 100 DEG C after wet-milling;
Step 4, in the dried material of step 3, add the polyvinyl alcohol of its quality 5%, after stirring, cross 60-80 object sieve and carry out granulation, afterwards the particle made is put into mould, under the pressure of 200MPa, be pressed into base substrate;
Step 5, base substrate obtained for step 4 is put into temperature programmed control box type furnace, rise to 650 DEG C with the heating rate of 10 DEG C/min, be incubated 60min afterwards and carry out binder removal process, be then cooled to room temperature;
Step 6, the base substrate after step 5 binder removal is put into microwave oven, material is incubated the sintering that 30-60 min carries out base substrate after being warming up to 1100-1300 DEG C, be cooled to room temperature afterwards;
One deck silver slurry is brushed again after step 7, the billet surface sanding and polishing that step 6 sintered, then, put into temperature programmed control box type furnace, at 550 DEG C of temperature, be incubated 30 min carry out roasting silver, afterwards, it is 20-30 DEG C that base substrate after roasting silver is put into temperature, and dielectric strength is polarize in the silicone oil of 3-5 kV/mm, namely completes preparation;
Wherein, in the wet-milling process of step one and step 3, the wet grinding media of employing comprises absolute ethyl alcohol and zirconia ball, and treats that the mass ratio of wet-milling siccative, absolute ethyl alcohol and zirconia ball is: 1:1:2, and the rotating speed of wet-milling balls grinding machine is 250-300 r/min;
Warming machine in step 2 and step 6 in microwave oven is made as: the heating rate between room temperature to 1000 DEG C is 20 DEG C/min; 1000 DEG C of heating rates to the intensification upper limit are 15 DEG C/min.
2. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramic according to claim 1, is characterized in that: described step one and step 3 all adopt planetary ball mill to carry out wet-milling to material.
3. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramic according to claim 1, is characterized in that: in described step 4, and the base substrate of compacting is disc-shaped structure, and blank diameter is 10mm, and thickness is 1.5mm.
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| CN104402436B (en) * | 2014-11-28 | 2016-06-01 | 吴江佳亿电子科技有限公司 | A kind of piezoceramic material and its preparation method |
| CN104692798B (en) * | 2015-03-16 | 2016-11-30 | 吴江华诚复合材料科技有限公司 | A kind of piezoceramic material and preparation method thereof |
| CN105060882A (en) * | 2015-07-23 | 2015-11-18 | 罗美柏 | Piezoceramic material and preparation method therefor |
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| CN110436919A (en) * | 2019-08-23 | 2019-11-12 | 西安交通大学 | A kind of dielectric adjustable ceramic material and preparation method thereof |
| CN111333413B (en) * | 2020-03-06 | 2021-08-06 | 中国科学院上海硅酸盐研究所 | Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof |
| CN111943666A (en) * | 2020-06-23 | 2020-11-17 | 太原理工大学 | Temperature-stable ceramic dielectric material and preparation method thereof |
| CN114149258B (en) * | 2021-12-29 | 2023-03-24 | 全球能源互联网研究院有限公司 | Piezoelectric ceramic with laminated structure and preparation method and application thereof |
| CN114478007A (en) * | 2022-02-17 | 2022-05-13 | 同济大学 | Sodium niobate-based ceramic material with good process tolerance, high piezoelectric property and high dielectric property, and preparation method and application thereof |
| CN114644523A (en) * | 2022-04-16 | 2022-06-21 | 昆明理工大学 | Perovskite structure high-entropy dielectric ceramic and preparation method thereof |
| CN116082033B (en) * | 2022-04-26 | 2023-12-22 | 西安交通大学 | Preparation method of barium titanate-based refrigerating ceramic and electric card material |
| CN116102349A (en) * | 2023-02-27 | 2023-05-12 | 伊犁师范大学 | Tantalum oxide doped hafnium barium calcium titanate lead-free piezoelectric ceramic with large dielectric constant and preparation method thereof |
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