CN104016674A - Barium titanate-based leadless piezoelectric ceramic and preparation method thereof - Google Patents
Barium titanate-based leadless piezoelectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 83
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 36
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000001238 wet grinding Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000017105 transposition Effects 0.000 claims 1
- 238000009768 microwave sintering Methods 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 28
- 239000000126 substance Substances 0.000 description 18
- 238000009413 insulation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000000748 compression moulding Methods 0.000 description 9
- 238000009770 conventional sintering Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000003068 static effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 235000015895 biscuits Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910004140 HfO Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 238000001778 solid-state sintering Methods 0.000 description 1
- 238000009475 tablet pressing Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention relates to a barium titanate-based leadless piezoelectric ceramic and a preparation method thereof. The component formula of the ceramic is [Ba(1-x)Cax][Ti(1-y)My]O3, wherein x is greater than 0 but less than or equal to 0.3, y is greater than 0 but less than or equal to 0.3, and M is Sn or Hf. The preparation method comprises the following steps: dosing; mixing; drying; carrying out microwave synthesizing; prilling; forming; discharging glue; carrying out microwave sintering; coating silver; polarizing and the like. By optimizing the components of the ceramic and the preparation process, the prepared piezoelectric ceramic is high in density and excellent in piezoelectric performance. Compared with conventional ceramic preparation process, the preparation method has the advantages that the preparation period is greatly shortened and the electric energy is greatly saved under the condition of maintaining same or high piezoelectric performance.
Description
Technical field
The invention belongs to environmentally friendly ceramic material field, specifically a kind of barium titanate-based lead-free piezoelectric ceramics and preparation method thereof.
Background technology
Piezoelectric ceramics is a class widely used new and high technology material in electron trade.But prevailing is in the market Pb-based lanthanumdoped zirconate titanates Pb (Zr, Ti) O
3(PZT) base piezoelectric ceramic, in PZT Pb content up to more than 60wt. %, its preparation, use and discarded process in all can work the mischief to human body health and living environment thereof.Therefore development environment leadless piezoelectric ceramics friendly, excellent performance is urgent, to have an important social effect problem.
In leadless piezoelectric ceramics system, barium titanate-based lead-free piezoelectric ceramics be a kind of research and development early, piezoceramic material that performance is more stable.Through scientific research personnel's unremitting effort, its piezoelectric property has obtained increasing substantially, and is the lead-free piezoceramic material that current unique 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 sintering aid and can reduce ceramic densification sintering temperature, but can greatly damage other performance of pottery, and sintering temperature reduction is very limited.
Microwave sintering is a kind of energy-efficient sintering method, has compared following characteristics with traditional solid state sintering: (1) heating rate is fast, and soaking time is short; (2) micro-wave energy directly penetrates the sample of certain depth, at different depths, heats simultaneously, does not need heat transfer process, has avoided the abnormal growth of ceramic crystalline grain in sintering process, can prepare at a lower temperature the stupalith that uniform crystal particles distributes; (3) by regulating the output rating of microwave, can make the heating state of sample that inertialess change occurs immediately, be convenient to automatically control and operate continuously; (4) thermal inertia of microwave sintering is little, energy fast cooling after sintering finishes, and 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 of preparing by conventional sintering technique is the highest
d 33=220 pC/N,
k p =28%, the reason that they improve piezoelectric property be summed up as higher density and less grain-size (Japanese Journal of Applied Physics, 2006,45(1): 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 this type of ceramic performance of preparing 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 ceramics, 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 ceramics that temperature stability is good.
The present invention solves the problems of the technologies described above the technical scheme of employing to be: a kind of barium titanate-based lead-free piezoelectric ceramics, 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 ceramics, comprises the following steps:
Step 1, the ratio that is 1-x:x:1-y:y according to the molar ratio of Ba, Ca, Ti and tetra-kinds of elements of M, by BaCO
3, CaCO
3, TiO
2mix with the compound proportioning of doped element M, wherein 0<
x≤ 0.3,0<
y≤ 0.3, then mix wet-milling 4 ~ 8h, after wet-milling, take out the loft drier inner drying 8-12h that is positioned over 100 ℃;
The compound of described doped element M is SnO
2or HfO
2;
Step 2, the dried material of step 1 is put into microwave oven, material is incubated 5-60 min after being warming up to 1100-1200 ℃, obtain barium titanate based ceramic powder, standby;
Step 3, the ceramic powder that step 2 is obtained carry out secondary wet-milling 4-6 h, take out the loft drier inner drying 8-12h that is placed in 100 ℃ after wet-milling;
Step 4, to the polyvinyl alcohol that adds its quality 5% in the dried material of step 3, after stirring, cross 60-80 object sieve and carry out granulation, afterwards the particle of making is put into mould, under the pressure of 200MPa, be pressed into base substrate;
Step 5, the base substrate that step 4 is made are put into temperature programmed control box-type furnace, with the temperature rise rate of 10 ℃/min, rise to 650 ℃, are incubated afterwards 60min and carry out binder removal processing, are then cooled to room temperature;
Step 6, the base substrate after step 5 binder removal is put into microwave oven, material is warming up to after 1100-1300 ℃ and is incubated the sintering that 30-60 min carries out base substrate, is cooled to afterwards room temperature;
After step 7, billet surface sanding and polishing that step 6 is sintered, brush again one deck silver slurry, then, put into temperature programmed control box-type furnace, at 550 ℃ of temperature, be incubated 30 min and roast silver, afterwards, it is 20-30 ℃ that base substrate by roasting after silver is put into temperature, and dielectric strength is to polarize in the silicone oil of 3-5 kV/mm, completes preparation.
Described step 1 and step 3 all adopt planetary ball mill to carry out wet-milling to material.
In the wet-milling process of described step 1 and step 3, the wet grinding media of employing comprises dehydrated alcohol and zirconia ball, and treats that the mass ratio of wet-milling siccative, dehydrated 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 temperature rise rate between room temperature to 1000 ℃ is 20 ℃/min; 1000 ℃ of temperature rise rates to the upper limit that heats up are 15 ℃/min.
In described step 4, the base substrate of compacting is disc-shaped structure, and base substrate 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:
The prepared barium titanate-based lead-free piezoelectric ceramics of the present invention has higher piezoelectric constant, good mechanical property 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 to synthesize and sintering temperature reduction, time shorten, the preparation cycle that has greatly reduced barium titanate-based lead-free piezoelectric ceramics, is conducive to suitability for industrialized production.Meanwhile, the pottery that microwave sintering obtains, grain-size reduces, and density is high, is conducive to the raising of piezoelectric property, and finished product has clear superiority, and application prospect is very wide.
Embodiment
Following embodiment is only described in further detail the present invention.
A barium titanate-based lead-free piezoelectric ceramics, 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 ratio is carried out accurate weighing batching, and ball mill mixing is dry, microwave synthesizing ceramic powder, compression moulding, microwave sintering.The steps such as its preparation process comprises batching, batch mixing, dry, microwave is synthetic, granulation, moulding, binder removal, microwave sintering, quilt silver, polarization.Advantage of the present invention is, keeping identical or more high tension performance in the situation that, makes the preparation cycle of barium titanate based ceramic shorten 4-6 h; Each save energy 20-30 degree electricity.
The technological process that microwave sintering of the present invention is prepared barium titanate based ceramic is:
(1) raw material is pressed to 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 planetary ball mill ball milling 4-8 h for the material preparing, the slurry having mixed is placed in loft drier and obtains dry powder after 100 ℃ of oven dry 8-12h;
(2) step (1) gained dry powder is put into microwave oven, be warming up to 1100-1200 ℃, insulation 5-60 min, synthesis of barium titanate based ceramic powder body;
(3) synthetic barium titanate based ceramic powder carries out secondary ball milling, and Ball-milling Time is 4-6 h.Again the slurry of milled is placed in loft drier, at 100 ℃ of insulation 8-12h, is dried;
(4) using adding the polyvinyl alcohol (PVA) of 5wt.% as binding agent in step (3) gained ceramic powder, stir, with the granulation of 60-80 object sieve aperture.Powder after granulation is put into mould, with Manual tablet pressing machine, under 200MPa, be pressed into the disc-shaped biscuit of Ф 10 * 1.5mm;
(5) biscuit step (4) being suppressed is put into temperature programmed control box-type furnace, with the temperature rise rate of 10 ℃/min, rises to 650 ℃, and 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 ℃ of temperature, is incubated the sintering that 30-60 min carries out ceramics sample.
(7) ceramics sample sintering grinds two smooth planes on 300 order sand paper, evenly coats silver slurry in two planes, is heated to 550 ℃ of insulations, 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 polarization temperature is 20-30 ℃; Polarizing voltage is 3-5 kV/mm; Polarization time is 10-30 min.The ceramics sample having polarized carries out the test of electric property.
In described technique (1) and (3), ball-milling medium is dehydrated alcohol and zirconia ball, and the mass ratio of raw material, dehydrated alcohol and zirconia ball is: 1:1:2, drum's speed of rotation is 250-300 r/min.
In described technique (2) and (6), microwave sintering warming machine is made as: the temperature rise rate before 1000 ℃ is 20 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 r/min, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 60 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1100 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1100 ℃, being incubated 60min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 300 r/min, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 30 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1150 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 6 h, and rotating speed is 250 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1200 ℃, being incubated 30min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 r/min, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 30 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 5 h, and rotating speed is 270 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1200 ℃, being incubated 45 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 6 h, rotating speed is 250 r/min, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 30 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 250 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1250 ℃, being incubated 50 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 50 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1300 ℃, being incubated 45 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip is dried 10 h at 100 ℃.After drying, powder is incubated 30 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip is dried 12 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1250 ℃, being incubated 50 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 4 h, rotating speed is 250 rpm, and slip is dried 8 h at 100 ℃.After drying, powder is incubated 30 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip is dried 10 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1300 ℃, being incubated 50 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil, at 25 ℃, 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 dehydrated alcohol as ball-milling medium, with planetary ball mill batch mixing 8 h, rotating speed is 300 rpm, and slip is dried 12h at 100 ℃.After drying, powder is incubated 40 min, synthesis of barium titanate based ceramic powder body in microwave oven at 1200 ℃.Synthetic ceramic powder carries out secondary ball milling, and Ball-milling Time is 4 h, and rotating speed is 300 r/min, and milled slip is dried 8 h at 100 ℃.The polyvinyl alcohol (PVA) that adds 5wt.% in powder, compression moulding under 200MPa.First use conventional sintering method to rise to 650 ℃ with the temperature rise rate of 10 ℃/min, insulation 60 min carry out binder removal, are cooled to room temperature.And then at 1300 ℃, being incubated 50 min by microwave sintering method, 1000 ℃ of temperature rise rates are in the past 25 ℃/min; 1000 ℃ of later temperature rise rates are 15 ℃/min.Upper and lower two surfaces of burned ceramics sample are parallel polishes the rear silver slurry evenly coated, and puts into box-type furnace, at 550 ℃, is incubated 30min, roast silver-colored.Roast silver-colored ceramic plate and put into silicone oil, at 25 ℃, 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 (6)
1. a barium titanate-based lead-free piezoelectric ceramics, is characterized in that: the component general formula of described 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.
2. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramics according to claim 1, is characterized in that, comprises the following steps:
Step 1, the ratio that is 1-x:x:1-y:y according to the molar ratio of Ba, Ca, Ti and tetra-kinds of elements of M, by BaCO
3, CaCO
3, TiO
2mix with the compound proportioning of doped element M, wherein 0<
x≤ 0.3,0<
y≤ 0.3, then mix wet-milling 4-8h, after wet-milling, take out transposition in the loft drier inner drying 8-12h of 100 ℃;
The compound of described doped element M is SnO
2or HfO
2;
Step 2, the dried material of step 1 is put into microwave oven, material is incubated 5-60 min after being warming up to 1100-1200 ℃, obtain barium titanate based ceramic powder, standby;
Step 3, the ceramic powder that step 2 is obtained carry out secondary wet-milling 4-6 h, take out the loft drier inner drying 8-12h that is placed in 100 ℃ after wet-milling;
Step 4, to the polyvinyl alcohol that adds its quality 5% in the dried material of step 3, after stirring, cross 60-80 object sieve and carry out granulation, afterwards the particle of making is put into mould, under the pressure of 200MPa, be pressed into base substrate;
Step 5, the base substrate that step 4 is made are put into temperature programmed control box-type furnace, with the temperature rise rate of 10 ℃/min, rise to 650 ℃, are incubated afterwards 60min and carry out binder removal processing, are then cooled to room temperature;
Step 6, the base substrate after step 5 binder removal is put into microwave oven, material is warming up to after 1100-1300 ℃ and is incubated the sintering that 30-60 min carries out base substrate, is cooled to afterwards room temperature;
After step 7, billet surface sanding and polishing that step 6 is sintered, brush again one deck silver slurry, then, put into temperature programmed control box-type furnace, at 550 ℃ of temperature, be incubated 30 min and roast silver, afterwards, it is 20-30 ℃ that base substrate by roasting after silver is put into temperature, and dielectric strength is to polarize in the silicone oil of 3-5 kV/mm, completes preparation.
3. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramics according to claim 2, is characterized in that: described step 1 and step 3 all adopt planetary ball mill to carry out wet-milling to material.
4. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramics according to claim 3, it is characterized in that: in the wet-milling process of described step 1 and step 3, the wet grinding media adopting comprises dehydrated alcohol and zirconia ball, and the mass ratio of siccative to be ground, dehydrated alcohol and zirconia ball is: 1:1:2, and the rotating speed of planetary ball mill is 250-300 r/min.
5. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramics according to claim 2, is characterized in that: the warming machine in described step 2 and step 6 in microwave oven is made as: from the temperature rise rate between room temperature to 1000 ℃, be 20 ℃/min; 1000 ℃ of temperature rise rates to the upper limit that heats up are 15 ℃/min.
6. the preparation method of a kind of barium titanate-based lead-free piezoelectric ceramics according to claim 2, is characterized in that: in described step 4, the base substrate of compacting is disc-shaped structure, and base substrate diameter is 10mm, and thickness is 1.5mm.
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