CN106348754A - Barium zirconate titanate ceramic thick film and preparation method and application thereof - Google Patents
Barium zirconate titanate ceramic thick film and preparation method and application thereof Download PDFInfo
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- CN106348754A CN106348754A CN201610696265.9A CN201610696265A CN106348754A CN 106348754 A CN106348754 A CN 106348754A CN 201610696265 A CN201610696265 A CN 201610696265A CN 106348754 A CN106348754 A CN 106348754A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract 4
- 229910021523 barium zirconate Inorganic materials 0.000 title abstract 4
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 title abstract 4
- 238000005057 refrigeration Methods 0.000 claims abstract description 9
- 238000004146 energy storage Methods 0.000 claims abstract description 4
- VEAHHGDAQKXNNG-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Zr+4].[Ba+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Zr+4].[Ba+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-] VEAHHGDAQKXNNG-UHFFFAOYSA-H 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- -1 phosphate ester Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 4
- 241000251468 Actinopterygii Species 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000010410 layer Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000010345 tape casting Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 36
- 230000005684 electric field Effects 0.000 description 30
- 230000008859 change Effects 0.000 description 21
- 239000012071 phase Substances 0.000 description 16
- 230000000630 rising effect Effects 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 8
- 238000001757 thermogravimetry curve Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000007766 curtain coating Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical group [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004247 hand Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
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Abstract
The invention discloses a barium zirconate titanate ceramic thick film and a preparation method thereof; the BaZrxTi(1-x)O3 ceramic thick film is 5-50 Mum in thickness, with x=0.05-0.30. The barium zirconate titanate ceramic thick film 5-50 Mum in thickness is prepared by subjecting barium carbonate, titanium dioxide and zirconium dioxide to normal-pressure air sintering process at a required barium zirconate titanate stoichiometric ratio by means of tape casting. The method of the invention is simple, the manufacturing cost is low, the manufacturing cycle is short, and the method facilitates industrial flow production; single-layer thick films required for multi-layer ceramic devices can be prepared and are widely applicable to the fields of sensors, solid refrigeration and energy storage devices.
Description
Technical field
The invention belongs to field of ceramic preparation, more particularly, to a kind of barium zirconium phthalate ceramic thick film and preparation method thereof
And application.
Background technology
With the rising of Global Temperature, the electric refrigerator such as air-conditioning has become as an indispensable part in life, in addition
For the heating controlling unit such as our mobile phone, computer, wearable small intelligent device, heat management to proper device operation
Effect is particularly important.But the waste gas that compressor cooling mode common at present is discharged can damage the ozone layer and increase global greenhouse
Effect, so it is very necessary to find a kind of refrigerating method of Novel pollution-free.Research shows, the electric card effect based on solid-state phase changes
Refrigeration Technique realizing high efficiency and undersized aspect shows huge potentiality, and with low cost it is easy to give birth on a large scale
Produce.
Compared to tfe polymer electric material, ceramic ferroelectric materials have higher thermal conductivity, are suitable for the heat of refrigeration device
Exchange capacity, contributes to reducing the thermal losses of device, improves device performance.But, ceramic membrane material structure needs substrate,
It is unfavorable for the design of refrigeration device, in performance, amount of stored heat is little does not meet the requirement to refrigerating function yet.Therefore, based on thick film
Prospect in terms of refrigeration for the multi-layer ceramics electric card device especially prominent.
Barium zirconium phthalate, as one of ferroelectric material, has excellent dielectric and ferroelectric properties, latent heat of phase change is big, structure is simple
The advantages of, and barium zirconium phthalate is not leaded, is a kind of ferroelectricity refrigerating material of environment-friendly type, so barium zirconium phthalate is in electric card refrigeration side
Face has larger potentiality.
In prior art, the resistance to breakdown field strength of lead zirconate-titanate ceramic relatively low (< 10mv/m), works not under existing fringing field
Problematic, but can not meet requirement under high electric field for the electric card refrigerating material.Trace it to its cause, be the thickness of block materials relatively
Greatly, experiment has been found that pottery is thinner, and its resistance to breakdown field strength is higher, so needing to reduce the thickness of pottery further.This
The bright thickness problem being just intended to solution pottery, thus improve resistance to breakdown field strength.
Content of the invention
The invention aims to overcoming the deficiencies in the prior art, provide a kind of barium zirconium phthalate ceramic thick film.
It is a further object of the present invention to provide the preparation method of above-mentioned barium zirconium phthalate ceramic thick film material.
Another object of the present invention is to provide above-mentioned barium zirconium phthalate ceramic thick film material in multi-layer ceramics solid-state refrigeration device
In application.
Above-mentioned purpose of the present invention is to be achieved by the following technical programs:
A kind of barium zirconium phthalate ceramic thick film, its molecular formula is bazrxti(1-x)o3, wherein x=0.05～0.30；Described pottery
The thickness of porcelain thick film is 5～50 μm.
The preparation method of above-mentioned barium zirconium phthalate ceramic thick film, comprises the following specific steps that:
S1. by baco3、zro2And tio2Raw material is stoichiometrically bazrxti(1-x)o3, x=0.05～0.30 is carried out
Dispensing, adds dehydrated alcohol and zirconium ball, after planetary ball mill 12～24h obtains mixing material, leaches slurry, dries, obtain raw material
The dry powder of mixing；
S2. by the dry powder of s1 gained raw material mixing in 1200～1280 DEG C of pre-burning 2h, through secondary ball milling 8～12h, by one
Determine proportioning and add binding agent, dispersant, plasticiser and organic solvent and zirconium ball mixing barreling 36～48h, be cast into film strips；
S3. by film strips cut into required form give birth to potsherd, under atmospheric air atmosphere 1300～1400 DEG C sinter 2～
10h, obtains barium zirconium phthalate ceramic thick film.
Preferably, dehydrated alcohol described in step s1: zirconium ball: the volume ratio of raw material is 1～1.5:1～2:1.
Preferably, the temperature dried described in step s1 is 70～100 DEG C, and the time of described drying is 6h.
Preferably, binding agent described in step s2 is pvb or pva.
Preferably, dispersant described in step s2 be toluene, phosphate ester, fresh fish oil or ethyl cellulose.
Preferably, plasticiser described in step s2 is o-2 potassium acid diisobutyl ester, Polyethylene Glycol or ethylene glycol.
Preferably, organic solvent described in step s2 is ethanol, toluene or dimethylbenzene.
Preferably, binding agent described in step s2: dispersant: plasticiser: the mass ratio of organic solvent is (0.1～0.2):
1:1:(0.05～0.15).
Above-mentioned barium zirconium phthalate ceramic thick film sensor, solid-state freeze and energy storage device field application also in the present invention
Protection domain in.
In the present invention, relatively low calcining heat is unfavorable for the formation of barium zirconium phthalate crystallite, and higher temperature can cause crystallite
Overgrowth.Suitably, I haven't seen you for ages excessively makes filming piece mobility bad to the ratio of binding agent, and filming piece excessively can be led to uneven
Even.The viscosity of slurry is relevant with the amount of solvent, too dilute raw cook can be caused relatively thin, but uneven, too thick, make raw cook thicker, all
Desired ceramic thick film can not be obtained.
With the rising of zirconium content in the present invention, ceramic thick film Curie temperature declines, and this is because ionic radius is bigger
Zirconium ion mixes in Barium metatitanate. lattice and causes distortion of lattice, thus causing material spontaneous polarization to increase and lead to, equally also table
The rising of clear doping content makes ceramic thick film under room temperature be changed into paraelectric phase from original ferroelectric phase, and same contrast understands to mix
Miscellaneous make simultaneously ceramic thick film from normal frroelectrics to relaxation property ferroelectric change.And the increase with zirconium content, electric card effect
The value (isothermal Entropy Changes and adiabatic temperature variate) answered diminishes, and this is because thick film ceramic material becomes relaxation type from normal frroelectrics
Ferroelectric, S order parameter-polarization intensity diminishes, and its pyroelectric coefficient also accordingly diminishes.Further, since pyroelectric coefficient is in high temperature
Section (100 DEG C) is larger, thus the electric card effect of thick film ceramic is larger.The resistance to electric field intensity of especially thick film ceramic is up to 12mv/
M, can obtain larger electric card effect value.If reducing the thickness of thick film further, resistance to breakdown field strength can be further
Improve, corresponding electric card effect value also can increase therewith.It should be noted that the electric card of the maximum of relaxation ferroelectric thick film ceramic
, not near the phase transition temperature or average phase change temperature of material, this is different from normal frroelectrics material for effect value.
Compared with prior art, the method have the advantages that
The present invention adopts the tape casting to make barium zirconium phthalate film, and atmospheric air sintering process makes the pottery that thickness is 5～50 μm
Porcelain thick film.This ceramic thick film can tolerate higher breakdown electric field (> 10mv/m), reason is resistance to breakdown electric field and the material of pottery
Defect density relevant, pottery is thicker, and defect density is higher, and resistance to breakdown field strength is lower, otherwise higher.
The method of the present invention is easy, low manufacture cost, and cycle is short is it is easy to industrial flow metaplasia is produced；For preparing multi-layer ceramics
Device provides required each single layer thick film, can be widely applied to sensor, solid-state refrigeration and energy storage device field.
Brief description
Fig. 1 is barium zirconium phthalate ceramic thick film x-ray diffraction collection of illustrative plates in embodiment 1-5.
Fig. 2 is barium zirconium phthalate ceramic thick film electron scanning micrograph in embodiment 1-5.
Fig. 3 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 1.
Fig. 4 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 2.
Fig. 5 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 3.
Fig. 6 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 4.
Fig. 7 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 5.
Fig. 8 is barium zirconium phthalate ceramic thick film ferroelectric hysteresis loop in embodiment 1.
Fig. 9 is barium zirconium phthalate ceramic thick film ferroelectric hysteresis loop in embodiment 2.
Figure 10 is barium zirconium phthalate ceramic thick film ferroelectric hysteresis loop in embodiment 3.
Figure 11 is barium zirconium phthalate ceramic thick film ferroelectric hysteresis loop in embodiment 4.
Figure 12 is barium zirconium phthalate ceramic thick film ferroelectric hysteresis loop in embodiment 5.
Figure 13 is barium zirconium phthalate ceramic thick film electric card effect diagram in embodiment 1, and wherein, (a) is that adiabatic temperature becomes δ t, (b)
For isothermal Entropy Changes δ s.
Figure 14 is barium zirconium phthalate ceramic thick film electric card effect diagram in embodiment 2, and wherein, (a) is that adiabatic temperature becomes δ t, (b)
For isothermal Entropy Changes δ s.
Figure 15 is barium zirconium phthalate ceramic thick film electric card effect diagram in embodiment 3, and wherein, (a) is that adiabatic temperature becomes δ t, (b)
For isothermal Entropy Changes δ s.
Figure 16 is barium zirconium phthalate ceramic thick film electric card effect diagram in embodiment 4, and wherein, (a) is that adiabatic temperature becomes δ t, (b)
For isothermal Entropy Changes δ s.
Figure 17 is barium zirconium phthalate ceramic thick film electric card effect diagram in embodiment 5, and wherein, (a) is that adiabatic temperature becomes δ t, (b)
For isothermal Entropy Changes δ s.
Specific embodiment
Further illustrate present disclosure with reference to Figure of description and specific embodiment, but should not be construed as to this
The restriction of invention.If not specializing, the conventional handss that in embodiment, technological means used are well known to those skilled in the art
Section.Unless stated otherwise, the reagent that the present invention adopts, method and apparatus are the art conventional reagent, method and apparatus.
Embodiment 1
S1. by required 99% baco3、zro2、tio2Raw material presses bazr0.05ti0.95o3Stoichiometric proportion is made into batch mixing,
Add volume ratio to be the dehydrated alcohol of 1:1:1 and zirconium ball, planetary ball mill 24h, after leach slurry, 80 DEG C of drying.
S2. 1230 DEG C of pre-burning 2h of atmospheric air atmosphere pre-burning.
S3. after secondary ball milling 8h, weigh the powder obtained by 100g step s2, with the toluene of pvb, 5g of 10g, 15g
The zirconium ball of o-2 potassium acid diisobutyl ester, the ethanol of 100g and 200g is mixed into casting slurry, barreling 48h, and curtain coating formation is less than
100 μm of film strips.
S4. sinter 2h at 1330 DEG C under atmospheric air atmosphere, obtain bazr0.05ti0.95o3Ceramic thick film sample.
After tested, bazr0.05ti0.95o3The thickness of ceramic thick film is 18 ± 2 μm.
Embodiment 2
S1. by required 99% baco3、zro2、tio2Raw material presses bazr0.1ti0.9o3Stoichiometric proportion is made into batch mixing,
Add volume ratio to be the dehydrated alcohol of 1:1:1 and zirconium ball, planetary ball mill 24h, after leach slurry, 80 DEG C of drying.
S2. 1240 DEG C of pre-burning 2h of atmospheric air atmosphere pre-burning.
S3. after secondary ball milling 8h, weigh the powder obtained by 100g step s2, with the toluene of pvb, 5g of 10g, 15g
The zirconium ball of o-2 potassium acid diisobutyl ester, the ethanol of 100g and 200g is mixed into casting slurry, barreling 48h, and curtain coating formation is less than
100 μm of film strips.
S4. sinter 3h at 1400 DEG C under atmospheric air atmosphere, obtain bazr0.1ti0.9o3Ceramic thick film sample.
After tested, bazr0.1ti0.9o3The thickness of ceramic thick film is 18 ± 2 μm.
Embodiment 3
S1. by required 99% baco3、zro2、tio2Raw material presses bazr0.15ti0.85o3Stoichiometric proportion is made into batch mixing,
Add volume ratio to be the dehydrated alcohol of 1:1:1 and zirconium ball, planetary ball mill 24h, after leach slurry, 70 DEG C of drying.
S2. 1250 DEG C of pre-burning 2h of atmospheric air atmosphere pre-burning.
S3. after secondary ball milling 8h, weigh the powder obtained by 100g step s2, with the toluene of pvb, 5g of 10g, 15g
The zirconium ball of o-2 potassium acid diisobutyl ester, the ethanol of 100g and 200g is mixed into casting slurry, barreling 48h, and curtain coating formation is less than
100 μm of film strips.
S4. sinter 4h at 1450 DEG C under atmospheric air atmosphere, obtain bazr0.15ti0.85o3Ceramic thick film sample.
After tested, bazr0.15ti0.85o3The thickness of ceramic thick film is 18 ± 2 μm.
Embodiment 4
S1. the baco being 99% by required purity3、zro2、tio2Raw material presses bazr0.2ti0.8o3Stoichiometric proportion is made into
Batch mixing, adds volume ratio to be the dehydrated alcohol of 1:1:1 and zirconium ball, planetary ball mill 24h, after leach slurry, 70 DEG C of drying.
S2. 1260 DEG C of pre-burning 2h of atmospheric air atmosphere pre-burning.
S3. after secondary ball milling 8h, weigh the powder obtained by 100g step s2, with the toluene of pvb, 5g of 10g, 15g
The zirconium ball of o-2 potassium acid diisobutyl ester, the ethanol of 100g and 200g is mixed into casting slurry, barreling 48h, and curtain coating formation is less than
100 μm of film strips.
S4. sinter 5h at 1480 DEG C under atmospheric air atmosphere, obtain bazr0.2ti0.8o3Ceramic thick film sample.
After tested, bazr0.2ti0.8o3The thickness of ceramic thick film is 18 ± 2 μm.
Embodiment 5
S1. the baco being 99% by required purity3、zro2、tio2Raw material presses bazr0.3ti0.7o3Stoichiometric proportion is made into
Batch mixing, adds volume ratio to be the dehydrated alcohol of 1:1:1 and zirconium ball, planetary ball mill 24h, after leach slurry, 70 DEG C of drying.
S2. 1270 DEG C of pre-burning 2h of atmospheric air atmosphere pre-burning.
S3. after secondary ball milling 8h, weigh the powder obtained by 100g step s2, with the toluene of pvb, 5g of 10g, 15g
The zirconium ball of o-2 potassium acid diisobutyl ester, the ethanol of 100g and 200g is mixed into casting slurry, barreling 48h, and curtain coating formation is less than
100 μm of film strips.
S4. sinter 6h at 1500 DEG C under atmospheric air atmosphere, obtain bazr0.3ti0.7o3Ceramic thick film sample.
After tested, bazr0.3ti0.7o3The thickness of ceramic thick film is 18 ± 2 μm.
Fig. 1 is barium zirconium phthalate ceramic thick film x-ray diffraction collection of illustrative plates in embodiment 1-5.Wherein, Fig. 1 (a)-(e) represents successively
X=0.05,0.10,015,0.20 and 0.30 bazrxti(1-x)o3.It can be seen that the characteristic peak such as (001) is corresponding
The indices of crystallographic plane, show that barium zirconium phthalate ceramic thick film has perovskite structure, do not have dephasign to occur.And bazrxti(1-x)o3System
In with zirconium ion content rising (i.e. the increase of the value of x), diffraction maximum toward low power angular direction mobile it was demonstrated that tetravalence zirconium ion becomes
Work(mix oxygen octahedra lattice in, substitute original tetravalence titanium ion position, due to tetravalent zirconium ion ratio tetravalence titanium ion from
Sub- radius is bigger, so leading to oxygen octahedra lattice dilatation, lattice coefficient increases, and shows as diffraction in x-ray diffraction collection of illustrative plates
Peak is toward the movement of low power angular direction.
Fig. 2 is barium zirconium phthalate ceramic thick film electron scanning micrograph in embodiment 1-5.Fig. 2 (a)-(e) represents
bazrxti(1-x)o3, it is followed successively by x=0.05,0.10,015,0.20,0.30.As can be seen from the figure grain growth is complete, crystal boundary
Clearly, dephasign, glass phase, liquid phase etc. is not had to exist, crystallite dimension is 10-20 μm.
Fig. 3-4 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 1-2.It can be seen that gained
bazr0.05ti0.95o3And bazr0.1ti0.9o3Barium zirconium phthalate ceramic thick film all shows the dielectric properties of normal frroelectrics, ferroelectricity
The transformation mutually arriving paraelectric phase is obvious.Wherein, in Fig. 3 transition temperature be Curie temperature be 107 DEG C, dielectric constant is up to 15000；It is situated between
Electrical loss rises with frequency and rises, but the maximum of loss is less than 0.2 under high frequency 100khz；In Fig. 4, Curie temperature is
80 DEG C, dielectric constant is up to 44500, and dielectric constant peak temperature does not change with the change of frequency, and dielectric loss is with frequency
Rise and rise, but the maximum of loss is less than 0.05 it is meant that under high frequency electrical signal effect, making pottery under high frequency 100khz
The leakage current of porcelain thick film is low, functional and stable.
Fig. 5-7 is barium zirconium phthalate ceramic thick film dielectric thermogram in embodiment 3-5.It can be seen that gained
bazr0.15ti0.85o3、bazr0.2ti0.8o3、bazr0.3ti0.7o3Barium zirconium phthalate ceramic thick film all shows Relaxation Ferroelectrics
Dielectric properties, dielectric constant peak temperature moves to high temperature direction with the increase of frequency.The transformation of ferroelectric phase to paraelectric phase is opened
Begin to show the feature of wide scope transformation, wherein, the transition temperature in Fig. 5 is (corresponding to dielectric constant peak value under 1khz low frequency
Temperature), that is, Curie temperature is 70 DEG C, and dielectric constant is up to 11700.Dielectric loss rises with frequency and rises, but in high frequency
Under 100khz, the maximum of loss is less than 0.3；Curie temperature in Fig. 6 is 38 DEG C, and dielectric constant is up to 9000.Dielectric loss
Rise with frequency and rise, but the maximum of loss is less than 0.4 under high frequency 100khz；In Fig. 7, Curie temperature is -41 DEG C,
Dielectric constant is up to 10000.Dielectric loss rises with frequency and rises, but the maximum of loss is less than under high frequency 100khz
0.05.Result shows, under high frequency electrical signal effect, gained barium zirconium phthalate ceramic thick film has that leakage current is low, and stable performance is good
Good feature.
Contrast above-mentioned Fig. 3～7 it can be seen that rising with zirconium content, ceramic thick film Curie temperature declines, this be due to
The bigger zirconium ion of ionic radius mixes in Barium metatitanate. lattice and causes distortion of lattice, thus causing material spontaneous polarization to increase and lead
Cause, equally also show the rising of doping content so that ceramic thick film is changed into paraelectric phase from original ferroelectric phase under room temperature,
Same contrast understands, doping makes ceramic thick film change to relaxation property ferroelectric from normal frroelectrics simultaneously.
Fig. 8-12 is the ferroelectric hysteresis loop of barium zirconium phthalate ceramic thick film in embodiment 1-5.Wherein, can from Fig. 8 and 9
Go out, gained bazr0.05ti0.95o3And bazr0.1ti0.9o3Barium zirconium phthalate ceramic thick film can bear the strong ac voltage signal of 12mv,
Disruptive field intensity is high, and polarization intensity is big.And become the ferroelectric hysteresis loop revealing and there is wider loop line, this is the electric hysteresis of normal frroelectrics
Loop line.Gained bazr is can be seen that in Figure 10-120.15ti0.85o3、bazr0.2ti0.8o3、bazr0.3ti0.7o3Barium zirconium phthalate pottery
Thick film all can bear the strong ac voltage signal of 12mv, and disruptive field intensity is high, and polarization intensity is big.The ferroelectric hysteresis loop embodying has relatively
Thin loop line, this is the ferroelectric hysteresis loop of Relaxation Ferroelectrics.When temperature is raised, ferroelectric hysteresis loop is reduced by fat, shows ferroelectric phase
Transformation to paraelectric phase.
Figure 13-17 is barium zirconium phthalate ceramic thick film electric card effect in embodiment 1-5.Wherein, (a) is that adiabatic temperature becomes δ t,
B () is isothermal Entropy Changes δ s, test barium zirconium phthalate ceramic thick film electric card effect respectively under the electric field of 3mv, 6mv, 9mv and 12mv
Should.As can be seen that the index characterizing electric card effect raises with the rising of electric field from Figure 13 (a), reflect higher hitting
Wear field intensity to the key effect improving electric card effect.Within the temperature range of in this sample, test characterizes, take under 12mv electric field
Obtain t=3.5 DEG C of δ.As can be seen that the absolute value of isothermal Entropy Changes value increases with the increase of electric field from Figure 13 (b), and take
Obtain maximum δ s=-6 (j k-1·kg-1), result shows under isothermy, and the increase of tolerance electric field causes material internal pole
The change changing entropy changes with the change of electric field intensity.Consistent with the variation tendency that adiabatic temperature becomes.Can from Figure 14 (a)
Go out, the index characterizing electric card effect raises with the rising of electric field, reflect higher disruptive field intensity to raising electric card effect
Key effect.Within the temperature range of test characterizes in this sample, under 12mv electric field, obtain t=0.8 DEG C of δ.From Figure 14
As can be seen that the absolute value of isothermal Entropy Changes value increases with the increase of electric field in (b), and obtain maximum δ s=-1.5
(j·k-1·kg-1), result shows under isothermy, and the increase of tolerance electric field causes the change of material internal polarization entropy with electricity
The change of field intensity and change.Consistent with the variation tendency that adiabatic temperature becomes.As can be seen that characterizing electric card effect from Figure 15 (a)
Index raise with the rising of electric field, reflect higher disruptive field intensity to improve electric card effect key effect.From
As can be seen that within the temperature range of test characterizes in this sample, obtaining t=0.4 DEG C of δ under 12mv electric field in Figure 15 (b).From
As can be seen that the absolute value of isothermal Entropy Changes value increases with the increase of electric field in Figure 15 (b), and obtain maximum δ s=-
0.7(j·k-1·kg-1), result shows under isothermy, tolerance electric field increase cause material internal polarize entropy change with
The change of electric field intensity and change.Consistent with the variation tendency that adiabatic temperature becomes.As can be seen that characterizing electric card from Figure 16 (a)
The index of effect raises with the rising of electric field, reflects higher disruptive field intensity to the key work improving electric card effect
With.Within the temperature range of test characterizes in this sample, under 12mv electric field, obtain t=0.3 DEG C of δ.Can from Figure 16 (b)
Go out, the absolute value of isothermal Entropy Changes value increases with the increase of electric field, and obtain maximum δ s=-0.7 (j k-1·kg-1),
Result shows under isothermy, tolerance electric field increase cause material internal polarize entropy change with electric field intensity change and
Change.Consistent with the variation tendency that adiabatic temperature becomes.As can be seen that characterizing the index of electric card effect with electric field from Figure 17 (a)
Rising and raise, reflect higher disruptive field intensity to improve electric card effect key effect.Table is tested in this sample
Within the temperature range of levying, under 12mv electric field, obtain t=0.3 DEG C of δ.The absolute of isothermal Entropy Changes value is can be seen that from Figure 17 (b)
Value increases with the increase of electric field, and obtains maximum δ s=-0.55 (j k-1·kg-1), result shows isothermy
Under, the increase of tolerance electric field causes the change of material internal polarization entropy to change with the change of electric field intensity.Become with adiabatic temperature
Variation tendency consistent.
Contrast above-mentioned Fig. 8～17 it can be seen that increase with zirconium content, value (isothermal Entropy Changes and the thermal insulation of electric card effect
Warm variate) diminish, this is because thick film ceramic material becomes Relaxation Ferroelectrics from normal frroelectrics, and S order parameter-polarization is strong
Degree diminishes, and its pyroelectric coefficient also accordingly diminishes.Further, since pyroelectric coefficient is larger in high temperature section (100 DEG C), thus thick
The electric card effect of film pottery is larger.The resistance to electric field intensity of especially thick film ceramic, up to 12mv/m, can obtain larger electric card
Effect value.If reducing the thickness of thick film further, resistance to breakdown field strength can improve further, corresponding electric card effect value
Also can increase therewith.It should be noted that the electric card effect value of maximum is not attached in the phase transition temperature of material or average phase change temperature
Closely, this is different from normal frroelectrics material.
The above embodiment of the present invention only clearly demonstrates example of the present invention, and is not the reality to the present invention
Apply the restriction of mode.For those of ordinary skill in the field, other can also be made on the basis of the above description
The variation of multi-form.There is no need to be exhaustive to all of embodiment.All in the spirit and principles in the present invention
Within any modification, equivalent and improvement of being made etc., should be included within the protection domain of the claims in the present invention.
Claims (10)
1. a kind of barium zirconium phthalate ceramic thick film is it is characterised in that its molecular formula is bazrxti(1-x)o3, wherein x=0.05～
0.30；The thickness of described ceramic thick film is 5～50 μm.
2. a kind of preparation method of the ceramic thick film of barium zirconium phthalate according to claim 1 is it is characterised in that include concrete as follows
Step:
S1. by baco3、zro2And tio2Raw material is stoichiometrically bazrxti(1-x)o3, x=0.05～0.30 carries out dispensing,
Add dehydrated alcohol and zirconium ball, after planetary ball mill 12～24h obtains mixing material, leach slurry, dry, obtain raw material mixing
Dry powder；
S2. by the dry powder of s1 gained raw material mixing in 1200～1280 DEG C of pre-burning 2h, through secondary ball milling 8～12h, by necessarily joining
Ratio adds binding agent, dispersant, plasticiser and organic solvent and zirconium ball mixing barreling 36～48h, is cast into film strips；
S3. film strips are cut into required form and give birth to potsherd, sinter 2～10h at 1300～1400 DEG C under atmospheric air atmosphere, obtain
To barium zirconium phthalate ceramic thick film.
3. according to claim 2 the preparation method of barium zirconium phthalate ceramic thick film it is characterised in that anhydrous described in step s1
Ethanol: zirconium ball: the volume ratio of raw material is (1～1.5): (1～2): 1.
4. according to claim 2 barium zirconium phthalate ceramic thick film preparation method it is characterised in that described in step s1 dry
Temperature be 70～100 DEG C, time of described drying is 6h.
5. according to claim 2 barium zirconium phthalate ceramic thick film preparation method it is characterised in that described in step s2 bond
Agent is pvb or pva.
6. according to claim 2 barium zirconium phthalate ceramic thick film preparation method it is characterised in that described in step s2 disperse
Agent is toluene, phosphate ester, fresh fish are oily or ethyl cellulose.
7. according to claim 2 barium zirconium phthalate ceramic thick film preparation method it is characterised in that described in step s2 plastify
Agent is o-2 potassium acid diisobutyl ester, Polyethylene Glycol or ethylene glycol.
8. according to claim 2 the preparation method of barium zirconium phthalate ceramic thick film it is characterised in that organic described in step s2
Solvent is ethanol, toluene or dimethylbenzene.
9. according to claim 2 barium zirconium phthalate ceramic thick film preparation method it is characterised in that described in step s2 bond
Agent: dispersant: plasticiser: the mass ratio of organic solvent is (0.1～0.2): 1:1:(0.05～0.15).
10. barium zirconium phthalate ceramic thick film described in claim 1 is in the application of sensor, solid-state refrigeration and energy storage device field.
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| CN106957173A (en) * | 2017-03-30 | 2017-07-18 | 广东工业大学 | A kind of tin barium titanate thick film ceramic and its application |
| CN107986775A (en) * | 2017-12-19 | 2018-05-04 | 广东工业大学 | A kind of barium strontium titanate (BST) thick film and preparation method thereof |
| CN108424140A (en) * | 2018-05-23 | 2018-08-21 | 广东工业大学 | A kind of high tetragonal-phase barium titanate powder and preparation method thereof, barium titanate thick film ceramic and its preparation method and application |
| CN110526707A (en) * | 2019-06-28 | 2019-12-03 | 广东工业大学 | A kind of zirconium titanium stannic acid lanthanum lead thick film ceramic of high tin content and its preparation method and application |
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| CN104310995A (en) * | 2014-09-24 | 2015-01-28 | 陕西理工学院 | Thick BZT film having EC effect, and its making method |
| CN104557033A (en) * | 2014-12-19 | 2015-04-29 | 广东风华高新科技股份有限公司 | Preparation method of barium zirconate titanate powder |
| CN105418067A (en) * | 2015-12-08 | 2016-03-23 | 天津大学 | Preparation method of barium calcium zirconate titanate lead-free piezoelectric textured ceramic |
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| CN104310995A (en) * | 2014-09-24 | 2015-01-28 | 陕西理工学院 | Thick BZT film having EC effect, and its making method |
| CN104557033A (en) * | 2014-12-19 | 2015-04-29 | 广东风华高新科技股份有限公司 | Preparation method of barium zirconate titanate powder |
| CN105418067A (en) * | 2015-12-08 | 2016-03-23 | 天津大学 | Preparation method of barium calcium zirconate titanate lead-free piezoelectric textured ceramic |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106957173A (en) * | 2017-03-30 | 2017-07-18 | 广东工业大学 | A kind of tin barium titanate thick film ceramic and its application |
| CN107986775A (en) * | 2017-12-19 | 2018-05-04 | 广东工业大学 | A kind of barium strontium titanate (BST) thick film and preparation method thereof |
| CN108424140A (en) * | 2018-05-23 | 2018-08-21 | 广东工业大学 | A kind of high tetragonal-phase barium titanate powder and preparation method thereof, barium titanate thick film ceramic and its preparation method and application |
| CN108424140B (en) * | 2018-05-23 | 2021-09-03 | 广东工业大学 | High tetragonal phase barium titanate powder and preparation method thereof, barium titanate thick film ceramic and preparation method and application thereof |
| CN110526707A (en) * | 2019-06-28 | 2019-12-03 | 广东工业大学 | A kind of zirconium titanium stannic acid lanthanum lead thick film ceramic of high tin content and its preparation method and application |
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