CN104310995B - A kind of BZT thick film with EC effect and preparation method thereof - Google Patents
A kind of BZT thick film with EC effect and preparation method thereof Download PDFInfo
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- CN104310995B CN104310995B CN201410493736.7A CN201410493736A CN104310995B CN 104310995 B CN104310995 B CN 104310995B CN 201410493736 A CN201410493736 A CN 201410493736A CN 104310995 B CN104310995 B CN 104310995B
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Abstract
The invention discloses a kind of BZT thick film with EC effect and preparation method thereof, utilize casting method to prepare BZT thick film, comprise the following steps: the 1) preparation of pre-burning powder: weigh according to amount of substance, ball milling, then carry out pre-burning at 900-1200 DEG C, obtain pre-burning powder; 2) preparation of slurry: pre-burning powder is carried out ball milling, then utilizes medium A and medium B to prepare Tape-casting slurry; 3) BZT thick film preparation: the Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, make the thin-film material with electrode, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.In BZT (Zr:Ti=(0-30): (100-70)) thick film systems, obtaining enthalpy change by indirect measuring technology is 2.8-5J.Kg
-1.K
-1eC effect.This technology is find new refrigerating material to provide a new way.
Description
Technical field
The invention belongs to new function energy-saving material field, relate to a kind of BZT thick film with EC effect and preparation method thereof.
Background technology
Industrial technology develops into today, the Environment and energy problem that facing mankind is many.For example refrigeration industry, in developed country and some developing countries, air-conditioning, refrigerator and other refrigerating machine consume electric energy more than 20% every year.Traditional air-conditioning and refrigerator utilize mechanical work to drive vapor-compression cycle (mechanicalvaporcompressioncycle, VCC) refrigeration is realized, this mode utilization rate of electrical is very low, does not also have so far to improve its utilization rate of electrical new technology; In addition, air conditioning electricity is generally more at power system peak load, and due to network system integrity problem, regulates and controls power system peak load not only costly, and validity is poor, therefore changes the active demand that current refrigeration technology is save energy; On the other hand, current VCC Refrigeration Technique adopts containing fluorinated refrigerant, very havoc effect is had to ozonosphere containing fluorinated refrigerant, although people utilize fluorocarbon (hydrofluorocarbon, HFC) alternative fluorocarbon (chlorofluorocarbons is carried out, CFC), but still produce a large amount of greenhouse gases, therefore this is that national governments and science are worried and are badly in need of the environmental problem of solution.Along with people are to requirement of improving the quality of living, refrigerator and air conditioning requirements amount significantly increase, and therefore, based on above factor, in the refrigeration system such as air-conditioning, refrigerator, exploring efficient and eco-friendly new technology and method is the new problem that research is badly in need of in this field.
Find there is a class material under outer field action under study for action, when its certain physical quantity changes from disorder to order, reversible entropy occurs and changes, the scientist's great interest caused.At present, meriting attention most is this physical phenomenon in magneticsubstance and dielectric materials.Inside ferromagnetic substance, magnetic calorie effect (MagnetocaloricEffect has been observed at Warbourg in 1881, MCE) (Ann.Phys. (Leipzig) 13 (1881) 141), i.e. material occurrence temperature change under the action of a magnetic field of change.In the last few years, research worker did a lot of work in this respect.But due to the restriction in magnetic field, make it be very limited in industrial applications.Therefore, people wish from ferroelectric material, to obtain adaptable electric heating card effect (ElectrocaloricEffect, ECE).
Electric heating card effect be pyroelectrics under adiabatic conditions, when extra electric field causes state to change from disorder to order, the phenomenon that its entropy will change.In Rochelle salt (Rochellesalt) ferroelectric material, observe electric field refrigeration phenomenon as far back as nineteen thirty KobekoP and KurchatovI., be namely referred to as electric heating card effect by descendant; Regrettably these results of various reasons such as material electric heating effect is very weak found due to the past do not obtain everybody attention; Simultaneously to the conceptual understanding of ECE and measuring technology immature, dispute is existed to ECE always.Until ScottJF group of univ cambridge uk and ZhangQM group of Pennsylvania State University of the U.S. measure very large EC effect respectively in Pb (Zr0.95Ti0.05) O3 and PVDF, the research in this field just obtains the concern of countries in the world.
Summary of the invention
The object of the present invention is to provide a kind of BZT thick film with EC effect and preparation method thereof, obtained BZT thick film has the EC effect being tending towards room temperature.
For reaching above object, technical scheme of the present invention is:
There is a BZT thick film preparation method for EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be 1:(0.7-1 according to mass ratio): (0-0.3) weighs, ball milling, then carries out pre-burning at 900-1200 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:(0.2-0.6): (0.3-0.6);
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
Described step 1) the sintering time of pre-burning be 2-8 hour.
Described curtain coating agent A by concentration to be the ethanol of 90 ~ 95% and the mixing solutions of butanone and concentration be 5 ~ 10% PVB form according to arbitrary proportion, wherein, described ethanol and the mixing of butanone peace arbitrary proportion.
Described curtain coating agent B by concentration be 65 ~ 70% ethanol and the mixing solutions of butanone, concentration be 20 ~ 25% PVB and concentration be that 10 ~ 15% softening agent form according to arbitrary proportion, wherein, described ethanol and the mixing of butanone peace arbitrary proportion.
Have a BZT thick film for EC effect, the Zr:Ti mol ratio of described BZT thick film is (0-30): (100-70), and BZT thick film has the feature of ferroelectric relaxation below transition temperature; Its specific inductivity 4300, dielectric loss is 1%.
Compared with the prior art, beneficial effect of the present invention is:
The invention provides a kind of BZT thick film with EC effect, owing to the addition of Zr to change the phase transition temperature of BaTiO3 in prepared BZT thick film, obtain being tending towards the larger EC effect of room temperature.Prepared thick film shows the feature of ferroelectric relaxation below transition temperature, and its specific inductivity 4300, reduces dielectric loss, BZT thick film is improved in quoting, improves result of use.
Present invention also offers a kind of BZT thick film preparation method with EC effect, utilize casting method (Tapecasting) to prepare BZT thick film, in BZT ((0-30): (100-70)) thick film systems, obtaining enthalpy change by indirect measuring technology is 2.8-5J.Kg
-1.K
-1eC effect.This technology is find new refrigerating material to provide a new way.
Accompanying drawing explanation
Fig. 1 is the sintering process of BZT thick film of the present invention;
Fig. 2 is the SEM figure of BZT thick film of the present invention;
Fig. 3 is the normal characteristic curve diagram of the dielectric of BZT thick film of the present invention, wherein, and the temperature profile graphic representation that (a) is the specific inductivity of BZT thick film, the temperature profile graphic representation of the specific inductivity loss that (b) is BZT thick film;
Fig. 4 is the temperature profile graphic representation of BZT thick-film dielectric performance of the present invention, and wherein, the P-Eloop graphic representation that (a) is BZT thick film, (b) is the P-T graphic representation of BZT thick film under not same electric field.
Fig. 5 is the Entropy Changes figure of BZT thickness of the present invention under differing temps not same electric field.
Concrete enforcement
Below in conjunction with accompanying drawing, the present invention is described in detail.
The invention provides a kind of BZT thick film with EC effect and preparation method thereof, BZT thick film prepared by the BZT thick film preparation method that the BZT thick film with EC effect has EC effect, the Zr:Ti mol ratio of described BZT thick film is (0-30): (100-70), and BZT thick film has the feature of ferroelectric relaxation below transition temperature; Its specific inductivity 4300, dielectric loss is 1%.
Embodiment one
The invention provides a kind of preparation method with the BZT thick film of EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be that 1:1:0.3 weighs according to mass ratio, ball milling, then carries out pre-burning 2 hours at 1200 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, curtain coating agent A is made up of according to arbitrary proportion the PVB of the ethanol of 95% and the mixing solutions of butanone and 5%; Curtain coating agent B by concentration be 65 ~ 70% ethanol and the mixing solutions of butanone, concentration be 20 ~ 25% PVB and concentration be that 10 ~ 15% softening agent form according to arbitrary proportion; Wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:0.2:0.3;
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
Embodiment two
The invention provides a kind of preparation method with the BZT thick film of EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2be that 1:0.7 weighs according to mass ratio, ball milling, then carries out pre-burning 8 hours at 900 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, curtain coating agent A is made up of according to arbitrary proportion the PVB of the ethanol of 90% and the mixing solutions of butanone and 10%; Curtain coating agent B by concentration be 70% ethanol and the mixing solutions of butanone, concentration be 25% PVB and concentration be that 15% softening agent forms according to arbitrary proportion; Wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:0.6:0.6;
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
Embodiment three
The invention provides a kind of preparation method with the BZT thick film of EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be that 1:0.8:0.2 weighs according to mass ratio, ball milling, then carries out pre-burning 6 hours at 1000 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, curtain coating agent A is made up of according to arbitrary proportion the PVB of the ethanol of 94% and the mixing solutions of butanone and 8%; Curtain coating agent B by concentration be 68% ethanol and the mixing solutions of butanone, concentration be 24% PVB and concentration be that 12% softening agent forms according to arbitrary proportion; Wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:0.4:0.4;
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
Embodiment four
The invention provides a kind of preparation method with the BZT thick film of EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be that 1:0.9:0.3 weighs according to mass ratio, ball milling, then carries out pre-burning 7 hours at 1100 DEG C, obtains pre-burning powder; As shown in Figure 1.
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, curtain coating agent A is made up of according to arbitrary proportion the PVB of the ethanol of 95% and the mixing solutions of butanone and 8%; Curtain coating agent B by concentration be 68% ethanol and the mixing solutions of butanone, concentration be 24% PVB and concentration be that 12% softening agent forms according to arbitrary proportion; Wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:0.5:0.3;
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
Embodiment five
The invention provides a kind of preparation method with the BZT thick film of EC effect, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be that 1:0.6:0.1 weighs according to mass ratio, ball milling, then carries out pre-burning 6 hours at 1000 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with Tape-casting slurry, wherein, curtain coating agent A is made up of according to arbitrary proportion the PVB of the ethanol of 95% and the mixing solutions of butanone and 5%; Curtain coating agent B by concentration be 68.4% ethanol and the mixing solutions of butanone, concentration be 21.1% PVB and concentration be that 10.5% softening agent forms according to arbitrary proportion; Wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:0.2:0.5;
3) BZT thick film preparation
The Tape-casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
As shown in Figure 2, BZT thick film prepared by the BZT thick film preparation method that the present invention has prepared a kind of EC of having effect, SEM is utilized to observe the structure of BZT thick film, the Zr:Ti mol ratio of described BZT thick film is 15:85, Fig. 3 (a), (b) and Fig. 4 (a), b () is the temperature profile of the dielectric properties of BZT thick film respectively, wherein, the temperature profile curve that Fig. 3 (a) is the specific inductivity of BZT thick film, the temperature profile of the specific inductivity loss that Fig. 3 (b) is BZT thick film, Fig. 4 (a) is the P-Eloop of BZT thick film, the P-Eloop of Fig. 4 (b) BZT thick film, BZT thick film has the feature of ferroelectric relaxation below transition temperature, its specific inductivity 4300, dielectric loss is 2%.
The EC effect of BZT (Zr:Ti=(0-30): (100-70)) thick film:
Indirect measuring technology: being by measuring P-Eloop at different temperature, drawing P (T) curve, utilize formula 1 to calculate Δ S.
Ferroelectric measuring system is utilized to record P-Eloop under differing temps, as Fig. 4 (a); Thus P (T) curve under obtaining not same electric field, as Fig. 5, by P (T) curve, utilize formula (1) to calculate Δ S, its Midst density is 3.9g/cm
3, its result as shown in Figure 5.We obtain 2.8-5J.Kg near the phase transition temperature of BZT thick film
-1.K
-1eC effect.
Claims (2)
1. there is a BZT thick film preparation method for EC effect, it is characterized in that, comprise the following steps:
1) preparation of pre-burning powder
By BaCO
3, TiO
2, ZrO
2be 1:(0.7-1 according to mass ratio): (0.1-0.3) weighs, ball milling, then carries out pre-burning at 900-1200 DEG C, obtains pre-burning powder;
2) preparation of slurry
Pre-burning powder is carried out ball milling, after adding curtain coating agent A and curtain coating agent B, is mixed with casting slurry, wherein, the mass ratio of pre-burning powder and curtain coating agent A and curtain coating agent B is 1:(0.2-0.6): (0.3-0.6); Described curtain coating agent A by concentration to be the ethanol of 90 ~ 95% and the mixing solutions of butanone and concentration be 5 ~ 10% PVB form according to arbitrary proportion; Described curtain coating agent B by concentration be 65 ~ 70% ethanol and the mixing solutions of butanone, concentration be 20 ~ 25% PVB and concentration be that 10 ~ 15% softening agent form according to arbitrary proportion;
3) BZT thick film preparation
The casting slurry prepared is carried out curtain coating processing, makes film; Utilize view printing press to make electrode on film, the thin-film material with electrode is laminated, make BZT thick film, finally carry out sinter molding.
2. the BZT thick film preparation method with EC effect according to claim 1, is characterized in that, described step 1) the sintering time of pre-burning be 2-8 hour.
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| CN105236960A (en) * | 2015-09-15 | 2016-01-13 | 奈申（上海）智能科技有限公司 | Barium-titanate-based colossal-electrocaloric-effect chip-type laminate ceramic electrocaloric refrigeration device |
| CN106348754B (en) * | 2016-08-18 | 2019-08-27 | 广东工业大学 | A kind of barium zirconium phthalate ceramic thick film and its preparation method and application |
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| CN101436597A (en) * | 2008-12-10 | 2009-05-20 | 华中科技大学 | Ferro-electricity film capacitor for ferro-electric memory and preparation method thereof |
| CN102241511A (en) * | 2010-05-11 | 2011-11-16 | 中国科学院上海硅酸盐研究所 | Ferroelectric-antiferroelectric (FE-AFE) phase change pyroelectric ceramic material, ceramic element thereof and preparation methods of material and element |
| CN103214241A (en) * | 2013-05-03 | 2013-07-24 | 聊城大学 | Barium titanate-based lead-free piezoelectric luminous material and preparation method thereof |
| CN103981573A (en) * | 2014-05-21 | 2014-08-13 | 宁波大学 | Method for improving curie temperature of perovskite structure ferroelectric material |
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| CN1623954A (en) * | 2004-11-02 | 2005-06-08 | 清华大学 | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method |
| CN101436597A (en) * | 2008-12-10 | 2009-05-20 | 华中科技大学 | Ferro-electricity film capacitor for ferro-electric memory and preparation method thereof |
| CN102241511A (en) * | 2010-05-11 | 2011-11-16 | 中国科学院上海硅酸盐研究所 | Ferroelectric-antiferroelectric (FE-AFE) phase change pyroelectric ceramic material, ceramic element thereof and preparation methods of material and element |
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