CN103541014A - Lead-free high-voltage active crystal material and preparation method thereof - Google Patents

Lead-free high-voltage active crystal material and preparation method thereof Download PDF

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CN103541014A
CN103541014A CN201310479704.7A CN201310479704A CN103541014A CN 103541014 A CN103541014 A CN 103541014A CN 201310479704 A CN201310479704 A CN 201310479704A CN 103541014 A CN103541014 A CN 103541014A
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crystal
preparation
piezoelectric
high voltage
voltage electric
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陈建军
郑燕青
涂小牛
孔海宽
涂一帆
杨建华
施尔畏
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Priority to PCT/CN2014/083035 priority patent/WO2015055034A1/en
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/32—Titanates; Germanates; Molybdates; Tungstates

Abstract

The invention relates to a lead-free high-voltage active crystal material and a preparation method thereof. The chemical formula of the crystal material is Ba(1-x)CaxTi(1-y)ZryO3, wherein x=0.005-0.5, y=0.005-0.5, and space group is 99. The BCZT crystal material provided by the invention, compared with a ceramic material thereof, has greatly improved piezoelectric property, wherein a piezoelectric constant is that d33=300-5000pC/N. The invention provides the method and a patch for converting lead-free piezoelectric ceramic Ba(1-x)CaxTi(1-y)ZryO3 (BCZT) into lead-free piezoelectric crystal. For a first time, a pluralistic complicated ceramic material is converted into a complicated monocrystalline material, such that material performance and application are greatly improved and expanded.

Description

Unleaded high voltage electric active crystal material and preparation method thereof
Technical field
The present invention relates to a kind of leadless piezoelectric crystal novel, that there is high voltage electric activity, belong to electronic functional material technical field, further belong to piezoquartz field.
Background technology
Since Curie brother in 1880 finds that piezoelectric effect starts, until the mid-40 in 20th century piezoelectric effect in material engineering since concrete application, piezoelectric is more and more extensive at hyundai electronics and message area application, in each civilian and military industry such as communication, electronics, laser, ultrasonic, navigation, get a lot of applications, become a class material very important in various functional materialss.Through the development and application of decades, piezoelectric ceramics or the piezoquartz at present with large piezoelectric activity are all to contain plumbous material, and lead tolerance is quite large.The extensive piezoceramic material system with large piezoelectric activity of using is mainly lead base piezoelectric ceramics, i.e. PbTiO in the market 3-PbZrO 3, PbTiO 3-PbZrO 3-ABO 3(ABO 3for composite perofskite type ferroelectrics) and PbTiO 3the piezoelectric ceramics such as system, its main component is plumbous oxide (more than 60%-70%); The crystalline material PMNT with good piezoelectric activity, its main component is also plumbous oxide.Because plumbous oxide is a kind of toxic substance; when high temperature sintering, can volatilize in a large number; cause the Lead contamination to environment; to human health, bring very large harm; lead base piezoelectric produce, use and discarded last handling process in all can bring serious harm to the mankind and ecotope, be dissolved in the lead in acid rain, can be by water and animals and plants and direct or indirect invasion human body; the neural system of plumbous major effect human body, this is against in the requirement of human development and environment protection.Meanwhile, lead base piezoelectric ceramics needs sealed sintering in preparation process, has not only increased production cost, has also caused the consistency of performance of product poor.Therefore the piezoceramic material of researching and developing novel environmental close friend has become one of focus material of World Developed Countries research and development.
Calendar year 2001, European Parliament passed through the decree about " limiting objectionable impurities in electrical equipment and electronics ", and wherein leaded piezoelectric device is exactly to be limited one of objectionable impurities of using, and this decree was implemented due to 2008.For this reason, 1,510,000 Euros of research and development of carrying out non-plumbous series piezoelectric ceramic of European Community's project verification.On February 13rd, 2003, parliament of European Union and EU Committee have issued again < < about using the instruction > > (2002/95/EC of the alliance instruction of some objectionable constituent in being limited in electronic electric equipment on its < < Official Journal > >, be called for short ROHS (Restriction of Hazard Ousmaterials)), in this instruction restriction electronic product, lead content must not surpass 0.1%(and refer to massfraction).< < RoHS > > instruction regulation was from 1 day July in 2006, in the electric/electronic device product of newly putting on market, forbid or limit 6 kinds of objectionable impuritiess such as using lead, mercury, cadmium, sexavalent chrome, polybromodiphenyl ether (PBDE) and Polybrominated biphenyl (PBB).
The instruction > > that also has < < electronics and electric installation waste simultaneously promulgating with RoHS, conventionally be called for short WEEE (Waste Electrical and Electronic Equipment), these two instructions are called for short two instructions conventionally, their object is to reduce the negative impact of electronic product to environment with legal means, therefore also referred to as " green instruction ".And said unleaded in most of occasions at present, in fact refer to the unleaded of broad sense, implement " green instruction " relevant systems engineerings such as various decrees, policy, standard, product and technology, and be not only unleaded manufacture.The appearance of " green instruction " is the sign of human civilization progress, and unleaded enforcement shows that the mankind have started to face electronic waste pollution problem, and it has become irreversible trend.Our only one earth, develops the economy and should not take contaminate environment as cost.People-oriented, and humanistic care is world today's main flow.To the such electronics manufacture developing rapidly of China and consumption big country, if only say economy, ignore environment protection, not only harm is contemporary, and misfortune and descendants.Protection of the environment will be paid a price, and unleadedly means equally that electronics manufacture can not be pursued unrestrictedly simply and excessively manufactures in enormous quantities, and unleaded difficulty is considerably beyond common people's understanding.
The present economic trade Estate Division METI of in April, the 1997 Japan internationality trade industry MITI(of portion), lead content in car industry product (except battery) has been formulated to a series of target, regulation " in product in 2000 plumbous mass content be reduced to 1996 50%, to 2005 be reduced to 1996 1/3 ".The U.S. and China also will be in succession by similar decrees, and improved year by year the supporting dynamics to development leadless piezoelectric ceramics project.Along with being rooted in the hearts of the people of human social, develop unleaded environment compatibility piezoelectric ceramics become one urgent and there is the problem of Great significance.Leadless piezoelectric ceramics, be also referred to as environment compatibility piezoelectric ceramics, it requires stupalith not only to have satisfied use properties but also have good environment compatibility, require material system itself not contain the hurtful material of ecotope possibility (particularly plumbous), and in preparation, use, waste treatment process, do not produce may be harmful to environment material, and preparation technology should have power consumption less, the good environment compatibility such as environmental pollution is little.
Therefore, study, prepare and develop good leadless piezoelectric material material the mankind's survival and development are all had great importance.The research of leadless piezoelectric material material mainly be take piezoelectric ceramics as main, and from the sixties in 20th century, scientific research personnel has just started take niobate and titanate is the research of master's perovskite structure leadless piezoelectric ceramics.Up to now, leadless piezoelectric ceramics mainly contains following several system.
1.1BaTiO 3base piezoelectric ceramic
BaTiO 3base piezoelectric ceramic research comparative maturity, is practical the earliest piezoelectric ceramics, belongs to ABO 3type perovskite structure, when room temperature, has very high specific inductivity, larger electromechanical coupling factor, has relatively high piezoelectric constant (d 33can reach 190pC/N) and less loss, but due to low curie point (120 ℃) with exist ferroelectric four directions to the transformation temperature of quadrature near 5 ℃, so Applicable temperature interval is very narrow, near room temperature temperature stability is poor.Therefore can not substitute lead titanate piezoelectric ceramics (PZT) in the widespread use in piezoelectricity ferro field, be mainly because following not enough: Curie temperature not high (Tc=120 ℃), the time of performance and temperature stability are also poor; There is phase transformation near room temperature, dielectricity, piezoelectricity, elastic performance noticeable change, and operation temperature area is narrow; Piezoelectric property is compared with leaded series ceramic, also has certain gap, and is difficult to significantly improve its performance by doping vario-property; Need high temperature sintering (1300-1350 ℃), and there is certain difficulty in sintering; Be difficult to change performance to meet the different needs by doping.These shortcomings have limited its application to a great extent, for example can not be for powerful transverter.
1.2 laminated structure bismuth piezoelectric ceramic
Piezoelectricmaterials is found in 1949 by people such as Aurivllius, and its structure is analyzed.Piezoelectricmaterials is generally by chemical general formula (Bi 2o 2) 2+(A x-1b xo 3x+1) 2-represent, this compounds is by two-dimentional uhligite and bismuth layer (Bi 2o 2) 2+well-regulated being arranged alternately with each other forms.Laminated structure bismuth piezoelectric ceramic has low-k, high-curie temperature, electromechanical coupling factor anisotropy obviously, the character such as high resistivity, low aging rate and sintering temperature and low, be particularly suitable for high-temperature high-frequency occasion, solved the lower unsettled defect of PZT ceramic performance of superpower resonance.This class stupalith also has following shortcoming: crystalline structure determines that its spontaneous turning to is subject to two dimensional constraint, causes piezoelectric activity low; Coercive field (Ec) is too high is unfavorable for polarization.In order to improve bismuth laminated piezoelectric activity, conventionally adopt two kinds of methods, doping vario-property and process modification reduce its Ec, improve piezoelectric activity, thereby with it, manufacture the parts such as piezoelectric filter, vibrator, piezo-resonator.
Research shows: Nb 5+and V 5+ion mixes respectively Bi 4ti 3o 12, the Ti of replacement B position 4+can improve its resistivity, after doping, can obtain relative density and reach more than 95% densification pottery, and by donor doping, resistivity improves greatly, and the raising of resistivity can improve polarization performance effectively, as Bi 4ti 2.86nb 0.14o 12d 33can reach 20.0pC/N, and after V doping, can, when not reducing other character, Pr be improved to 40 * 10 -6c/cm.
In addition, by new manufacture craft, can improve ceramic microstructure, thereby improve the piezoelectric property of non-lead piezoelectric ceramics, by controlling the grain orientation of this class pottery in technique, can make material there is needed optimum performance in a direction.Adopt suitable heat treatment technics can at high temperature make, in crystal grain, dislocation motion and intercrystalline Grain Boundary Sliding occur, ceramic crystalline grain is realized and aligned.TAKEUCHI adopts respectively the texturing CaBi obtaining after curtain coating and extrusion process orientation 4ti 40 15the electric property of pottery compares they and the pottery of arbitrary orientation simultaneously, and electric property ceramic after crystal grain orienting has obtained effective raising.
1.3 niobate system piezoelectric ceramics
Niobate lead-free piezoelectric ceramics is mainly divided into base metal niobate pottery and tungsten bronze structure niobate ceramics.
1.3.1 base metal niobate is ceramic
LiNbO 3, NaNbO 3, KNbO 3piezoelectricity Deng compound crystal is larger, comes into one's own in early days mainly as photoelectric material.Nineteen fifty-nine, American scholar has been studied KNbO 3-NaNbO 3the piezoelectricity of pottery, this is the beginning of base metal niobate ceramic research.The traditional ceramic preparation technologies of employing such as YiPing Guo have obtained fine and close KNbO 3-NaNbO 3-LiNbO 3ternary system piezoelectric ceramics, its Curie temperature is up to 450 ℃, piezoelectric constant d 33can reach 235pC/N.Nature reports that in November, 2004 research and development department of Japanese Toyota Company has succeeded in developing the lead-free piezoceramic material that piezoelectric property is suitable with lead base piezoelectric ceramics, (K 0.5na 0.5) NbO 3and LiTaO 3mix according to a certain percentage, use traditional ceramics preparation method sintering, can obtain piezoelectric constant d 33polycrystalline ceramics for 235pC/N; If use active template legal system for highly-textured pottery, and a small amount of Sb modification of adulterating, piezoelectric constant d can be obtained 33up to the textured ceramic of 416pC/N, this piezoelectric ceramics performance almost can be equal to mutually with commercial PZT piezoelectric ceramics, but because preparation process is complicated, cost is too high, therefore can't become to produce on a large scale.Base metal niobate pottery is mainly used in the flexible transverter of high frequency thickness aspect now.
1.3.2 tungsten bronze structure niobate ceramics
Tungsten bronze compounds is the Equations of The Second Kind ferroelectrics inferior to (class) perovskite-type compounds.It is characterized in that existing [BO 6] (B is Nb to formula oxygen octahedra 5+, Ta 5+or W 6+plasma), tungsten bronze structure niobate compound pottery has material impact at composition and constructional difference to its ferroelectric properties, this class pottery has the features such as spontaneous polarization strength is large, Curie temperature is higher, specific inductivity is lower, therefore be mainly used in high frequency field.Found in recent years that rare earth element replaced and can improve its piezoelectric property in A position, this field more and more comes into one's own.
1.4 bismuth-containing perovskite typed piezoelectric ceramics
Bi 0.5na 0.5tiO 3(BNT) be the representative of this type of pottery, it is to be found first by Smolenskii nineteen sixty, and BNT pottery has the following advantages: the large (k of electromechanical coupling factor anisotropy tapproximately 50%, k pbe about 13%), Curie temperature is up to 320 ℃, relative permittivity less (240-340), acoustical behavior is good, and application is better than PZT aspect ultrasonic, and sintering temperature is low, generally below 1200 ℃.The superperformance of BNT base pottery causes that numerous scholars note, are considered to one of lead-free systems most possibly replacing lead base piezoelectric ceramics.It has perovskite structure, has equally the features such as piezoelectric activity is low, Ec is large, mainly by adding multiple perovskite structure hotchpotch, it is carried out to modification at present, and a lot of scholars do a lot of work for this reason.
In a word; although comparing with lead base piezoelectric ceramics, the performance of leadless piezoelectric ceramics also there is larger gap; but along with the raising of people to environment protection understanding; along with scientific and technological development and progress; in the near future, leadless piezoelectric ceramics even other equivalent material be bound to occupy very large share in whole piezoceramic material and application thereof.Therefore leadless piezoelectric ceramics or piezoelectric crystal material that, development has a high voltage electric activity have very major and immediate significance.
Owing to having very outstanding piezoelectric properties, lead-based perovskite structured material is at present most widely used general (as PbZr xti (1-x)o 3system's pottery, is abbreviated as PZT) and most study, as (1-x) Pb (Mg 1/3nb 2/3) O 3-PbTiO 3crystal, is abbreviated as the piezoelectric of PMNT, is usually used in making the piezoelectric devices such as sensor, transverter.Yet, these plumbum-based materials have all been used virose plumbous oxide (PbO) and have been made raw material, and PbO easily volatilization in the preparation process of plumbum-based material in use also easily enters surrounding environment or human body, cause environmental pollution, seriously jeopardize the healthy of people.Along with the day by day raising of society to environmental protection requirement, plumbum-based material will be eliminated alternative gradually.Under this background, research and development leadless piezoelectric material material has become a large study hotspot in current investigation of materials field.
Closely during the last ten years, people have successively developed many leadless piezoelectric material materials, as (Na 0.5bi 0.5) TiO3(NBT), (Na 0.5bi 0.5) TiO 3-BaTiO 3(NBBT), BaZr xti (1-x)o 3(BZT), Ba (1-x)ca xtiO 3(BCT) etc., regrettably, the piezoelectricity of these lead-free is all not as plumbum-based material.The researchs such as nearest W.F.Liu are found, at unleaded (1-x) BaZr that approaches accurate homotype phase boundary (morphotropic phase boundary, MPB) 0.2ti 0.8) O 3-x (Ba 0.7ca 0.3) TiO 3be in pottery, to have found to have up to now the piezoelectric activity (d that leadless piezoelectric material material is the highest 33=560～620pC/N, x=0.5), have again subsequently report to find at Ba (1-x)ca xti 0.98zr 0.02o 3in pottery, also there is high voltage electric activity (d 33=375pC/N, x=0.01), people have been caused thus to Ba (1-x)ca xti (1-y) Zr yo 3(BCZT) be the research boom of leadless piezoelectric material material.As everyone knows, for ferroelectricity piezoelectric, crystal piezoelectric property is far better than same component pottery, although this has been also that the very difficult growth of PZT monocrystalline has people constantly to make great efforts the reason of attempting since the widespread use of PZT pottery always.So, to the BCZT system pottery with high voltage electric activity of latest report, it also will have very high piezoelectric activity with component crystal accordingly.Therefore, if can grow, obtain the electrical BCZT crystal of high pressure, will greatly promote development and the application of environmentally friendly non-plumbum ferroelectric crystalline material, but there is no up to now the report of relevant BCZT crystal growth.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide eco-friendly high-performance Pb-free novel ferroelectric BCZT crystal, thereby make to there is high voltage electric activity, the exploration of unleaded crystalline material comes true.
At this, on the one hand, the invention provides a kind of unleaded high voltage electric active crystal material, the chemical formula of described crystalline material is Ba (1-x)ca xti (1-y) Zr yo 3(be called for short BCZT), x=0.005～0.5 wherein, y=0.005～0.5; Spacer is 99.
BCZT crystalline material of the present invention, compares with its stupalith, and piezoelectric property is greatly improved, and wherein piezoelectric constant is d 33=300～5000pC/N.
In the present invention, preferably, x=0.005～0.2, y=0.005～0.2; More preferably, x=0.01, y=0.02, and there is maximum piezoelectric activity.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned unleaded high voltage electric active crystal material, comprising: with BaCO 3, CaCO 3, TiO 2and ZrO 2powder is that raw material is prepared burden by stoichiometric ratio, adds TiO 2and/or ZrO 2powder, as fusing assistant, is prepared the operation A of polycrystal through ball milling, briquetting and sintering; Described polycrystal is placed in to crucible and adopts after intermediate frequency or resistance-type type of heating heating and melting the process B with Czochralski grown crystal; And the crystal after growth is finished is lifted from melt and is down to the operation C of room temperature.
In the present invention, by BaTiO 3crystal (ABO 3) carry out the doping of A position and B position simultaneously, select the fusing assistant (TiO for example of suitable ingredients 2and/or ZrO 2), by crystal pulling method (Czochralski method), carrying out crystal growth, the solid-solution type crystal obtaining is the leadless piezoelectric crystal with high voltage electric activity.
Select suitable fluxing agent growth BCZT crystal, can reduce its growth temperature, avoid separating out six side's phase BaTiO 3the high-temperature zone of crystal, thus avoid cracked from the six sides caused crystal of reconstruct that Perovskite Phase changes in opposite directions in temperature-fall period, therefore can from melt, grow and obtain the BCZT solid-solution type crystal of large-size.In the present invention, for fear of introducing new impurity when effectively reducing crystal growth temperature, being preferably, adopt the precursor of described BCZT component that crystalline material comprises to make fusing assistant, select the precursor TiO corresponding to B bit element of described BCZT crystal 2and/or ZrO 2make fusing assistant.
In described operation A, as the TiO of fusing assistant 2with ZrO 2mol ratio be preferably (5～30): 1.
Again, in described operation A, the weight percent that described fusing assistant accounts for described raw material is 10%～60%, is preferably 15%～30%, thereby more effectively reduces crystal growth temperature.
In described operation A, be preferably and adopt purity to be not less than 99.99% high-purity raw again.
Again, in described operation A, described sintering should make carbonate (BaCO 3, CaCO 3) fully decompose and react the composite crystals polycrystal used of growing, preferably can be under air atmosphere in 1000～1500 ℃ of sintering 10～40 hours.
In described process B, the pull rate of described crystal pulling method can be 0.2～5mm/24h, is preferably 1～1.5mm/24h.Speed of rotation can be 1～30rpm, is preferably 3～5rpm.
Again, in described process B, the rate of temperature fall of described crystal pulling method can be 0.5～5 ℃/day, is preferably 1～2 ℃/day.
Again, in described process B, described Czochralski grown crystal can carry out in oxygen, air or inert gas atmosphere, is preferably in air atmosphere and carries out.
In described operation C, the crystal after growth can being finished is lifted from melt 5～10mm, and lowers the temperature with the rate of temperature fall of 30～60 ℃/h.
The present invention has realized leadless piezoelectric ceramics Ba (1-x)ca xti (1-y) Zr yo 3(BCZT) change method and the approach of leadless piezoelectric crystal into, the single crystal material that is a kind of complexity by a kind of ceramic body material transition of polynary complexity first, makes the performance of material and application be greatly enhanced and expand.
Accompanying drawing explanation
Fig. 1 illustrates BCZT crystal of the present invention with the block diagram of Czochralski grown;
Fig. 2 is the photo of the embodiments of the invention 1 BCZT crystal of growing, and wherein Fig. 2 (a) is the whole photo of BCZT crystal, and Fig. 2 (b) is the crystal block photo in processing sample making course;
Fig. 3 is the embodiments of the invention 2 BCZT crystal of growing and the photo of c pellet thereof.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that following embodiment is only for the present invention is described, and unrestricted the present invention.
The present invention has realized quaternary lead-free piezoceramic material a kind of environmental sound, that have high voltage electric activity---barium calcium zirconate titanate (Ba (Ti 0:8zr 0:2) O 3-x (Ba 0:7ca 0:3) TiO 3, BTZ-x BCT, or BCZT) and the growth of crystal.In the present invention, by BaTiO 3crystal (ABO 3) carry out A position and the doping of B position simultaneously, select the fusing assistant of suitable ingredients, by the growth of crystal pulling method (Czochralski method) crystal, the solid-solution type obtaining has the leadless piezoelectric crystal of high voltage electric activity.
First, the invention provides a kind of unleaded high voltage electric active crystal material, the chemical formula of described crystalline material is Ba (1- x)ca xti (1-y) Zr yo 3(being called for short BCZT), x=0.005～0.5 in formula, y=0.005～0.5; X=0.005～0.2 preferably, y=0.005～0.2; X=0.01 more preferably, y=0.02, now described crystalline material has maximum piezoelectric activity.The spacer of described crystalline material is 99.
Compare with its stupalith, the piezoelectric property of BCZT crystalline material of the present invention is greatly improved, and wherein piezoelectric constant is d 33=300～5000pC/N.
In the present invention, by BaTiO 3crystal (ABO 3) carry out A position and the doping of B position simultaneously, select the fusing assistant of suitable ingredients, by the growth of crystal pulling method (Czochralski method) crystal, the solid-solution type crystal obtaining is the BCZT crystal with high voltage electric activity.
From BaO-TiO 2phasor can be seen, BaTiO 3what first crystal separated out from its high-temperature fusant is six side's phases.Owing to there is very big-difference in six side's phases and common Perovskite Phase on atom stack manner, in temperature-fall period, from the six sides reconstruct that Perovskite Phase changes in opposite directions, will cause that crystal is cracked, cause being difficult to directly the pure BaTiO that from its melt growth obtains large-size 3or the solid-solution type crystal of its doping.Therefore, we will adopt flux method (Flux method) growth BCZT crystal, thereby reduce growth temperature, the high-temperature zone of avoiding separating out six side's phases.For fear of introduce new impurity when effectively reducing crystal growth temperature, people normally preferentially select the precursor of the component that crystal comprises of growth to make fusing assistant, select Na during as growth NBBT crystal 2o makees fusing assistant, during growth PMNT, selects PbO to make fusing assistant etc.Equally, we,, when growth BCZT crystal, also select precursor TiO corresponding to crystal B bit element 2and/or ZrO 2make fusing assistant.
Fig. 1 illustrates BCZT crystal of the present invention with the block diagram of Czochralski grown.With reference to Fig. 1, the preparation method of BCZT crystalline material of the present invention comprises: with BaCO 3, CaCO 3, TiO 2and ZrO 2powder is that raw material is prepared burden by stoichiometric ratio, adds TiO 2and/or ZrO 2powder, as fusing assistant, is prepared polycrystal through ball milling, briquetting and sintering; Described polycrystal is placed in to crucible adopts after intermediate frequency or resistance-type type of heating heating and melting with Czochralski grown crystal; And crystal after growth is finished is lifted from melt and is down to room temperature.
For the Zr in maintenance melt and gained crystal and the ratio of Ti element, in an example embodiment, select TiO 2with ZrO 2mol ratio be (5～30): 1 binary mixed oxide is made fusing assistant.
In another example embodiment, for effectively reducing crystal growth temperature, the consumption of described fusing assistant adds by 10%～60% of proportioning raw material, is preferably by 15%～30% of proportioning raw material and adds.
In another example embodiment, after preparation of raw material completes, carry out sufficient ball milling mixing, briquetting then in 1000～1500 ℃ of sintering 10～40 hours, fully decomposes carbonate and reacts the composite crystals polycrystal used of growing under air atmosphere.
In another example embodiment, in oxygen, air or inert gas atmosphere, with Czochralski grown crystal, be preferably air atmosphere.
In another example embodiment, pull rate is 0.2～5mm/24h, is preferably 1～1.5mm/24h.。
In another example embodiment, speed of rotation is 1～30rpm, is preferably 3～5rpm.
In another example embodiment, the rate of temperature fall of crystal pulling method is 0.5～5 ℃/day, is preferably 1～2 ℃/day.
In another example embodiment, the crystal after growth is finished is lifted from melt 5～10mm, and lowers the temperature with the rate of temperature fall of 30～60 ℃/h.
The present invention has realized leadless piezoelectric ceramics Ba (1-x)ca xti (1-y) Zr yo 3(BCZT) change method and the approach of leadless piezoelectric crystal into, the single crystal material that is a kind of complexity by a kind of ceramic body material transition of polynary complexity first, makes the performance of material and application be greatly enhanced and expand.
Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and all belong to protection scope of the present invention., those skilled in the art can do in suitable scope and be selected by explanation herein the temperature of reaction that following example is concrete, time, charging capacity etc. are only also examples in OK range,, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
By purity, be not less than high-purity BaCO of 99.99% 3, CaCO 3, TiO 2and ZrO 2powder is as starting raw material, by these four kinds of powders according to Ba 0.85ca 0.15ti 0.9zr 0.1o 3carry out proportioning.Meanwhile, selection percentage is TiO 2: ZrO 2=9 binary mixed oxide is made fusing assistant, and the consumption of binary mixed flux adds by the 25wt% of said ratio raw material.After preparation of raw material completes, carry out sufficient ball milling mixing, briquetting then, in air atmosphere, at 1250 ℃ of temperature, sintering is 20 hours, carbonate is fully decomposed and react the composite crystals polycrystal used of growing.
This synthesised polycrystalline material is positioned in platinum crucible, in resistance-type heating crystal growing furnace, under air atmosphere, heats polycrystal until melt.The seed crystal that crystal growth adopts is the BaTiO of <001> direction 3seed crystal, due to the existence of fusing assistant, and the impact of fusing assistant volatilization, do not have fixing inoculation temp, need to repeatedly plant experimentally just and can find suitable inoculation temp, after finding suitable inoculation temp, seed crystal be contacted to liquid level and start to carry out pulling crystal growth.Crystal growing and pulling speed is that 1～1.5mm/24h, rotation rotating speed are more applicable while being about 3～5rpm, cooling rate is 1-2 ℃/day, after crystal growth finishes, crystal is lifted and departs from the about 5-10mm of liquid level, with the speed slow cooling of 50 ℃/h to room temperature, blow-on just can obtain BCZT crystal, and the crystal block photo in its whole photo and processing sample making course as shown in Figure 2.The piezoelectric constant of the prepared BCZT crystal of the present embodiment is d 33=600～1200pC/N.
Embodiment 2
By purity, be not less than high-purity BaCO of 99.99% 3, CaCO 3, TiO 2and ZrO 2powder is as starting raw material, by these four kinds of powders according to Ba 0.75ca 0.25ti 0.9zr 0.1o 3carry out proportioning.Meanwhile, selection percentage is TiO 2: ZrO 2=18 binary mixed oxide is made fusing assistant, and the consumption of binary mixed flux adds by the 30wt% of said ratio raw material.After preparation of raw material completes, carry out sufficient ball milling mixing, briquetting then, in air atmosphere, at 1250 ℃ of temperature, sintering is 30 hours, carbonate is fully decomposed and react the composite crystals polycrystal used of growing.
This synthesised polycrystalline material is positioned in platinum crucible, in resistance-type heating crystal growing furnace, under air atmosphere, heats polycrystal until melt.The seed crystal that crystal growth adopts is the BaTiO of <001> direction 3seed crystal, repeatedly plants experimentally and finds after suitable inoculation temp, seed crystal is contacted to liquid level and start to carry out pulling crystal growth.Crystal growing and pulling speed is that 1～1.5mm/24h, rotation rotating speed are about 3～5rpm, cooling rate is 1-2 ℃/day, after crystal growth finishes, crystal is lifted and departs from the about 5-10mm of liquid level, with the speed slow cooling of 40 ℃/h to room temperature, blow-on just can obtain BCZT crystal, and its whole photo and c pellet are as shown in Figure 3.The piezoelectric constant of the prepared BCZT crystal of the present embodiment is d 33=500～1300pC/N.
Industrial applicability: novel lead-free piezoquartz environmental friendliness of the present invention, there is good piezoelectric property, preparation technology is simple, can be applied to the piezoelectric device fields such as sensor, transverter.

Claims (13)

1. a unleaded high voltage electric active crystal material, is characterized in that, the chemical formula of described crystalline material is Ba (1-x)ca xti (1-y)zr yo 3, x=0.005～0.5 wherein, y=0.005～0.5; Spacer is 99.
2. unleaded high voltage electric active crystal material according to claim 1, is characterized in that x=0.005～0.2, y=0.005～0.2.
3. unleaded high voltage electric active crystal material according to claim 2, is characterized in that x=0.01, y=0.02.
4. according to the unleaded high voltage electric active crystal material described in any one in claims 1 to 3, it is characterized in that, the piezoelectric constant of described crystalline material is d 33=300～5000 pC/N.
5. a preparation method for the unleaded high voltage electric active crystal material described in any one in claim 1 to 4, is characterized in that, comprising: with BaCO 3, CaCO 3, TiO 2and ZrO 2powder is that raw material is prepared burden by stoichiometric ratio, adds TiO 2and/or ZrO 2powder, as fusing assistant, is prepared the operation A of polycrystal through ball milling, briquetting and sintering; Described polycrystal is placed in to crucible and adopts after intermediate frequency or resistance-type type of heating heating and melting the process B with Czochralski grown crystal; And the crystal after growth is finished is lifted from melt and is down to the operation C of room temperature.
6. preparation method according to claim 5, is characterized in that, in described operation A, as the TiO of fusing assistant 2with ZrO 2mol ratio be (5～30): 1.
7. according to the preparation method described in claim 5 or 6, it is characterized in that, in described operation A, the weight percent that described fusing assistant accounts for described raw material is 10%～60%.
8. preparation method according to claim 7, is characterized in that, in described operation A, the weight percent that described fusing assistant accounts for described raw material is 15%～30%.
9. according to the preparation method described in any one in claim 5 to 8, it is characterized in that, in described operation A, described sintering is in 1000～1500 ℃ of sintering 10～40 hours under air atmosphere.
10. according to the preparation method described in any one in claim 5 to 11, it is characterized in that, in described process B, the pull rate of described crystal pulling method is 0.2～5 mm/24h, and speed of rotation is 1～30 rpm.
11. preparation methods according to claim 10, is characterized in that, in described process B, the pull rate of described crystal pulling method is 1～1.5 mm/24h, and speed of rotation is 3～5 rpm.
12. according to the preparation method described in any one in claim 5 to 11, it is characterized in that, in described process B, the rate of temperature fall of described crystal pulling method is 0.5～5 ℃/day.
13. according to the preparation method described in any one in claim 5 to 12, it is characterized in that, in described operation C, rate of temperature fall is 30～60 ℃/h.
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