CN107268084B - Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method - Google Patents
Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method Download PDFInfo
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Abstract
The present invention relates to potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method, the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline chemical formula is (1-y) (KxNa1‑x)NbO3‑y(Bi0.5Na0.5)ZrO3, wherein 0.4≤x≤0.6,0≤y≤0.1.In the present invention, by raw material and growth auxiliary agent mixing pre-burning, and potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline is obtained using Bridgman-Stockbarge method for growing, Bridgman-Stockbarge method for growing crystal after growing auxiliary agent by addition has many advantages, such as to be easy to be nucleated, crystalline size larger (2~20mm) and crackle is less.
Description
Technical field
The invention belongs to piezoelectric monocrystal fields, more particularly to potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its life
Long method.
Background technique
Piezoelectric material is a kind of very important functional material, using its elastic property, dielectric properties, piezoelectric property,
Pyroelectric property, ferroelectric properties and optical property etc., so that piezoelectric material is in ultrasonic transducer, sensor, driver, filtering
The fields such as device, memory have been widely used.The piezoelectric material being most widely used at present is PZT sill, especially
It take lead magnesio-niobate (PMNT) and lead zinc niobate (PZNT) as the relaxation Ferroelectric monocrystalline of representative.Although they have very high pressure
Electrostrictive coefficient and electromechanical coupling factor, but PbO in lead base piezoelectric material (or Pb3O4) content be more than 60%, the toxicity of lead makes
Lead base piezoelectric ceramics all can bring serious harm to the mankind and ecological environment producing, use and discard in last handling process, this
Sustainable development with human society is runed counter to, therefore research and development leadless piezoelectric ceramics is one and has great social effect and warp
The project for meaning of helping.
Potassium-sodium niobate (KxNa1-xNbO3, write a Chinese character in simplified form KNN) and base leadless piezoelectricity material in the fifties in last century just has dielectric constant
Low, density is light, and Curie temperature is high, and mechanical quality factor is big, and frequency constant is big, piezoelectricity and the general feature of mechanical-electric coupling performance.
And potassium sodium niobate ceramic haves the shortcomings that consistency is low, sintering character is poor etc. during the preparation process, therefore, it is difficult to be burnt by conventional
Knot method realizes densification, causes piezoelectric property that can not compare favourably with lead material.
So far, the doping of domestic and international potassium-sodium niobate monocrystalline is mainly the doping of the elements such as Li, Sb, Ta, the life of use
Long method has high temperature flux growth metrhod, solid crystals growth method and Bridgman-Stockbarger method etc..Above the grown crystal is at 200 DEG C or so
Have a high-T_c superconductors peak, after before phase change, piezoelectric property changes very greatly, the application to material be it is extremely disadvantageous,
Piezoelectric ceramics have been reported that by be added zirconic acid bismuth sodium phase transition temperature can be made to drop near room temperature, but so far without crystal in terms of
Report.Crystal and ceramic phase ratio, there is an optimal crystalline orientation, the monocrystalline of same composition than ceramics have superior piezoelectricity, ferroelectricity,
The performances such as dielectric.Since zirconium oxide is added, common crystal growth is difficult to grow potassium-sodium niobate-zirconic acid bismuth sodium monocrystalline, brilliant
Body crystallization is poor, crystalline size smaller (usual 5mm or less) and there are many crackle.
Summary of the invention
In view of the problems of the existing technology the present invention, provides a kind of new potassium niobate sodium base leadless piezoelectric monocrystal, and
Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline potassium-sodium niobate-zirconium of bulky grain, few crackle is prepared by addition growth auxiliary agent
The growing method of sour bismuth sodium leadless piezoelectric monocrystalline.
The present invention provides a kind of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, and the potassium-sodium niobate-zirconic acid bismuth sodium is unleaded
The chemical formula of piezoelectric monocrystal is (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3, wherein 0.4≤x≤0.6,0≤y≤0.1.
The potassium-sodium niobate of the invention-zirconic acid bismuth sodium leadless piezoelectric monocrystalline crystallite dimension can be 2~20mm.
Potassium-sodium niobate of the invention-zirconic acid bismuth sodium leadless piezoelectric monocrystalline high-T_c superconductors temperature can be 70~110
DEG C, Curie temperature can be 310~330 DEG C, and piezoelectric constant can be~320pC/N.
The present invention also provides a kind of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline growing method, the growing methods
Include:
1) K is weighed according to the stoichiometric ratio of (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO32CO3、
Na2CO3、Nb2O5、Bi2O3、ZrO2Raw material powder is uniformly mixed with 0.1~10mol% growth auxiliary agent and is mixed by raw material powder
Close powder；
2) mixed powder is subjected to pre-burning, obtains crystal growth Preburning material；
3) Preburning material is put into crucible, crucible is fitted into skirt, it is small in 500~1000 DEG C of heat preservations 3~10
When, then heat to 1200~1500 DEG C, keep the temperature 6~18 hours, raw material is made all to be fused into melt, then by crucible with 0.1~
Speed decline in 1.5mm/ hours, the temperature gradient of growth interface is 10~80 DEG C/cm, is cooled to room temperature with 10~100 DEG C/h
Obtain potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
In the present invention, potassium-sodium niobate-zirconium is obtained by raw material and growth auxiliary agent mixing pre-burning, and using Bridgman-Stockbarge method for growing
Sour bismuth sodium leadless piezoelectric monocrystalline.Bridgman-Stockbarger method is also known as Bridgman method, has the advantages that one, raw material is sealed in crucible
In, influence of the volatility of raw material to uneven components and integrality is reduced, the easy control of components of crystal is made, while having been prevented
The leakage bring pollution of evil gas；Two, it can be grown big by temperature gradient or seed crystal induction nucleation, control nucleation number
The crystal of size；Three, easy to operate, and easily realize sequencing growth；It can also be grown simultaneously, can be greatly improved with multiple crucibles
Yield rate and working efficiency.A certain amount of growth auxiliary agent is added in raw material powder to grow after mixing with raw material, Ke Yigai
Twin crystal is nucleated difficulty during the growth process, and crystal grain is small, the problem more than crackle.
Preferably, the K2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2The purity of raw material powder is 99.9% or more.
Preferably, the growth auxiliary agent is copper oxide.Selective oxidation copper is because of copper oxide and crystal as growth auxiliary agent
Raw material is complete immiscible system, reduces the pollution to material；During the growth process, copper ion can also promote crystal to analyse
It is brilliant；By the addition of copper oxide, monocrystal material dissolution can be made wherein, by slowly reducing system temperature or gradually making to grow
Auxiliary agent volatilizees and precipitates crystal.
Preferably, 600~1000 DEG C of the temperature of the pre-burning, soaking time 3~6 hours.By the way that raw material and growth are helped
Agent mixing pre-burning, can make material powder preliminarily form perovskite structure, be conducive to crystal growth, while can also remove raw material and exist
The moisture absorbed in mixed process decomposes the carbanion in raw material.
Preferably, step 3) includes that the Preburning material is put into crucible, 5~10 hours are kept the temperature in 600~1000 DEG C, so
After be warming up to 1200~1350 DEG C, keep the temperature 6~10 hours.
Preferably, the decrease speed of crucible is 0.3~0.8mm/ hours in step 3), the temperature gradient of growth interface is
20~60 DEG C/cm.
Preferably, the cooling rate being cooled to room temperature is 30~50 DEG C/h in step 3).
Beneficial effects of the present invention:
The Bridgman-Stockbarger method of addition growth auxiliary agent of the present invention, solves the niobium prepared using conventional crucible descent method
What sour potassium sodium monocrystalline had be difficult to crystallization, crystalline size it is small (general size 5mm or less), crackle is more the problems such as.Pass through addition
Bridgman-Stockbarge method for growing crystal after growing auxiliary agent, which has, is easy nucleation, and crystalline size larger (2~20mm) and crackle are less etc.
Advantage.Prepared potassium-sodium niobate-zirconic acid bismuth sodium piezoelectric monocrystal is compared with the potassium-sodium niobate-based monocrystalline usually prepared, and crystal is just
Friendship-four directions phase transition temperature has and significantly reduces, and 70~110 DEG C is fallen below from 200 DEG C or so, the Curie temperature of crystal compares
Height is 310~330 DEG C, improves the use temperature range of piezoelectric monocrystal；Furthermore potassium-sodium niobate-zirconic acid bismuth sodium piezoelectric property
Also more excellent with ferroelectric properties, piezoelectric constant is~320pC/N, is had great application prospect.
Detailed description of the invention
Fig. 1 is potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline shape appearance figure of embodiment 1；
Fig. 2 is potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystal X-ray diffractogram of embodiment 1；
Fig. 3 is that potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric single-crystal wafer dielectric constant with temperature of embodiment 1 changes
Be situated between warm curve graph.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
The present invention provides a kind of growth potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline methods, comprising: weighs original
Material；Weigh growth auxiliary agent, and with raw material pre-burning after mixing；Raw material after pre-burning is put into crucible, is placed in furnace；Crucible
In 500~1000 DEG C of 3~18h of heat preservation, temperature is then increased to 1200~1500 DEG C, 6~18h of heat preservation melts raw material all,
In-furnace temperature is cooled to room temperature to obtain potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline with the speed of 10~100 DEG C/h.
In the present invention, potassium niobate sodium base leadless piezoelectric monocrystal chemical formula (1-y) (KxNa1-x) NbO3-y
(Bi0.5Na0.5) ZrO3,0 < x < 1,0≤y < 1；Preferably, 0.4≤x≤0.6,0≤y≤0.08.
The present invention uses Bridgman-Stockbarge method for growing potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.Add in raw material powder
Entering a certain amount of growth auxiliary agent to grow after mixing with raw material, thus it is possible to vary crystal is nucleated difficulty during the growth process, and crystal grain is small,
Problem more than crackle.Using Bridgman-Stockbarger method, raw material is sealed in crucible, reduces volatility of raw material to uneven components and complete
The influence of whole property, makes the easy control of components of crystal, while preventing the leakage bring of pernicious gas to pollute, while operating letter
It is single, and easily realize sequencing growth.
Hereinafter, illustrating Bridgman-Stockbarge method for growing potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
Preparation about raw material.Claim according to the stoichiometric ratio of (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3
Take the K of 99.9% or more purity2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2Raw material powder；Weigh account for raw material powder amount to 0.1~
The growth auxiliary agent of 10mol% is uniformly mixed with raw material.Mixed mode can use ball milling, former using corundum ball as ball milling medium
Material is 4:1 with ball-milling medium molar ratio, and Ball-milling Time 30min ball milling 3 times, obtains uniformly mixed mixed powder.
Growth auxiliary agent can be copper oxide.Selective oxidation copper is to be because copper oxide is with crystal raw material as growth auxiliary agent
Complete immiscible system, reduces the pollution to material；During the growth process, copper ion can also promote crystal crystallization；Pass through
The addition of copper oxide can make monocrystal material dissolution wherein, by slowly reducing system temperature or gradually waving growth auxiliary agent
It sends out and precipitates crystal.Growth auxiliary agent, which can be, accounts for raw material powder total 0.1~10mol% preferably 5%.It is excessive to grow auxiliary agent, meeting
Promote crystallization, inhibits growing up for nucleus, be unable to get the crystal grain of larger size.
Before carrying out Bridgman-Stockbarge method for growing crystal, the mixed powder of raw material and growth auxiliary agent can be subjected to pre-burning,
Obtain crystal growth Preburning material.By that material powder can be made to preliminarily form calcium titanium by raw material and growth auxiliary agent mixing pre-burning
Mine structure is conducive to crystal growth, while can also remove the moisture that raw material absorbs in mixed process, makes the carbonate in raw material
Ion dissociation prevents gas in growth course excessive, bursts crucible, is mixed the leakage of material.The condition of pre-burning may is that pre-
600~1000 DEG C of temperature are burnt, 3~6h of soaking time.Calcined temperature is excessively high, so that powder is condensed into blocks, intergranular contact surface
Become smaller, is unfavorable for the subsequent growth of crystal.Calcined temperature is too low, does not have obvious effects on.
In a preferred embodiment, calcined temperature can be 800 DEG C.
Also, the soaking time of pre-burning can be 4h in a preferred embodiment.
Bridgman-Stockbarge method for growing crystal: Bridgman-Stockbarger method is used, raw material is sealed in crucible, volatility of raw material pair is reduced
The influence of uneven components and integrality, makes the easy control of components of crystal, while preventing the leakage bring of pernicious gas
Pollution, at the same it is easy to operate, and easily realize sequencing growth.
Firstly, Preburning material is put into crucible, then crucible is fitted into skirt, crucible is placed in furnace.As one
A example, crucible used can be platinum crucible, and the skirt can be alumina ceramic tube.
By crucible in 500~1000 DEG C of 3~10h of heat preservation；Then, increase temperature to 1200~1500, preferably 1200~
1350 DEG C, 6~18h is kept the temperature, raw material is made all to be fused into melt；Then crucible was declined with 0.1~1.5mm/ hours speed, was melted
Gradually crystalline growth becomes crystal to body, and in-furnace temperature is cooled to room temperature to obtain potassium-sodium niobate-with 10~100 DEG C/h of speed
Zirconic acid bismuth sodium leadless piezoelectric monocrystalline.The decrease speed of crucible is too fast, and melt is cooling very fast, and nucleus can not continue to grow up.Under crucible
Reduction of speed is spent slowly, and more nucleus can be precipitated, so that crystal grain is mostly again small, cannot get the crystal grain of larger size.
In a preferred embodiment, the temperature of heat preservation can be 600~1000 DEG C for the first time.
Also, the time of heat preservation can be 5~10h for the first time in a preferred embodiment.
Also, the temperature of second of heat preservation can be 1200~1300 DEG C in a preferred embodiment.
Also, the time of second of heat preservation can be 6~10h in a preferred embodiment.
In a preferred embodiment, the decrease speed of crucible be can be 0.3~0.8mm/ hours.The temperature ladder of growth interface
Degree can be 10~80 DEG C/cm, preferably 20~60 DEG C/cm.
In a preferred embodiment, the cooling rate being cooled to room temperature can be 30~50 DEG C/h.
Advantages of the present invention: the Bridgman-Stockbarger method of addition growth auxiliary agent of the present invention is solved using common crystal
Growth method prepares potassium-sodium niobate monocrystalline, and crystal crystallization is difficult, crystal grain small (problem of the size more than 2mm or less), the crackle, the crystalline substance of growth
Particle size is 2~20mm, and crackle is few.The present invention have many advantages, such as process equipment be simple and convenient to operate, a furnace it is voluminous, be suitable for
The growth or production of industrial scale crystal.Prepared potassium-sodium niobate-zirconic acid bismuth sodium piezoelectric monocrystal, with the niobic acid usually prepared
Potassium sodium base monocrystalline is compared, and the high-T_c superconductors temperature of crystal has and significantly reduces, fall below 70 from 200 DEG C or so~
110 DEG C, the Curie temperature of crystal is relatively high, is 310~330 DEG C, improves the use temperature range of piezoelectric monocrystal；Furthermore niobic acid
Potassium sodium-zirconic acid bismuth sodium piezoelectric property and ferroelectric properties are also more excellent, and piezoelectric constant is~320pC/N, have very big answer
Use prospect.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Examples 1 to 4 Bridgman-Stockbarge method for growing (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3.Wherein, portion
Division technique parameter is as shown in Table 1.
One, K is weighed according to the stoichiometric ratio of (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO32CO3,
Na2CO3, Nb2O5, Bi2O3, ZrO2Raw material powder.
Two, growth auxiliary agent is weighed, is uniformly mixed with raw material.Mixed mode uses ball milling, using corundum ball as ball milling matchmaker
It is situated between, raw material and ball milling medium molar ratio are 4:1, and Ball-milling Time 30min ball milling 3 times, obtains uniformly mixed mixing after ball milling
Powder.
Three, by uniformly mixed powder pre-burning, obtain crystal growth Preburning material: 800 DEG C of calcined temperature, soaking time 4 is small
When.
Four, Preburning material is fitted into platinum crucible, by crucible in alumina ceramic crucible skirt, then by crucible
It is placed in Bridgman-Stockbarge method for growing crystal oven.
Five, crucible keeps the temperature t1 hour in T1, and then high temperature rises to T2, keeps the temperature t2 hour, makes the whole fusings of raw material, crucible with
The speed of v1 declines, when by the high-temperature region in growth furnace and the temperature gradient field between low-temperature space, melt gradually crystalline growth
At crystal.
Six, after the completion of crystal growth, in-furnace temperature is cooled to room temperature with the speed of v2, and crystal is come out of the stove.
Seven, platinum crucible is removed, crystal is taken out, the brilliant base taken out is cleaned with deionized water, that is, obtains potassium-sodium niobate-based nothing
Lead piezoelectric monocrystal.
Table one: the technological parameter of Bridgman-Stockbarge method for growing (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3 is utilized
The potassium-sodium niobate of the resulting embodiment 1 of Bridgman-Stockbarger method-zirconic acid bismuth sodium monocrystalline pattern is as shown in Figure 1.From figure with
It can be seen that grain shape comparison rule, crystallite dimension is bigger, 2~20mm.
The resulting potassium niobate sodium base leadless piezoelectric monocrystal grind into powder of embodiment 1, analyzes its knot using x-ray diffraction
Structure, potassium niobate sodium base leadless piezoelectric monocrystal is pure perovskite structure as seen from Figure 2, without other miscellaneous phases.
It is bent in Jie's temperature curve of the resulting potassium niobate sodium base leadless piezoelectric monocrystal of testing example 1 at different frequencies
Line respectively corresponds high-T_c superconductors as shown in figure 3, there is 2 abnormal Dielectric peaks under all frequencies as can be seen from Figure 3
(99 DEG C) and four directions-cube phase transformation (Curie temperature peak, 320 DEG C).Piezoelectric property test is finally carried out to it, piezoelectric constant is most
High up to 320pC/N, resulting crystal-phase transformation temperature is lower, and Curie temperature is high, and piezoelectric property is preferable, before very big application
Scape.
Claims (7)
1. a kind of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline growing method, which is characterized in that the potassium-sodium niobate-zirconium
The chemical formula of sour bismuth sodium leadless piezoelectric monocrystalline is (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3, wherein 0.4≤x≤0.6,
0.03≤y≤0.1, the growing method include:
1) according to (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3Stoichiometric ratio weigh K2CO3、Na2CO3、Nb2O5、
Bi2O3、ZrO2Raw material powder is uniformly mixed to obtain mixed powder, the life by raw material powder with 0.1~10mol% growth auxiliary agent
Long auxiliary agent is copper oxide；
2) mixed powder is subjected to pre-burning, obtains crystal growth Preburning material；600~1000 DEG C of the temperature of the pre-burning,
Soaking time 3~6 hours；
3) Preburning material is put into crucible, crucible is fitted into skirt, keep the temperature 3~10 hours in 500~1000 DEG C, so
After be warming up to 1200~1500 DEG C, keep the temperature 6~18 hours, then crucible was declined with 0.1~1.5mm/ hours speed, with 10~
100 DEG C/h are cooled to room temperature to obtain potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
2. growing method according to claim 1, which is characterized in that the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric list
Brilliant crystallite dimension is 2~20mm.
3. growing method according to claim 1, which is characterized in that the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric list
Brilliant high-T_c superconductors temperature is 70~110 DEG C, and Curie temperature is 310~330 DEG C, and piezoelectric constant is~320pC/N.
4. growing method according to claim 1, which is characterized in that the K2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2It is former
The purity at feed powder end is 99.9% or more.
5. growing method according to claim 1, which is characterized in that step 3) includes that the Preburning material is put into crucible
In, 5~10 hours are kept the temperature in 600~1000 DEG C, then heats to 1200~1350 DEG C, keeps the temperature 6~10 hours.
6. growing method according to claim 1, which is characterized in that in step 3), the decrease speed of crucible is 0.3~
0.8mm/ hours.
7. growing method according to any one of claim 1 to 6, which is characterized in that in step 3), be cooled to room temperature
Cooling rate is 30~50 DEG C/h.
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