CN107268084A - 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
- Publication number
- CN107268084A CN107268084A CN201610217456.2A CN201610217456A CN107268084A CN 107268084 A CN107268084 A CN 107268084A CN 201610217456 A CN201610217456 A CN 201610217456A CN 107268084 A CN107268084 A CN 107268084A
- Authority
- CN
- China
- Prior art keywords
- sodium
- potassium
- zirconic acid
- acid bismuth
- leadless piezoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to potassium-sodium niobate zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method, the chemical formula of the potassium-sodium niobate zirconic acid bismuth sodium leadless piezoelectric monocrystalline 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, by adding the advantages of Bridgman-Stockbarge method for growing crystal after growth auxiliary agent has easy nucleation, crystalline size larger (2~20mm) and less crackle.
Description
Technical field
The invention belongs to piezoelectric monocrystal field, more particularly to potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growth side
Method.
Background technology
Piezoelectric is the very important functional material of a class, using its elastic performance, dielectric properties, piezoelectric property,
Pyroelectric property, ferroelectric properties and optical property etc. so that piezoelectric is in ultrasonic transducer, sensor, driver, filter
The fields such as ripple device, memory are obtained a wide range of applications.The piezoelectric being most widely used at present is PZT sills, especially
It is the relaxation Ferroelectric monocrystalline for representative with lead magnesio-niobate (PMNT) and lead zinc niobate (PZNT).Although they have
Very high piezoelectric modulus and electromechanical coupling factor, but PbO in lead base piezoelectric (or Pb3O4) content exceed
60%, the toxicity of lead causes lead base piezoelectric ceramics produce, use and discard in last handling process all can be to the mankind and ecological environment
Serious harm is brought, the sustainable development of this and human society is runed counter to, therefore research and development leadless piezoelectric ceramics is one weight
The problem of great society meaning and economic implications.
Potassium-sodium niobate (KxNa1-xNbO3, write a Chinese character in simplified form KNN) base leadless piezoelectricity material the fifties in last century just have dielectric
Constant is low, and density is light, and Curie temperature is high, and Qm is big, frequency constant is big, and piezoelectricity and mechanical-electric coupling performance are general
Feature.And potassium sodium niobate ceramic haves the shortcomings that consistency is low, sintering character is poor etc. in preparation process, therefore, it is difficult to by normal
Advise sintering method and realize densification, cause piezoelectric property can not be compared 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..The crystal that the above is grown is at 200 DEG C or so
There is a high-T_c superconductors peak, before and after phase transformation, piezoelectric property changes very greatly, and the application to material is extremely disadvantageous obtains
, piezoelectric ceramics has been reported that can make phase transition temperature drop near room temperature by adding zirconic acid bismuth sodium, but so far without in terms of crystal
Report.Crystal and ceramic phase ratio, there is optimal crystalline orientation, and the monocrystalline of same composition has more excellent piezoelectricity, iron than ceramics
The performances such as electricity, dielectric.Due to adding zirconium oxide, conventional crystal growth is difficult to grow potassium-sodium niobate-zirconic acid bismuth sodium list
Crystalline substance, crystal structure is poor, crystalline size smaller (usual below 5mm) and crackle is a lot.
The content of the invention
There is provided a kind of new potassium niobate sodium base leadless piezoelectric monocrystal, Yi Jitong for the problem of present invention exists for prior art
Cross addition growth auxiliary agent and prepare bulky grain, potassium-sodium niobate-zirconic acid bismuth of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline of few crackle
The growing method of sodium leadless piezoelectric monocrystalline.
The present invention provides a kind of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, the potassium-sodium niobate-unleaded pressure of zirconic acid bismuth sodium
The chemical formula of electric monocrystalline is (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3, wherein 0.4≤x≤0.6,0≤y≤0.1.
The crystallite dimension of the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline of the present invention can be 2~20mm.
The high-T_c superconductors temperature of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline of the present invention can be 70~110 DEG C, occupy
In temperature can be 310~330 DEG C, piezoelectric constant can be~320pC/N.
The present invention also provides a kind of growing method of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, the growing method bag
Include：
1) K is weighed according to (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3 stoichiometric proportion2CO3、Na2CO3、Nb2O5、
Bi2O3、ZrO2Material powder, material powder is well mixed with 0.1~10mol% growth auxiliary agents and obtains mixed 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, be incubated 3~10 hours in 500~1000 DEG C, so
After be warming up to 1200~1500 DEG C, be incubated 6~18 hours, raw material is all fused into melt, then by crucible with 0.1~
Speed declines within 1.5mm/ hours, and the thermograde of growth interface is 10~80 DEG C/cm, and room temperature is cooled to 10~100 DEG C/h
Obtain potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
In the present invention, potassium-sodium niobate-zirconic acid is obtained by raw material and growth auxiliary agent mixing pre-burning, and using Bridgman-Stockbarge method for growing
Bismuth sodium leadless piezoelectric monocrystalline.Bridgman-Stockbarger method is also known as Bridgman methods, has the following advantages that：First, raw material is sealed in crucible
In, influence of the volatility of raw material to uneven components and integrality is reduced, makes the easy control of components of crystal, while having prevented
The pollution that the leakage of evil gas is brought；2nd, nucleation can be induced by thermograde or seed crystal, controls nucleation number, growth is big
The crystal of size；3rd, it is simple to operate, and easily realize that sequencing grows；Can also multiple crucibles grow simultaneously, can carry significantly
High finished product rate and operating efficiency.Add after a certain amount of growth auxiliary agent is well mixed with raw material and grow in material powder, Ke Yigai
Twin crystal nucleation in growth course is difficult, and crystal grain is small, the problem of crackle is more.
It is preferred that the K2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2The purity of material powder is more than 99.9%.
It is preferred that the growth auxiliary agent is cupric oxide.Selective oxidation copper, as growth auxiliary agent, is because cupric oxide and crystal
Raw material is complete immiscible system, reduces the pollution to material；In growth course, copper ion can also promote crystal to analyse
It is brilliant；By the addition of cupric oxide, monocrystal material dissolving can be made wherein, by slowly reducing system temperature or little by little making growth
Auxiliary agent volatilizees and separates out crystal.
It is preferred that 600~1000 DEG C of the temperature of the pre-burning, soaking time 3~6 hours.By the way that raw material is helped with growth
Agent mixing pre-burning, can make material powder preliminarily form perovskite structure, beneficial to crystal growth, exist while raw material can also be removed
The moisture absorbed in mixed process, decomposes the carbanion in raw material.
It is preferred that step 3) include the Preburning material being put into crucible, 5~10 hours are incubated in 600~1000 DEG C,
1200~1350 DEG C are then heated to, 6~10 hours are incubated.
It is preferred that step 3) in, the decrease speed of crucible is 0.3~0.8mm/ hours, and the thermograde of growth interface is
20~60 DEG C/cm.
It is preferred that step 3) in, the cooling rate for being cooled to room temperature is 30~50 DEG C/h.
Beneficial effects of the present invention：
The Bridgman-Stockbarger method of addition growth auxiliary agent of the present invention, solves the potassium-sodium niobate monocrystalline prepared using conventional crucible descent method
What is had is difficult to crystallization, crystalline size small (general size is in below 5mm), the problems such as crackle is more.By adding growth auxiliary agent
The advantages of Bridgman-Stockbarge method for growing crystal afterwards has easy nucleation, crystalline size larger (2~20mm) and less crackle.It is made
Standby potassium-sodium niobate-zirconic acid bismuth sodium piezoelectric monocrystal is compared with the potassium-sodium niobate-based monocrystalline generally prepared, the high-T_c superconductors of crystal
Temperature, which has, significantly to be reduced, and 70~110 DEG C is fallen below from 200 DEG C or so, the Curie temperature of crystal is higher, is
310~330 DEG C, improve the temperature in use scope of piezoelectric monocrystal；In addition the piezoelectric property and ferroelectricity of potassium-sodium niobate-zirconic acid bismuth sodium
Performance is also more excellent, and piezoelectric constant is~320pC/N, is had great application prospect.
Brief description of the drawings
Fig. 1 is the shape appearance figure of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline of embodiment 1；
Fig. 2 is the X-ray diffractogram of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystal of embodiment 1；
Jie's temperature curve that Fig. 3 changes for the dielectric constant with temperature of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric single-crystal wafer of embodiment 1
Figure.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments are only
For illustrating the present invention, it is not intended to limit the present invention.
The invention provides a kind of method for growing potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, including：Weigh raw material；
Growth auxiliary agent is weighed, and pre-burning after being well mixed with raw material；Raw material after pre-burning is put into crucible, is placed in stove；Crucible exists
500~1000 DEG C of 3~18h of insulation, then raise temperature to 1200~1500 DEG C, and 6~18h of insulation makes raw material all fusings,
In-furnace temperature is cooled to room temperature with 10~100 DEG C/h speed and obtains potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
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 is using Bridgman-Stockbarge method for growing potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.One is added in material powder
Quantitative growth auxiliary agent grows after being well mixed with raw material, thus it is possible to vary crystal nucleation in growth course is difficult, and crystal grain is small, crackle
Many the problem of.Using Bridgman-Stockbarger method, raw material is sealed in crucible, volatility of raw material is reduced to uneven components and integrality
Influence, make the easy control of components of crystal, while prevent the pollution that the leakage of pernicious gas is brought, while simple to operate,
And easily realize that sequencing grows.
Hereinafter, Bridgman-Stockbarge method for growing potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline is illustrated.
Preparation on raw material.Stoichiometric proportion according to (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3 weighs pure
The K of degree more than 99.9%2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2Material powder；Weigh and account for material powder total
0.1~10mol% growth auxiliary agent is well mixed with raw material.The mode of mixing can use ball milling, using corundum ball as ball milling matchmaker
It is situated between, raw material is 4 with ball-milling medium mol ratio:1, Ball-milling Time is 30min, and ball milling 3 times obtains well mixed mixed powder
Body.
It can be cupric oxide to grow auxiliary agent.Selective oxidation copper, as growth auxiliary agent, is because cupric oxide is complete with crystal raw material
Immiscible system, reduces the pollution to material；In growth course, copper ion can also promote crystal crystallization；Pass through oxidation
The addition of copper, can make monocrystal material dissolving wherein, be analysed by slowly reducing system temperature or little by little making growth auxiliary agent volatilize
Go out crystal.Growth auxiliary agent can account for material powder to amount to 0.1~10mol% preferably 5%.Grow auxiliary agent excessive, analysis can be promoted
Crystalline substance, suppresses growing up for nucleus, it is impossible to obtain the crystal grain of large-size.
Before Bridgman-Stockbarge method for growing crystal is carried out, the mixed powder of raw material and growth auxiliary agent can be subjected to pre-burning, obtained
To crystal growth Preburning material.By that by raw material and growth auxiliary agent mixing pre-burning, material powder can be made to preliminarily form perovskite knot
Structure, beneficial to crystal growth, while the moisture that raw material absorbs in mixed process can also be removed, makes the carbanion in raw material
Decompose, prevent that gas is excessive in growth course, bursts crucible, the leakage for occurring compound.The condition of pre-burning can be：Pre-burning
600~1000 DEG C of temperature, 3~6h of soaking time.Calcined temperature is too high so that powder condenses blocking, intergranular contact surface
Diminish, be unfavorable for the subsequent growth of crystal.Calcined temperature is too low, without obvious effect.
In a preferred scheme, calcined temperature can be 800 DEG C.
Also, in a preferred scheme, the soaking time of pre-burning can be 4h.
Bridgman-Stockbarge method for growing crystal：Using Bridgman-Stockbarger method, 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 dirt that the leakage of pernicious gas is brought
Dye, at the same it is simple to operate, and easily realize that sequencing grows.
First, Preburning material is put into crucible, then crucible is fitted into skirt, crucible is placed in stove.It is used as one
Individual example, crucible used can be platinum crucible, and described skirt can be alumina ceramic tube.
Crucible is incubated 3~10h at 500~1000 DEG C；Then, rise temperature to 1200~1500, preferably 1200~
1350 DEG C, 6~18h is incubated, raw material is all fused into melt；Then crucible was declined with the speed of 0.1~1.5mm/ hours,
Melt gradually crystalline growth turn into crystal, in-furnace temperature with 10~100 DEG C/h of speed be cooled to room temperature obtain potassium-sodium niobate-
Zirconic acid bismuth sodium leadless piezoelectric monocrystalline.The decrease speed of crucible is too fast, and melt cooling is very fast, and nucleus can not continue to grow up.Under crucible
Reduction of speed is spent slowly, can separate out more nucleus so that again small more than crystal grain, cannot get the crystal grain of large-size.
In a preferred scheme, the temperature of insulation can be 600~1000 DEG C for the first time.
Also, in a preferred scheme, the time of insulation can be 5~10h for the first time.
Also, in a preferred scheme, the temperature of second of insulation can be 1200~1300 DEG C.
Also, in a preferred scheme, the time of second of insulation can be 6~10h.
In a preferred scheme, the decrease speed of crucible can be 0.3~0.8mm/ hours.The thermograde of growth interface
Can be 10~80 DEG C/cm, preferably 20~60 DEG C/cm.
In a preferred scheme, the cooling rate for 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 life
Regular way prepares potassium-sodium niobate monocrystalline, and crystal crystallization is difficult, crystal grain small (size is in below 2mm), the problem of crackle is more, growth
Crystallite dimension is 2~20mm, and crackle is few.The present invention have the advantages that process equipment be simple and convenient to operate, stove fecund, it is suitable
Together in the growth or production of industrial scale crystal.Prepared potassium-sodium niobate-zirconic acid bismuth sodium piezoelectric monocrystal, with generally preparing
Potassium-sodium niobate-based monocrystalline is compared, and the high-T_c superconductors temperature of crystal, which has, significantly to be reduced, and is fallen below from 200 DEG C or so
70~110 DEG C, the Curie temperature of crystal is higher, is 310~330 DEG C, improves the temperature in use scope of piezoelectric monocrystal；This
The piezoelectric property and ferroelectric properties of outer potassium-sodium niobate-zirconic acid bismuth sodium are also more excellent, and piezoelectric constant is~320pC/N, with very big
Application prospect.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
It is bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by this paper explanation
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
The Bridgman-Stockbarge method for growing of embodiment 1~4 (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3.Wherein, part work
Skill parameter is as shown in Table 1.
One, weigh K according to (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3 stoichiometric proportion2CO3,
Na2CO3, Nb2O5, Bi2O3, ZrO2Material powder.
Two, growth auxiliary agent is weighed, is well mixed with raw material.The mode of mixing uses ball milling, and ball milling matchmaker is used as using corundum ball
It is situated between, raw material is 4 with ball milling medium mol ratio:1, Ball-milling Time is 30min, and ball milling 3 times is obtained well mixed after ball milling
Mixed powder.
Three, by well 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, crucible is mounted in alumina ceramic crucible skirt, then by crucible
It is placed in Bridgman-Stockbarge method for growing crystal oven.
Five, crucible is incubated t1 hours in T1, and then high temperature rises to T2, is incubated t2 hours, makes raw material all fusing, earthenware
Crucible is declined with v1 speed, and during by temperature gradient field between the high-temperature region in growth furnace and low-temperature space, melt is gradually crystallized
Grow into crystal.
Six, after the completion of crystal growth, in-furnace temperature is cooled to room temperature with v2 speed, and crystal is come out of the stove.
Seven, platinum crucible is peeled off, 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：Utilize Bridgman-Stockbarge method for growing (1-y) (KxNa1-x) NbO3-y (Bi0.5Na0.5) ZrO3 technological parameter
The pattern of the potassium-sodium niobate of embodiment 1 obtained by Bridgman-Stockbarger method-zirconic acid bismuth sodium monocrystalline is as shown in Figure 1.From figure with can
To find out grain shape comparison rule, crystallite dimension is than larger, 2~20mm.
The potassium niobate sodium base leadless piezoelectric monocrystal grind into powder of the gained of embodiment 1, its knot is analyzed using x-ray diffraction
Structure, potassium niobate sodium base leadless piezoelectric monocrystal is pure perovskite structure as seen from Figure 2, without other dephasigns.
In Jie's temperature curve of the potassium niobate sodium base leadless piezoelectric monocrystal obtained by testing example 1 at different frequencies, its curve
As shown in figure 3, there are 2 abnormal Dielectric peaks under all frequencies as can be seen from Figure 3, high-T_c superconductors are corresponded to respectively
(99 DEG C) and four directions-cube phase transformation (Curie temperature peak, 320 DEG C).Piezoelectric property test finally is carried out to it, its piezoelectricity is normal
Number reaches as high as 320pC/N, and the crystal-phase transformation temperature of gained is relatively low, and Curie temperature is high, and piezoelectric property is preferable, with very big
Application prospect.
Claims (10)
1. a kind of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, it is characterised in that the chemical formula of the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline is (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3, wherein 0.4≤x≤0.6,0≤y≤0.1.
2. potassium-sodium niobate according to claim 1-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, it is characterised in that the crystallite dimension of the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline is 2~20mm.
3. potassium-sodium niobate according to claim 1 or 2-zirconic acid bismuth sodium leadless piezoelectric monocrystalline, it is characterized in that, the high-T_c superconductors temperature of the potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline is 70~110 DEG C, and Curie temperature is 310~330 DEG C, and piezoelectric constant is~320pC/N.
4. a kind of growing method of potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline any one of claims 1 to 3, the growing method includes：
1）According to (1-y) (KxNa1-x)NbO3-y(Bi0.5Na0.5)ZrO3Stoichiometric proportion weigh K2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2Material powder, material powder is well mixed with 0.1~10mol% growth auxiliary agents and obtains mixed powder；
2）The mixed powder is subjected to pre-burning, crystal growth Preburning material is obtained；
3）The Preburning material is put into crucible, crucible is fitted into skirt, 3~10 hours are incubated in 500~1000 DEG C, then heat to 1200~1500 DEG C, insulation 6~18 hours, crucible was declined with 0.1~1.5mm/ hours speed again, being cooled to room temperature with 10~100 DEG C/h obtains potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline.
5. growing method according to claim 4, it is characterised in that the K2CO3、Na2CO3、Nb2O5、Bi2O3、ZrO2The purity of material powder is more than 99.9%.
6. the growing method according to claim 4 or 5, it is characterised in that the growth auxiliary agent is cupric oxide.
7. the growing method according to any one of claim 4 to 6, it is characterised in that 600~1000 DEG C of the temperature of the pre-burning, soaking time 3~6 hours.
8. the growing method according to any one of claim 4 to 7, it is characterised in that step 3）Including the Preburning material is put into crucible, 5~10 hours are incubated in 600~1000 DEG C, 1200~1350 DEG C are then heated to, 6~10 hours are incubated.
9. the growing method according to any one of claim 4 to 8, it is characterised in that step 3）In, the decrease speed of crucible is 0.3~0.8mm/ hours.
10. the growing method according to any one of claim 4 to 9, it is characterised in that step 3）In, the cooling rate for being cooled to room temperature is 30~50 DEG C/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610217456.2A CN107268084B (en) | 2016-04-08 | 2016-04-08 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610217456.2A CN107268084B (en) | 2016-04-08 | 2016-04-08 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107268084A true CN107268084A (en) | 2017-10-20 |
| CN107268084B CN107268084B (en) | 2019-10-15 |
Family
ID=60052472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610217456.2A Active CN107268084B (en) | 2016-04-08 | 2016-04-08 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107268084B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560698A (en) * | 2022-04-15 | 2022-05-31 | 中国科学院合肥物质科学研究院 | Method for enhancing performance of calcium bismuth niobate high-temperature piezoelectric ceramic by inducing texture through oxide sintering aid |
| CN114621009A (en) * | 2022-03-16 | 2022-06-14 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN115572165A (en) * | 2021-06-21 | 2023-01-06 | 四川大学 | Niobium zirconium acid bismuth potassium sodium copper iron leadless piezoelectric ceramic with high mechanical quality factor |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288451A (en) * | 2013-05-24 | 2013-09-11 | 四川大学 | Sodium potassium niobate-sodium bismuth zirconate titanate lead-free piezoelectric ceramic |
| CN103288450A (en) * | 2013-05-24 | 2013-09-11 | 四川大学 | Potassium-sodium niobate-bismuth potassium zirconate-titanate/lithium-base leadless piezoelectric ceramic |
| CN103482977A (en) * | 2013-09-02 | 2014-01-01 | 四川大学 | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof |
| CN103966659A (en) * | 2013-01-25 | 2014-08-06 | 中国科学院上海硅酸盐研究所 | Potassium sodium niobate KNN single crystal preparation method |
| CN104131333A (en) * | 2014-08-12 | 2014-11-05 | 哈尔滨工业大学 | Method for preparing K0.5Na0.5NbO3 single crystal |
| CN104152999A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor |
| CN104152982A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院上海硅酸盐研究所 | Growing method of (KxNa1-x)1-yLiyNbO3-based lead-free piezoelectric monocrystal |
| CN104357910A (en) * | 2014-11-04 | 2015-02-18 | 中国科学院上海硅酸盐研究所 | Potassium sodium niobate based single crystal and preparation method thereof |
| CN105198417A (en) * | 2015-09-08 | 2015-12-30 | 四川大学 | Preparation method of zirconic acid sodium bismuthide lithium cerium doped potassium-sodium niobate based ceramic material |
| CN105254298A (en) * | 2015-09-30 | 2016-01-20 | 中国科学院上海硅酸盐研究所 | Lithium-doped potassium-sodium niobate single crystal with high piezoelectric property and preparation method thereof |
-
2016
- 2016-04-08 CN CN201610217456.2A patent/CN107268084B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966659A (en) * | 2013-01-25 | 2014-08-06 | 中国科学院上海硅酸盐研究所 | Potassium sodium niobate KNN single crystal preparation method |
| CN104152999A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor |
| CN104152982A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院上海硅酸盐研究所 | Growing method of (KxNa1-x)1-yLiyNbO3-based lead-free piezoelectric monocrystal |
| CN103288451A (en) * | 2013-05-24 | 2013-09-11 | 四川大学 | Sodium potassium niobate-sodium bismuth zirconate titanate lead-free piezoelectric ceramic |
| CN103288450A (en) * | 2013-05-24 | 2013-09-11 | 四川大学 | Potassium-sodium niobate-bismuth potassium zirconate-titanate/lithium-base leadless piezoelectric ceramic |
| CN103482977A (en) * | 2013-09-02 | 2014-01-01 | 四川大学 | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof |
| CN104131333A (en) * | 2014-08-12 | 2014-11-05 | 哈尔滨工业大学 | Method for preparing K0.5Na0.5NbO3 single crystal |
| CN104357910A (en) * | 2014-11-04 | 2015-02-18 | 中国科学院上海硅酸盐研究所 | Potassium sodium niobate based single crystal and preparation method thereof |
| CN105198417A (en) * | 2015-09-08 | 2015-12-30 | 四川大学 | Preparation method of zirconic acid sodium bismuthide lithium cerium doped potassium-sodium niobate based ceramic material |
| CN105254298A (en) * | 2015-09-30 | 2016-01-20 | 中国科学院上海硅酸盐研究所 | Lithium-doped potassium-sodium niobate single crystal with high piezoelectric property and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOPENG WANG等: "Phase structure, electrical properties, and stability of 0.96(K0.48Na0.52)1-xLixNbO3-0.04Bi0.5Na0.5ZrO3 lead-free piezoceramics", 《CURRENT APPLIED PHYSICS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572165A (en) * | 2021-06-21 | 2023-01-06 | 四川大学 | Niobium zirconium acid bismuth potassium sodium copper iron leadless piezoelectric ceramic with high mechanical quality factor |
| CN115572165B (en) * | 2021-06-21 | 2023-08-29 | 四川大学 | Bismuth potassium sodium copper iron niobate leadless piezoelectric ceramic with high mechanical quality factor |
| CN114621009A (en) * | 2022-03-16 | 2022-06-14 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN114621009B (en) * | 2022-03-16 | 2023-02-28 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN114560698A (en) * | 2022-04-15 | 2022-05-31 | 中国科学院合肥物质科学研究院 | Method for enhancing performance of calcium bismuth niobate high-temperature piezoelectric ceramic by inducing texture through oxide sintering aid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107268084B (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105374931B (en) | Titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof | |
| CN101913868B (en) | Method for preparing potassium-sodium niobate textured ceramic and potassium-sodium niobate single crystal | |
| CN101024574B (en) | Sodium-potassium niobate series substituted by bismuth-base calcium-titanium ore and preparing method | |
| CN102628186B (en) | Preparation method of quadrature-phase lithium tantalum doped potassium sodium niobate based lead-free piezoelectric single crystal | |
| WO2016015462A1 (en) | Tetragonal pyroelectric relaxor ferroelectric single crystal material and preparation method therefor | |
| CN105198417B (en) | A kind of preparation method of zirconic acid bismuth sodium lithium cerium dopping potassium-sodium niobate base ceramic material | |
| CN102910907A (en) | Potassium-sodium niobate-based leadless piezoelectric ceramic and two-step sintering preparation method thereof | |
| JP2011510898A (en) | Method for producing ternary piezoelectric crystal | |
| CN105254298B (en) | A kind of lithium doping potassium-sodium niobate monocrystalline of high tension performance and preparation method thereof | |
| CN107268084A (en) | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method | |
| CN102817080A (en) | Lead lutetioniobate-lead magnesioniobate-lead titanate ternary-system relaxation ferroelectric monocrystal and preparation method thereof | |
| CN105948736A (en) | Lithium oxide-trivalent oxide co-doped ABO3 structure-based high-temperature stability piezoelectric ceramic material and preparation method thereof | |
| CN111362695A (en) | Lead zirconate titanate piezoelectric ceramic and preparation method thereof | |
| CN104419984A (en) | Preparation method of perovskite-structure relaxor ferroelectric single crystal lead indium niobate-lead magnesium niobate-lead titanate | |
| CN104152999A (en) | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor | |
| CN106350869B (en) | A kind of orthorhombic phase Mn doping niobium tantalum potassium antimonate sodium lithium leadless piezoelectric monocrystalline of extra-high voltage performance and preparation method thereof | |
| CN104372409B (en) | Ternary system relaxation base ferroelectric piezoelectric single crystal and its growing method | |
| CN102953116B (en) | Centimeter-level pure-phase BiFeO3Method for producing single crystal | |
| CN104131333B (en) | Method for preparing K0.5Na0.5NbO3 single crystal | |
| CN103436963A (en) | Preparation method of tantalump-doped potassium-sodium niobate lead-free piezoelectric single crystal with high electromechanical coupling property | |
| CN103172377B (en) | Reaction solid state growth prepares the method for high performance piezoelectric pottery | |
| CN104152997B (en) | Quaternary system relaxation type monocrystalline piezoelectric material and its growing method | |
| CN106521627B (en) | A kind of potassium-sodium niobate-based piezoelectric monocrystal and preparation method thereof | |
| CN109868502B (en) | Rare earth doped niobate monocrystal up-conversion luminescent material and preparation method thereof | |
| EP1351326A2 (en) | Oxide ion conductor and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |