CN110342933A - A method of regulation sodium niobate ceramics Curie temperature - Google Patents

A method of regulation sodium niobate ceramics Curie temperature Download PDF

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CN110342933A
CN110342933A CN201910532357.7A CN201910532357A CN110342933A CN 110342933 A CN110342933 A CN 110342933A CN 201910532357 A CN201910532357 A CN 201910532357A CN 110342933 A CN110342933 A CN 110342933A
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curie temperature
sodium niobate
ceramics
powder
ball milling
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CN110342933B (en
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靳立
景瑞轶
徐卓
魏晓勇
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Xian Jiaotong University
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Abstract

The invention discloses a kind of methods of regulation sodium niobate ceramics Curie temperature, belong to electron ceramic material technical field.It is matrix that the present invention, which mainly utilizes the lead-free anti-ferroelectric ceramics of this high-curie temperature of sodium niobate, adds BMT and BMN on this basis and adjusts ceramic Curie temperature.It uses oxide and carbonate for raw material, by traditional solid phase synthesis preparation method thereof, has obtained a kind of leadless electronic that consistency is high ceramics.The material composition and processing step of preparation method of the present invention are simple, and method is easily operated, reproducible；The every increase by 1% of the content of BMT or BMN, 33 DEG C or 34 DEG C of Curie temperature linear decline.By the regulation to Curie temperature, its dielectric, ferroelectricity and strain property can be regulated and controled in turn, there is very high application value.

Description

A method of regulation sodium niobate ceramics Curie temperature
Technical field
The invention belongs to electron ceramic material technical fields, specially regulate and control the method for sodium niobate ceramics Curie temperature.
Background technique
Representative of the sodium niobate ceramics as antiferroelectric ceramics has very high researching value, but due to pure sodium niobate Ceramics introduce a certain amount of perovskite system (titanium magnesium acid bismuth or magnoniobate bismuth) compared with hard-to-sinter, are stabilized structure.Ceramics Material has different symmetry in different temperature ranges.From low temperature asymmetry mutually toward the transformation of high temperature center symmetry phase Temperature is referred to as Curie temperature.More than Curie temperature, because of central symmetry, material does not have piezoelectricity and ferroelectricity.Therefore, right Curie temperature freely regulate and control to help to strain it and the regulation of dielectric properties.Curie temperature is higher, ferroelectric phase or anti-iron It is electric mutually more stable, but coefficient is smaller.Closer to Curie temperature, because of abnormal Dielectric, coefficient is bigger.How in stability and A balance is done between signal magnitude, core is exactly the regulation to Curie temperature.How a kind of effective means regulation pottery is found The Curie temperature of porcelain is the major issue of this field urgent need to resolve.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of regulation sodium niobate ceramics Curie temperature, and this method is easy to operate, It is reproducible, it can effectively adjust the Curie temperature of ceramic material.
In order to achieve the above object, the present invention is achieved by the following scheme:
A kind of method of regulation sodium niobate ceramics Curie temperature disclosed by the invention passes through addition using sodium niobate as matrix Bi(Mg0.5Ti0.5)O3Or Bi (Mg2/3Nb1/3)O3Regulate and control sodium niobate ceramics Curie temperature.
Preferably, the method for regulation sodium niobate ceramics Curie temperature of the present invention, comprising the following steps:
1) weighing: chemical formula (1-x) NaNbO is pressed3-xBi(Mg0.5Ti0.5)O3The proportion of middle each element takes raw material Na2CO3、 Nb2O5、Bi2O3, MgO and TiO2, wherein x=0-0.05；
Alternatively, pressing chemical formula (1-x) NaNbO3-xBi(Mg2/3Nb1/3)O3The proportion of middle each element takes raw material Na2CO3、 Nb2O5、Bi2O3And MgO, wherein x=0-0.06；
2) ball milling: being put into ball grinder after raw material is mixed, and is added dehydrated alcohol and zirconia ball, abundant ball milling, drying, 60 meshes are crossed in grinding, obtain powder；
3) pre-burning: by powder in 900 DEG C of progress pre-burnings, 3 hours is kept the temperature, naturally cools to room temperature, the powder after obtaining pre-burning Material；
4) secondary ball milling: the powder that pre-burning is obtained grinds, crosses 60 meshes, is packed into ball grinder, and it is anhydrous that ball milling solvent is added Ethyl alcohol and zirconia ball, after secondary ball milling, drying, the powder after obtaining secondary ball milling；
5) form: by the powder grinding after secondary ball milling it is thin after, be put into mold and be molded, be just pressed into it is cylindric, then The static pressure such as utilize to depress to green body in 250MPa pressure；
6) it is sintered: green body is put into crucible, cover, bury material with similar powder and bury burning, be sintered in 1300 DEG C, keep the temperature 2 hours, with furnace cooled to room temperature, potsherd is made；
7) it burns electrode: potsherd is polishing to a thickness of 0.6mm, naturally dry, lower surface coats silver paste on it, is placed in By room temperature to 600 DEG C in furnace, 20min is kept the temperature, high-compactness lead-free ceramics are made in cooled to room temperature.
Preferably, secondary ball milling revolving speed is 300 revs/min in rotational speed of ball-mill and step 4) in step 2).
Preferably, drying and the middle drying of step 4) are carried out at 80 DEG C in step 2).
Preferably, the molding in step 5) is to be put into powder in the stainless steel mould that diameter is 10mm to be pressed into Type.
Preferably, the heating rate in step 3), step 6) and step 7) is 3 DEG C/min.
Preferably, raw material Na2CO3、Nb2O5、Bi2O3, MgO and TiO2Purity be respectively 99.8%, 99.99%, 99%, 98.5% and 98%.
Preferably, when by adding Bi (Mg0.5Ti0.5)O3It is obtained high-densit when regulating and controlling sodium niobate ceramics Curie temperature The Curie temperature of degree lead-free ceramics is approximately linearly reduced to 216 DEG C, and Bi (Mg from undoped 375 DEG C0.5Ti0.5)O3Doping Every increase by 1% is measured, Curie temperature reduces by 33 DEG C；
When by adding Bi (Mg2/3Nb1/3)O3When regulating and controlling sodium niobate ceramics Curie temperature, the unleaded pottery of high-compactness obtained The Curie temperature of porcelain is approximately linearly reduced to 169 DEG C, and Bi (Mg from undoped 375 DEG C2/3Nb1/3)O3The every increase of doping 1%, Curie temperature reduces by 34 DEG C
Compared with prior art, the invention has the following beneficial technical effects:
Regulation sodium niobate (NaNbO disclosed by the invention3, abridge NN) and the method for ceramic Curie temperature, using synthesis in solid state Method adds Bi (Mg using the lead-free anti-ferroelectric ceramics of this high-curie temperature of sodium niobate as matrix on this basis0.5Ti0.5) O3(abbreviation BMT) or Bi (Mg2/3Nb1/3)O3(abbreviation BMN) adjusts NN ceramics Curie temperature, present component and technique step Rapid simple, easily operated, reproducible, high yield rate.Curie's temperature of unleaded NN ceramics can be effectively controlled by this method Degree reduces the Curie temperature of ceramics approximately linearly by doping from undoped 375 DEG C.The every increase of the doping of BMT 1%, NN Curie temperature just reduce about 33 DEG C.The doping of BMN every increase by 1%, NN Curie temperature just reduces about 34 DEG C.
High (relative density is greater than 96%) through ceramic dense degree made from the method for the present invention, Curie temperature is controllable, Jin Erke To regulate and control the electrical behavior of ceramics, there is good application value.
Detailed description of the invention
Fig. 1 is the dielectric constant with temperature variation relation figure of the NN system sample of present invention selection various concentration BMT doping. Arrow does the Curie temperature that the peak position marked is corresponding component in figure.
Fig. 2 is the dielectric constant with temperature variation relation figure of the NN system sample of present invention selection various concentration BMN doping. Arrow does the Curie temperature that the peak position marked is corresponding component in figure.
Fig. 3 is what the Curie temperature for the NN system sample that various concentration BMT of the present invention and BMN is adulterated changed with doping content Relational graph.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction with the embodiment of the present invention and its Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work It encloses.
It should be noted that term " includes " in description and claims of this specification and " having " and they Any deformation, it is intended that cover it is non-exclusive include, for example, containing the process, method of a series of steps or units, being System, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include be not clearly listed or For the intrinsic other step or units of these process, methods, product or equipment.
The invention will be described in further detail with reference to the accompanying drawing:
Embodiment 1
(1) weighing
By chemical formula (1-x) NaNbO3-xBi(Mg0.5Ti0.5)O3(referred to as (1-x) NN-xBMT, wherein x=0.00,0.01, 0.02,0.03,0.04,0.05) in each element proportion, take raw material Na2CO3、Nb2O5、Bi2O3, MgO and TiO2Preparation is seperated, Each group of assignment system 100g powder, wherein
When x=0, Na is weighed2CO3And Nb2O5It is respectively as follows: 28.5453g, 71.4547g；
When x=0.01, Na is weighed2CO3、Nb2O5、Bi2O3, MgO and TiO2Be respectively as follows: 28.0929g, 70.3224g, 1.2576g, 0.1093g and 0.2178g；
When x=0.02, Na is weighed2CO3、Nb2O5、Bi2O3, MgO and TiO2Be respectively as follows: 27.6459g, 69.2034g, 2.5004g, 0.2174g and 0.4330g；
When x=0.03, Na is weighed2CO3、Nb2O5、Bi2O3, MgO and TiO2Be respectively as follows: 27.2041g, 68.0974g, 3.7287g, 0.3241g and 0.6457g；
When x=0.04, Na is weighed2CO3、Nb2O5、Bi2O3, MgO and TiO2Be respectively as follows: 26.7674g, 67.0043g, 4.9428g, 0.4297g and 0.8559g；
When x=0.05, Na is weighed2CO3、Nb2O5、Bi2O3, MgO and TiO2Be respectively as follows: 26.3357g, 65.9238g, 6.1429g, 0.5340g and 1.0637g；
Raw materials used Na2CO3、Nb2O5、Bi2O3, MgO and TiO2Purity be respectively 99.8%, 99.99%, 99%, 98.5% and 98%.
(2) ball milling
It is put into ball grinder after the weighed raw material of step (1) is mixed, ball milling solvent dehydrated alcohol and zirconia ball is added, Ball milling 6 hours, rotational speed of ball-mill was 300 revs/min, then mixture is put into 80 DEG C of drying in baking oven, was ground being put into mortar, mistake 60 meshes obtain powder；
(3) pre-burning
Powder after being ground up, sieved in step (2) is put into crucible, cover, sealing: in Muffle furnace in 900 DEG C into Row pre-burning keeps the temperature 3 hours, naturally cools to room temperature, come out of the stove to obtain the powder after pre-burning；
(4) secondary ball milling
By the powder of pre-burning in step (3), it is anhydrous that ball milling solvent is added in ground 60 mesh, loading ball grinder in mortar Ethyl alcohol and zirconia ball, secondary ball milling 24 hours, revolving speed was 300 revs/min, and powder is put into 80 DEG C of drying of baking oven and obtains secondary ball Powder after ink；
(5) it forms
By step (4) drying secondary spheroidal graphite after powder it is levigate after, be put into mold, be just pressed into it is cylindric, recycle Equal static pressure depress to green body in 250MPa pressure；
(6) it is sintered
The green body pressed in step (5) is put into crucible, is covered, is buried material with similar powder and bury burning, in 1300 DEG C Sintering keeps the temperature 2 hours, and with furnace cooled to room temperature, potsherd is made；
(7) electrode is burnt
The burned potsherd of step (6) is polishing to a thickness of 0.6mm, naturally dry, lower surface coats silver paste on it, It is placed in furnace by room temperature to 600 DEG C, keeps the temperature 20min, high-compactness lead-free ceramics are made in cooled to room temperature.
The dielectric properties of high-compactness lead-free ceramics made from the present embodiment are tested, are as a result different dense referring to Fig. 1, Fig. 1 The dielectric constant with temperature variation relation figure of the NN system sample of BMT doping is spent, dielectric constant maximum value corresponding temperature is Curie Temperature.The Curie temperature of each component ceramics sample can be determined from Fig. 1.And it was found that with the increase of BMT doping, not Lead to the generation for spreading phase transformation.
Embodiment 2
(1) weighing
By chemical formula (1-x) NaNbO3-xBi(Mg2/3Nb1/3)O3(referred to as (1-x) NN-xBMN, wherein x=0.00,0.02, 0.04,0.06) in each element proportion, take raw material Na2CO3、Nb2O5、Bi2O3And MgO preparation is seperated, each group of assignment system 100g Powder, wherein
When x=0, Na is weighed2CO3And Nb2O5It is respectively as follows: 28.5453g, 71.4547g；
When x=0.02, Na is weighed2CO3、Nb2O5、Bi2O3And MgO be respectively as follows: 27.6154g, 69.5974g, 2.4977g, 0.2895g；
When x=0.04, Na is weighed2CO3、Nb2O5、Bi2O3And MgO be respectively as follows: 26.7092g, 67.7871g, 4.9321g, 0.5716g；
When x=0.06, Na is weighed2CO3、Nb2O5、Bi2O3And MgO be respectively as follows: 25.8256g, 66.0222g, 7.3055g, 0.8467g；
Raw materials used Na2CO3、Nb2O5、Bi2O3And the purity of MgO is respectively 99.8%, 99.99%, 99% and 98.5%；
(2) ball milling
It is put into ball grinder after the weighed raw material of step (1) is mixed, ball milling solvent dehydrated alcohol and zirconia ball is added, Ball milling 6 hours, rotational speed of ball-mill was 300 revs/min, then mixture is put into 80 DEG C of drying in baking oven, was ground being put into mortar, mistake 60 meshes obtain powder；
(3) pre-burning
Powder after being ground up, sieved in step (2) is put into crucible, cover, sealing: in Muffle furnace in 900 DEG C into Row pre-burning keeps the temperature 3 hours, naturally cools to room temperature, come out of the stove to obtain the powder after pre-burning；
(4) secondary ball milling
By the powder of pre-burning in step (3), it is anhydrous that ball milling solvent is added in ground 60 mesh, loading ball grinder in mortar Ethyl alcohol and zirconia ball, secondary ball milling 24 hours, revolving speed was 300 revs/min, and powder is put into 80 DEG C of drying of baking oven and obtains secondary ball Powder after ink；
(5) it forms
By step (4) drying secondary spheroidal graphite after powder it is levigate after, be put into mold, be just pressed into it is cylindric, recycle Equal static pressure depress to green body in 250MPa pressure；
(6) it is sintered
The green body pressed in step (5) is put into crucible, is covered, is buried material with similar powder and bury burning, in 1300 DEG C Sintering keeps the temperature 2 hours, and with furnace cooled to room temperature, potsherd is made；
(7) electrode is burnt
The burned potsherd of step (6) is polishing to a thickness of 0.6mm, naturally dry, lower surface coats silver paste on it, It is placed in furnace by room temperature to 600 DEG C, keeps the temperature 20min, high-compactness lead-free ceramics are made in cooled to room temperature.
The dielectric properties of high-compactness lead-free ceramics made from the present embodiment are tested, as a result referring to fig. 2, Fig. 2 is different dense The dielectric constant with temperature variation relation figure of the NN system sample of BMN doping is spent, dielectric constant maximum value corresponding temperature is Curie Temperature.The Curie temperature of each component ceramics sample can be determined from Fig. 2.And it was found that with the increase of BMN doping, not Lead to the generation for spreading phase transformation.
Meanwhile the Curie temperature of the NN system sample of various concentration BMT and BMN doping is shown with doping content in Fig. 3 The relational graph of variation, horizontal axis are doping concentration, and the longitudinal axis is Curie temperature, carry out linear fit later.From figure 3, it can be seen that with The raising of BMT doping content, the system Curie temperature generation sharply decline, be approximately linearly reduced to 216 from 375 DEG C DEG C, Bi (Mg0.5Ti0.5)O3Doping it is every increase by 1%, Curie temperature reduce about 33 DEG C；With the raising of BMN doping content, The Curie temperature variation of the system is similar with BMT doping, 169 DEG C is approximately linearly reduced to from 375 DEG C, Bi (Mg0.5Ti0.5)O3 Doping it is every increase by 1%, Curie temperature reduce about 34 DEG C.
In conclusion it is matrix that the present invention, which mainly utilizes the lead-free anti-ferroelectric ceramics of this high-curie temperature of sodium niobate, BMT and BMN is added on the basis of this adjusts ceramic Curie temperature.Specific chemical expression is (1-x) NaNbO3-xBi (Mg0.5Ti0.5)O3(referred to as (1-x) NN-xBMT, x=0-0.05) and (1-x) NaNbO3-xBi(Mg2/3Nb1/3)O3(referred to as (1- X) NN-xBMN, x=0-0.06).It uses oxide and carbonate for raw material, by traditional solid phase synthesis preparation method thereof, obtains A kind of leadless electronic that consistency is high ceramics.The material composition and processing step of preparation method of the present invention are simple, and method is easy to It operates, is reproducible；The every increase by 1% of the content of BMT or BMN, 33 DEG C or 34 DEG C of Curie temperature linear decline.By to Curie's temperature The regulation of degree can regulate and control its dielectric, ferroelectricity and strain property in turn, have very high application value.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention Protection scope within.

Claims (8)

1. a kind of method of regulation sodium niobate ceramics Curie temperature, which is characterized in that using sodium niobate as matrix, pass through and add Bi (Mg0.5Ti0.5)O3Or Bi (Mg2/3Nb1/3)O3Regulate and control sodium niobate ceramics Curie temperature.
2. the method for regulation sodium niobate ceramics Curie temperature according to claim 1, which is characterized in that including following step It is rapid:
1) weighing: chemical formula (1-x) NaNbO is pressed3-xBi(Mg0.5Ti0.5)O3The proportion of middle each element takes raw material Na2CO3、 Nb2O5、Bi2O3, MgO and TiO2, wherein x=0-0.05；
Alternatively, pressing chemical formula (1-x) NaNbO3-xBi(Mg2/3Nb1/3)O3The proportion of middle each element takes raw material Na2CO3、Nb2O5、 Bi2O3And MgO, wherein x=0-0.06；
2) ball milling: being put into ball grinder after raw material is mixed, and dehydrated alcohol is added and zirconia ball, abundant ball milling are dried, ground Mill crosses 60 meshes, obtains powder；
3) pre-burning: by powder in 900 DEG C of progress pre-burnings, 3 hours is kept the temperature, naturally cools to room temperature, the powder after obtaining pre-burning；
4) secondary ball milling: the powder that pre-burning is obtained grinds, crosses 60 meshes, is packed into ball grinder, and ball milling solvent dehydrated alcohol is added And zirconia ball, after secondary ball milling, drying, the powder after obtaining secondary ball milling；
5) it forms: after the powder grinding carefully after secondary ball milling, being put into mold and be molded, be just pressed into cylindric, recycling Equal static pressure depress to green body in 250MPa pressure；
6) it is sintered: green body is put into crucible, cover, bury material with similar powder and bury burning, be sintered in 1300 DEG C, heat preservation 2 is small When, with furnace cooled to room temperature, potsherd is made；
7) it burns electrode: potsherd is polishing to a thickness of 0.6mm, naturally dry, lower surface coats silver paste on it, is placed in furnace By room temperature to 600 DEG C, 20min is kept the temperature, high-compactness lead-free ceramics are made in cooled to room temperature.
3. the method for regulation sodium niobate ceramics Curie temperature according to claim 2, which is characterized in that ball milling in step 2) Secondary ball milling revolving speed is 300 revs/min in revolving speed and step 4).
4. the method for regulation sodium niobate ceramics Curie temperature according to claim 2, which is characterized in that drying in step 2) It with drying in step 4) is carried out at 80 DEG C.
5. the method for regulation sodium niobate ceramics Curie temperature according to claim 2, which is characterized in that the mould in step 5) Pressure is to be put into powder in the stainless steel mould that diameter is 10mm to be pressed.
6. the method for regulation sodium niobate ceramics Curie temperature according to claim 2, which is characterized in that step 3), step 6) and the heating rate in step 7) is 3 DEG C/min.
7. the method for regulation sodium niobate ceramics Curie temperature according to claim 2, which is characterized in that raw material Na2CO3、 Nb2O5、Bi2O3, MgO and TiO2Purity be respectively 99.8%, 99.99%, 99%, 98.5% and 98%.
8. regulating and controlling the method for sodium niobate ceramics Curie temperature described according to claim 1~any one of 7, feature exists In when by adding Bi (Mg0.5Ti0.5)O3When regulating and controlling sodium niobate ceramics Curie temperature, high-compactness lead-free ceramics obtained Curie temperature is approximately linearly reduced to 216 DEG C, and Bi (Mg from undoped 375 DEG C0.5Ti0.5)O3Doping is every to increase by 1%, Curie temperature reduces by 33 DEG C；
When by adding Bi (Mg2/3Nb1/3)O3When regulating and controlling sodium niobate ceramics Curie temperature, high-compactness lead-free ceramics obtained Curie temperature is approximately linearly reduced to 169 DEG C, and Bi (Mg from undoped 375 DEG C2/3Nb1/3)O3Doping is every to increase by 1%, Curie temperature reduces by 34 DEG C.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111704463A (en) * 2020-07-18 2020-09-25 桂林理工大学 Dielectric ceramic material and preparation method thereof
CN112159227A (en) * 2020-10-11 2021-01-01 浙江清华长三角研究院 Potassium-sodium niobate-based leadless piezoelectric ceramic and manufacturing process thereof
CN113929458A (en) * 2021-08-13 2022-01-14 桂林理工大学 High-efficiency high-energy-storage sodium niobate-based ceramic material and preparation method thereof
CN115353385A (en) * 2022-08-30 2022-11-18 苏州攀特电陶科技股份有限公司 Preparation method for enhancing thermal stability of lead-free piezoelectric ceramic
CN115536390A (en) * 2022-10-12 2022-12-30 长安大学 Transparent dielectric energy storage ceramic material and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111704463A (en) * 2020-07-18 2020-09-25 桂林理工大学 Dielectric ceramic material and preparation method thereof
CN111704463B (en) * 2020-07-18 2022-04-12 桂林理工大学 Dielectric ceramic material and preparation method thereof
CN112159227A (en) * 2020-10-11 2021-01-01 浙江清华长三角研究院 Potassium-sodium niobate-based leadless piezoelectric ceramic and manufacturing process thereof
CN113929458A (en) * 2021-08-13 2022-01-14 桂林理工大学 High-efficiency high-energy-storage sodium niobate-based ceramic material and preparation method thereof
CN115353385A (en) * 2022-08-30 2022-11-18 苏州攀特电陶科技股份有限公司 Preparation method for enhancing thermal stability of lead-free piezoelectric ceramic
CN115536390A (en) * 2022-10-12 2022-12-30 长安大学 Transparent dielectric energy storage ceramic material and preparation method and application thereof

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