CN108863350B - Bismuth titanate-based perovskite phase thermal sensitive ceramic composite material and preparation method and application thereof - Google Patents
Bismuth titanate-based perovskite phase thermal sensitive ceramic composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material, a preparation method and application thereof0.5Bi0.5TiO3‑(1‑x)Zn0.5Bi0.5TiO3（0<x<1) The bismuth titanate-based perovskite phase heat-sensitive ceramic material is prepared by drying, presintering, grinding, prepressing for forming, cold isostatic pressing and sintering the powder, has small and uniform crystal grains and good density, and has obvious negative temperature coefficient characteristic in the temperature range of 350-900 ℃, and the electrical property research result shows that: along with the increase of the composite amount of the bismuth zinc titanate, the resistance value of the ceramic material is increased, the B value is reduced, and the ceramic material is suitable for novel thermosensitive ceramic materials for temperature measurement and temperature control in a high-temperature region.
Description
Technical Field
The invention relates to a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material, a preparation method and application thereof, in particular to a perovskite phase thermal sensitive ceramic material which is applied to the field of high-temperature thermistors, has obvious negative temperature coefficient characteristic in the temperature range of 350-900 ℃, and is suitable for preparing high-temperature thermistors.
Background
The material is one of three major pillars of human society, and plays a significant role in national economy. With the rapid development of high-technology content industries such as electronics, communication, control and the like, the requirements for intellectualization, multifunction, miniaturization of devices and the like of materials are continuously improved, and research and development of functional materials occupy more and more important positions in the high and new technology field. The resistance value of the negative temperature coefficient thermal sensitive material, namely the NTC thermal sensitive material, is exponentially reduced along with the rise of the temperature, the resistance value-temperature coefficient is generally several percent, and the excellent sensitivity enables the material to detect the extremely small temperature change, so the material is an ideal thermal sensitive element material. In recent years, the demand for thermistors in the industries of medical treatment, automotive, aerospace, and the like has been on the rise, and particularly in the aerospace field, high-temperature thermistors are required to accurately measure the temperature of the exhaust gas of a turbine engine and the temperature of the high-temperature combustion gas of a gas turbine; in the automotive field, high temperature thermistors are needed to accurately control the temperature of the engine, thereby improving fuel efficiency and optimizing gas emissions. Generally, a thermistor with the temperature higher than 300 ℃ is considered to be a high-temperature thermistor, and the high-temperature thermistor is an ideal product for replacing an industrial noble metal sensor, has a wide prospect, and becomes one of four main problems in the field of thermistors. When the traditional spinel-type transition metal oxide thermal sensitive material is used at high temperature, a serious aging phenomenon often occurs, even irreversible change of the temperature resistance characteristic occurs, the research of the high-temperature thermal sensitive resistance material is promoted, and a new challenging subject is provided for the development of a novel high-temperature thermal sensitive resistance material.
Perovskite structures (ABO) in recent years3) The material is widely used in the fields of piezoelectricity, ferroelectricity, dielectric and the like, wherein sodium bismuth titanate and zinc bismuth titanate are a composite perovskite structure material with A-site ions substituted, and the total coordination is A: b: o is 12: 6: 6, Bi3+And Na+/Zn+Has a very close ionic radius, generally occupies the A site together in a ratio of 1:1, Ti4+The ions occupy the B site. For perovskite-type NTC thermosensitive ceramic materials, the main mechanism of electrical conduction is considered to be small polaron hopping conductance, i.e. small polaron hopping conductanceResulting from metal or oxygen vacancies formed by deviations from stoichiometry, and acceptor or donor impurity defects formed by substitution of cations having different valences. The sodium bismuth titanate and the zinc bismuth titanate contain Ti2+、Ti3+、Ti4+And Bi3+、Bi5+Several ions with different valence states have different valence states, and the acting force on the surrounding crystal lattices is different, so that the ions deviate from the equilibrium position, and the distortion forms a distortion field. The electron (hole) and the distortion field (polarization state) form a polaron, and the polaron accords with the polarization conduction theory of a perovskite phase, so that the invention firstly imagines and verifies that the bismuth titanate-based ceramic material substituted by the A-site ion has the temperature resistance characteristic of negative temperature coefficient. The powder prepared by adopting the Pechini method has the advantages of small particle size, good uniformity, high purity, low reaction temperature and the like, the electrical properties of the powder are tested after the powder is sintered into ceramic, and the result shows that the temperature and the resistance of the material show good linear rules in a high-temperature region of 350-plus-900 ℃, and the material can be used as a high-temperature negative temperature coefficient thermistor.
The novel perovskite thermistor material prepared by adopting the Pechini method is a negative temperature coefficient thermistor material suitable for a high-temperature region, has excellent negative temperature coefficient characteristics within the temperature range of 350-900 ℃, has stable electrical property and good consistency of a material system, and is suitable for manufacturing high-temperature thermistors for temperature measurement and control in the fields of aerospace and automobiles.
Disclosure of Invention
The invention aims to provide a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material, a preparation method and application thereof0.5Bi0.5TiO3-(1-x)Zn0.5Bi0.5TiO3(0<x<1) The bismuth titanate-based perovskite phase thermal sensitive ceramic material is obtained by the processing technologies of drying, presintering, grinding, prepressing and forming, cold isostatic pressing and sintering the powder, has small and uniform crystal grains, good density and obvious negative temperature coefficient characteristic within the temperature range of 350-900 ℃,is a novel thermal sensitive ceramic material suitable for preparing a high-temperature thermistor.
The invention relates to a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material, which is xNa0.5Bi0.5TiO3-(1-x)Zn0.5Bi0.5TiO3Wherein x is more than 0 and less than 1.
The preparation method of the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material comprises the following steps:
a. dissolving bismuth nitrate in ethylene glycol, heating in water bath at constant temperature and 40-70 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. mixing sodium acetate and zinc acetate serving as raw materials, dissolving in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for later use;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, magnetically stirring for 10-30min, uniformly mixing, adding a citric acid complexing agent, wherein the citric acid complexing agent and total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d while stirring, fully mixing, controlling the reaction temperature at 40-70 ℃, standing for 24-72h after the mixed solution is completely dripped, and obtaining transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 125-145 ℃, and drying for 48-72h to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 4-8h to obtain fine powder, presintering for 2-4h at the temperature of 400-600 ℃ to obtain light yellow powder, and grinding for 4-8h for later use;
h. the powder obtained in the step g is added with 5-15Kg/cm2The pressure is kept for 0.5-1min, and the formed block material is pressed into tabletsAnd (3) carrying out cold isostatic pressing on the material, maintaining the pressure for 2-10min at the pressure of 100-500MPa, and then sintering at the temperature of 950-1150 ℃ to prepare the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material.
The bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is applied to the preparation of a high-temperature thermistor in a negative temperature coefficient thermistor.
The application range of the material in the field of high-temperature thermistors is 350-900 ℃.
The invention relates to a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material, a preparation method and application thereof, wherein a Pechini method is adopted to prepare xNa0.5Bi0.5TiO3-(1-x)Zn0.5Bi0.5TiO3(0<x<1) The powder particles are small and uniform, the ceramic material after molding and cold isostatic pressing sintering has the advantages of small and uniform crystal grains, high density and the like, and the xNa obtained by the invention0.5Bi0.5TiO3-(1-x)Zn0.5Bi0.5TiO3(0<x<1) The ceramic material is applied to the field of negative temperature coefficient thermistors for the first time, and the NTC thermistor material which can be used in a high-temperature region and has high stability is obtained, and the electrical property research result shows that: along with the increase of the composite amount of the bismuth zinc titanate, the resistance value of the ceramic material is increased, the B value is reduced, and the ceramic material is suitable for temperature measurement and temperature control in a high-temperature region.
Drawings
FIG. 1 is a graph showing the relationship between the temperature-sensitive ceramic composite rho and T when x is 0.9;
FIG. 2 is a graph showing the relationship between the temperature-sensitive ceramic composite rho and T when x is 0.1;
fig. 3 is a graph showing the relationship between the temperature-sensitive ceramic composite material ρ and T when x is 0.5.
Detailed Description
The following examples are merely preferred embodiments of the present invention, and do not limit the scope of the present invention;
example 1
a. Dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature and 40 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with the molar percentage of Na to Zn of 9 to 1 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 40 ℃, standing for 72 hours after all the mixed solution is dripped to obtain transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 125 ℃, and drying for 72 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 4 hours to obtain fine powder, presintering the fine powder for 1 hour at the temperature of 600 ℃ to obtain light yellow powder, taking out the light yellow powder and grinding for 4 hours for later use;
h. the powder obtained in step g is added at a rate of 5Kg/cm2The pressure is kept for 1min, the formed block material is subjected to cold isostatic pressing, the pressure is kept for 2min under the pressure of 500MPa, and then the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is prepared by high-temperature sintering at the temperature of 950 ℃;
the obtained bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is coated with platinum slurry to prepare a thermal sensitive resistance electrode for electrochemical test, the measurement temperature zone is 350-900 ℃, the resistivity interval of the electrode at 350-900 ℃ is 19395482.2-475.7 +/-3% omega-cm, as shown in figure 1, the resistivity-temperature curve chart in figure 1 can be intuitively seen, and the resistivity of the electrode is in a linear decreasing relation along with the increase of the temperature; material constant ofB500/800The material has wide use temperature range and good stability as 14886.1 +/-1 percent K.
Example 2
a. Dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature of 70 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with the molar percentage of Na to Zn being 1 to 9 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and then adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 70 ℃, standing for 24 hours after the mixed solution is completely dripped, and obtaining transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 145 ℃, and drying for 48 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 4 hours to obtain fine powder, presintering the fine powder at the temperature of 600 ℃ for 1 hour to obtain light yellow powder, taking out the light yellow powder and grinding for 8 hours for later use;
h. the powder obtained in step g is mixed at 15Kg/cm2The pressure is pressed and molded, the pressure maintaining time is 0.5min, the molded block material is subjected to cold isostatic pressing, the pressure is maintained for 2min under the pressure of 500MPa, and then the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is prepared by high-temperature sintering at the temperature of 1150 ℃;
coating platinum slurry on the obtained bismuth titanate-based perovskite phase thermal sensitive ceramic composite material to prepare a thermistor electrode for electrochemical test, and measuring the temperatureThe region is 350-900 ℃, and the resistivity interval of the electrode at 350-900 ℃ is 1.77 multiplied by 109To 1661.0 ± 3% Ω · cm, see fig. 2, and it is apparent from the resistivity-temperature graph in fig. 2 that the resistivity of the electrode decreases linearly with increasing temperature; material constant of B500/80021703.1 ± 1% K; the material has wide use temperature range and good stability.
Example 3
a. Dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature and 55 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with the molar percentage of Na to Zn being 1 to 1 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and then adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 55 ℃, standing for 48 hours after the mixed solution is completely dripped, and obtaining transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 135 ℃, and drying for 52 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 6 hours to obtain fine powder, presintering the fine powder at 500 ℃ for 2 hours to obtain light yellow powder, taking out the light yellow powder and grinding for 6 hours for later use;
h. the powder obtained in step g is mixed at a rate of 10Kg/cm2The pressure of the pressure is kept for 0.7min, the formed block material is subjected to cold isostatic pressing, the pressure is kept for 5min under the pressure of 300MPa, and then the pressure is kept for 5minSintering at 1050 ℃ to prepare the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material;
the obtained bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is coated with platinum slurry to prepare a thermal sensitive resistance electrode for electrochemical test, the measurement temperature zone is 350-900 ℃, the resistivity interval of the electrode at 350-900 ℃ is 123608342.9-849.8 +/-3% omega-cm, as shown in figure 3, and the resistivity-temperature curve chart in figure 3 can be intuitively seen that the resistivity of the electrode is in a linear decreasing relation along with the increase of the temperature; material constant of B500/800The material has wide use temperature range and good stability as 17544.2 +/-1 percent K.
Claims (5)
1. A preparation method of a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is characterized by comprising the following steps:
a. dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature and 40 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with molar percentage of Na to Zn being 9 to 1 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 40 ℃, standing for 72 hours after all the mixed solution is dripped to obtain transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 125 ℃, and drying for 72 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 4 hours to obtain fine powder, presintering the fine powder for 1 hour at the temperature of 600 ℃ to obtain light yellow powder, taking out the light yellow powder and grinding for 4 hours for later use;
h. the powder obtained in step g is added at a rate of 5Kg/cm2The pressure is kept for 1min, the formed block material is subjected to cold isostatic pressing, the pressure is kept for 2min under the pressure of 500MPa, and then the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is prepared by high-temperature sintering at the temperature of 950 ℃.
2. A preparation method of a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is characterized by comprising the following steps:
a. dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature of 70 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with the molar percentage of Na to Zn being 1 to 9 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and then adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 70 ℃, standing for 24 hours after the mixed solution is completely dripped, and obtaining transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 145 ℃, and drying for 48 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 4 hours to obtain fine powder, presintering the fine powder at the temperature of 600 ℃ for 1 hour to obtain light yellow powder, taking out the light yellow powder and grinding for 8 hours for later use;
h. the powder obtained in step g is mixed at 15Kg/cm2The pressure is used for tabletting and forming, the pressure maintaining time is 0.5min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 2min under the pressure of 500MPa, and then the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is prepared by high-temperature sintering at the temperature of 1150 ℃.
3. A preparation method of a bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is characterized by comprising the following steps:
a. dissolving bismuth nitrate in ethylene glycol, heating in a water bath at constant temperature and 55 ℃, stirring until the bismuth nitrate is completely dissolved, and preparing into 0.5mol/L alkoxide solution for later use;
b. sodium acetate and zinc acetate with the molar percentage of Na to Zn being 1 to 1 are taken as raw materials, mixed and dissolved in absolute ethyl alcohol to prepare 0.5mol/L ion mixed solution for standby;
c. dissolving tetrabutyl titanate in absolute ethyl alcohol to prepare a solution of 1mol/L, dropwise adding acetylacetone to stabilize tetrabutyl titanate, and uniformly stirring to obtain a mixed solution for later use;
d. slowly dripping the solution obtained in the step a into the solution obtained in the step b, uniformly mixing, and then adding a citric acid complexing agent, wherein the citric acid complexing agent and the total metal ions Bi3+、Na+、Zn2+And Ti4+In a molar ratio of 1.5: 1;
e. slowly dripping the mixed solution obtained in the step c into the mixed solution obtained in the step d, stirring while dripping, fully mixing, controlling the reaction temperature at 55 ℃, standing for 48 hours after the mixed solution is completely dripped, and obtaining transparent light yellow sol;
f. putting the sol obtained in the step e into an oven, adjusting the temperature to 135 ℃, and drying for 52 hours to obtain brown xerogel;
g. f, putting the xerogel obtained in the step f into a mortar for grinding for 6 hours to obtain fine powder, presintering the fine powder at 500 ℃ for 2 hours to obtain light yellow powder, taking out the light yellow powder and grinding for 6 hours for later use;
h. the powder obtained in step g is mixed at a rate of 10Kg/cm2The pressure is used for tabletting and forming, the pressure maintaining time is 0.7min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 5min under the pressure of 300MPa, and then the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material is prepared by high-temperature sintering at the temperature of 1050 ℃.
4. Use of the bismuth titanate-based perovskite phase thermal sensitive ceramic composite material according to claim 1, 2 or 3 in preparation of a high temperature thermistor in a negative temperature coefficient thermistor.
5. Use according to claim 4, characterized in that the material has an application range in the field of high temperature thermistors of 350-900 ℃.
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| Bi0.5Na0.5TiO3:ZnO lead-free piezoelectric composites with deferred thermal;Ji Zhang;《Applied Physics Letters》;20150609;第232904-1~232904-4页 * |
| Morphotropic phase boundary and electrical properties in (1−x)Bi0.5Na0.5TiO3−xBi(Zn0.5Ti0.5)O3 lead-free piezoceramics;Shan-Tao Zhang;《Journal of Applied Physics》;20100610;第114110-1~114110-4页 * |
| Preparation and Properties of Lead Free Bismuth Sodium TitanateBismuth Zinc Titanate Ceramics;Muanghlua R;《Ferroelectrics》;20100920;第383卷(第1期);第1-7页 * |
| The crystallization and dielectric tunability of Zn doped Bi0.5Na0.5TiO3 thin films;Jin Qian;《Ceramics International》;20150901;第976–981页 * |
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