CN113563067A - Preparation method of high-density thin-layer electronic ceramic material - Google Patents
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Abstract
The invention relates to the field of electronic ceramic materials, in particular to a preparation method of a high-density thin-layer electronic ceramic material, which comprises the steps of adding water into bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate for mixing, adding ethylene glycol and activated carbon, and dropwise adding a reducing agent to adjust the pH value of a system to 1-2; heating and ball milling to obtain powder, uniformly mixing the powder and glass powder to obtain premix, transferring the premix into a mold, igniting the premix under the pressure of 100-150MPa to perform self-propagating reaction, naturally cooling the blank to room temperature, taking out the blank, heating and sintering for 2-3h, and then cooling and annealing.
Description
Technical Field
The invention relates to the field of electronic ceramic materials, in particular to a preparation method of a high-density thin-layer electronic ceramic material.
Background
The electronic ceramic material has two development directions at present, wherein one development direction is porous, a large number of interconnected or closed air holes are formed in the electronic ceramic material structure through a specific process, the electronic ceramic material has higher porosity, small volume density, developed specific surface and certain unique physical characteristics, and can be generally applied to the field where high-compactness electronic ceramic cannot be applied, such as the field of low-frequency sonar, and the other development direction is high-compactness, so that the pores in the electronic ceramic material structure are reduced, the grain size distribution is more uniform, the mechanical strength is higher, and the electronic ceramic material is generally applied to the field of buildings.
Chinese patent CN109503157A discloses a high-density high-piezoelectric constant piezoelectric ceramic, whose chemical formula is:
PbxM1-x(ZryTi1-y)0.75(Ni1/3Nb2/3)0.2(Sb1/3Nb2/3)0.015(Mg1/3Nb2/3)0.035O3+zwt％Bi2O3wherein x is 0.0 to 0.15, y is 0.45 to 0.55, z is 0 to 1, and M is Ba2+、Sr2+、Ca2+、La3+The density of the ceramic green body can reach 5.4g/cm3, the density uniformity is good, the ceramic performance consistency is high, the density of the sintered ceramic can reach 98% of the theoretical density, but the structure of the ceramic green body contains toxic element lead which is easy to volatilize during high-temperature sintering and causes environmental pollution.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects or the improvement requirements of the prior art, the invention provides a preparation method of a high-density thin-layer electronic ceramic material.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-density thin-layer electronic ceramic material comprises the following steps:
s1: adding bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate into deionized water, stirring and mixing for 20-50min, adding ethylene glycol and activated carbon, continuously stirring for 5-10min, and then dropwise adding a reducing agent to adjust the pH value of the system to 1-2;
s2: heating the reaction solution to 80-85 ℃ for the first time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 120-130 ℃ for the second time, preserving heat for 1-3h, and then ball-milling for 1-3h under the protection of nitrogen to obtain powder;
s3: uniformly mixing the powder and the glass powder to obtain a premix, transferring the premix into a mold, igniting the premix under the pressure of 100-150MPa to perform a self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, taking out the blank, heating to 1100-1200 ℃, sintering for 2-3h, cooling to 700-800 ℃, carrying out heat preservation annealing for 1-2h, and cooling in the furnace to room temperature to obtain the electronic ceramic material, wherein the electronic ceramic material is represented by the following chemical structural formula:
xBi0.5(NaaLi0.5-a)TiO3-(1-x)(BabCa1-b)TiO3
wherein x, a and b represent mole percent, x is 0.80-0.98, a is 0.40-0.45, and b is 0.80-0.95.
Further, the reducing agent in S1 is composed of citric acid, glutamic acid, and water.
Further, the mass ratio of citric acid to glutamic acid is 4-10: 1.
further, the mass ratio of citric acid to glutamic acid is preferably 5: 1.
furthermore, the using amount of the activated carbon in the S1 is 3-5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate.
Furthermore, the amount of the activated carbon in the S1 is 5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate.
Further, in S2, the primary heating rate is 1-2 ℃/min, and the secondary heating rate is 0.1-0.5 ℃/min.
Further, in S2, the first temperature rise rate is 1 ℃/min, and the second temperature rise rate is 0.2 ℃/min.
Further, the glass frit in S3 is CBS glass frit or BSB glass frit, and preferably CBS glass frit.
Furthermore, the using amount of the glass powder in the S3 is 0.5-1% of the mass of the powder.
Furthermore, the amount of the glass powder in the S3 powder is 0.5 percent of the mass of the powder.
Further, the ignition method in S3 is any one of plasma ignition, laser ignition, microwave ignition, and electric spark ignition, and preferably plasma ignition.
Further, in S3, the temperature rising speed is 5-10 ℃/min, and the temperature reducing speed is 1-2 ℃/min.
Furthermore, in S3, the temperature rising speed is 5 ℃/min, and the temperature reducing speed is 1 ℃/min.
Further, x is 0.94, a is 0.45, and b is 0.90.
The invention has the beneficial effects that:
the invention provides a high-density thin-layer electronic ceramic material, on one hand, a second component (Ba) is introduced into BNT0.90Ca0.10)TiO3The substitution of A site to form a solid solution system, the introduction of doping of lithium can cause charge compensation, lead to lattice relaxation and improve electrical properties, a three-square Morphotropic Phase Boundary (MPB) is generated after the two are dissolved in a solid solution, the electrical properties are obviously improved, the selectivity of a self-propagating combustion method to reactants is higher, the inventor also tries to prepare other electronic ceramic materials, but the effect is not good, but the material of the invention has good effect when being prepared, and the electronic ceramic material of the invention has good effect when being burnt, undergoes large temperature changes, has very high heating and cooling rates, concentrates defects in products compared with non-equilibrium, therefore, compared with the product manufactured by the traditional solid phase sintering method, the product has activity, the density of the material can be greatly improved by subsequent sintering, and the electronic ceramic material prepared by the invention has high density which is more than or equal to 7.57 g/cm.3The material has excellent mechanical properties, wherein the bending strength is more than or equal to 135.38MPa, the elastic modulus is more than or equal to 48.96GPa, and the material also has excellent electrical properties and wide application prospect.
Drawings
Fig. 1 is an SEM image of the electronic ceramic material prepared in example 1 of the present invention, which can be observed to have an extremely high degree of densification and uniformity.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a high-density thin-layer electronic ceramic material is represented by the following chemical structural formula:
0.94Bi0.5(Na0.45Li0.05)TiO3-0.06(Ba0.90Ca0.10)TiO3
the preparation method comprises the following steps:
weighing bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate according to the metering ratio of the chemical structural formula, adding the weighed materials into deionized water, stirring and mixing for 40min, adding ethylene glycol and activated carbon, wherein the dosage of the activated carbon is 5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate, continuously stirring for 10min, and then dropwise adding a reducing agent to enable the pH of a system to be 2, wherein the reducing agent is composed of citric acid, glutamic acid and water, and the mass ratio of the citric acid to the glutamic acid is 5: 1, heating the reaction liquid to 85 ℃ at the speed of 1 ℃/min for one time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 130 ℃ at the speed of 0.2 ℃/min for two times, preserving heat for 2 hours, then carrying out ball milling for 2 hours under the protection of nitrogen to obtain powder, uniformly mixing the powder and 0.5% of CBS glass powder in mass to obtain premix, transferring the premix into a mold, igniting plasma under the pressure of 120MPa to carry out self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, taking out the blank, heating to 1200 ℃ at the speed of 5 ℃/min to sinter for 2 hours, cooling to 800 ℃ at the speed of 1 ℃/min to preserve heat and anneal for 1 hour, and cooling to room temperature in a furnace.
Example 2:
a high-density thin-layer electronic ceramic material is represented by the following chemical structural formula:
0.94Bi0.5(Na0.45Li0.05)TiO3-0.06(Ba0.90Ca0.10)TiO3
the preparation method comprises the following steps:
weighing bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate according to the metering ratio of the chemical structural formula, adding the weighed materials into deionized water, stirring and mixing for 50min, adding ethylene glycol and activated carbon, wherein the dosage of the activated carbon is 5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate, continuously stirring for 10min, and then dropwise adding a reducing agent to enable the pH of a system to be 2, wherein the reducing agent is composed of citric acid, glutamic acid and water, and the mass ratio of the citric acid to the glutamic acid is 10: 1, heating the reaction liquid to 85 ℃ at the speed of 2 ℃/min for one time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 130 ℃ at the speed of 0.5 ℃/min for two times, preserving heat for 3 hours, then carrying out ball milling for 3 hours under the protection of nitrogen to obtain powder, uniformly mixing the powder and 1% of CBS glass powder in mass to obtain premix, transferring the premix into a mold, igniting plasma under the pressure of 150MPa to carry out self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, then taking out the blank, heating to 1200 ℃ at the speed of 10 ℃/min to sinter for 3 hours, cooling to 800 ℃ at the speed of 2 ℃/min to preserve heat and anneal for 2 hours, and cooling in a furnace to room temperature.
Example 3:
a high-density thin-layer electronic ceramic material is represented by the following chemical structural formula:
0.94Bi0.5(Na0.45Li0.05)TiO3-0.06(Ba0.90Ca0.10)TiO3
the preparation method comprises the following steps:
weighing bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate according to the metering ratio of the chemical structural formula, adding the weighed materials into deionized water, stirring and mixing for 40min, adding ethylene glycol and activated carbon, wherein the dosage of the activated carbon is 3% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate, continuously stirring for 5min, and then dropwise adding a reducing agent to enable the pH of a system to be 1, wherein the reducing agent is composed of citric acid, glutamic acid and water, and the mass ratio of the citric acid to the glutamic acid is 4: 1, heating the reaction liquid to 80 ℃ at the speed of 1 ℃/min for one time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 120 ℃ at the speed of 0.1 ℃/min for two times, preserving heat for 1h, then carrying out ball milling for 1h under the protection of nitrogen to obtain powder, uniformly mixing the powder and 0.5% of CBS glass powder in mass to obtain premix, transferring the premix into a mold, igniting plasma under the pressure of 100MPa to carry out self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, taking out the blank, heating to 1100 ℃ at the speed of 5 ℃/min to sinter for 2h, cooling to 700 ℃ at the speed of 1 ℃/min to preserve heat and anneal for 1h, and cooling to room temperature in a furnace.
Example 4:
a high-density thin-layer electronic ceramic material is represented by the following chemical structural formula:
0.94Bi0.5(Na0.45Li0.05)TiO3-0.06(Ba0.90Ca0.10)TiO3
the preparation method comprises the following steps:
weighing bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate according to the metering ratio of the chemical structural formula, adding the weighed materials into deionized water, stirring and mixing for 30min, adding ethylene glycol and activated carbon, wherein the dosage of the activated carbon is 5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate, continuously stirring for 5min, and then dropwise adding a reducing agent to enable the pH of a system to be 2, wherein the reducing agent is composed of citric acid, glutamic acid and water, and the mass ratio of the citric acid to the glutamic acid is 4: 1, heating the reaction liquid to 80 ℃ at the speed of 2 ℃/min for one time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 120 ℃ at the speed of 0.5 ℃/min for two times, preserving heat for 3 hours, then carrying out ball milling for 1 hour under the protection of nitrogen to obtain powder, uniformly mixing the powder and 1% of CBS glass powder in mass to obtain premix, transferring the premix into a mold, igniting plasma under the pressure of 150MPa to carry out self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, then taking out the blank, heating to 1200 ℃ at the speed of 5 ℃/min to sinter for 2 hours, cooling to 700 ℃ at the speed of 2 ℃/min to preserve heat and anneal for 2 hours, and cooling to room temperature in a furnace.
Example 5:
a high-density thin-layer electronic ceramic material is represented by the following chemical structural formula:
0.94Bi0.5(Na0.45Li0.05)TiO3-0.06(Ba0.90Ca0.10)TiO3
the preparation method comprises the following steps:
weighing bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate according to the metering ratio of the chemical structural formula, adding the weighed materials into deionized water, stirring and mixing for 50min, adding ethylene glycol and activated carbon, wherein the dosage of the activated carbon is 3% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate, continuously stirring for 10min, and then dropwise adding a reducing agent to enable the pH of a system to be 1, wherein the reducing agent is composed of citric acid, glutamic acid and water, and the mass ratio of the citric acid to the glutamic acid is 10: 1, heating the reaction liquid to 85 ℃ at the speed of 1 ℃/min for one time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 130 ℃ at the speed of 0.1 ℃/min for two times, preserving heat for 1h, then carrying out ball milling for 3h under the protection of nitrogen to obtain powder, uniformly mixing the powder and 0.5% of BSB glass powder in mass to obtain premix, transferring the premix into a mold, igniting plasma under the pressure of 150MPa to carry out self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, taking out the blank, heating to 1200 ℃ at the speed of 5 ℃/min to sinter for 2h, cooling to 700 ℃ at the speed of 2 ℃/min to preserve heat and anneal for 2h, and cooling to room temperature in a furnace.
Comparative example 1
Comparative example 1 is identical to example 1, except that no citric acid is added to the reducing agent.
Comparative example 2
Comparative example 2 is identical to example 1, except that no glutamic acid was added to the reducing agent.
Comparative example 3
Comparative example 3 is identical to example 1, except that no activated carbon was added.
Comparative example 4
Comparative example 4 is identical to example 1 except that no CBS glass frit was added.
And (3) testing mechanical properties:
the material density is measured according to the method of GBT2413-1980, the bending strength is measured in a three-point bending loading mode on an INSTRON-4505 universal testing machine according to the test method of GB/T6569-.
And (3) testing electrical properties:
the electronic ceramic materials prepared in the examples 1 to 5 and the comparative examples 1 to 5 are respectively polished, silver is applied to the electronic ceramic materials, silver electrodes are burnt at the temperature of 600 ℃, then the electronic ceramic materials are polarized for 10min by applying the direct current voltage of 4kV/mm to the silicon oil at the temperature of 80 ℃, and the electronic ceramic materials are stood for 24h to be subjected to performance test.
With quasi-static d of type ZJ-333The measuring instrument measures the piezoelectric constant of the sample; testing the resonance and anti-resonance frequency of the sample at room temperature and the parameters of equivalent resistance, equivalent capacitance and the like at 1kHz by using an impedance analyzer, and calculating the planar electromechanical coupling coefficient K of the samplepAnd a dielectric loss tan δ.
The results of the above tests are shown in table 1 below:
table 1:
as shown in Table 1, the electronic ceramic material prepared by the invention has high density which is more than or equal to 7.57g/cm3The material has excellent mechanical properties, wherein the bending strength is more than or equal to 135.38MPa, the elastic modulus is more than or equal to 48.96GPa, and the material also has excellent electrical properties and wide application prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a high-density thin-layer electronic ceramic material is characterized by comprising the following steps:
s1: adding bismuth nitrate, sodium nitrate, lithium nitrate, titanium nitrate, barium nitrate and calcium nitrate into deionized water, stirring and mixing for 20-50min, adding ethylene glycol and activated carbon, continuously stirring for 5-10min, and then dropwise adding a reducing agent to adjust the pH value of the system to 1-2;
s2: heating the reaction solution to 80-85 ℃ for the first time, preserving heat and stirring until no solvent exists, stopping stirring, heating to 120-130 ℃ for the second time, preserving heat for 1-3h, and then ball-milling for 1-3h under the protection of nitrogen to obtain powder;
s3: uniformly mixing the powder and the glass powder to obtain a premix, transferring the premix into a mold, igniting the premix under the pressure of 100-150MPa to perform a self-propagating reaction to obtain a blank, naturally cooling the blank to room temperature, taking out the blank, heating to 1100-1200 ℃, sintering for 2-3h, cooling to 700-800 ℃, carrying out heat preservation annealing for 1-2h, and cooling in the furnace to room temperature to obtain the electronic ceramic material, wherein the electronic ceramic material is represented by the following chemical structural formula:
xBi0.5(NaaLi0.5-a)TiO3-(1-x)(BabCa1-b)TiO3
wherein x, a and b represent mole percent, x is 0.80-0.98, a is 0.40-0.45, and b is 0.80-0.95.
2. The method for preparing a high-density thin-layer electronic ceramic material according to claim 1, wherein the reducing agent in S1 is composed of citric acid, glutamic acid and water.
3. The method for preparing a high-density thin-layer electronic ceramic material according to claim 2, wherein the mass ratio of citric acid to glutamic acid is 4-10: 1.
4. the preparation method of the high-density thin-layer electronic ceramic material according to claim 1, wherein the amount of the activated carbon in the S1 is 3-5% of the total mass of the bismuth nitrate, the sodium nitrate, the lithium nitrate, the titanium nitrate, the barium nitrate and the calcium nitrate.
5. The preparation method of the high-density thin-layer electronic ceramic material according to claim 1, wherein in S2, the primary heating rate is 1-2 ℃/min, and the secondary heating rate is 0.1-0.5 ℃/min.
6. The method for preparing a high-density thin-layer electronic ceramic material according to claim 1, wherein the glass frit in S3 is CBS glass frit or BSB glass frit.
7. The method for preparing a high-density thin-layer electronic ceramic material according to claim 1, wherein the amount of glass powder in S3 is 0.5-1% of the mass of the powder.
8. The preparation method of the high-density thin-layer electronic ceramic material according to claim 1, wherein the ignition mode in S3 is any one of plasma ignition, laser ignition, microwave ignition and electric spark ignition.
9. The preparation method of the high-density thin-layer electronic ceramic material according to claim 1, wherein the temperature rise rate in S3 is 5-10 ℃/min, and the temperature drop rate is 1-2 ℃/min.
10. The method for preparing a high-density thin-layer electronic ceramic material according to claim 1, wherein x is 0.94, a is 0.45, and b is 0.90.
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