CN110041073B - Preparation method of potassium-sodium niobate ceramic - Google Patents

Preparation method of potassium-sodium niobate ceramic Download PDF

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CN110041073B
CN110041073B CN201910471170.0A CN201910471170A CN110041073B CN 110041073 B CN110041073 B CN 110041073B CN 201910471170 A CN201910471170 A CN 201910471170A CN 110041073 B CN110041073 B CN 110041073B
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potassium
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nbo
sodium
sodium niobate
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顾永军
杨兴化
胡伟
黄金亮
李谦
李丽华
李新利
李海涛
孙晓岗
吴建彪
梅国建
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Henan University of Science and Technology
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Abstract

The invention relates to a method for preparing potassium-sodium niobate ceramicsThe preparation method is as follows. The preparation method comprises the following steps: will consist essentially of nano-KxNa1‑ xNbO3Grinding the mixture consisting of the powder, the niobium source, the potassium source, the sodium source and the solvent uniformly, pressing the mixture into a block at the temperature of 150-440 MPa and the pressure of 430-440MPa, drying the block, and then carrying out heat treatment at the temperature of more than 700 ℃ to obtain the niobium-potassium-sodium mixed oxide. The solid phase particles are rearranged in the pressing process of the preparation method, the point contact parts among the particles and the niobium source are dissolved, reacted and separated out in a natural mineralizing mode, and the separated out amorphous substance is filled in KxNa1‑xNbO3The internal holes are reduced at the periphery and the clearance of the particles, the density of the material is increased, and the amorphous substance is crystallized through post-heat treatment, so that the particles are gradually changed from a spherical shape to a polygonal shape, and finally a densified polycrystalline structure is formed, and the density and the piezoelectric property of the ceramic are obviously improved.

Description

Preparation method of potassium-sodium niobate ceramic
Technical Field
The invention belongs to the field of potassium-sodium niobate ceramics, and particularly relates to a preparation method of potassium-sodium niobate ceramics.
Background
The piezoelectric ceramic is a functional ceramic material capable of converting electric energy and mechanical energy into each other, and belongs to one of inorganic non-metallic materials. Since the discovery of the piezoelectric effect, lead-based piezoelectric ceramics (PZT) is a main variety in the market, but the content of lead in the PZT is high, and environmental problems can be encountered in the production and application processes of the PZT. The potassium-sodium niobate ceramic is widely concerned with environmental protection and superior piezoelectric performance.
The potassium-sodium niobate ceramic prepared by the traditional sintering process has the defects of high sintering temperature (1100-1200 ℃) and long process period. Many processes (e.g., microwave sintering, spark plasma sintering, two-step sintering, etc.) have been used to lower the sintering temperature of potassium-sodium niobate ceramics, but the effect of lowering the sintering temperature is still not ideal.
The chinese patent application with publication number CN108585847A discloses a method for preparing potassium sodium niobate-based ceramics, which comprises the following steps: first preparing K0.5Na0.5NbO3Pulverizing, and collecting a certain amount of K0.5Na0.5NbO3Adding 10 wt% of potassium hydroxide and sodium hydroxide mixed solution into the powder, fully and uniformly grinding the powder in a mortar, then applying 350MPa pressure to the ground material at 120 ℃ for compression molding, and maintaining the pressure for 120min to obtain a blank; and fully drying the prepared blank at 120 ℃, then placing the blank in a muffle furnace to sinter for 240min at the temperature of 650 ℃, and naturally cooling to room temperature to prepare the potassium-sodium niobate ceramic. Although the preparation method realizes the low-temperature sintering preparation of the potassium-sodium niobate ceramic, the compactness and the piezoelectric property of the potassium-sodium niobate ceramic still need to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of potassium-sodium niobate ceramic, which aims to solve the problem that the density and the piezoelectric property of the potassium-sodium niobate ceramic prepared by the existing sintering method need to be further improved.
In order to achieve the purpose, the preparation method of the potassium-sodium niobate ceramic adopts the technical scheme that:
a preparation method of potassium-sodium niobate ceramic comprises the following steps: will consist essentially of nano-KxNa1-xNbO3Grinding a mixture consisting of the powder, the niobium source, the potassium source, the sodium source and the solvent uniformly, pressing the mixture into a block at the temperature of 150-;
the dosage of the niobium source, the potassium source and the sodium source conforms to KxNa1-xNbO3After said heat treatment has been converted to KxNa1-xNbO3；KxNa1-xNbO3Wherein x is more than 0 and less than 1.
The preparation method of the potassium-sodium niobate ceramic provided by the invention is used for preparing nano KxNa1-xNbO3Pressing the semi-fluid mixture consisting of the powder, the niobium source, the potassium source, the sodium source and the solvent to prepare a blank, wherein solid phase particles are rearranged in the pressing process, and the nano KxNa1-xNbO3The point contact parts among the powder particles and the niobium source are dissolved, reacted and separated out in a natural mineralizing mode, and the separated out amorphous substance is filled in KxNa1-xNbO3The internal holes are reduced at the periphery and the clearance of the particles, the density of the material is increased, and the amorphous substance is crystallized through post-heat treatment, so that the particles are gradually changed from a spherical shape to a polygonal shape, and finally a densified polycrystalline structure is formed, and the density and the piezoelectric property of the ceramic are obviously improved.
In the grinding process, the solvent wets the surface of the solid particles, so that preparation is provided for later-stage particle migration and rearrangement through liquid phase, the mixture is preferably in a semi-fluid state, and preferably, the mass content of the solvent in the mixture is not more than 15%.
In the course of pressing, KxNa1-xNbO3Wetting the powder particles, pressing at a certain temperature and pressure, evaporating water, KxNa1-xNbO3The liquid on the surface of the powder particles reaches a supersaturated state and can be in KxNa1-xNbO3Amorphous substances (potassium sodium niobate or precursors thereof) are formed on the surfaces of powder particles, a morphotropic phase boundary tends to be formed in a blank, and the morphotropic phase boundary is good for forming a compact polycrystalline structure by subsequent heat treatmentAnd (4) preparing. Preferably, the pressing time is 1-120 min.
The mold can be directly heated to 150-. In order to further optimize the pressing process and promote the formation of a green body with good consistency and uniformity, it is preferable that the green body is pressed at normal temperature and 440MPa for 10-15min at 430-440MPa before being pressed at the temperature of 150-160 ℃ and the pressure of 430-440 MPa.
Preferably, the heat treatment time is 3-4h, in view of energy saving, promotion of full conversion of crystal form and further improvement of product density.
To further simplify the preparation of the mixture, the liquid phase is made to be opposite to the nano KxNa1-xNbO3The wetting effect of the powder is better, so that the formation of a densified polycrystalline structure is promoted, and preferably, the mixture is prepared by the following steps: firstly preparing a niobium source, a potassium source, a sodium source and a solvent into a suspension, and then preparing KxNa1-xNbO3Grinding and uniformly mixing the powder and the suspension; the mass of the suspension is nanometer KxNa1-xNbO330-40% of the powder mass.
Further optimizing the dispersion uniformity of the mixture, and preferably, the concentration of the potassium source in the suspension is 2-10 mol/L.
Detailed Description
The invention mainly provides a low-temperature densification process of potassium-sodium niobate ceramic, which mainly comprises the step of performing low-temperature densification on nano KxNa1- xNbO3Grinding and mixing the powder, the niobium source, the potassium source, the sodium source and the solvent to form a semi-fluid mixture, then applying certain pressure and temperature, rearranging solid-phase particles in the pressing process, and KxNa1-xNbO3The point contact parts among the powder particles and the niobium source are dissolved, reacted and separated out in a natural mineralizing mode, and the separated out amorphous substance is filled in KxNa1-xNbO3The positions of the periphery and the gaps of the particles reduce the inner holes,the density of the material is increased, and the amorphous substance is crystallized through post heat treatment, so that the particles are gradually changed from spherical to polygonal, and finally a densified polycrystalline structure is formed, and the density and the piezoelectric property of the ceramic are obviously improved.
The mixture can be directly fed, fully ground and mixed to achieve a uniform semi-fluid form. The total mass of the niobium source, the potassium source, the sodium source and the solvent is nano KxNa1-xNbO330-40% of the powder (with particle size of 50-100 nm). The content of solvent in the mix is very small, generally less than 15 wt.%, even if it is too small<1wt.％。
The preparation of the semi-fluid mixture can also adopt the following method: firstly, preparing a niobium source, a potassium source, a sodium source and a solvent into a suspension, and then preparing the nano KxNa1-xNbO3Grinding and mixing the powder and the suspension to form a semi-fluid mixture. Nb source can be selected from Nb2O5And the like. The suspension mode can improve Nb to a certain extent2O5Solubility of (2) and also of (K)xNa1-xNbO3The components of the mixed powder are uniformly dispersed, and the suspension can further contain cosolvents such as ethanol and the like to enhance the dispersion effect of the suspension.
The grinding and mixing can be achieved by means of a grinder, and in general, grinding at 800r/min for 1-2min is sufficient.
The pressing process at a certain temperature and pressure after grinding and mixing is crucial to the formation of a densified polycrystalline structure, and volatilization of water occurs during the pressing process, which further promotes the precipitation of amorphous substances; the passage of moisture discharged during pressing is limited, drying is incomplete, and a further drying process is required to remove residual water. The temperature of the drying treatment can be 110-200 ℃, and the time can be set to 10-14 h.
During the heat treatment, the temperature is kept above 700 ℃ for at least 3h to form the densified potassium-sodium niobate ceramic, and the temperature of the heat treatment is preferably 700-900 ℃ from the aspect of energy conservation. The rate of heating to 700 ℃ and 900 ℃ can be set to 2-8 ℃/min.
The following examples are provided to further illustrate the practice of the invention.
The specific embodiment of the preparation method of the potassium-sodium niobate ceramic of the invention is as follows:
example 1
The preparation method of the potassium-sodium niobate ceramic of the embodiment adopts the following steps:
1) taking Nb2O5KOH, NaOH and deionized water are prepared into suspension, wherein Nb2O5The mol ratio of KOH to NaOH is Nb2O5: KOH: NaOH 1: 1: 1, the concentration of KOH in the suspension is 5 mol/L;
2) mixing the suspension with K with a particle size of 100nm0.5Na0.5NbO3Grinding and mixing the powder for 2min, and placing the powder into a mould, wherein the weight of the suspension accounts for K0.5Na0.5NbO330% of the weight of the powder;
3) uniaxially pressurizing the material in the mold at 430MPa, preserving heat and pressure at room temperature for 13min, then heating to 160 ℃ at the heating rate of 9 ℃/min, preserving heat and pressure for 30min, and obtaining a blank;
4) and (3) preserving the temperature of the blank at 200 ℃ for 12h, then heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 3.5h to obtain the densified piezoelectric ceramic.
Example 2
The preparation method of the potassium-sodium niobate ceramic of the embodiment adopts the following steps:
1) taking Nb2O5KOH, NaOH and deionized water are prepared into suspension, wherein Nb2O5The mol ratio of KOH to NaOH is Nb2O5: KOH: NaOH 1: 1: 1, the concentration of KOH in the suspension is 2 mol/L;
2) mixing the suspension with K having a particle size of 80nm0.5Na0.5NbO3Grinding and mixing the powder for 1min, and placing the powder into a mould, wherein the weight of the suspension accounts for K0.5Na0.5NbO335% of the weight of the powder;
3) uniaxially pressurizing the material in the mold at 430MPa, preserving heat and pressure at room temperature for 12min, then heating to 158 ℃ at the heating rate of 9 ℃/min, preserving heat and pressure for 1min, and obtaining a blank;
4) and (3) keeping the blank at 200 ℃ for 12h, then heating to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3h to obtain the densified piezoelectric ceramic.
Example 3
The preparation method of the potassium-sodium niobate ceramic of the embodiment adopts the following steps:
1) taking Nb2O5KOH, NaOH and deionized water are prepared into suspension, wherein Nb2O5The mol ratio of KOH to NaOH is Nb2O5: KOH: NaOH 1: 1: 1, the concentration of KOH in the suspension is 8 mol/L;
2) mixing the suspension with K with a particle size of 50nm0.5Na0.5NbO3Grinding and mixing the powder for 1.5min, and placing the powder into a mould, wherein the weight of the suspension accounts for K0.5Na0.5NbO333% of the weight of the powder;
3) uniaxially pressurizing the material in the die at 435MPa, preserving heat and pressure at room temperature for 10min, then heating to 155 ℃ at the heating rate of 10 ℃/min, preserving heat and pressure for 100min, and obtaining a blank;
4) and (3) preserving the temperature of the blank at 200 ℃ for 12h, then heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 4h to obtain the densified piezoelectric ceramic.
Example 4
The preparation method of the potassium-sodium niobate ceramic of the embodiment adopts the following steps:
1) taking Nb2O5KOH, NaOH and deionized water are prepared into suspension, wherein Nb2O5The mol ratio of KOH to NaOH is Nb2O5: KOH: NaOH 1: 1: 1, the concentration of KOH in the suspension is 10 mol/L;
2) mixing the suspension with K with particle size of 65nm0.5Na0.5NbO3Grinding and mixing the powder for 2min, and placing the powder into a mould, wherein the weight of the suspension accounts for K0.5Na0.5NbO340% of the weight of the powder;
3) uniaxially pressurizing the material in the die at 432MPa, preserving heat and pressure for 15min at room temperature, then heating to 150 ℃ at the heating rate of 10 ℃/min, preserving heat and pressure for 120min, and obtaining a blank;
4) and (3) preserving the temperature of the blank at 200 ℃ for 12h, then heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 3h to obtain the densified piezoelectric ceramic.
Example 5
The process for producing the potassium-sodium niobate ceramic of this example is substantially the same as that of example 1 except that K isxNa1- xNbO3X in powder is 0.3, Nb2O5The mol ratio of KOH to NaOH is Nb2O5：KOH：NaOH＝0.5：0.3：0.7。
Example 6
The process for producing the potassium-sodium niobate ceramic of this example is substantially the same as that of example 1 except that K isxNa1- xNbO3X in powder is 0.7, Nb2O5The mol ratio of KOH to NaOH is Nb2O5：KOH：NaOH＝0.5：0.7：0.3。
Comparative example
The preparation method of the potassium-sodium niobate ceramic of the comparative example is basically the same as that of example 1, except that the suspension is prepared from KOH, NaOH and deionized water, and the molar ratio of KOH to NaOH is KOH: NaOH 1: and 1, the concentration of KOH in the suspension is 5 mol/L.
Examples of the experiments
This experimental example examined the performance indexes of the densified piezoelectric ceramics obtained in examples 1 to 6 of the method for producing potassium-sodium niobate ceramics, and the results are shown in table 1. Wherein the density test adopts Archimedes drainage method, and the piezoelectric constant measurement adopts ZJ-3AN type d33The tester detects the relative dielectric constant and dielectric loss by adopting a dielectric temperature spectrum measuring system (comprising an HP4294A impedance analyzer), and determines the Curie temperature (T) according to the temperature corresponding to the maximum value of the relative dielectric constantC)。
TABLE 1 Performance index of potassium-sodium niobate ceramics of examples and comparative examples
Degree of compactness% Piezoelectric constant d33，pC/N Curie temperature,. degree.C Relative dielectric constant Dielectric loss
Example 1 92.7 110 412 695 0.03
Example 2 93.5 106 416 678 0.04
Example 3 95.6 136 424 726 0.02
Example 4 91.8 92 409 657 0.04
Example 5 93.1 85 402 641 0.04
Example 6 92.9 76 385 648 0.03
Comparative example 90.5 84 407 637 0.05
As is clear from the results in Table 1, the density of the potassium-sodium niobate ceramics of examples was 91.8% or more, and the piezoelectric constant d at room temperature was found to be33Reaches 76-136pC/N, Curie temperature reaches 385-424 ℃, relative dielectric constant reaches 641-726, and dielectric loss is 2-5%. In comparison with the comparative example, K obtained by the process of the invention0.5Na0.5NbO3The density and the piezoelectric performance of the ceramic sample are both greatly improved.

Claims (6)

1. Method for preparing potassium-sodium niobate ceramicThe preparation method is characterized by comprising the following steps: will consist essentially of nano-KxNa1- xNbO3Grinding a mixture consisting of the powder, the niobium source, the potassium source, the sodium source and the solvent uniformly to obtain a semi-fluid mixture; pressing at 160 ℃ and 440MPa to form a block, drying, and performing heat treatment at above 700 ℃ to obtain the product;
the dosage of the niobium source, the potassium source and the sodium source conforms to KxNa1-xNbO3After said heat treatment has been converted to KxNa1-xNbO3；KxNa1-xNbO3In the specification, x is more than 0 and less than 1;
the mixture is prepared by the following steps: firstly preparing a niobium source, a potassium source, a sodium source and a solvent into a suspension, and then preparing KxNa1-xNbO3Grinding and uniformly mixing the powder and the suspension; the mass of the suspension is nanometer KxNa1-xNbO330-40% of the powder mass.
2. The method of producing a potassium-sodium niobate ceramic of claim 1, wherein the solvent content in the mixed material is not more than 15% by mass.
3. The method of preparing a potassium-sodium niobate ceramic of claim 1, wherein the pressing time is 1 to 120 min.
4. The method for preparing potassium-sodium niobate ceramic as claimed in claim 1 or 3, wherein the pressing is performed at normal temperature and at a pressure of 430-440MPa for 10-15min before the pressing is performed at a temperature of 150-160 ℃ and a pressure of 430-440 MPa.
5. The method of preparing a potassium-sodium niobate ceramic of claim 1, wherein the heat treatment time is 3 to 4 hours.
6. The method of producing a potassium-sodium niobate ceramic according to claim 5, wherein the concentration of the potassium source in the suspension is 2 to 10 mol/L.
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CN101792869A (en) * 2010-01-29 2010-08-04 刘文祥 Cluster body
WO2012114938A1 (en) * 2011-02-22 2012-08-30 Fdk株式会社 Alkaline niobate piezoelectric material and production method for alkaline niobate piezoelectric material
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