CN114409401A - Potassium-sodium niobate piezoelectric ceramic, preparation method thereof and electronic equipment - Google Patents
Potassium-sodium niobate piezoelectric ceramic, preparation method thereof and electronic equipment Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 136
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910002976 CaZrO3 Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 230000010287 polarization Effects 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000009466 transformation Effects 0.000 abstract description 11
- 230000007704 transition Effects 0.000 abstract description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 21
- 239000011324 bead Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 8
- 238000007873 sieving Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
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- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- -1 sodium bismuth titanate series Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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Abstract
The invention relates to a potassium-sodium niobate piezoelectric ceramic, which has the following general formula: (0.96-x) (K)0.48Na0.52)Nb0.96Sb0.04O3‑0.04(Bi0.5Na0.5)ZrO3‑xCaZrO3‑0.4％Fe2O3Wherein x is CaZrO3X is more than 0 and less than or equal to 0.02. CaZrO is introduced into the ion-doped ternary component potassium-sodium niobate leadless piezoelectric ceramic3Is a new system source and can be well maintainedCan make T have the same piezoelectric property0‑TThe phase transformation point is stably reduced to room temperature, the difference between orthogonal and tetragonal phases is reduced, and the stable transition of polymorphic phase transformation is realized, so that the polycrystalline phase transformation has excellent temperature stability. In addition, the preparation process of the potassium-sodium niobate piezoelectric ceramic is simple, and the raw materials are nontoxic and harmless, so that the potassium-sodium niobate piezoelectric ceramic is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the field of functional ceramic materials, in particular to potassium-sodium niobate piezoelectric ceramic, a preparation method thereof and electronic equipment.
Background
The piezoelectric ceramic is a functional ceramic capable of realizing mutual conversion of mechanical energy and electric energy, has the advantages of convenience in manufacturing various functional components with low loss, high reliability and miniaturization, and has very wide application in various fields of daily production and life, such as transducers, sensors, drivers and the like. The mainstream material of the piezoelectric ceramic device in the market at present is a lead-based lead zirconate titanate (PZT) material, and the heavy metal element lead contained in the PZT material has great harm to organisms and the environment. Therefore, it is an extremely important task for researchers to develop a lead-free piezoelectric ceramic material that can replace lead zirconate titanate (PZT).
Three perovskite type lead-free piezoelectric ceramic materials (including potassium sodium niobate series, sodium bismuth titanate series and barium titanate series) are expected to be substituted for lead-based piezoelectric ceramics at present because of no harmful elements such as lead, and the potassium sodium niobate series ceramics become hot research materials of researchers because of good piezoelectric performance and higher Curie temperature. The research result shows that the piezoelectric performance of the pure potassium sodium niobate ceramic is far different from that of the practical PZT ceramic, and the piezoelectric performance of the potassium sodium niobate piezoelectric ceramic can be obviously improved by ion doping and construction of a binary system and a ternary system by taking the research idea of the PZT ceramic as reference, and can be comparable with that of the practical PZT ceramic. In general, the nature of the binary system is to combine the rhombohedral-orthorhombic phases of the potassium-sodium niobate systemThe transformation point is moved up to the room temperature or the orthorhombic-tetragonal transformation point is moved down to the room temperature; the design of the ternary system can simultaneously move the high-temperature orthogonal-tetragonal phase change point and the low-temperature rhombic-orthogonal phase change point to room temperature to construct rhombic-tetragonal phase change, and the piezoelectric constant of the KNN piezoelectric ceramic in the room-temperature coexisting two-phase region is remarkably improved. At present, the ternary system is mainly: k1-XNaXNb1-YSbYO3-zBiFeO3-wBi0.5Na0.5ZrO3(KNNS-zBF-wBNZ) and K1-XNaXNb1-YSbYO3-zBaZrO3-wBi0.5K0.5HfO3(KNNS-zBZ-wBKH) and the like, the piezoelectric performance of which is greatly improved compared with that of a unit and a binary system from the reported results, but the inventor easily finds that the Curie temperature of the composite potassium-sodium niobate material is lowered along with the improvement of the piezoelectric constant of the composite potassium-sodium niobate material, the application temperature range is narrowed, and the application range is greatly limited.
Many attempts have been made by researchers to improve the temperature stability of piezoelectric properties of potassium sodium niobate-based ceramics. Firstly, the polycrystalline phase transition temperature is regulated to be lower than the room temperature through doping, and the polycrystalline phase transition near the room temperature exists as the root cause of poor temperature stability of the potassium sodium niobate-based ceramic; another is to make textured ceramics. However, the former inevitably degrades the piezoelectric performance of the ceramic by circumventing the polycrystalline phase transition effect; the latter requires a complicated preparation process and does not require large-scale industrial production.
Disclosure of Invention
Accordingly, there is a need for a potassium-sodium niobate piezoelectric ceramic having good piezoelectric properties and good temperature stability, and a simple preparation process.
In addition, a preparation method of the potassium-sodium niobate piezoelectric ceramic is also provided.
A potassium-sodium niobate-based piezoelectric ceramic having the following general formula: (0.96-x) (K)0.48Na0.52)Nb0.96Sb0.04O3-0.04(Bi0.5Na0.5)ZrO3-xCaZrO3-0.4％Fe2O3Wherein x is CaZrO3X is more than 0 and less than or equal to 0.02.
CaZrO is introduced into the ion-doped ternary component potassium-sodium niobate leadless piezoelectric ceramic3Is a new system source, improves the density of the piezoelectric ceramics, can keep good piezoelectric performance and simultaneously can ensure T0-TThe phase transformation point is stably reduced to room temperature, the difference between orthogonal and tetragonal phases is reduced, and the stable transition of polymorphic phase transformation is realized, so that the polycrystalline phase transformation has excellent temperature stability. In addition, the preparation process of the potassium-sodium niobate piezoelectric ceramic is simple, and the raw materials are nontoxic and harmless, so that the potassium-sodium niobate piezoelectric ceramic is suitable for industrial large-scale production.
In one embodiment, 0 < x ≦ 0.016.
In one embodiment, x has a value of 0.004, 0.008, or 0.012.
In one embodiment, the piezoelectric constant d of the potassium-sodium niobate-based piezoelectric ceramic is33The numerical range of (a) is 400pC/N to 450 pC/N.
In one embodiment, the electromechanical coupling coefficient Kp of the potassium-sodium niobate piezoelectric ceramic is in a range of 0.35 to 0.40.
A preparation method of potassium-sodium niobate piezoelectric ceramics comprises the following steps:
with K2CO3、Na2CO3、Nb2O5、Sb2O3、ZrO2、Bi2O3、CaZrO3And Fe2O3The potassium-sodium niobate piezoelectric ceramics are prepared by a solid phase method according to the general formula.
In one embodiment, the step of preparing the potassium-sodium niobate piezoelectric ceramic by the solid-phase method includes:
ball-milling the raw material mixture weighed according to the general formula to obtain first wet-process slurry;
drying the first wet-process slurry, primarily sintering at 830-870 ℃ for 5-7 h, and performing ball milling to obtain second wet-process slurry;
drying the second wet-process slurry and then grinding to obtain ceramic powder;
adding 3% (w/w) -4% (w/w) of polyvinyl alcohol solution into the ceramic powder, and drying;
grinding the dried ceramic powder and pressing into a ceramic blank;
sintering the ceramic ligand for 3-5 h at 1090-1100 ℃ again to obtain a ceramic product; and
and (3) carrying out silver treatment on the ceramic product, and soaking the ceramic product in silicone oil for polarization to obtain a ceramic finished product.
In one embodiment, before ball milling the raw material mixture weighed according to the general formula to obtain the first wet-process slurry, the method further comprises the step of synthesizing CaZrO3The synthesis of CaZrO3Comprises the following steps:
mixing CaCO3And ZrO2According to the molar weight (0.8-1.2): 1, mixing and ball-milling to obtain a first mixed material; and
drying the first mixed material, preserving the heat for 3 to 5 hours at 1480 to 1520 ℃, ball-milling and drying to obtain CaZrO3And (3) powder.
In one embodiment, in the step of adding 3% (w/w) to 4% (w/w) of a polyvinyl alcohol solution to the ceramic powder, the mass ratio of the ceramic powder to the polyvinyl alcohol solution is (8-12): 3.
an electronic device comprising the potassium-sodium niobate-based piezoelectric ceramic according to any one of the above embodiments.
The potassium-sodium niobate ceramic with the ternary component provided by the invention has excellent piezoelectric performance, higher Curie temperature and better temperature stability, can be applied to drivers and sensors, and has great significance in the future replacement of lead-based piezoelectric ceramics.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ceramic wafer prepared in each example;
FIG. 2 is a dielectric thermogram of a ceramic wafer prepared in each example;
FIG. 3 is a hysteresis loop of the ceramic product wafer prepared in each example measured at 1 kHz;
fig. 4 is a dielectric loss curve of the ceramic product wafer prepared in each example.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms "first", "second" and "first" herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
"piezoelectric constant d33"is one of the most common important parameters for characterizing the performance of piezoelectric materials, and generally, the higher the piezoelectric constant of ceramics, the better the piezoelectric performance, the first number in the subscripts refers to the direction of the electric field, the second number refers to the direction of the stress or strain, and" 33 "indicates that the polarization direction is the same as the force application direction during measurement.
"electromechanical coupling coefficient": in the vibration process of the piezoelectric vibrator, mechanical energy is converted into electric energy or electric energy is converted into mechanical energy, and one parameter which represents the mutual conversion degree between the mechanical energy and the electric energy in the piezoelectric body is called an electromechanical coupling coefficient and is a comprehensive physical quantity for measuring the quality of the piezoelectric conversion performance. And the plane electromechanical coupling coefficient Kp reflects the polarization and electric excitation of the thin wafer in the thickness direction, and the parameters of the electromechanical coupling effect when the thin wafer is subjected to radial stretching vibration.
One embodiment of the present application provides a potassium-sodium niobate-based piezoelectric ceramic, the niobiumThe potassium-sodium-based piezoelectric ceramic has the following general formula: (0.96-x) (K)0.48Na0.52)Nb0.96Sb0.04O3-0.04(Bi0.5Na0.5)ZrO3-xCaZrO3-0.4％Fe2O3Wherein x is CaZrO3X is more than 0 and less than or equal to 0.02.
CaZrO is introduced into the ion-doped ternary component potassium-sodium niobate leadless piezoelectric ceramic3Is a new system source, improves the density of the piezoelectric ceramics, can keep good piezoelectric performance and simultaneously can ensure T0-TThe phase transformation point is stably reduced to room temperature, the difference between orthogonal and tetragonal phases is reduced, and the stable transition of polymorphic phase transformation is realized, so that the polycrystalline phase transformation has excellent temperature stability. In addition, the preparation process of the potassium-sodium niobate piezoelectric ceramic is simple, and the raw materials are nontoxic and harmless, so that the potassium-sodium niobate piezoelectric ceramic is suitable for industrial large-scale production.
In one embodiment, 0 < x ≦ 0.016. Furthermore, x is more than or equal to 0.004 and less than or equal to 0.012.
Specifically, when x is more than 0 and less than or equal to 0.016, the piezoelectric constant d of the potassium-sodium niobate-based piezoelectric ceramic is33The numerical range of (1) is 400 pC/N-450 pC/N, the numerical range of electromechanical coupling coefficient Kp is 0.35-0.40, and the piezoelectric constant d is higher33And a higher electromechanical coupling coefficient Kp.
In one embodiment, x has a value of 0.004, 0.008, or 0.012.
In some embodiments, the maximum electric polarization strength of the potassium-sodium niobate piezoelectric ceramic can reach 19 μ C/cm2～22μC/cm2The residual polarization intensity (Pr) can reach 14 mu C/cm2～16μC/cm2. Specifically, the higher the remanent polarization, the more sufficient the polarization and the better the performance.
Specifically, the invention adjusts CaZrO by adjusting x3And (K)0.48Na0.52)Nb0.96Sb0.04O3To adjust T, O the ratio of the two phases to improve piezoelectric performance.
An embodiment of the present application further provides a method for preparing a potassium-sodium niobate piezoelectric ceramic, including the steps of:
with K2CO3、Na2CO3、Nb2O5、Sb2O3、ZrO2、Bi2O3、CaZrO3And Fe2O3The potassium-sodium niobate piezoelectric ceramics are prepared by a solid phase method according to the general formula.
Specifically, the potassium-sodium niobate piezoelectric ceramics can be effectively synthesized by using the above compound as a raw material. It is understood that, in other embodiments, the preparation of the potassium-sodium niobate-based piezoelectric ceramic may be performed using other carbonate and oxide raw materials containing the above-described compound elements, but the efficiency thereof may be reduced.
In some embodiments, the step of preparing the potassium-sodium niobate-based piezoelectric ceramic using the solid phase method described above includes step S11, step S12, step S13, step S14, step S15, step S16, and step S17. Specifically, the method comprises the following steps:
step S11: and (3) mixing the raw materials weighed according to the general formula, and performing ball milling to obtain first wet-process slurry.
In some embodiments, step S11 is preceded by synthesizing CaZrO3The synthesis of CaZrO3Includes step S01 and step S02.
Step S01: mixing CaCO3And ZrO2According to the molar weight (0.8-1.2): 1, mixing and ball-milling to obtain a first mixed material.
Further, in some embodiments, CaCO is added3And ZrO2According to a molar weight of 1: 1, mixing and ball-milling to obtain a first mixed material.
Step S02: drying the first mixed material, preserving the heat for 3 to 5 hours at 1480 to 1520 ℃, ball-milling and drying to obtain CaZrO3And (3) powder. In an optional specific example, the first mixed material is dried, then is subjected to heat preservation at 1500 ℃ for 4 hours, is subjected to ball milling again, and is dried to obtain CaZrO3And (3) powder. Specifically, the temperature for drying the first mixed material is 60-90 ℃.
In one embodiment, before weighing the raw materials, the method further comprises the step of mixing K2CO3And Na2CO3And drying. Specifically, K is2CO3And Na2CO3Putting the mixture into a drying oven to be dried for 2 to 5 hours at the temperature of between 200 and 250 ℃.
Step S12: and drying the first wet-process slurry, primarily sintering at 830-870 ℃ for 5-7 h, and performing secondary ball milling to obtain second wet-process slurry. In an optional specific example, the first wet-process slurry is dried, then primarily sintered for 6 hours at 850 ℃, and secondarily ball-milled to obtain a second wet-process slurry. Specifically, the drying temperature of the first wet-process slurry is 60-90 ℃.
Step S13: and drying the second wet-process slurry and grinding to obtain ceramic powder.
In some embodiments, a screening step is further included after the second wet slurry is dried and then ground. And drying the second wet-process slurry at the temperature of 60-90 ℃.
Step S14: adding 3% (w/w) to 4% (w/w) of polyvinyl alcohol solution into the ceramic powder, and drying.
In one embodiment, the mass ratio of the ceramic powder to the polyvinyl alcohol solution is 10: 3.
in some embodiments, the temperature of the drying is 60 ℃ to 90 ℃.
Step S15: and grinding the dried ceramic powder and pressing into a ceramic blank.
In an alternative specific example, the dried ceramic powder is pressed into a ceramic blank with the diameter of 11 mm-13 mm and the thickness of 0.8 mm-1.2 mm by a mould. Further, in some embodiments, the dried ceramic powder is pressed into a ceramic green body with a diameter of 12mm and a thickness of 1mm by using a mold. It is understood that in other embodiments, the ceramic green body may be of other specifications.
In one embodiment, after the dried ceramic powder is ground and pressed into a ceramic blank, the method further comprises the step of carrying out glue removal on the ceramic blank by keeping the temperature of 600-700 ℃ for 1-2 h.
Step S16: and sintering the ceramic ligand for 3 to 5 hours again at 1090 to 1100 ℃ to obtain the ceramic product.
Step S17: and (3) carrying out silver treatment on the ceramic product, and soaking the ceramic product in silicone oil for polarization to obtain a ceramic finished product.
Specifically, the silver treatment step includes: preserving the heat for 20min to 30min at the temperature of 750 ℃ to 780 ℃. The step of polarizing comprises: the ceramic coated with the silver electrode is polarized for 30min in silicone oil immersion at room temperature (25 +/-5 ℃), and the polarization electric field is 3 kV/mm.
In some embodiments, the ball milling step employs a planetary ball mill. It will be appreciated that in other embodiments, other ball mills may be used for ball milling to accommodate mass production.
In some embodiments, in the ball milling step, absolute ethanol is used as a ball milling medium, and the mass ratio of the zirconia beads with the diameter of 5mm to the zirconia beads with the diameter of 2mm is 1: 2, mixing the balls under the condition that the mass of the raw materials is as follows: quality of the mixed beads: the mass of the absolute ethyl alcohol is 1: 8: and 5, ball milling for 8-15 h by a ball mill at the rotating speed of 400 RPM. Specifically, the ball milling beads which are obtained by mixing zirconia beads with the diameter of 5mm and zirconia beads with the diameter of 2mm have the best effect, so that the powder can be milled more uniformly, and the complete performance and the improvement of the material are facilitated. The ceramic prepared by the method has very compact crystal grains and no pores.
In some embodiments, the step of sintering is performed in a muffle furnace. Specifically, the temperature of the muffle furnace is increased at the speed of 3-5 ℃/min. It will be appreciated that in other embodiments, other thermal processing means may be used for sintering.
In some embodiments, the step of discharging the gum is performed in a tube furnace. Specifically, the tubular furnace is heated at a rate of 3 ℃/min to 5 ℃/min. It is understood that in other embodiments, other thermal processing devices may be used to expel the adhesive.
The preparation method of the potassium-sodium niobate piezoelectric ceramic utilizes industrial raw materials, is nontoxic and harmless, adopts a solid-phase sintering method, has low sintering temperature, is easy to realize, has simple process, and can be used for industrial large-scale production.
An embodiment of the present application also provides an electronic device including the potassium-sodium niobate-based piezoelectric ceramic according to any one of the above embodiments.
The electronic equipment comprises the potassium-sodium niobate piezoelectric ceramic, and the potassium-sodium niobate piezoelectric ceramic has excellent piezoelectric performance, higher Curie temperature and better temperature stability, can be applied to drivers or sensors, and has great significance in the process of replacing lead-based piezoelectric ceramic in the future.
In some embodiments, the electronic device is an ultrasonic transducer, an underwater acoustic transducer, an electro-acoustic transducer, a ceramic filter, a ceramic transformer, a ceramic frequency discriminator, a high voltage generator, an infrared detector, a surface acoustic wave device, an electro-optic device, a squib, a piezoelectric gyro, or the like. It is to be understood that the electronic device is not limited to the above, and may be another device including the above-described potassium-sodium niobate-based piezoelectric ceramic.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following detailed description is given with reference to specific examples. The following examples are not specifically described, and other components except inevitable impurities are not included. Reagents and instruments used in the examples are all conventional in the art and are not specifically described. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer.
Example 1
Preparing the potassium-sodium niobate leadless piezoelectric ceramic material of the ion-doped ternary component.
(1) Synthesis of CaZrO3: mixing CaCO3And ZrO2According to a molar ratio of 1: 1, putting the weighed materials into a ball milling tank, and taking absolute ethyl alcohol as a ball milling medium in a mass ratio of 1: 2 zirconia beads having a diameter of 5mm and zirconia beads having a diameter of 2mm were mixed as ball milling beads. The mass ratio of raw materials, ball milling beads and absolute ethyl alcohol is 1: 8: 4, performing primary ball milling for 15 hours in a planetary ball mill at the rotating speed of 400RPM to obtain wet-process slurry, putting the wet-process slurry subjected to ball milling into an oven, drying for 30 minutes at the temperature of 80 ℃, taking out dried powder, sieving with a 75-mesh sieve, and putting into the ovenPutting the mixture into a crucible, feeding the mixture into a box-type muffle furnace, preserving the heat for 4 hours at the temperature rise rate of 5 ℃/min, taking out the mixture, performing ball milling again, drying, and sieving the mixture through a 75-mesh sieve to obtain CaZrO3And (3) powder.
(2) Calculating the mass of the raw materials: with K2CO3、Na2CO3、Nb2O5、Sb2O3、ZrO2、Bi2O3、CaZrO3、Fe2O3Is prepared from (K) and has a chemical formula of (0.96-x)0.48Na0.52)Nb0.96Sb0.04O3-0.04(Bi0.5Na0.5)ZrO3-xCaZrO3-0.4％Fe2O3Wherein x is 0.004, the mass of each raw material required for calculation.
(3) Preparing materials: will K2CO3And Na2CO3Drying in an oven at 220 ℃ for 2h to remove moisture, weighing the raw materials according to the calculated mass, putting the weighed raw materials into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in a mass ratio of 1: 2, mixing zirconia beads with the diameter of 5mm and zirconia beads with the diameter of 2mm to form ball grinding beads, wherein the mass ratio of the raw materials, the ball grinding beads and the absolute ethyl alcohol is 1: 8: and 4, carrying out primary ball milling for 15h in a planetary ball mill at the rotating speed of 400RPM to obtain wet slurry.
(4) Primary sintering: and putting the obtained slurry into an oven, baking for 6-8 h at 80 ℃ to obtain dry powder, then putting the dry powder into a crucible, compacting, covering the crucible, sending the crucible into a box-type muffle furnace for 850 ℃, heating at the rate of 5 ℃/min, and pre-burning for 6 h.
(5) Secondary ball milling: crushing the block after the pre-sintering, transferring the obtained powder into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and mixing the powder with the ball milling medium according to a mass ratio of 1: 2, mixing zirconia beads with the diameter of 5mm and zirconia beads with the diameter of 2mm for secondary ball milling, wherein the mass ratio of the raw materials, the ball milling beads and the absolute ethyl alcohol is 1: 8: 4, ball milling for 15h in a planetary ball mill at 400 RPM.
(6) Drying and sieving: and (3) drying the slurry obtained by ball milling in an oven at 80 ℃, grinding the dried powder, and sieving with a 75-mesh sieve to obtain powder with fine granularity and uniform particles.
(7) And (3) granulation: adding a polyvinyl alcohol solution with the mass fraction of 3% (w/w) -4% (w/w) into the powder obtained by grinding and sieving treatment, wherein the mass ratio of the powder to the polyvinyl alcohol solution is 10: 3, uniformly mixing the powder with a polyvinyl alcohol solution, putting the mixture into an oven at 80 ℃ for drying for 10min to dry the water, grinding the mixture and sieving the ground mixture with a 75-mesh sieve.
(8) And (3) pressing and forming: and pressing and molding the powder obtained after the sieving treatment by using a mold to obtain a wafer type ceramic green body, wherein the diameter of the ceramic green body is 12mm, and the thickness of the ceramic green body is 1 mm.
(9) And (3) common sintering: and placing the obtained ceramic blank into a tubular furnace, burning for 2 hours at the temperature rise rate of 3 ℃/min at 650 ℃, carrying out degumming treatment, placing the ceramic blank obtained after degumming into the tubular furnace, and preserving heat for 4 hours at 1100 ℃ to obtain the ceramic product.
(10) Ceramic chip polarization: and (3) carrying out silver treatment on the obtained ceramic product, keeping the temperature at 780 ℃ for 30min, polarizing the silver-coated ceramic product for 30min in silicone oil immersion at room temperature, wherein the polarizing electric field is 3kV/mm, and standing for 24h after polarizing to obtain the ceramic finished product.
Example 2
This example was carried out in substantially the same manner as example 1 except that in step (2) of this example, x in the chemical formula was 0.008.
Example 3
This example was carried out in substantially the same manner as example 1 except that in step (2) of this example, x in the chemical formula was 0.012.
Example 4
This example was carried out in substantially the same manner as example 1 except that in step (2) of this example, x in the chemical formula was 0.016.
Example 5
This example was carried out in substantially the same manner as example 1 except that in step (2) of this example, x in the chemical formula was 0.
Testing
The ceramic products prepared in the above examples were subjected to structural and performance tests, and the results are shown in fig. 1 to 4 and table 1.
FIG. 1 is an X-ray diffraction pattern of a ceramic wafer prepared in each example. As can be seen from the left image in FIG. 1, all the samples of the examples have perovskite structures and do not have any hetero-phase. As shown in the right graph of fig. 1, the left graph was subjected to an amplification analysis at 2 θ of 45.5 °, and a bimodal coexisting indicates that an orthogonal phase and a tetragonal phase coexist at room temperature, and as x increases, the diffraction peak gradually shifts to a low angle, indicating that the unit cell expands and the peak intensity difference becomes larger, the crystal amount difference between the two phases becomes larger, and the piezoelectric effect becomes worse. Therefore, x should not be excessively large, i.e., the amount of calcium zirconate added needs to be in a suitable range.
FIG. 2 is a dielectric thermogram of the ceramic final wafer prepared in each example. As can be seen from fig. 2, as x increases, the curie temperature of the piezoceramic material gradually decreases, but remains above 200 ℃. When x is 0.016, the piezoelectric constant corresponding to the curie temperature point is too low, and the performance is poor.
FIG. 3 shows the hysteresis loop of the ceramic wafer prepared in each example measured at 1 kHz. As can be seen from FIG. 3, under the electric field of 4000V/mm, the larger the piezoelectric constant is, the larger the remanent polarization is, the value can reach 15.7 μ C/cm2Higher than the value for pure sodium potassium niobate (i.e., when x is 0), the curve is saturated and approximately rectangular. It is proved that proper amount of calcium zirconate is doped in the process of preparing the piezoelectric ceramic, which is beneficial to improving the polarization strength of the piezoelectric ceramic.
Fig. 4 is a dielectric loss curve of the ceramic product wafer prepared in each example. As can be seen from FIG. 4, as x increases, the loss increases, indicating that the number of crystal defects increases, but the overall percentage is still at a low level, and the piezoelectric performance of the ceramic is not greatly affected.
Table 1 shows examplesPiezoelectric constant d of the prepared ceramic product wafer33Electromechanical coupling coefficient Kp, mechanical quality factor Qm, relative dielectric constant, dielectric loss value and density statistics.
TABLE 1
By comparison, when x is 0.008, the piezoelectric constant d is found33The most preferable value of the stoichiometric ratio of the system is 430pC/N max and Kp 0.39 max, and when there is no great difference in other properties, x 0.008 is the most preferable value of the stoichiometric ratio of the system.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions obtained by logical analysis, reasoning or limited experiments based on the technical solutions provided by the present invention are all within the protection scope of the appended claims of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (10)
1. A potassium-sodium niobate-based piezoelectric ceramic characterized by having the following general formula: (0.96-x) (K)0.48Na0.52)Nb0.96Sb0.04O3-0.04(Bi0.5Na0.5)ZrO3-xCaZrO3-0.4％Fe2O3Wherein x is CaZrO3X is more than 0 and less than or equal to 0.02.
2. The potassium-sodium niobate-based piezoelectric ceramic according to claim 1, wherein 0 < x.ltoreq.0.016.
3. The potassium-sodium niobate-based piezoelectric ceramic according to claim 1, wherein x has a value of 0.004, 0.008, or 0.012.
4. The potassium-sodium niobate-based piezoelectric ceramic according to claim 1, wherein the potassium-sodium niobate-based piezoelectric ceramic has a piezoelectric constant d33The numerical range of (a) is 400pC/N to 450 pC/N.
5. The potassium-sodium niobate-based piezoelectric ceramic according to any one of claims 1 to 4, wherein an electromechanical coupling coefficient Kp of the potassium-sodium niobate-based piezoelectric ceramic has a value in a range of 0.35 to 0.40.
6. A preparation method of potassium-sodium niobate piezoelectric ceramics is characterized by comprising the following steps:
with K2CO3、Na2CO3、Nb2O5、Sb2O3、ZrO2、Bi2O3、CaZrO3And Fe2O3The potassium-sodium niobate-based piezoelectric ceramic is prepared by a solid phase method according to the general formula in claim 1 as a raw material.
7. The method according to claim 6, wherein the step of preparing the potassium-sodium niobate-based piezoelectric ceramic by a solid phase method comprises:
ball-milling the raw material mixture weighed according to the general formula to obtain first wet-process slurry;
drying the first wet-process slurry, primarily sintering at 830-870 ℃ for 5-7 h, and performing ball milling to obtain second wet-process slurry;
drying the second wet-process slurry and grinding to obtain ceramic powder;
adding 3% (w/w) -4% (w/w) of polyvinyl alcohol solution into the ceramic powder, and drying;
grinding the dried ceramic powder and pressing into a ceramic blank;
sintering the ceramic ligand for 3-5 h at 1090-1100 ℃ again to obtain a ceramic product; and
and (3) carrying out silver treatment on the ceramic product, and soaking the ceramic product in silicone oil for polarization to obtain a ceramic finished product.
8. The preparation method according to claim 7, further comprising synthesizing CaZrO before ball milling the raw material mixture weighed according to the general formula to obtain the first wet slurry3The step of synthesizing CaZrO3Comprises the following steps:
mixing CaCO3And ZrO2According to the molar weight (0.8-1.2): 1, mixing and ball-milling to obtain a first mixed material; and
drying the first mixed material, preserving the heat for 3 to 5 hours at 1480 to 1520 ℃, ball-milling and drying to obtain CaZrO3And (3) powder.
9. The method according to any one of claims 7 to 8, wherein in the step of adding a polyvinyl alcohol solution in an amount of 3% (w/w) to 4% (w/w) to the ceramic powder, the mass ratio of the ceramic powder to the polyvinyl alcohol solution is (8 to 12): 3.
10. an electronic device comprising the potassium-sodium niobate-based piezoelectric ceramic according to any one of claims 1 to 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231921A (en) * | 2022-07-27 | 2022-10-25 | 贵州大学 | Ferromagnetic coupling material and preparation method thereof |
| CN116496083A (en) * | 2023-04-11 | 2023-07-28 | 四川大学 | Core-shell structure hardened potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN116715522A (en) * | 2023-06-14 | 2023-09-08 | 广东奥迪威传感科技股份有限公司 | Potassium sodium niobate-based piezoelectric ceramic and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242166A (en) * | 2008-03-31 | 2009-10-22 | Tdk Corp | Piezoelectric ceramic, its producing method and piezoelectric element using the piezoelectric ceramic |
| KR20120084039A (en) * | 2011-01-19 | 2012-07-27 | 한국세라믹기술원 | Piezoelectricity composite |
| CN109503160A (en) * | 2018-11-12 | 2019-03-22 | 济南大学 | A kind of potassium sodium niobate piezoelectric ceramics and preparation method thereof that can be sintered under reducing atmosphere |
| CN110713383A (en) * | 2019-10-25 | 2020-01-21 | 四川大学 | Piezoelectric ceramic material and preparation method thereof |
| CN111635229A (en) * | 2020-05-29 | 2020-09-08 | 上海甚恒生物科技有限公司 | Preparation method of lead-free piezoelectric ceramic material |
| CN111908917A (en) * | 2019-05-07 | 2020-11-10 | 四川大学 | Sodium bismuth zirconate strontium doped potassium sodium niobate based piezoelectric ceramic material and preparation method thereof |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN113666744A (en) * | 2021-09-17 | 2021-11-19 | 四川大学 | Component gradient potassium sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
-
2022
- 2022-01-21 CN CN202210070183.9A patent/CN114409401A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242166A (en) * | 2008-03-31 | 2009-10-22 | Tdk Corp | Piezoelectric ceramic, its producing method and piezoelectric element using the piezoelectric ceramic |
| KR20120084039A (en) * | 2011-01-19 | 2012-07-27 | 한국세라믹기술원 | Piezoelectricity composite |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN109503160A (en) * | 2018-11-12 | 2019-03-22 | 济南大学 | A kind of potassium sodium niobate piezoelectric ceramics and preparation method thereof that can be sintered under reducing atmosphere |
| CN111908917A (en) * | 2019-05-07 | 2020-11-10 | 四川大学 | Sodium bismuth zirconate strontium doped potassium sodium niobate based piezoelectric ceramic material and preparation method thereof |
| CN110713383A (en) * | 2019-10-25 | 2020-01-21 | 四川大学 | Piezoelectric ceramic material and preparation method thereof |
| CN111635229A (en) * | 2020-05-29 | 2020-09-08 | 上海甚恒生物科技有限公司 | Preparation method of lead-free piezoelectric ceramic material |
| CN113666744A (en) * | 2021-09-17 | 2021-11-19 | 四川大学 | Component gradient potassium sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHE KONG ET AL.: "Enhanced electromechanical properties of CaZrO3-modified (K0.5Na0.5)NbO3-based lead-free ceramics CaZrO3-modified (K0.5Na0.5)NbO3-based lead-free ceramics", 《CERAMICS INTERNATIONAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231921A (en) * | 2022-07-27 | 2022-10-25 | 贵州大学 | Ferromagnetic coupling material and preparation method thereof |
| CN115231921B (en) * | 2022-07-27 | 2023-03-31 | 贵州大学 | Ferromagnetic coupling material and preparation method thereof |
| CN116496083A (en) * | 2023-04-11 | 2023-07-28 | 四川大学 | Core-shell structure hardened potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN116496083B (en) * | 2023-04-11 | 2024-03-12 | 四川大学 | Core-shell structure hardened potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN116715522A (en) * | 2023-06-14 | 2023-09-08 | 广东奥迪威传感科技股份有限公司 | Potassium sodium niobate-based piezoelectric ceramic and preparation method and application thereof |
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