CN117776715A - Bismuth sodium titanate based relaxation ferroelectric ceramic material with component gradient structure and preparation method thereof - Google Patents
Bismuth sodium titanate based relaxation ferroelectric ceramic material with component gradient structure and preparation method thereof Download PDFInfo
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- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 14
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- 238000001354 calcination Methods 0.000 claims description 12
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 5
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 5
- 229940117972 triolein Drugs 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the technical field of electronic functional materials and devices, in particular to a sodium bismuth titanate based relaxor ferroelectric ceramic material with a component gradient structure and a preparation method thereof, wherein the ceramic material accords with the chemical general formula: bi (Bi) 0.47 Na 0.47 Ba 0.06 Ti 1‑x (Li 1/4 Nb 3/4 ) x O 3 The preparation method comprises the following steps: according to the chemical general formula, the ceramic material is obtained by mixing raw materials, and sequentially performing the processes of primary ball milling, discharging, drying, presintering, secondary ball milling, discharging, drying, roller milling, casting, lamination tabletting, glue discharging and sintering. Compared with the prior art, the material provided by the invention, as a multilayer composite leadless material, has a novel design structure, and the high electric clamping effect in the wide temperature range has great application prospect in the novel solid state refrigeration technical field, and has excellent performanceMeanwhile, the method is not easy to pollute and destroy the environment, and has the advantages of low preparation cost, good stability and the like.
Description
Technical Field
The invention relates to the technical field of electronic functional materials and devices, in particular to a sodium bismuth titanate based relaxation ferroelectric ceramic material with a component gradient structure and a preparation method thereof.
Background
Unlike traditional gas compression refrigeration technology, the novel refrigeration technology generally adopts solid materials as media to realize refrigeration, solves the problems of low energy conversion efficiency and adverse effect on ecological environment, and is easier to store. Compared with the traditional gas compression refrigeration, the refrigeration mode based on the solid material is more efficient, green, quiet and stable, so the solid refrigeration technology provides a new way for solving the ozone layer damage, the greenhouse effect and the like caused by the refrigeration process. Although the novel refrigeration technologies are different, the basic principles of the novel refrigeration technologies are similar, and the novel refrigeration technologies apply different external fields, such as magnetic fields, force fields, electric fields and the like, to a refrigeration material (generally solid), so that the internal structure and properties of the material are changed to a certain extent, mainly the internal structure confusion of the material is changed, and the novel refrigeration technologies are macroscopically represented as temperature change, so that the energy is converted by continuously applying and removing the external fields, and the refrigeration is realized.
The electric card refrigeration is used as a novel solid refrigeration mode, which generally takes ferroelectric materials as media, and changes the disorder degree of dipoles in the refrigeration materials by adjusting the electric field applied to the refrigeration materials, thereby triggering the change of the temperature of the materials to realize the refrigeration effect. The implementation of electric card refrigeration also follows the carnot cycle, but does not need a large-scale field generating device, and is not easy to influence the surrounding environment, so that more defects are overcome, and the electric card refrigeration system has more important significance in application.
In connection with most of the papers and reports previously concerning ferroelectric materials, lead-based materials have been given a great deal of attention due to their good dielectric properties, around which much research has been conducted. However, lead element is used as heavy metal element, the toxicity of the lead element is not negligible, adverse effects on human bodies are more easily generated in the processes from preparation and production to use and scientific research, and meanwhile, the increasingly serious environmental problems promote people to strictly stand for harmful materials in various fields, so that the exploration of an environment-friendly lead-free ferroelectric material is the hot spot direction of current research. The bismuth sodium titanate based relaxor ferroelectric ceramic (BNT-based ceramic) has higher polarization intensity and dielectric constant, has excellent performance and is not easy to pollute and destroy the environment, thus having good research value and application prospect. BNT-based materials have a diamond phase structure, have good ferroelectric properties, exhibit special dielectric properties at certain temperatures, but still have challenges in achieving large adiabatic temperature variations and wide operating temperature ranges. BNT material is used as basic material to regulate and control components and structure, so that the service performance of BNT material is expected to be further improved, and the cooperative optimization of the material electric clamping effect and the working temperature range can be realized by adopting the method of compounding the multi-layer phase transition temperature components with the gradient structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the sodium bismuth titanate based relaxor ferroelectric ceramic material with the composition gradient structure and the preparation method thereof, and the problems of low energy conversion efficiency and adverse effect on ecological environment in the refrigeration field are solved by replacing the traditional gas compression refrigeration material and lead based ferroelectric material, and the expansion of the working temperature range of the high electric card effect is realized by adopting a novel gradient composite structure, so that the electric card refrigeration material is pushed to further go to practical application.
The aim of the invention can be achieved by the following technical scheme:
a bismuth sodium titanate based relaxation ferroelectric ceramic material with a component gradient structure has a chemical general formula of Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Where x=0.005, 0.010, and 0.015.
Further, when x=0.005, 0.010, or 0.015, the ferroelectric-relaxation phase transition temperatures of the material are 74 ℃, 58 ℃ and 45 ℃, respectively.
Further, the multi-layer composite refers to the composite of three structures of bismuth sodium titanate based relaxor ferroelectric ceramic materials when x is 0.005, 0.010 and 0.015 respectively.
Further, in the multilayer compounding, the number ratio of the three structures is 1: (1-2): (1-3).
Furthermore, the multi-layer composite mode of the gradient structure comprises a sandwich multi-layer structure and other possible multi-layer designs of the gradient structure and the like, so that the temperature stability of the electric card effect is further optimized by widening a phase change temperature zone.
Furthermore, the ceramic material has high electric card effect, and the highest negative temperature of the electric card is more than 0.5K under the electric field of 6kV/mm, which is close to the lead-based material.
Furthermore, the ceramic material combines components with different ferroelectric-relaxation phase transition temperatures, so that continuous phase transition occurs in a wide temperature range, the working temperature of the electric card is greatly widened, and the refrigerating working range of the electric card is up to 68 ℃.
The preparation method of the bismuth sodium titanate based relaxation ferroelectric ceramic material with the composition gradient structure comprises the following steps:
according to the chemical general formula, mixing a bismuth source, a sodium source, a barium source, a titanium source, a lithium source and a niobium source, and sequentially performing the processes of primary ball milling, discharging, drying, presintering, secondary ball milling, roll casting, lamination tabletting, glue discharging and sintering to obtain the sodium bismuth titanate-based relaxation ferroelectric ceramic material with the component gradient structure.
Further, the bismuth source comprises Bi 2 O 3 The sodium source comprises Na 2 CO 3 The barium source includes BaCO 3 The titanium source comprises TiO 2 The lithium source comprises Li 2 CO 3 The niobium source includes Nb 2 O 5 。
Further, in the primary ball milling and the secondary ball milling, the ball milling time is 10-12h.
Further, in the roll milling and casting process, the roll milling time is 8-12h, and in the casting process, the used adhesive is ethanol, butanone, triolein, polyethylene glycol, dibutyl phthalate and polyvinyl alcohol.
Further, in the presintering process, the presintering temperature is 800-900 ℃ and the presintering time is 3-4h.
Further, in the lamination tabletting process, the lamination is pressed for 20min to be molded under the condition that the molding pressure is 10MPa and the temperature is 50 ℃.
Further, the glue discharging process specifically comprises the following steps: heating to 200-250 ℃ at a heating rate of 0.25-1 ℃/min, calcining at constant temperature for 1-3h, heating to 500-600 ℃ at a heating rate of 0.5-2 ℃/min, and calcining at constant temperature for 7-10h.
Further, the area of the ceramic green body used in the glue discharging is 15mm multiplied by 15mm, and the thickness is 0.48mm.
Further, the sintering process specifically comprises the following steps: heating to 1150-1170 ℃ at a heating rate of 3-5 ℃/min, and calcining at constant temperature for 2-3h.
Furthermore, the sintering process adopts a method of reducing the temperature, so that the defects of interlayer diffusion and volatilization of the organic adhesive at high temperature are restrained, and meanwhile, the ferroelectric-relaxation phase transition temperature is induced to be transferred to the vicinity of the room temperature, so that the high electric card effect is realized.
The method obtains the bismuth sodium titanate based relaxation ferroelectric ceramic material with the component gradient structure of a single perovskite phase through a solid phase sintering method. The x=0.005, 0.010, and 0.015 components have sharp non-traversing relaxation phase transitions around the phase transition temperature to dielectric anomaly peaks of traversing relaxation phase and move continuously to low temperatures as the doping amount increases. Li (Li) + 、Nb 5+ The incorporation of (a) can cause random distribution of ions of different sizes, valences, such that the local free electric field strength increases, the PNRs progressively decrease in size and the activity increases. Near the phase transition temperature, the residual polarization Pr of the ceramic decreases dramatically, notably while still maintaining a high saturation polarization Pm, which will facilitate large reversible entropy changes, corresponding to large electrical card responses, while continuing to warm up the localized electric field inhibits the directional alignment of PNRs, resulting in a decrease in electrical card response.
Meanwhile, by adopting a method of compounding multi-layer phase transition temperature components by a gradient structure, the material undergoes multiple phase transitions in the heating process, and corresponds to sudden increase of the electric card effect, so that higher negative temperature change of the electric card is maintained in a wider temperature interval, and the cooperative optimization of the electric card effect and the working temperature interval of the material is realized. The temperature change is directly obtained by adopting the high-sensitivity thermal resistor (PT 100), and the electric clamping temperature change of the component gradient structure sodium bismuth titanate based relaxation ferroelectric ceramic material at each temperature point is accurately collected.
The invention adopts the solid phase sintering method to prepare the lead-free Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 The ceramic material adopts a direct test method to collect the temperature change of the card. The ceramic has the advantages of high electric card effect in a wide temperature range, great application potential in the technical field of novel solid-state refrigeration, low cost, high efficiency, easy miniaturized application and the like, solves the problems of low refrigeration efficiency, environmental damage and the like of the traditional gas compression refrigeration method, and is expected to be applied to the technical field of information such as microelectronic devices, integrated circuits and the like.
Compared with the prior art, the invention has the following advantages:
1) The invention designs a novel structural ceramic, namely a component gradient structural bismuth sodium titanate based relaxation ferroelectric ceramic material;
2) The electric card refrigerating material has high electric card effect, and the highest negative temperature of the electric card under the electric field of 6kV/mm is up to 0.69K and is close to that of a lead-based material;
3) The invention adopts a method of compounding multi-layer phase transition temperature components by a gradient structure, the electric card refrigerating material keeps high electric card effect in a wide temperature interval, the width of the temperature interval of which the negative temperature of the electric card is more than 0.5K is up to 68 ℃ under a 6kV/mm electric field, and the temperature stability is optimized;
4) The electric card refrigerating material does not contain lead, is environment-friendly and is not easy to cause pollution and damage.
Drawings
FIG. 1 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 1 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Designing the dielectric constant and dielectric loss temperature spectrum of the A;
FIG. 2 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 1 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Designing a temperature-changing P-E curve of the A under the electric field of 6 kV/mm;
FIG. 3 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 1 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Designing a temperature change I-E curve of the A under the electric field of 6 kV/mm;
FIG. 4 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 1 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Designing a temperature-changing electric card effect test curve of the A under the electric field of 6 kV/mm;
FIG. 5 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 2 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Designing a dielectric constant and a dielectric loss temperature spectrum of B;
FIG. 6 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 2 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 B, designing a temperature-changing P-E curve of the electric field under 6 kV/mm;
FIG. 7 is a schematic diagram of a bismuth sodium titanate-based relaxor ferroelectric ceramic material Bi of a composition gradient structure prepared in example 2 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 B, designing a temperature change I-E curve of the B under the electric field of 6 kV/mm;
FIG. 8 is a component gradient structure bismuth sodium titanate based relaxor ferroelectric ceramic material Bi prepared in example 2 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 B, designing a temperature-changing electric card effect test curve under the electric field of 6 kV/mm;
fig. 9 is a graph showing the rate of change of the electrocaloric effect at an electric field of 6kV/mm for the sodium bismuth titanate based relaxed ferroelectric ceramic material of design B of example 2 and comparative example x=0.005.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
A bismuth sodium titanate based relaxation ferroelectric ceramic material with a component gradient structure has a chemical general formula of Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Wherein x=0.005, 0.010 and 0.015, the number ratio of layers of the designed multilayer composite ceramic based on the sodium bismuth titanate based relaxation ferroelectric ceramic material obtained when x is three values is 1:2:3 (noted as a) and 1:1, a step of; 1 (denoted as B).
The preparation method of the bismuth sodium titanate based relaxation ferroelectric ceramic material with the composition gradient structure comprises the following steps:
s1: bi with the purity of more than 99 percent is selected 2 O 3 、Na 2 CO 3 、BaCO 3 、TiO 2 、Li 2 CO 3 And Nb (Nb) 2 O 5 As the preparation raw material of the bismuth sodium titanate based relaxor ferroelectric ceramic with the component gradient structure, the bismuth sodium titanate based relaxor ferroelectric ceramic is weighed according to the chemical general formula and then mixed to obtain primary mixed powder;
s2: adding absolute ethyl alcohol and zirconium dioxide grinding balls into a ball milling tank, adding primary mixed powder, performing primary ball milling for 10-12 hours in a planetary ball mill, discharging, and drying in a blast drying oven at 80-120 ℃ to obtain dried powder;
s3: placing the dried powder into a muffle furnace, and presintering for 3-4 hours at 800-900 ℃ to obtain presintering powder;
s4: carrying out secondary ball milling, discharging and drying on the presintered powder for 10-12 hours; adding ethanol, butanone, triolein, polyethylene glycol, dibutyl phthalate and polyvinyl alcohol, roll-milling for 8-12h, casting, air-drying, laminating according to gradient structure design, pressing for 20min under the condition of 10MPa and 50 ℃ for molding, and slicing to obtain ceramic green compact;
s5: transferring the ceramic green body into a muffle furnace, heating to 200-250 ℃ at a heating rate of 0.25-1 ℃/min, calcining at a constant temperature for 1-3h, heating to 500-600 ℃ at a heating rate of 0.5-2 ℃/min, and calcining at a constant temperature for 7-10h to obtain a glue-discharging ceramic green body;
s6: heating the gel-discharging ceramic blank to 1150-1170 ℃ at a heating rate of 3-5 ℃/min, sintering at constant temperature for 2-3h, and cooling to room temperature to obtain the bismuth sodium titanate-based relaxor ferroelectric ceramic material with the composition gradient structure.
The following examples are given with the above technical solutions of the present invention as a premise, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The following are more detailed embodiments, by which the technical solutions of the invention and the technical effects that can be obtained are further illustrated.
In the following examples, unless otherwise specified, starting materials or processing techniques are indicated as being conventional commercial products or conventional processing techniques in the art.
Example 1
The embodiment provides a bismuth sodium titanate based relaxor ferroelectric ceramic material with a component gradient structure, which has three layer structures, wherein the chemical general formula of each layer of material is Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Wherein the first x=0.005, the second x=0.010, and the third x=0.015, the designed multilayer composite ceramic has a layer number ratio of 1 based on the three components: 2:3 (24 layers in this example, denoted as a) prepared by:
s1: bi with purity more than 99 percent is selected 2 O 3 、Na 2 CO 3 、BaCO 3 、TiO 2 、Li 2 CO 3 And Nb (Nb) 2 O 5 As the raw material of the bismuth sodium titanate based relaxor ferroelectric ceramic with the component gradient structure, accurately weighing and mixing the bismuth sodium titanate based relaxor ferroelectric ceramic with the component gradient structure by an analytical balance according to the chemical general formula and the proportion relation of the three components to obtain primary mixed powder;
s2: adding 80g of absolute ethyl alcohol and 48g of zirconium dioxide grinding balls as grinding media into a ball milling tank, adding 40g of primary mixed powder, performing primary ball milling for 12 hours in a planetary ball mill, discharging, and drying in a blast drying oven at 100 ℃ to obtain dried powder;
s3: placing the dried powder into a crucible for compaction, then placing the crucible into a muffle furnace, and heating to 850 ℃ at a heating rate of 3 ℃/min for presintering for 4 hours to obtain presintering powder; repeating the steps S1-S3 to obtain three parts of presintering powder material with x=0.005, 0.010 and 0.015;
s4: respectively performing secondary ball milling, discharging and drying on the three parts of presintered powder for 12 hours; respectively selecting 9g of raw material powder, adding 20g of zirconium dioxide balls, 4.5g of ethanol, 9g of butanone, 0.3g of triolein, 0.3g of polyethylene glycol, 0.3g of dibutyl phthalate and 0.9g of polyvinyl alcohol, carrying out roll milling for 8 hours, setting the thickness to be 20 mu m, and carrying out casting according to the layer number proportion of the first component, the second component and the third component of 1 after airing: 2:3, sequentially laminating, pressing for 20min under the conditions of 10MPa and 50 ℃ to form a ceramic green body with the area of 15mm multiplied by 15mm and the thickness of 0.48mm, and cutting into small pieces;
s5: transferring the ceramic blank into a muffle furnace, heating to 200 ℃ at a heating rate of 0.25 ℃/min, calcining at a constant temperature for 2 hours, heating to 600 ℃ at a heating rate of 0.5 ℃/min, and calcining at a constant temperature for 8 hours to obtain a glue-discharging ceramic blank;
s6: heating the gel-discharging ceramic blank to 1150 ℃ at a heating rate of 3 ℃/min, sintering at constant temperature for 2 hours, and naturally cooling to room temperature to obtain the sodium bismuth titanate-based relaxor ferroelectric ceramic material with the composition gradient structure.
The embodiment also comprises the step of testing the electrical properties of the obtained bismuth sodium titanate-based relaxor ferroelectric ceramic material with the composition gradient structure, and specifically comprises the following steps:
1) The obtained ceramic material is subjected to dielectric constant and dielectric loss temperature spectrum test after being subjected to grinding, polishing and double-sided silver electrode coating in sequence, and the test results are as follows:
as shown in FIG. 1, the dielectric constant and dielectric loss temperature spectrum of the obtained ceramic material at the temperature range of 25-400 ℃ can be seen from the graph, at the test frequencies of 1kHz, 10kHz and 100kHz, ferroelectric-relaxation phase transition peaks of the ceramic are combined into a gentle broad peak, and the broad span of the peak is larger than 17 ℃ above room temperature.
2) After the obtained ceramic material is subjected to grinding, polishing and double-sided silver electrode coating in sequence, a temperature-changing P-E curve, a temperature-changing I-E curve and a temperature-changing electric clamping effect test are carried out in a temperature range of 25-130 ℃, and the test results are as follows:
as shown in FIG. 2, in the heating process of the obtained ceramic material, the polarization intensity of the obtained ceramic material at a saturated electric field of 6kV/mm changes along with the change of the electric field intensity, and as can be seen from the graph, the saturated polarization and the residual polarization of the material slowly decrease along with the increase of the temperature;
as shown in FIG. 3, in the heating process of the obtained ceramic material, the current value at the saturated electric field of 6kV/mm changes along with the change of the electric field strength to form a temperature-changing I-E curve, and as the temperature rises, the two peaks of ferroelectric and relaxation two phases coexist continuously weaken and slowly evolve into a current peak of a platform;
as shown in FIG. 4, the change curve of the negative temperature change of the electric card of the obtained ceramic material at the temperature change under the saturated electric field of 6kV/mm is shown in the graph, the negative temperature change of the electric card of the material is increased and then reduced along with the temperature rise, the maximum value is 0.61K, the negative temperature change of the electric card is greater than 0.5K in the temperature range of 39-94 ℃, and the width of the temperature range is 55 ℃.
Example 2
The embodiment provides a bismuth sodium titanate based relaxor ferroelectric ceramic material with a composition gradient structure, which has three layer structures, wherein the chemical general formula of each layer is Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Wherein the first x=0.005, the second x=0.010, and the third x=0.015, the designed multilayer composite ceramic has a layer number ratio of 1 based on the three components: 1:1 (24 layers in this example, denoted as B), the preparation method is:
s1: selecting Bi with purity more than 99 percent 2 O 3 、Na 2 CO 3 、BaCO 3 、TiO 2 、Li 2 CO 3 And Nb (Nb) 2 O 5 Bismuth sodium titanate based relaxor ferroelectric ceramic as component gradient structureThe preparation raw materials of the porcelain are weighed and mixed through an analytical balance according to the chemical general formula and the proportion relation of the three components, so as to obtain primary mixed powder;
s2: sequentially adding 80g of absolute ethyl alcohol and 48g of zirconium dioxide grinding balls serving as grinding media into a ball milling tank, adding 40g of primary mixed powder, transferring into a planetary ball mill, performing primary ball milling for 12 hours, discharging, and drying in a blast drying oven at 100 ℃ to obtain dried powder;
s3: placing the dried powder into a crucible, lightly compacting, transferring into a muffle furnace, and heating to 850 ℃ at a heating rate of 3 ℃/min for presintering for 4 hours to obtain presintering powder;
s4: performing secondary ball milling, discharging and drying on the presintered powder for 12 hours; respectively selecting 9g of raw material powder, adding 20g of zirconium dioxide balls, 4.5g of ethanol, 9g of butanone, 0.3g of triolein, 0.3g of polyethylene glycol, 0.3g of dibutyl phthalate and 0.9g of polyvinyl alcohol, carrying out roll milling for 8 hours, and carrying out tape casting, wherein the layer number ratio of the first component, the second component and the third component is 1 after natural drying: 1:1 sequentially laminating, setting the pressure to be 10MPa, pressing at 50 ℃ for 20min for molding to obtain a ceramic green body with the area of 15mm multiplied by 15mm and the thickness of 0.48mm, and cutting into small blocks;
s5: transferring the ceramic blank into a muffle furnace, heating to 200 ℃ at a heating rate of 0.25 ℃/min, calcining at a constant temperature for 2 hours, heating to 600 ℃ at a heating rate of 0.5 ℃/min, and calcining at a constant temperature for 8 hours to obtain a glue-discharging ceramic blank;
s6: heating the gel-discharging ceramic blank to 1150 ℃ at a heating rate of 3 ℃/min, sintering at constant temperature for 2 hours, and cooling to room temperature to obtain the sodium bismuth titanate-based relaxor ferroelectric ceramic material with the composition gradient structure.
The embodiment also comprises the step of testing the electrical properties of the obtained bismuth sodium titanate-based relaxor ferroelectric ceramic material with the composition gradient structure, and specifically comprises the following steps:
1) After the obtained ceramic material is ground, polished and coated with silver electrodes on both sides, dielectric constant and dielectric loss temperature spectrum tests are carried out, and the test results are as follows:
as shown in FIG. 5, the dielectric constant and dielectric loss temperature spectrum of the obtained ceramic material at the temperature range of 25-400 ℃ is shown, and it can be seen from the graph that at the test frequencies of 1kHz, 10kHz and 100kHz, the ferroelectric-relaxation phase transition peaks of the ceramic are combined into a gentle broad peak, and the broad span of the peak is more than 22 ℃ above room temperature.
2) After the obtained ceramic material is subjected to grinding, polishing and double-sided silver electrode coating in sequence, a temperature-changing P-E curve, a temperature-changing I-E curve and a temperature-changing electric clamping effect test are carried out in a temperature range of 25-130 ℃, and the test results are as follows:
as shown in fig. 6, the obtained ceramic material has a temperature-changing P-E curve of the polarization intensity at 6kV/mm of saturated electric field along with the change of electric field intensity in the heating process, and it can be seen from the graph that the P-E curve shows a square curve with stronger ferroelectricity due to the increase of x=0.005 component content at normal temperature, and the saturated polarization and the residual polarization of the material slowly decrease along with the increase of temperature;
as shown in fig. 7, a temperature change I-E curve of the current value of the obtained ceramic material under the saturated electric field of 6kV/mm along with the change of the electric field strength is shown in the graph, and it can be seen from the graph that due to the increase of the content of x=0.005 component at normal temperature, the two peaks of ferroelectric and relaxation two phases coexist more obviously, and the two peaks of ferroelectric and relaxation two phases coexist continuously weaken and slowly evolve into a current peak of a platform along with the increase of the temperature;
as shown in FIG. 8, the change curve of the negative temperature change of the electric card of the ceramic material at the temperature change of 6kV/mm of the saturated electric field is shown in the graph, the negative temperature change of the electric card of the material is increased and then reduced along with the temperature rise, the maximum value is 0.69K, the negative temperature change of the electric card is greater than 0.5K in the temperature range of 39-94 ℃, and the temperature range width is 68 ℃.
As can be seen from the test results of examples 1 and 2, bi in the present invention 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/ 4 Nb 3/4 ) x O 3 The ceramic material with high electric clamping effect and wide working temperature range can maintain high electric clamping effect in wide temperature range and realize cooperative optimization of material electric clamping effect and working temperature rangeCan effectively push the electric card refrigerating material to further go to practical application.
Comparative example
The comparative example provides a single-component bismuth sodium titanate based relaxation ferroelectric ceramic material, 24 layers are added in the comparative example, and the chemical general formula is Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 (x=0.005) the preparation differs from example 2 in that in S1, only Bi is present in the primary mix 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 (x=0.005) single component, and the other steps are the same as in example 2.
Example 2 at a saturated electric field of 6kV/mm during the temperature increase is shown in FIG. 9: design B and comparative example: the single-component x=0.005, the electric card effect change rate curve of the ceramic, it can be seen from the graph that the component gradient structure design effectively widens the working temperature interval of the ceramic electric card effect, and greatly optimizes the temperature stability.
The electric card temperature change in the application is obtained through directly collecting the high-sensitivity thermal resistor (PT 100), and the accuracy is higher.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A bismuth sodium titanate based relaxation ferroelectric ceramic material with a component gradient structure is characterized in that the bismuth sodium titanate based relaxation ferroelectric ceramic material is obtained by stacking and compounding three layered bismuth sodium titanate based relaxation ferroelectric ceramic materials, and the chemical general formula of each layer of bismuth sodium titanate based relaxation ferroelectric ceramic material is Bi 0.47 Na 0.47 Ba 0.06 Ti 1-x (Li 1/4 Nb 3/4 ) x O 3 Wherein the first x=0.005, the second x=0.010, and the third x=0.015.
2. The bismuth sodium titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in claim 1, wherein the ratio of the number of the first layer structure, the second layer structure and the third layer structure is 1: (1-2): (1-3).
3. A method for preparing a sodium bismuth titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in any one of claims 1 to 2, comprising the steps of:
according to the chemical general formula of three bismuth sodium titanate based relaxor ferroelectric ceramic materials, mixing a bismuth source, a sodium source, a barium source, a titanium source, a lithium source and a niobium source, sequentially performing primary ball milling, discharging, drying, presintering, secondary ball milling and roll milling casting to respectively obtain three casting sheets, and performing lamination tabletting, glue discharging and sintering on the three casting sheets to obtain the bismuth sodium titanate based relaxor ferroelectric ceramic material with the component gradient structure.
4. The method for preparing a sodium bismuth titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in claim 3, wherein the bismuth source comprises Bi 2 O 3 The sodium source comprises Na 2 CO 3 The barium source includes BaCO 3 The titanium source comprises TiO 2 The lithium source comprises Li 2 CO 3 The niobium source includes Nb 2 O 5 。
5. The method for preparing the bismuth sodium titanate based relaxor ferroelectric ceramic material with the composition gradient structure according to claim 3, wherein the ball milling time is 10-12h in the primary ball milling and the secondary ball milling processes.
6. The method for preparing a sodium bismuth titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in claim 3, wherein the pre-sintering temperature is 800-900 ℃ and the pre-sintering time is 3-4 hours during the pre-sintering process.
7. The method for preparing the bismuth sodium titanate based relaxor ferroelectric ceramic material with the composition gradient structure according to claim 3, wherein the roll milling time is 8-12h in the roll milling casting process, and the binder used in the casting process is ethanol, butanone, triolein, polyethylene glycol, dibutyl phthalate or polyvinyl alcohol.
8. The method for preparing a sodium bismuth titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in claim 3, wherein the lamination and tabletting are carried out under a forming pressure of 10MPa and a temperature of 50 ℃ for 20 min.
9. The method for preparing a bismuth sodium titanate based relaxor ferroelectric ceramic material with a composition gradient structure according to claim 3, wherein the adhesive discharging process specifically comprises the following steps: heating to 200-250 ℃ at a heating rate of 0.25-1 ℃/min, calcining at constant temperature for 1-3h, heating to 500-600 ℃ at a heating rate of 0.5-2 ℃/min, and calcining at constant temperature for 7-10h.
10. The method for preparing a sodium bismuth titanate based relaxor ferroelectric ceramic material having a composition gradient structure as claimed in claim 3, wherein the sintering process comprises the following steps: heating to 1150-1170 ℃ at a heating rate of 3-5 ℃/min, and calcining at constant temperature for 2-3h.
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