CN111925123B - Linear glass ceramic and preparation method and application thereof - Google Patents
Linear glass ceramic and preparation method and application thereof Download PDFInfo
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 70
- 238000005245 sintering Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002070 nanowire Substances 0.000 claims abstract description 6
- 239000001103 potassium chloride Substances 0.000 claims abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 claims description 3
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 63
- 238000007792 addition Methods 0.000 description 27
- 239000000919 ceramic Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- ADQUQHZAQKMUDV-UHFFFAOYSA-N barium boron Chemical compound [B].[Ba] ADQUQHZAQKMUDV-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- 229910015846 BaxSr1-xTiO3 Inorganic materials 0.000 description 1
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910008479 TiSi2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
本发明属于陶瓷材料技术领域，具体涉及一种线状玻璃陶瓷及其制备方法和用途。所述方法包括以氯化钾、硝酸钡、二氧化钛为原料，通过熔盐法制备钛酸钡纳米线；以硼酸三正丁酯、正硅酸乙酯、六水合硝酸锌为原料制备ZnO‑B2O3‑SiO2玻璃相前驱液；将BTNW和ZBSO玻璃相前驱液按照10‑30wt.％浓度混合，制得的溶胶经干燥、造粒、压片、烧结得到BTNW‑ZBSO玻璃陶瓷；烧结条件为1150‑1250℃条件下烧结30‑60min，待炉温降至850‑950℃时保温2‑3h。本发明采用溶胶‑凝胶法合成玻璃陶瓷的粉体，并采用先高温后低温的“两步烧结法”制备具有钙钛矿结构和线状晶粒的BTNW‑ZBSO玻璃陶瓷，为进一步研究新的陶瓷相形貌和相结构可控的玻璃陶瓷奠定基础，BTNW‑ZBSO玻璃陶瓷在制备良好储能性能的玻璃陶瓷领域具有良好的应用前景。
The invention belongs to the technical field of ceramic materials, in particular to a linear glass ceramic and a preparation method and application thereof. The method includes using potassium chloride, barium nitrate and titanium dioxide as raw materials to prepare barium titanate nanowires by a molten salt method; using tri-n-butyl borate, ethyl orthosilicate and zinc nitrate hexahydrate as raw materials to prepare ZnO-B 2 O 3 ‑SiO 2 glass phase precursor liquid; BTNW and ZBSO glass phase precursor liquid are mixed according to a concentration of 10‑30 wt.%, and the prepared sol is dried, granulated, tableted and sintered to obtain BTNW‑ZBSO glass ceramics; sintered The conditions are sintering at 1150-1250°C for 30-60min, and hold for 2-3h when the furnace temperature drops to 850-950°C. The invention adopts the sol-gel method to synthesize the powder of the glass ceramics, and adopts the "two-step sintering method" of first high temperature and then low temperature to prepare the BTNW-ZBSO glass ceramics with perovskite structure and linear crystal grains, so as to further research new BTNW-ZBSO glass-ceramic has a good application prospect in the field of preparing glass-ceramic with good energy storage performance.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a linear glass ceramic and a preparation method and application thereof.
Background
With the miniaturization of power electronic devices, high power and high energy storage density materials are urgently needed for dielectric capacitors. Dielectric constant and breakdown strength are important performance parameters that affect dielectric energy storage density. The glass has very high breakdown strength (up to 10)3～104kV/cm), but low dielectric constant (-100); the ceramic is a mixture of a ceramic and a metal,in particular ferroelectric ceramics, can exhibit a higher dielectric constant: (>103) But the breakdown strength is lower (100-102 kV/cm). Researches find that the performance of the composite material formed by compounding the ferroelectric and the glass can combine the sum, product and the like of the performances of the components to improve the performance of the material. In recent decades, researchers have found that glass-ceramics combine the high breakdown field strength of the glass phase with the high dielectric constant of the ceramic phase to be very potential energy storage materials. The breakdown field strength of glass-ceramics is significantly affected by the ceramic phase content, phase composition and microstructure. However, the conventional methods for preparing glass ceramics cannot control the phase structure and the micro-morphology of the ceramics during the micro-crystallization process. Therefore, a great number of methods are explored to control the ceramic phase structure and morphology of the glass ceramic in the crystallization control process.
Typically, three approaches are used to achieve the desired low densification temperature and excellent dielectric properties. The first method is based on glass systems, such as CaO-B2O3-SiO2Glass, MgO-Al2O3-SiO2Glass and Li2O-Al2O3-SiO2Glasses, in these systems, crystalline phases will precipitate from the dense glass matrix, thereby improving dielectric and mechanical properties. However, the nucleation and crystallization processes of glass are susceptible to a variety of factors, which make it difficult to ensure the sintering process design and product consistency. The second is by developing ceramic systems with low intrinsic sintering temperatures, e.g. Bi2O3Base systems, but problems with adjustability and cost remain to be solved. The last method is to form a glass/ceramic composite system in which the low softening temperature glass acts as a sintering aid and the ceramic filler acts as a means to adjust the physical properties of the composite.
The above methods can easily obtain a non-porous microstructure, but it is difficult to control the composition, crystal phase and crystal form of the glass-ceramic. For example, BaTiO3The base glass-ceramics tend to form ferroelectric phases with low dielectric constants and uniform microstructures during sintering, resulting in reduced breakdown field strengths of samples, such as Xiu et al (Xiu s.m., Xiao s., Zhang w.q., et al.e.ffect of rare-earth additions on the structure and dielectric energy storage properties of BaxSr1-xTiO3-based barium boronaluminosilicate glass-ceramics[J]Journal of Alloys and Compounds,2016,670:217-xSr1-xTiO3The dendritic structure generated in the sintering process of the barium boron aluminosilicate glass ceramic can reduce the dielectric breakdown performance of the barium boron aluminosilicate glass ceramic. Song et al (Song X.Z., Zhang Y., Chen Y.Z., et al.Effect of insulating and properties on the microstructure and dielectric properties of barium strontium titanate glasses-ceramics [ J]The results of the Journal of Materials Science: Materials in Electronics,2018,29(1):56-62) show that BaO-SrO-TiO2-SiO2-Al2O3The glass ceramic generates low-dielectric-constant Ba in the sintering process2TiSi2O8. In NaNbO3Similar results are also observed in base glass-ceramics, such as Yang et al (Yang K., Liu J.R., Shen B., et al, Large improvement on energy storage and charge-discharge properties of Gd2O3-doped BaO-K2O-Nb2O5-SiO2 glass-ceramic dielectrics[J]Materials Science and Engineering B,2017,223:178-2O-Nb2O5-SiO2The glass-ceramic produces a layered structure during sintering which is not conducive to densification. Xiu et Al (Xiu S.M., Xiao S., Xue S.X., et al.Effect of differential Al/Si ratios on the structure and energy storage properties of structural barum nitride-based glass-ceramics [ J]Journal of Electronic Materials,2016,45(2):1017-2O5-SiO2-Al2O3The glass ceramic has a second phase BaAl with low dielectric constant during sintering2Si2O8. From the above research results, it can be seen that the microscopic morphology and crystal structure of the glass ceramic have a great influence on the breakdown field strength (BDS) thereof. Therefore, there is a need to explore a new strategy for controlling the crystallization process of glass-ceramics.
Disclosure of Invention
In order to solve the technical problems, the invention provides a linear glass ceramic and a preparation method and application thereof.
The invention aims to provide a preparation method of linear glass ceramic, which comprises the following steps:
step 1, potassium chloride (KCl) and barium nitrate (Ba (NO)3)2) Preparing barium titanate (BaTiO) by using titanium dioxide as raw material through molten salt method3) Nanowires (abbreviated BTNW hereinafter);
step 2, preparing BTNW-ZBSO glass ceramic
Weighing BTNW and putting the BTNW into a mixed solution of deionized water and ethanol to prepare a BTNW suspension;
respectively preparing tri-n-butyl borate (C) by using a mixed solution of glacial acetic acid and ethanol as a solvent12H27BO3) Solution and Ethyl orthosilicate (C)8H20O4Si) solution;
zinc nitrate hexahydrate (Zn (NO) in deionized water as solvent3)2·6H2O) solution is added into the mixed solution of the tri-n-butyl borate solution and the ethyl orthosilicate solution, and the pH of the solution is adjusted to 2-3 to obtain ZnO-B2O3-SiO2(abbreviated as ZBSO hereinafter) glass phase precursor solution;
mixing the prepared BTNW suspension with the ZBSO glass phase precursor solution, and stirring to obtain a BTNW-ZBSO sol; the BTNW accounts for 10-30 wt% of the ZBSO glass phase precursor solution;
drying and ball-milling the BTNW-ZBSO sol to obtain BTNW-ZBSO composite powder;
granulating, tabletting and sintering the BTNW-ZBSO composite powder to obtain BTNW-ZBSO glass ceramic;
the sintering condition is 1150-1250 ℃, the sintering time is 30-60min, and the temperature is kept for 2-3h when the furnace temperature is reduced to 850-950 ℃.
Preferably, in the method for preparing the linear glass ceramic, the ratio of BTNW, deionized water and ethanol in the mixed solution of BTNW and deionized water-ethanol is 4:15: 15.
Preferably, in the above method for producing a wire-like glass ceramic, the volume ratio of glacial acetic acid to ethanol in a mixed solution of glacial acetic acid and ethanol is 1: 1.
Preferably, in the above process for producing a linear glass ceramic, the ratio of tri-n-butyl borate to glacial acetic acid to ethanol in the tri-n-butyl borate solution is 0.01mol:5mL:10 mL;
in the ethyl orthosilicate solution, the proportion of ethyl orthosilicate, glacial acetic acid and ethanol is 0.01mol:5mL:10 mL;
the proportion of the zinc nitrate hexahydrate to the deionized water in the zinc nitrate hexahydrate solution is 0.01mol:15 mL;
the molar ratio of the tri-n-butyl borate, the ethyl orthosilicate and the zinc nitrate hexahydrate used for preparing the ZBSO glass phase precursor solution is 1:1: 1.
Preferably, in the above method for preparing a linear glass ceramic, the BTNW-ZBSO sol is dried in a water bath at 85 ℃ to form a dry gel, and the dry gel is dried at 70 ℃ for 24 hours.
Preferably, in the above method for producing a linear glass ceramic, the BTNW accounts for 30 wt.% of the ZBSO glass phase precursor solution.
Preferably, in the preparation method of the linear glass ceramic, the sintering condition is 1150-1200 ℃ for 30min, and the temperature is kept for 2h when the furnace temperature is reduced to 900 ℃.
The invention also provides the linear glass ceramic prepared by any one of the methods.
The invention also provides application of the linear glass ceramic in preparing dielectric materials.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the BTNW capable of directionally growing is selected as the ceramic phase, so that the method has important significance for monitoring the appearance of the ceramic; and selecting a ZBSO system with large breakdown field intensity as a glass phase to prepare the BTNW-ZBSO glass ceramic, and provides a novel method capable of controlling the crystallization process of the glass ceramic. The glass ceramic powder is synthesized by adopting a sol-gel method, and the BTNW-ZBSO glass ceramic is prepared by adopting a two-step sintering method of firstly high temperature and then low temperature. The BTNW-ZBSO glass ceramic with the perovskite structure and the linear crystal grains is obtained, the foundation is laid for further researching the novel glass ceramic with controllable ceramic phase morphology and phase structure, and the BTNW-ZBSO glass ceramic has good application prospect in the field of preparing glass ceramic with good energy storage performance.
2. The invention prepares the compact BTNW-ZBSO glass ceramic material by mixing and granulating BTNW and ZBSO glass phase precursors, and obtains the glass ceramic with controllable ceramic phase morphology and composition by controlling a sintering procedure. When the BTNW content is 30 wt.%, the room-temperature dielectric constant of the BTNW-ZBSO glass ceramic reaches a maximum of 842, and the discharge energy density value reaches a maximum of 1.19J/cm3. The dielectric constant and the discharge energy density of the sample are maximized at a sintering temperature of 1200 ℃.
Drawings
FIG. 1 is a diagram of a BTNW-ZBSO glass-ceramic preparation process according to the present invention;
FIG. 2 is an XRD pattern and SEM pattern of the BTNW and BTNW-ZBSO composite powder;
a. b is XRD pattern and SEM pattern of BTNW, and c and d are XRD pattern and SEM pattern of BTNW-ZBSO composite powder added with 30 wt.% of BTNW;
FIG. 3 is an XRD pattern of BTNW-ZBSO glass-ceramics with different BTNW addition amounts;
FIG. 4 is an SEM image of BTNW-ZBSO glass ceramics with different BTNW addition amounts;
in fig. 3-4, a, 0 wt.%; b. 10 wt.%; c. 20 wt.%; d. 30 wt.%; e. 40 wt.%; f. 50 wt.%;
FIG. 5 shows a dielectric temperature spectrum (a) and a dielectric loss curve (b) of BTNW-ZBSO glass ceramics with different BTNW addition amounts;
FIG. 6 is a P-E hysteresis curve diagram of BTNW-ZBSO glass ceramics with different BTNW addition amounts;
FIG. 7 is an XRD pattern of BTNW-ZBSO glass-ceramics at different sintering temperatures;
FIG. 8 is an SEM image of BTNW-ZBSO glass-ceramics at different sintering temperatures;
a, 1100 ℃ in FIGS. 7-8; b. 1150 ℃; c. 1200 ℃; d. 1250 ℃;
FIG. 9 shows the dielectric temperature spectrum (a) and the dielectric loss curve (b) of BTNW-ZBSO glass-ceramics at different sintering temperatures;
FIG. 10 is a P-E hysteresis curve plot for BTNW-ZBSO glass-ceramics at different sintering temperatures.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention to be implemented, the present invention will be further described with reference to the following specific embodiments and accompanying drawings.
In the invention, the used reagents barium nitrate (with a mass purity of 99%), titanium dioxide (with a mass purity of 99%), tributyl borate (with a volume purity of 99%), potassium chloride (with a mass purity of 99%), ethyl orthosilicate (with a volume purity of 28%), sodium hydroxide (with a mass purity of 99%), glacial acetic acid (with a volume purity of 36%) and absolute ethyl alcohol (with a volume purity of 99.7%) are analytically pure.
The X-ray powder diffraction instrument D8 Advance used was from Bruker, USA, the scanning electron microscope SU8010 from Hitachi, Japan, the LCR tester Model HP4284A from Hewlett-Packard, USA, and the ferroelectric tester Model 609B from Radiationtechnology, USA.
Example 1
A method for preparing a linear glass-ceramic, as shown in fig. 1, comprising the steps of:
step 1, preparing BTNW by a molten salt method by using potassium chloride, barium nitrate and titanium dioxide as raw materials, wherein the BTNW comprises the following steps:
mixing barium nitrate and titanium dioxide according to a molar ratio of 1:1, then mixing the mixture and potassium chloride according to a mass ratio of 1:10, wherein a ball milling medium is a mixed solution of deionized water and absolute ethyl alcohol with a volume ratio of 1:1, the ball milling time is 2 hours, fully and uniformly mixing, drying at 70 ℃ for 24 hours, putting the obtained solid in a corundum crucible for calcination, the calcination temperature is 850 ℃, the calcination time is 4 hours, naturally cooling the calcination product to room temperature, then washing with deionized water, and drying at 80 ℃ for 12 hours to obtain the BTNW.
Step 2, preparing BTNW-ZBSO glass ceramic
Firstly, 2g of BTNW is weighed, and 15mL of deionized water-ethanol mixed solution with the volume ratio of 1:1 is added for ultrasonic dispersion for 30min to obtain BTNW suspension. Then, under the condition of stirring, dissolving 0.01mol of tri-n-butyl borate in a mixed solution of 5mL of glacial acetic acid and 10mL of ethanol to obtain a tri-n-butyl borate solution; 0.01mol ofDissolving ethyl orthosilicate in 5mL of ice and 10mL of ethanol to obtain an ethyl orthosilicate solution, and stirring the tri-n-butyl borate solution and the ethyl orthosilicate solution for 30min to fully mix to obtain a mixed solution. 0.01mol Zn (NO) dissolved in 15mL deionized water3)2·6H2And adding O into the mixed solution, adjusting the pH of the solution to 2-3 by using ammonia water, and stirring for 30min to obtain the ZBSO glass phase precursor solution. Finally, the prepared BTNW suspension was mixed with zso glass phase precursor solution at a ratio of BTNW to zso glass phase precursor solution of 30 wt.%, stirred for 2h to obtain BTNW-zso sol, and the sol was placed in a water bath at 85 ℃ to form xerogel. The xerogel is dried for 24h at 70 ℃, then ground for 12h in a polyethylene bottle by a zirconia ball, and dried to obtain the BTNW-ZBSO composite powder with the diameter of about 1 μm and the length of about 3-5 μm. And (3) granulating the obtained powder, tabletting, and sintering the obtained green body by using a two-step sintering method, namely sintering at 1200 ℃ for 30min, and preserving heat for 2h when the furnace temperature is naturally reduced to 900 ℃ to prepare the BTNW-ZBSO glass ceramic.
Example 2
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the prepared suspension of BTNW was mixed with ZBSO glass phase precursor in a ratio of 10 wt.% BTNW to ZBSO glass phase precursor.
Example 3
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the prepared suspension of BTNW was mixed with zso glass phase precursor in a ratio of 20 wt.% BTNW to zso glass phase precursor.
Example 4
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the obtained green body is sintered by a two-step sintering method, namely sintering for 30min at 1150 ℃, and preserving heat for 2h when the furnace temperature naturally drops to 900 ℃ to prepare the BTNW-ZBSO glass ceramic.
Example 5
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the obtained green body is sintered by a two-step sintering method, namely sintering is carried out for 30min at 1250 ℃, and the temperature is kept for 2h when the furnace temperature is naturally reduced to 900 ℃, so as to prepare the BTNW-ZBSO glass ceramic.
Comparative example 1
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the prepared suspension of BTNW was mixed with zso glass phase precursor in a ratio of 0 wt.% BTNW to zso glass phase precursor.
Comparative example 2
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the prepared suspension of BTNW was mixed with zso glass phase precursor in a ratio of 40 wt.% BTNW to zso glass phase precursor.
Comparative example 3
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the prepared suspension of BTNW was mixed with ZBSO glass phase precursor in a 50 wt.% BTNW to ZBSO glass phase precursor.
Comparative example 4
A preparation method of linear glass ceramic comprises the following steps:
step 1, same as example 1;
step 2, essentially the same as example 1, except that:
the obtained green body is sintered by a two-step sintering method, namely sintering for 30min at 1100 ℃, and preserving the temperature for 2h when the furnace temperature naturally drops to 900 ℃ to prepare the BTNW-ZBSO glass ceramic.
To demonstrate the beneficial effects of the present invention, the following experiments were performed:
1. microstructure and electrical properties of BTNW-ZBSO glass ceramics with different BTNW addition amounts
Fig. 2 is an XRD chart and an SEM chart of the BTNW and BTNW-ZBSO composite powder prepared in example 1. In FIG. 2a, BaTiO can be clearly observed3Characteristic peaks of the phases (PDF #05-0626), no other miscellaneous phases were found; typical BaTiO can be observed in FIG. 2c3Diffraction peaks of the phases and diffraction packets distributed in the 10-40 ° amorphous state can be observed. The microstructure characteristics of the BTNW and BTNW-ZBSO composite powder are presented by fig. 2b and fig. 2 d. The BTNW has a diameter of about 10-50nm and a length of about 10-15 μm, and the BTNW-ZBSO powder after compounding has a shorter length of about 3-5 μm (FIG. 2 d). This is because the morphology of the BTNW changes due to the ball milling of the composite powder during the preparation process.
XRD patterns of BTNW-ZBSO glass ceramics with different BTNW addition amounts for examples 1 to 3 and comparative examples 1 to 3 are shown in FIG. 3. As is evident from FIG. 3, the pure glass phase ZBSO is a diffraction package distributed at 10-40 deg., since ZBSO is amorphous. When BTNW was added, it was clearly observed that not only the diffraction packets distributed in the 10-40 ° amorphous state in fig. 3, but also the typical BaTiO appeared3The diffraction peaks of the phases (PDF #05-0626) showed that the phase structure of BTNW did not change in the BTNW-ZBSO glass ceramic. ByIt can also be seen in FIG. 3 that as the amount of BTNW added was gradually increased, the relative intensity of the glass background in the XRD pattern of the BTNW-ZBSO glass-ceramic was gradually decreased, while the intensity of the diffraction peak of the perovskite phase was increased, mainly due to the addition of BaTiO3The phases are gradually increased. Therefore, the BTNW-ZBSO glass-ceramic structures of examples 1-3 are more suitable.
FIG. 4 is an SEM photograph of BTNW-ZBSO glass ceramics with different BTNW addition amounts. All samples showed a dense microstructure. The BTNW addition amounts were 0 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.%, respectively, and the corresponding glass-ceramic densities were 4.97g/cm, respectively3、5.09g/cm3、5.27g/cm3、5.57g/cm3、5.43g/cm3And 5.33g/cm3. It can be seen that the density of the glass ceramic shows a tendency to increase first and then decrease, and the density reaches the maximum when the BTNW addition amount is 30 wt.%. As can be seen from fig. 4a, the pure ZBSO glass sample exhibited a dense amorphous state, and no other grains were found to be present. The appearance of linear or rod-like grains in the samples was clearly observed when BTNW was added. When the content of BTNW was increased from 10 wt.% to 30 wt.% (examples 1-3), the linear grains of the BTNW were clearly visible in the sample. When the BTNW content exceeds 30 wt.%, the linear grains gradually transform into rod-like grains. This process can be explained from two aspects: in one aspect, the glass-ceramic is sintered using a two-step sintering process, where the ZBSO glass forms a molten liquid at 1200 ℃ and increases the sample density, immediately after which the molten glass phase surrounds the BTNW. The sample with good density and controllable appearance is obtained in the liquid phase sintering process within the long time of keeping the temperature at 900 ℃; on the other hand, although the phase structure of BTNWs can be controlled during sintering, when the content of BTNWs exceeds 30 wt.%, linear grains are converted into rod-like grains. The content of the glass phase can control the growth of the ceramic grains during the liquid phase sintering process. The addition of the glass phase promotes mass transfer between particles according to a dissolution-precipitation mechanism. When the BTNW addition amount is small and the glass phase amount is too large, the viscosity of the glass increases during sintering, the mobility of atoms in the material decreases, and mass transfer between BTNWs is difficult, so that the BTNWs do not agglomerate during sintering and the BTNWs do not agglomerate during sinteringThere is not enough driving force to grow, so the length of the linear crystal grains is almost the same as that of the starting composite powder. As the amount of BTNW added continues to increase, however, the glassy phase content decreases and mass transfer occurs between adjacent BTNWs, so that BTNW grains grow by reacting with agglomeration or with adjacent linear grains, resulting in the formation of rod-like grains. Generally, the more glass phase is beneficial to mass transfer, and here, because the special sintering characteristics of the glass material make the BTNW content less and the holding time is limited to be unfavorable for the growth of the BTNW, the shape of the ceramic phase can be controlled. Thus, the use of the BTNW content of examples 1-3 enables control of the formation of linear glass-ceramic structures.
FIG. 5 shows a dielectric temperature spectrum (a) and a dielectric loss curve (b) of BTNW-ZBSO glass ceramics with different BTNW addition amounts; for comparison, the dielectric properties of pure ZBSO glass prepared by the two-step sintering method were also measured. As is apparent from the figure, the room temperature dielectric constant of the glass-ceramic increases significantly when BTNW is added to the glass, mainly due to the fact that the added BTNW has a higher dielectric constant than ZBSO glass. Meanwhile, as the BTNW addition amount gradually increases, the room temperature dielectric constant of the glass ceramic tends to increase first and then decrease. When the BTNW addition amount is 0 wt.%, the room temperature dielectric constant of the glass-ceramic is only 100. When the addition amount of BTNW was gradually increased to 30 wt.%, the room-temperature dielectric constant of the BTNW-ZBSO glass ceramic reached 842 at the maximum; however, when the BTNW content is further increased, the dielectric constant of the glass-ceramic starts to decrease again, which may be caused by the decrease of the content of the glass phase, mass transfer between adjacent BTNWs, and growth of BTNW grains by reaction with agglomeration or other adjacent linear grains, resulting in the formation of rod-like grains, so that the glass-ceramic grains at this time have poor uniformity and low density. Although the dielectric loss was higher for the samples with different BTNW contents than for the ZBSO glass, overall, the dielectric loss was less than 0.015 for all samples in the-60 to 130 ℃ test temperature range.
FIG. 6 is a P-E hysteresis curve diagram of BTNW-ZBSO glass ceramics with different BTNW addition amounts. For comparison, P-E hysteresis loops for ZBSO glass are also shown. The corresponding energy storage performance parameters are listed in table 1.As is clear from fig. 6, when the BTNW addition amount was 0 wt.%, the hysteresis loop of pure ZBSO glass exhibited a fine linearity, indicating that it behaves as a linear dielectric. However, relaxation phenomena of the hysteresis loop can be clearly observed with the addition of BTNW, and the relaxation phenomena become increasingly apparent with increasing BTNW addition. This phenomenon indicates that the addition of BTNW to the glass makes the glass-ceramic exhibit ferroelectricity. As can be seen from the data in table 1, the energy storage density of the glass-ceramic was significantly higher when BTNW was added to the glass than pure glass, mainly due to the fact that the added BTNW had a higher polarization than ZBSO glass. Meanwhile, as the addition amount of BTNW gradually increases, the discharge energy density of the glass ceramic tends to increase first and then decrease. This is mainly because, as the addition amount of BTNWs was gradually increased from 0 wt.% to 30 wt.%, the amount of BTNWs having higher saturation polarization was gradually increased, resulting in the saturation polarization of the glass-ceramic being from 1.21 μ C/cm2Gradually increased to 7.20 mu C/cm2. However, when the BTNW addition amount is further increased to 40 wt.%, saturation polarization is decreased because mass transfer between adjacent BTNWs occurs due to the decrease in the content of the glass phase, and thus BTNW grains in the glass ceramic grow by reacting with aggregation or other adjacent linear grains, resulting in the formation of rod-like grains, thereby deteriorating saturation polarization. When the addition amount of BTNW was 30% (example 1), the sample obtained the maximum discharge energy density of 1.19J/cm under the maximum polarization field of 45.91kV/mm35 times that of pure ZBSO glass.
TABLE 1 energy storage Performance parameters of BTNW-ZBSO glass ceramics with different BTNW addition amounts
2. BTNW-ZBSO glass ceramic microstructure and electrical properties at different sintering temperatures
XRD patterns of BTNW-ZBSO glass ceramics of different sintering temperatures for examples 1, 4-5 and comparative example 4 are shown in FIG. 7. From the figure, the typical BaTiO of all samples can be observed3The structure and the bulk distribution of the amorphous glass phase at 10-40 deg. indicate that the phase structure of BTNW does not change in BTNW-ZBSO glass-ceramics. As can be seen from the figure, the relative intensity of the glass background in the XRD pattern gradually increases with the gradual increase of the sintering temperature, while BaTiO3The diffraction peaks of the phases decreased in intensity because part of the BTNW gradually dissolved in the ZBSO glass phase with increasing temperature. Therefore, the sintering temperature is most preferably 1200 ℃ as in example 1.
FIG. 8 is SEM images of BTNW-ZBSO glass-ceramics of examples 1, 4-5 and comparative example 4 at different sintering temperatures. As can be seen from the figure, the density of the sample shows a tendency to increase first and then decrease. As can be seen from fig. 8a, when the sintering temperature is 1100 ℃ (comparative example 4), the surface of the glass ceramic has many pores, and BTNW grains therein are in the shape of short rods, the sintering temperature is not high enough to disperse all BTNW grains in the molten glass phase and form a dense glass ceramic, thereby reducing the density of the glass ceramic, so comparative example 4 is less effective. When the sintering temperature reached 1200 ℃ (example 1), the sintering temperature at high temperature was high enough to bring the ZBSO glass into a molten state, reach the critical density of the glass-ceramic, and break the connected pore network structure. The molten glass phase immediately surrounds the BTNW and then the temperature is maintained at a low 900 c for a long time, the glass phase can fill the pores during the liquid phase sintering process, thereby obtaining a dense, topographically controlled sample. However, when the sintering temperature was further increased to 1250 ℃ (example 5), the linear grains in the sample gradually decreased, and a large number of rod-like grains appeared, and if the requirements for the linear grains were not strict, the method of example 5 could also be used to prepare the sample. This phenomenon occurs because, on the one hand, the grain boundary migration mechanism dominates the mass transfer mechanism through the grain boundary according to the dissolution-precipitation mechanism, and mass transfer occurs between adjacent BTNWs, so that BTNW grains grow up by reacting with aggregation or with adjacent linear grains, resulting in the formation of rod-like grains. On the other hand, part of the BTNW dissolved in the ZBSO glass phase, causing impurities in the glass phase to also deposit on the BTNW. Therefore, the sintering temperature is preferably 1200 ℃.
FIG. 9 shows the dielectric temperature spectra and dielectric loss curves of BTNW-ZBSO glass-ceramics at different sintering temperatures for examples 1, 4-5 and comparative example 4. The dielectric constants of all samples varied relatively flat with increasing test temperature, showing good temperature stability. With the gradual increase of the sintering temperature, the dielectric constant of the sample is increased and then decreased. The dielectric constant at room temperature is 842 at most at 1200 deg.C (example 1). When the sintering temperature is 1100 ℃ (comparative example 4), it can be seen from fig. 8a that the sample is poorly dense, and some pores exist on the surface of the sample, resulting in a decrease in dielectric constant. The dielectric constant gradually increases with the increase of the density of the sample; however, when the sintering temperature was increased to 1250 ℃ (example 5), the dielectric constant was reduced. This is because part of the BTNW was dissolved in the ZBSO glass phase, resulting in a smaller amount of BTNW in the sample. With the gradual increase of the sintering temperature, the dielectric loss of the samples is firstly reduced and then increased, and the dielectric loss of all the samples is less than 0.015. Therefore, the sintering temperature is preferably 1200 ℃.
FIG. 10 is a P-E hysteresis curve plot of BTNW-ZBSO glass-ceramics for different sintering temperatures for examples 1, 4-5 and comparative example 4, with the corresponding energy storage performance parameters listed in Table 2. As is clear from fig. 10, the hysteresis loops of all the samples are slimmer, and a more pronounced relaxation phenomenon can be observed. As can be seen from the data in the table, as the sintering temperature is increased from 1100 ℃ to 1250 ℃, the compressive strength of the glass-ceramic increases and then decreases. The change rule of the discharge energy density of the sample and the change of the compressive strength of the sample show the same trend. When the sintering temperature was 1100 ℃ (comparative example 4), the surface of the glass ceramic had many pores, which were not enough to allow all BTNW grains to be dispersed in the molten glass phase, so pores were generated, decreasing the density of the glass ceramic, and making the compressive strength of the ceramic sample low, only 27.66 kV/mm. When the sintering temperature was raised to 1150-1250 c, especially to 1200 c (example 1), the densification of the ceramic sample reached a maximum and thus had a maximum compressive strength of 45.91 kV/mm. However, with further increase in sintering temperature, the BTNWs in the glass-ceramic appeared to deposit and agglomerate, which was largeMass transfer occurs between a certain amount of linear grains, which results in the formation of rod-like grains, and irregular grains cause the density of the glass sample to be poor, and thus the compressive strength tends to be reduced. When the sintering temperature of the glass ceramic is 1200 ℃, the discharge energy density of the glass ceramic reaches 1.19J/cm under the maximum polarization field of 45.91kV/mm3。
TABLE 2 summary of the parameters of BTNW-ZBSO glass ceramics at different sintering temperatures
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
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