CN105541115A - Titanic acid and niobic acid compound glass ceramic as well as preparation method and application thereof - Google Patents

Titanic acid and niobic acid compound glass ceramic as well as preparation method and application thereof Download PDF

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CN105541115A
CN105541115A CN201610077266.5A CN201610077266A CN105541115A CN 105541115 A CN105541115 A CN 105541115A CN 201610077266 A CN201610077266 A CN 201610077266A CN 105541115 A CN105541115 A CN 105541115A
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metatitanic acid
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CN105541115B (en
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刘金花
翟继卫
王海涛
沈波
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Tongji University
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    • 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
    • C03C10/0036—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

The invention relates to a titanic acid and niobic acid compound glass ceramic as well as a preparation method and application thereof. The glass ceramic has principal crystalline phases of Sr0.5Ba0.5Nb2O6, Ba0.27Sr0.75Nb2O5.7 and Sr6Ti2Nb4O20, a glass phase of SiO2, and a chemical formula of 8Al2O3.32SiO2.20BaO.20SrO.xTiO2.(20-x)Nb2O5, wherein x is equal to 5-15; and the preparation process adopts two-step crystallization, and the titanic acid and niobic acid compound glass ceramic can be applied to the aspect of an energy storage capacitor material. Compared with the prior art, the titanic acid and niobic acid compound glass ceramic provided by the invention has the advantages of big breakdown-resistant field strength value, big energy storage density and the like.

Description

A kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application
Technical field
The invention belongs to field of dielectric energy storage material, be specifically related to a kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application.
Background technology
Glass-ceramic, is devitrified glass again, and the characteristic of devitrified glass zero air void rate makes glass-ceramic have dielectric breakdown strength far above sintered ceramic, so will show better adaptability when glass-ceramic is applied under high direct voltage.Therefore, glass-ceramic has not only assembled the high breakdown field strength characteristic of glass, also be provided with the high-k performance of dielectric ceramic system, in view of the advantage of these two aspects, glass-ceramic have also been obtained the concern of more and more people, therefore, also becomes the focus (Science of high energy storage material research in recent years, 2006,313 (5785): 334-336; PhysicaB, 2007,396 (1-2): 62-69).The high-compactness of this material, zero void content devitrified glass is become preferred material that current people study high energy density ceramic capacitor and High pulse power technology.
The energy storage density of glass ceramic material is directly proportional to the dielectric coefficient of medium, to square being directly proportional of the highest resistance to breaking down field strength of medium.Therefore, improve the energy storage density of electrical condenser, can start with from the resistance to breaking down field strength improving dielectric coefficient and material.At present, in various dielectric substance, there is not the medium simultaneously possessing high-dielectric coefficient and Gao Nai breaking down field strength, comparatively suitable trading off can only be chosen from both, can consider the compound of material yet.
At present, the glass-ceramic of people's research mainly contains metatitanic acid alkali glass-ceramic and niobate glass-ceramic.Wherein, the people such as the Herczog of Corning Incorporated (Trans.onPartsHybridsPackage, Vol.9, No.14, pp.247-256,1973; JournaloftheAmericanCeramicSociety, vol.67, no.7, pp.484 – 490,1984) successfully prepare the devitrified glass taking barium titanate as principal crystalline phase the earliest.The glass-ceramic of metatitanic acid alkali is the dielectric glass ceramic studied the earliest.The ceramic phase of separating out in metatitanic acid alkali is relatively simple for structure, is a class ferroelectrics most widely used at present.Titanate glass pottery can make such material spontaneous polarization can occur due to the skew of Ti ion, therefore, such material has higher specific inductivity, metatitanic acid alkali glass-ceramic has a fatal weakness simultaneously, Ti vacancy is easily formed when being exactly melting annealing, this is easy to cause comparatively large (the Assemblies & MaterialsAssociation of leakage current, 1997, 255-260), therefore, improve the energy storage density of glass ceramic material, improving specific inductivity is only one of prerequisite realizing raising system energy storage density, the resistance to breaking down field strength improving glass ceramic material is also a prerequisite improving system energy storage density.Consider linear dielectric materials, energy storage density is directly proportional to specific inductivity, to square being directly proportional of resistance to breaking down field strength, this just means that the resistance to breaking down field strength of raising system is more conducive to the energy storage density of raising system, therefore, select, in the process of raising system energy storage density, the resistance to breaking down field strength improving glass ceramic material can be paid the utmost attention to.For barium strontium titanate niobate composite glass-ceramic system, differential thermal analysis curve display barium strontium titanate niobate composite glass-ceramic system has obvious nucleation temperature, in order to make to separate out ceramic crystalline phase uniformly in the glass idiosome of preparation, so just need the best nucleation temperature determining this glass-ceramic system accurately, about nucleation temperature determination before research seldom (devitrified glass, P.W. William McMillan, p115).
Chinese patent CN101531461B discloses a kind of dielectric material of glass-ceramics with high energy storage density and preparation method thereof.The main ingredient of dielectric material of glass-ceramics is BaO, SrO, TiO 2, SiO 2and Al 2o 3, it forms doped with Al F 3and MnO 2, doped with Al F 3mole number account for 2 ~ 8%, doped with Mn O of component total mole number 2mole number account for 0.1 ~ 1% of component total mole number.By igneous fusion after raw material ball milling, prepare glass flake, carry out Controlled Crystallization, the ferroelectric glass-ceramic dielectric coating silver paste obtained, sintering curing forms argent electrode, obtained glass-ceramics with high energy storage density dielectric medium.Nb is not comprised in the glass ceramic material provided in this patent 2o 5, only containing TiO 2, Ti ion is easy to when forming crystalline phase form Ti room, causes glass ceramic material easily to form leakage conductance electric current under high field intensity.
Summary of the invention
Object of the present invention is exactly provide to overcome defect that above-mentioned prior art exists a kind of resistance to breakdown field intensity values is large, energy storage density is large metatitanic acid niobic acid composite glass-ceramic and adopt two step crystallization legal systems for the method for this glass-ceramic and the application of this glass-ceramic in energy storage capacitor material.
Object of the present invention can be achieved through the following technical solutions:
A kind of metatitanic acid niobic acid composite glass-ceramic, this glass-ceramic principal crystalline phase is Sr 0.5ba 0.5nb 2o 6, Ba 0.27sr 0.75nb 2o 5.7and Sr 6ti 2nb 4o 20, glassy phase is SiO 2, chemical formula is 8Al 2o 332SiO 220BaO20SrOxTiO 2(20-x) Nb 2o 5, wherein, x=5 ~ 15.
Described x=10.
A preparation method for metatitanic acid niobic acid composite glass-ceramic, the method comprises the following steps:
(1) Al is taken 2o 3, SiO 2, BaCO 3, SrCO 3, TiO 2and Nb 2o 5according to mol ratio Al 2o 3: SiO 2: BaCO 3: SrCO 3: TiO 2: Nb 2o 5=8:32:20:20:x:(20-x) to carry out preparing burden and mixing, high temperature melting obtains high temperature melting melt body;
(2) high temperature melting melt body is poured in the metal die of preheating, and carries out stress relief annealing, obtained transparent glass, and cut into glass flake;
(3) glass flake is first incubated 1 ~ 3h under the nucleation temperature of 770 ~ 830 DEG C, then the crystallization temperature of 930 ~ 970 DEG C is warming up to the temperature rise rate of 1 ~ 3 DEG C/min, and be incubated 2 ~ 4h and carry out Controlled Crystallization, namely obtain metatitanic acid niobic acid composite glass-ceramic.
Described Al 2o 3, SiO 2, BaCO 3, SrCO 3, TiO 2and Nb 2o 5purity be all greater than 99%.
Mixing in step (1) adopts to be added batching after alcohol through ball mill mixing and dry method, and the time of ball mill mixing is 10 ~ 20h; The temperature of high temperature melt is 1500 ~ 1650 DEG C, and the high temperature melt time is 2 ~ 4h;
Preferably, the time of the ball mill mixing in step (1) is 12 ~ 16h, and the temperature of high temperature melt is 1500 ~ 1600 DEG C, and the high temperature melt time is 2 ~ 3h.
Stress relief annealing temperature in step (2) is 550 ~ 700 DEG C, and the stress relief annealing time is 4 ~ 7h; The thickness of glass flake is 0.9 ~ 1.2mm.
Stress relief annealing temperature in step (2) is 600 ~ 680 DEG C, and the stress relief annealing time is 5h.
In step (3), glass flake is first incubated 2h at the temperature of 800 DEG C, is incubated 3h under being then warming up to the temperature of 950 DEG C and carries out Controlled Crystallization.
Temperature rise rate in described step (3) is 2 DEG C/min.The too fast meeting of heat-up rate causes, in temperature-rise period, sample exists the temperature difference, causes in sample Crystallization Process uneven causing of being heated to rupture; On the contrary, if heat-up rate is excessively slow, the nucleus formed can be caused to there will be uneven to grow up or to occur that some undesirably occur miscellaneous.
The application of a kind of metatitanic acid niobic acid composite glass-ceramic in energy storage capacitor material.
The present invention is by Al 2o 3, SiO 2, BaCO 3, SrCO 3, TiO 2and Nb 2o 5according to mol ratio 8:32:20:20:x:(20-x) prepare burden, two step crystallization methods (crystallization under present nucleation temperature is adopted after determining best nucleation temperature, crystallization under crystallization temperature again) Controlled Crystallization is carried out to metatitanic acid niobic acid composite glass-ceramic system, this heat treating method can provide a kind of effective scheme for the withstand voltage improving glass ceramic material.Different nucleation temperatures (770 DEG C, 800 DEG C, 830 DEG C) is selected to be optimized with differential thermal analysis curve, it is 950 DEG C that different nucleation temperatures all chooses crystallization temperature, as nucleation temperature T=800 DEG C of recrystallization temperature T=950 DEG C, resistance to breaking down field strength reaches optimum value 1817kV/cm, be 1.88 times of the resistance to breakdown field intensity values 963kV/cm of the glass ceramic material drawn under a step crystallization (not being considered to nuclear temperature), the energy storage density value of the glass-ceramic that two step crystallizatioies obtain is 2.9 times of the glass ceramic material that a step crystallization draws.
In the present invention, Nb2O5's adds the resistance to breaking down field strength that can significantly improve glass ceramic material, the compactness of increase glass-ceramic microtexture, and Nb 2o 5add the generation that greatly can improve leakage conductance electric current.
One step crystallization method is not considered to nuclear temperature, directly be warming up to recrystallization temperature, this Crystallization method is not considered to nuclear temperature, just be warming up to recrystallization temperature to the enough nucleation times of sample, the nucleus quantity of generation can be caused so few, and it is uneven to there will be nucleus size, it is uneven that the crystal after crystallization just there will be grain size, has a strong impact on the resistance to breaking down field strength of glass ceramic material.
In two step crystallization methods, the first step is nucleation, and second step is crystallization, under nucleation temperature, be incubated 2h, can guarantee that glass ceramic material can grow the nucleus of abundant tiny densification, then, being warming up to recrystallization temperature insulation 3h, these nucleus can be made can to grow up to the crystal grain of even compact.Therefore, two step crystallizatioies can improve the energy storage density of glass ceramic material greatly.
Compared with prior art, the present invention has the following advantages:
(1) first nucleation temperature is determined by differential thermal analysis curve, two step crystallizatioies are carried out again according to the concrete numerical value of nucleation temperature, here the determination mode of nucleation temperature is as follows: first, read best recrystallization temperature, here we according to temperature (950 DEG C) corresponding to exothermic peak the highest on differential thermal curve as recrystallization temperature.The second, choose different nucleation temperatures (choosing 770 DEG C, 800 DEG C, 830 DEG C here respectively) respectively, identical recrystallization temperature (950 DEG C) studies their energy storage density value respectively.Result shows, nucleation temperature is 800 DEG C, and recrystallization temperature is that the energy storage density of 950 DEG C is the highest, therefore, selects 800 DEG C as nucleation temperature.By comparing, the resistance to breaking down field strength of the glass ceramic material that two step crystallization methods draw is 1.88 times of the glass ceramic material that a step crystallization draws.Its energy storage density is 2.9 times of the glass ceramic material that a step crystallization method obtains;
(2) the method can determine the nucleation temperature of metatitanic acid niobic acid composite glass-ceramic energy storage material simply, accurately, and then improves this glass-ceramic system Controlled Crystallization degree.
Accompanying drawing explanation
Fig. 1 is chemical formula is 8Al 2o 332SiO 220BaO20SrO10TiO 210Nb 2o 5the differential thermal analysis curve of metatitanic acid niobic acid composite glass-ceramic;
Fig. 2 is the Controlled Crystallization figure of the metatitanic acid niobic acid composite glass-ceramic of embodiment 2;
Fig. 3 is dielectric temperature spectrum and the dielectric loss figure of the metatitanic acid niobic acid composite glass-ceramic of embodiment 1 ~ 3 and comparative example 1;
Fig. 4 is the Weibull distribution plan of the resistance to breaking down field strength of the metatitanic acid niobic acid composite glass-ceramic of embodiment 1 ~ 3 and comparative example 1;
In figure, ε rfor specific inductivity, tan δ is dielectric loss, E ibe the resistance to breaking down field strength of i-th test sample, n is the summation of resistance to breakdown field intensity values, E bfor the resistance to breaking down field strength obtained that distributed by Weibull, exdhermic is heat release, and endothermic absorbs heat.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The abbreviation used in whole specification sheets has following implication, unless obviously referred else in literary composition: DEG C=degree Celsius, and kV=kilovolt, cm=centimetre; Mol=mole, h=hour; Min=minute, mol%=molar percentage.Various raw material and the equal available from commercial supplier of reagent, without being further purified, except as otherwise noted.The raw material of moisture-sensitive and reagent are all deposited in hermetically sealed bottle, and directly use, all without special processing.
The preparation of the metatitanic acid niobic acid composite glass-ceramic of embodiment 1 ~ 3 and comparative example 1 is all choose the BaCO that purity is greater than 99wt% 3, SrCO 3, Nb 2o 5, TiO 2, SiO 2and Al 2o 3for feed proportioning, the molar percentage of above-mentioned each component is respectively 20%, 20%, 10%, 10%, 32% and 8%, after ball mill mixing 16h, dry, high temperature melting melt body is formed, then in melt cast to copper mould, at 600 DEG C of temperature stress relief annealing 6h at 1500 DEG C of high temperature melting 2h, then obtaining thickness through cutting is the glass flake of 0.9 ~ 1.2mm, then carries out the preparation of the metatitanic acid niobic acid composite glass-ceramic of embodiment 1 ~ 3 and comparative example 1.
Embodiment 1
Glass flake obtained is in advance kept constant temperature 2h in the Crystallization Furnace of 770 DEG C, is warming up to 950 DEG C with the temperature rise rate of 2 DEG C/min subsequently, and carry out Controlled Crystallization at 950 DEG C of insulation 3h, obtain the 8Al of the present embodiment 2o 332SiO 220BaO20SrO10TiO 210Nb 2o 5metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is all chosen according to Fig. 1.The dielectric properties of obtained sample are as shown in Fig. 3 (embodiment 1), and withstand voltage properties test is as shown in Fig. 4 (embodiment 1), and the value of resistance to breaking down field strength and theoretical energy storage density is as shown in table 1.
Embodiment 2
Glass flake obtained is in advance kept constant temperature 2 hours in the Crystallization Furnace of 800 DEG C, is then warming up to 950 DEG C with the temperature rise rate of 2 DEG C/min, and carry out Controlled Crystallization at 950 DEG C of insulation 3h, obtain the 8Al of the present embodiment 2o 332SiO 220BaO20SrO10TiO 210Nb 2o 5metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is all chosen according to Fig. 1.The dielectric properties of obtained sample are as shown in Fig. 3 (embodiment 2), and withstand voltage properties test is as shown in Fig. 4 (embodiment 2), and the value of resistance to breaking down field strength and theoretical energy storage density is as shown in table 1.
Embodiment 3
Glass flake obtained is in advance kept constant temperature 2 hours in the Crystallization Furnace of 830 DEG C, is then warming up to 950 DEG C with the temperature rise rate of 2 DEG C/min, and carry out Controlled Crystallization at 950 DEG C of insulation 3h, obtain the 8Al of the present embodiment 2o 332SiO 220BaO20SrO10TiO 210Nb 2o 5metatitanic acid niobic acid composite glass-ceramic.
The selection of the present embodiment nucleation temperature and crystallization temperature is all chosen according to Fig. 1.The dielectric properties of obtained sample are as shown in Fig. 3 (embodiment 3), and withstand voltage properties test is as shown in Fig. 4 (embodiment 3), and the value of resistance to breaking down field strength and theoretical energy storage density is as shown in table 1.
Comparative example 1
By glass flake obtained in advance without nucleation temperature, directly carry out Controlled Crystallization at 950 DEG C of insulation 3h, obtain the 8Al of a step crystallization 2o 332SiO 220BaO20SrO10TiO 210Nb 2o 5metatitanic acid niobic acid composite glass-ceramic material.
The dielectric properties of the sample obtained by the present embodiment are as shown in Fig. 3 (comparative example 1), and withstand voltage properties test is as shown in Fig. 4 (comparative example 1), and the value of resistance to breaking down field strength and theoretical energy storage density is as shown in table 1.
Table 1
From case study on implementation above, we illustrate the method that is improved the withstand voltage of glass-ceramic, effectively can also improve the surface topography of glass ceramic material simultaneously.This two step Crystallization method not only can improve the microscopic appearance that resistance to breakdown field intensity values can also improve glass ceramic material greatly.In Fig. 3 embodiment 1 ~ 3 sets forth nucleation temperature 770 DEG C, 800 DEG C and 830 DEG C, and the specific inductivity of recrystallization temperature 950 DEG C and dielectric loss value, nucleation temperatures different as seen from Figure 3, the dielectric constant values that identical recrystallization temperature draws is more or less the same (about 57), and dielectric loss is also more or less the same (being less than 2%); In Fig. 3, the value (about 65) of what comparative example 1 provided the is specific inductivity of a step crystallization method, dielectric loss does not have considerable change (being less than 2%) compared with two step crystallizatioies.Fig. 4 embodiment 1-3 sets forth nucleation temperature 770 DEG C, 800 DEG C, 830 DEG C, the resistance to breaking down field strength of recrystallization temperature 950 DEG C.Different nucleation temperatures, the value difference of resistance to breaking down field strength of identical recrystallization temperature material is not comparatively large, and wherein, namely the resistance to breaking down field strength that provides of embodiment 2 (nucleation temperature be 800 DEG C, recrystallization temperature be 950 DEG C) is the highest, reaches 1817KV/cm; In Fig. 4, that comparative example provides is the resistance to breakdown field intensity values 962KV/cm that a step crystallization method draws, the resistance to breaking down field strength of the glass ceramic material that two step crystallization methods draw is 1.88 times of the glass ceramic material that a step crystallization draws.
Embodiment 4
The BaCO that purity is greater than 99wt% is chosen in the preparation of the metatitanic acid niobic acid composite glass-ceramic of the present embodiment 3, SrCO 3, Nb 2o 5, TiO 2, SiO 2and Al 2o 3for feed proportioning, the molar percentage of above-mentioned each component is respectively 20%, 20%, 5%, 15%, 32% and 8%, and preparation method is substantially the same manner as Example 1, finally obtains the 8Al of the present embodiment 2o 332SiO 220BaO20SrO15TiO 25Nb 2o 5metatitanic acid niobic acid composite glass-ceramic, resistance to breakdown field intensity values is large, energy storage density large, can be applied in energy storage capacitor material aspect.
Embodiment 5
The BaCO that purity is greater than 99wt% is chosen in the preparation of the metatitanic acid niobic acid composite glass-ceramic of the present embodiment 3, SrCO 3, Nb 2o 5, TiO 2, SiO 2and Al 2o 3for feed proportioning, the molar percentage of above-mentioned each component is respectively 20%, 20%, 15%, 5%, 32% and 8%, and preparation method is substantially the same manner as Example 1, finally obtains the 8Al of the present embodiment 2o 332SiO 220BaO20SrO5TiO 215Nb 2o 5metatitanic acid niobic acid composite glass-ceramic, resistance to breakdown field intensity values is large, energy storage density large, can be applied in energy storage capacitor material aspect.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference is, the temperature rise rate that in the preparation process of the present embodiment metatitanic acid niobic acid composite glass-ceramic, Controlled Crystallization process is warming up to crystallization temperature from nucleation temperature is 1 DEG C/min.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, and difference is, the temperature rise rate that in the preparation process of the present embodiment metatitanic acid niobic acid composite glass-ceramic, Controlled Crystallization process is warming up to crystallization temperature from nucleation temperature is 3 DEG C/min.
Embodiment 8
The process of the proportioning raw materials that the present embodiment adopts and two step crystallizatioies is identical with embodiment 1, difference is, also dry through ball mill mixing after adding alcohol after the feed proportioning of the present embodiment, the ball mill mixing time is 10h, then high temperature melt 2h at the temperature of 1650 DEG C, obtain high temperature melting melt body, then molten mass is poured in copper mould, at 550 DEG C of temperature stress relief annealing 7h, then obtaining thickness through cutting is the glass flake of 0.9 ~ 1.2mm, is then carried out the preparation of metatitanic acid niobic acid composite glass-ceramic by two step crystallization methods.
Embodiment 8
The process of the proportioning raw materials that the present embodiment adopts and two step crystallizatioies is identical with embodiment 1, difference is, also dry through ball mill mixing after adding alcohol after the feed proportioning of the present embodiment, the ball mill mixing time is 20h, then high temperature melt 2h at the temperature of 1600 DEG C, obtain high temperature melting melt body, then molten mass is poured in copper mould, at 700 DEG C of temperature stress relief annealing 4h, then obtaining thickness through cutting is the glass flake of 0.9 ~ 1.2mm, is then carried out the preparation of metatitanic acid niobic acid composite glass-ceramic by two step crystallization methods.

Claims (10)

1. a metatitanic acid niobic acid composite glass-ceramic, is characterized in that, this glass-ceramic principal crystalline phase is Sr 0.5ba 0.5nb 2o 6, Ba 0.27sr 0.75nb 2o 5.7and Sr 6ti 2nb 4o 20, glassy phase is SiO 2, chemical formula is 8Al 2o 332SiO 220BaO20SrOxTiO 2(20-x) Nb 2o 5, wherein, x=5 ~ 15.
2. a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 1, is characterized in that, described x=10.
3. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic as claimed in claim 1, it is characterized in that, the method comprises the following steps:
(1) Al is taken 2o 3, SiO 2, BaCO 3, SrCO 3, TiO 2and Nb 2o 5according to mol ratio Al 2o 3: SiO 2: BaCO 3: SrCO 3: TiO 2: Nb 2o 5=8:32:20:20:x:(20-x) to carry out preparing burden and mixing, high temperature melting obtains high temperature melting melt body;
(2) high temperature melting melt body is poured in the metal die of preheating, and carries out stress relief annealing, obtained transparent glass, and cut into glass flake;
(3) glass flake is first incubated 1 ~ 3h under the nucleation temperature of 770 ~ 830 DEG C, then be warming up to the crystallization temperature of 930 ~ 970 DEG C with the temperature rise rate of 1 ~ 3 DEG C/min, and be incubated 2 ~ 4h and carry out Controlled Crystallization, namely obtain metatitanic acid niobic acid composite glass-ceramic.
4. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 3, is characterized in that, described Al 2o 3, SiO 2, BaCO 3, SrCO 3, TiO 2and Nb 2o 5purity be all greater than 99%.
5. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 3, is characterized in that,
Mixing in step (1) adopts to be added batching after alcohol through ball mill mixing and dry method, and the time of ball mill mixing is 10 ~ 20h; The temperature of high temperature melt is 1500 ~ 1650 DEG C, and the high temperature melt time is 2 ~ 4h;
Preferably, the time of the ball mill mixing in step (1) is 12 ~ 16h, and the temperature of high temperature melt is 1500 ~ 1600 DEG C, and the high temperature melt time is 2 ~ 3h.
6. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 3, it is characterized in that, the stress relief annealing temperature in step (2) is 550 ~ 700 DEG C, and the stress relief annealing time is 4 ~ 7h; The thickness of glass flake is 0.9 ~ 1.2mm.
7. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 6, it is characterized in that, the stress relief annealing temperature in step (2) is 600 ~ 680 DEG C, and the stress relief annealing time is 5h.
8. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 3, it is characterized in that, in step (3), glass flake is first incubated 2h at the temperature of 800 DEG C, is incubated 3h under being then warming up to the temperature of 950 DEG C and carries out Controlled Crystallization.
9. the preparation method of a kind of metatitanic acid niobic acid composite glass-ceramic according to claim 3, is characterized in that, the temperature rise rate in described step (3) is 2 DEG C/min.
10. the application of a kind of metatitanic acid niobic acid composite glass-ceramic as claimed in claim 1 in energy storage capacitor material.
CN201610077266.5A 2016-02-03 2016-02-03 A kind of metatitanic acid niobic acid composite glass-ceramic and its preparation method and application Expired - Fee Related CN105541115B (en)

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