CN113233772A - Glass ceramic for realizing high dielectric constant and high breakdown performance by regulating and controlling glass network structure and preparation method thereof - Google Patents

Glass ceramic for realizing high dielectric constant and high breakdown performance by regulating and controlling glass network structure and preparation method thereof Download PDF

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CN113233772A
CN113233772A CN202110423003.6A CN202110423003A CN113233772A CN 113233772 A CN113233772 A CN 113233772A CN 202110423003 A CN202110423003 A CN 202110423003A CN 113233772 A CN113233772 A CN 113233772A
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dielectric constant
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glass ceramic
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CN113233772B (en
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蒲永平
彭鑫
杜欣怡
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Shaanxi University of Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • 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

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Abstract

The invention relates to a glass ceramic for regulating and controlling a glass network structure to realize high dielectric constant and high breakdown performance and a preparation method thereof, wherein the glass ceramic material is prepared by compounding a crystal phase and a glass phase, which are prepared by mixing, melting, cooling and forming, annealing and crystallizing heat treatment of raw materials; wherein the crystal phase is formed by the molar ratio ofx:35‑x:5:40(xLa of =0,1,3,5,10)2O3、Na2CO3、K2CO3And Nb2O5(ii) a The glassy phase being SiO2(ii) a The molar ratio of the crystal phase to the glass phase is 4: 1. the potassium-sodium niobate-based dielectric glass ceramic material prepared by the invention has high dielectric constant and high breakdown strength; la added by the invention2O3To obtain a tight glass network for the glass substrateThe structure is adopted, and then the dielectric constant is improved through a reasonable crystallization treatment system.

Description

Glass ceramic for realizing high dielectric constant and high breakdown performance by regulating and controlling glass network structure and preparation method thereof
Technical Field
The invention relates to the field of glass ceramic materials and a preparation method thereof, in particular to a glass ceramic for regulating and controlling a glass network structure to realize high dielectric constant and high breakdown performance and a preparation method thereof.
Background
The energy storage material is widely applied to the technical fields of spaceflight, civil life and national defense. High dielectric constant and high breakdown are the main parameters for achieving high energy storage, but the two are inversely related. The glass ceramic material improves the dielectric constant by crystallizing a crystal phase through controllable crystallization treatment on a glass matrix, but the breakdown strength of the glass matrix is reduced, so that high energy storage density is difficult to realize.
If the breakdown strength is not reduced or the value of the breakdown strength is reduced a little while the dielectric constant is increased by crystallization, the energy storage density can be greatly improved. This requires that the glass matrix itself have a high resistivity and that the resistivity of the material is not significantly reduced after devitrification. The compact glass network structure can reduce the motion activity of current carriers, so that the material has high resistivity, and the compact glass network structure cannot be damaged in the process of forming a ceramic phase.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the glass ceramic for realizing high dielectric constant and high breakdown performance by regulating and controlling the glass network structure and the preparation method thereof.
The performance of the material is generally improved by adding rare earth elements into the material, and the rare earth element lanthanum is generally La3+A state exists. Due to La3+The lanthanum oxide is not a glass forming body, can not enter a network, but is positioned in network gaps, and has high coordination number, so that the La-containing lanthanum is high in coordination number2O3The glass structure is relatively compact. After preparing the glass matrix with high resistivity, a ceramic phase with high dielectric constant is separated out through controllable crystallization treatment. In addition, the residual glass phase with high resistivity can inhibit interfacial polarization, and the two phases form an interface due to precipitation of the ceramic phase, which can cause charge accumulation at the interface to cause reduction of the breakdown strength of the material when an external electric field is applied. The ability of space charge to accumulate at the interface can be impaired by the dense glass network structure.
In order to realize the purpose, the technical scheme adopted by the glass ceramic is as follows:
the crystal phase is formed by the molar ratio ofx: （35-x）: 5: 40 (x=01,3,5,10) La2O3、Na2CO3、K2CO3And Nb2O5(ii) a The glass phase is SiO2(ii) a The molar ratio of the crystal phase to the glass phase is 4: the formula 1 is prepared by mixing, melting, molding, annealing and crystallizing.
The preparation method of the glass ceramic material adopts the technical scheme that the preparation method comprises the following steps:
1) in a molar ratio ofx: （35-x）: 5: 40 (xLa of =0,1,3,5,10)2O3、Na2CO3、K2CO3And Nb2O5(ii) a The glassy phase being SiO2(ii) a The molar ratio of the crystal phase to the glass phase is 4: 1 and mixing;
2) adding the mixture obtained in the step 1) into a quartz crucible and heating until a uniformly mixed melt is formed; pouring the melt into a mold for molding to obtain a glass sample, and annealing the glass sample;
3) crystallizing the annealed glass sample, and keeping the temperature for 2h according to the crystallization treatment to obtain K2O-Na2O-Nb2O5-SiO2-La2O3The system is made of glass ceramic material.
Further, the heating temperature in the step 2) is 1450-1500 ℃.
Further, the annealing treatment in the step 2) is heat preservation for 8-11 hours at 500-600 ℃.
Further, the crystallization temperature of the glass sample in the step 3) is 951 ℃, 934 ℃, 942oC，911 oCAnd 916oC。
Further, the devitrification temperature in step 3) is determined by DSC differential thermal analysis of the glass substrate sample.
Compared with the prior art, the invention has the beneficial effects that:
the potassium-sodium niobate glass ceramic material prepared by the invention obtains a glass matrix with a compact glass network structure, and obtains a high dielectric constant and a high dielectric constant by controllable crystallization treatment on the premise of not greatly deteriorating the breakdown strengthHigh energy storage is achieved. Due to La3+The lanthanum oxide is not a glass forming body, can not enter a network, but is positioned in network gaps, and has high coordination number, so that the La-containing lanthanum is high in coordination number2O3The glass structure is relatively compact. The ability of space charge to accumulate at the interface can be impaired by the dense glass network structure. After preparing the glass matrix with high resistivity, a ceramic phase with high dielectric constant is separated out through controllable crystallization treatment. The high resistivity residual glass phase may inhibit interfacial polarization, and the precipitation of the ceramic phase may cause the two phases to form an interface, which may result in charge accumulation at the interface when an external electric field is applied, causing a decrease in the breakdown strength of the material.
The preparation method of the invention only needs to carry out mixing melting, molding, annealing and crystallization treatment on all raw materials to obtain the potassium-sodium niobate glass ceramic material.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) test plot of glass substrates of potassium sodium niobate-based glass ceramic materials prepared in examples 1, 2, 3, 4 and 5 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of a potassium sodium niobate-based glass ceramic material prepared by the present invention;
FIG. 3 is a graph of dielectric constant and dielectric loss of the potassium sodium niobate-based glass ceramic material prepared by the present invention.
Detailed Description
The method comprises the following specific steps:
1) in a molar ratio ofx: 35-x: 5: 40 (xLa of =0,1,3,5,10)2O3、Na2CO3、K2CO3And Nb2O5(ii) a The glassy phase being SiO2(ii) a The molar ratio of the crystal phase to the glass phase is 4: 1 and mixing to obtain a mixture;
2) heating a quartz crucible to 1000-1200 ℃ along with a furnace from room temperature, starting adding the mixture, then continuously heating to 1450-1500 ℃, and preserving heat for 50-60 min to ensure that the mixture is fully melted and has no bubbles to finally obtain a mixed molten material; molding the mixed molten material on a copper plate mold at room temperature, and quickly putting the copper plate mold into a furnace to anneal for 8-11 hours at 500-600 ℃ so as to eliminate internal stress and obtain a glass sample;
preserving the temperature of the glass sample at a crystallization peak, performing segmented crystallization treatment for 2 hours, and cooling to room temperature along with the furnace to obtain K2O-Na2O-Nb2O5-SiO2-La2O3The system is made of glass ceramic material.
The present invention is further illustrated in detail below with reference to specific examples:
example 1:
crystallization treatment of the glass sample in this example: and keeping the temperature for 2h at the crystallization peak.
The preparation method of the glass ceramic material comprises the following steps:
1) the molar ratio of the present example isx: 1-x: 7: 8 (xLa of =0)2O3、Na2CO3、K2CO3And Nb2O5(ii) a The glassy phase being SiO2(ii) a The molar ratio of the crystal phase to the glass phase is 4: 1 and mixing.
2) Heating a quartz crucible along with a furnace from room temperature to 1100 ℃, starting adding the mixture, then continuing heating to 1500 ℃, and preserving heat at 1500 ℃ for 60min to uniformly melt the mixture to obtain a mixed molten material; molding the mixed molten material on a copper plate, and quickly putting the copper plate into a furnace to anneal for 11 hours at 500 ℃ to obtain an annealed glass substrate;
3) keeping the temperature for 2h at the respective crystallization peak temperature, and then cooling to room temperature along with the furnace to obtain K2O-Na2O-Nb2O5-SiO2-La2O3The system is made of glass ceramic material.
Cutting the potassium-sodium niobate glass ceramic obtained in the embodiment into a sheet with the thickness of 0.1-0.2 mm by using a cutting machine, polishing and cleaning the sheet, uniformly coating silver electrode slurry on the front surface and the back surface of the sheet, and preserving heat at 600 ℃ for 20 minutes to obtain a glass ceramic sample to be detected.
Example 2:
in this examplex=1;
Example 3:
in this examplex=3;
Example 4:
in this examplex=5;
Example 5:
in this examplex=10;
Table 1 shows the dielectric constant and breakdown field strength of the glass-ceramic materials obtained in the above 5 examples.
FIG. 1 is a DSC analysis of the above 5 examples showing the crystallization temperatures of different experimental formulations;
FIG. 2 is an XRD phase analysis of the glass ceramic materials obtained in the above 5 examples, and it can be seen that high dielectric constant phases (K, Na) NbO are precipitated3;
FIG. 3 is a pressure resistance test of the glass ceramic material prepared in the above 5 examples, with La2O3The glass matrix has a compact network structure and high breakdown strength, and has high dielectric constant and high breakdown strength after crystallization.
Figure DEST_PATH_IMAGE001
Table 1 shows the dielectric constant and the breakdown strength of the potassium sodium niobate-based glass ceramic obtained in each example.
The invention adopts the melting method to prepare the potassium-sodium niobate glass ceramic material, and has the advantages of simple and convenient preparation method, simple process flow, randomly controlled molding according to the requirement, short production period and particular suitability for industrial production. The glass material with a compact glass network structure has high breakdown strength, and the glass ceramic with high dielectric constant and high breakdown strength can be obtained through proper crystallization treatment. (Na, K) NbO3Has high dielectric constant, piezoelectric coefficient and polarization strength, and is excellent dielectric material and piezoelectric ceramicElectrical materials and ferroelectric materials. Due to La3+The lanthanum oxide is not a glass forming body, can not enter a network, but is positioned in network gaps, and has high coordination number, so that the La-containing lanthanum is high in coordination number2O3The glass structure of (2) is relatively compact.
The above description is only one embodiment of the present invention, and not all or only one embodiment, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.

Claims (9)

1.La2O3And/or La3+Application to the improvement of dielectric constant and/or the improvement of breakdown strength in a potassium-sodium niobate glass ceramic system.
2. Use according to claim 1, characterized in that La, which is not a glass former and has a large radius, is present3+Ions cannot enter the network and are positioned in network gaps; and La3+The ions have a high coordination number, so that La is contained2O3The glass structure is more compact.
3. Use according to claim 1, characterized in that La is present2O3And/or La3+The resulting dense glass network structure upon incorporation impairs the ability of space charge to accumulate at the interface.
4. Use according to claim 1, wherein the crystalline phase of the potassium-sodium niobate glass-ceramic system is (K, Na) NbO3The glass phase is SiO2(ii) a La, Na, K and Nb satisfy the molar ratiox:（35-x）: 5: 40，0<x≤10。
5. A preparation method of glass ceramic for regulating and controlling a glass network structure to realize high dielectric constant and high breakdown performance is characterized by comprising the following steps:
crystalline phaseComprising a molar ratio ofx:（35-x）: 5: 40，0<xLa less than or equal to 102O3、Na2CO3、K2CO3And Nb2O5The glass phase is SiO2The molar ratio of the crystal phase to the glass phase is 4: 1, mixing; heating and melting the mixture, annealing to eliminate internal stress, and carrying out crystallization heat treatment to obtain Na containing potassium-sodium niobate2O-K2O-Nb2O5-SiO2-La2O3The system energy storage glass ceramic material.
6. The method of claim 5, comprising the steps of:
1) weighing Na2CO3、K2CO3、Nb2O5、SiO2And La2O3And mixing;
2) heating the mixture in step 1) until a uniformly mixed melt is formed; pouring the melt into a mold for molding to obtain a glass sample, and annealing the glass sample;
3) crystallizing the annealed glass sample, wherein the exothermic peak of the crystallization treatment is 909-951 ℃, and the total heat preservation time is 2h to obtain Na2O-K2O-Nb2O5-SiO2-La2O3The system is made of glass ceramic material.
7. The method according to claim 6, wherein the heating temperature in step 2) is 1450 to 1500 ℃.
8. The method according to claim 6, wherein the annealing treatment in the step 2) is performed under the condition of heat preservation at 500-600 ℃ for 8-11 h.
9. A glass-ceramic obtainable by the process according to any one of claims 5 to 8.
CN202110423003.6A 2021-04-20 2021-04-20 Glass ceramic for realizing high dielectric constant and high breakdown performance by regulating and controlling glass network structure and preparation method thereof Active CN113233772B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001632A1 (en) * 1998-07-06 2000-01-13 Corning Incorporated Tantalum containing glasses and glass ceramics
CN103159405A (en) * 2011-12-13 2013-06-19 北京有色金属研究总院 Glass ceramic with high dielectric constant and low dielectric loss and preparation method thereof
JP2018087125A (en) * 2016-11-18 2018-06-07 株式会社オハラ Dielectric
CN108840570A (en) * 2018-07-18 2018-11-20 陕西科技大学 Containing NaNbO3The Na of phase2O-K2O-Nb2O5-SiO2Low-dielectric loss energy storage glass ceramics
CN110357624A (en) * 2019-07-09 2019-10-22 陕西师范大学 Modified zirconic acid strontium doping potassium-sodium niobate lead-free transparent ceramic material of high dielectric constant frit and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001632A1 (en) * 1998-07-06 2000-01-13 Corning Incorporated Tantalum containing glasses and glass ceramics
CN103159405A (en) * 2011-12-13 2013-06-19 北京有色金属研究总院 Glass ceramic with high dielectric constant and low dielectric loss and preparation method thereof
JP2018087125A (en) * 2016-11-18 2018-06-07 株式会社オハラ Dielectric
CN108840570A (en) * 2018-07-18 2018-11-20 陕西科技大学 Containing NaNbO3The Na of phase2O-K2O-Nb2O5-SiO2Low-dielectric loss energy storage glass ceramics
CN110357624A (en) * 2019-07-09 2019-10-22 陕西师范大学 Modified zirconic acid strontium doping potassium-sodium niobate lead-free transparent ceramic material of high dielectric constant frit and preparation method thereof

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