CN110803923A - Preparation method of titanium dioxide-based ceramic with high resistivity, giant dielectric constant and low loss in reducing atmosphere - Google Patents
Preparation method of titanium dioxide-based ceramic with high resistivity, giant dielectric constant and low loss in reducing atmosphere Download PDFInfo
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Abstract
The invention discloses a preparation method of titanium dioxide based ceramics with high resistivity, huge dielectric constant and low loss in reducing atmosphere, which comprises the steps of simultaneously adding trivalent element Al and equal molar mass of pentavalent element Nb into titanium dioxide, placing presintering powder in a magnetic field of 3-12T to obtain a green body, and then placing the green body in N2And (2) sintering at high temperature in the atmosphere to form giant defect dipoles in the ceramic to form more localized electrons to obtain giant dielectric ceramic, and orienting the dipoles by a magnetic field under the magnetic field to limit the movement of free charges so as to improve the resistivity and reduce the dielectric loss. The ceramic prepared by the invention shows excellent temperatureStability and frequency stability, relative dielectric constant greater than 103Dielectric loss can reach 0.05-0.1, resistivity can reach 107～109Omega cm is an environmentally friendly electronic material and has practical application value in multilayer electronic component capacitors which are required to be small and light.
Description
Technical Field
The invention belongs to the technical field of electronic ceramics and manufacture thereof, and particularly relates to a preparation method of a titanium dioxide-based dielectric ceramic material with high dielectric constant and good temperature and frequency stability.
Background
With the demand of the microelectronic technology market for the miniaturization, integration and intellectualization of Ceramic Capacitors and microwave dielectric components, the research on Multi-layer Ceramic Capacitors (MLCCs) with huge dielectric constant, low loss and good temperature/frequency stability is receiving more and more attention, and particularly has a wide application prospect in high dielectric Capacitors. To meet these requirements of the electronic material MLCC, a giant dielectric constant having good temperature and frequency stability under a reducing atmosphere has been developed: (>103) Inorganic dielectrics have become a challenging issue in the materials field.
CaCu of perovskite-like structure in common giant dielectric material3Ti4O12(CCTO) ceramics, La2xSrxNiO4(x-1/3 and 1/8), NiO, and metal and insulation composites all can achieve up to 105But it cannot be co-fired with a nickel electrode in a reducing atmosphere, limiting its practical application in capacitors. In 2013, the Liu Yun subject group of Australian national university reports a novel giant dielectric low-loss dielectric material (In) In Nature materials (2013,12(9):821-0.5Nb0.5)xTi1-xO2Such titanium dioxide-based high dielectrics (>104) Low loss (<0.05) are also reported competitively, for example, patent publication nos. CN 104529430A, CN105948743A, CN106747410A, CN105906340A, CN105732020A, CN107200576A, CN107640970A, CN108530069A, CN108727013A, CN109133914A, but their sensitivity to oxygen partial pressure, cannot be co-fired with nickel electrodes, limiting the application of such materials in MLCCs.
Disclosure of Invention
The technical problem to be solved by the invention is to provideMethod for preparing a titania-based ceramic material having high resistivity, a giant dielectric constant and low loss in a reducing atmosphere, and ceramic prepared by the method over a wide frequency range (10)2Hz～105Hz) internal dielectric constants of more than 103Dielectric loss can reach 0.05-0.1, resistivity can reach 107～109Ω·cm。
The technical scheme adopted for solving the problems comprises the following steps:
1. preparation of titanium dioxide-based ceramic powder
According to (Al)0.5Nb0.5)0.005Ti0.995O2Weighing raw material Al according to the stoichiometric ratio2O3、Nb2O5And TiO2And ball-milling and mixing the raw materials with zirconia balls and absolute ethyl alcohol, and drying to obtain the titanium dioxide-based ceramic powder.
2. Preparation of titanium dioxide-based ceramics
Presintering titanium dioxide-based ceramic powder at 1050-1150 ℃ for 2-4 hours, grinding the presintered powder into powder, performing secondary ball milling and mixing with zirconia balls and absolute ethyl alcohol, drying, performing third ball milling and mixing on the secondary ball milled powder, a dispersing agent and deionized water according to the volume ratio of 1: 0.005-0.02: 1.5-4, and adjusting the pH value to 6.0-7.0 by using hydrochloric acid during third ball milling; placing the slurry obtained by the third ball milling in a magnetic field of 3-12T for standing for 24-72 h, and obtaining a cylindrical plastic blank after the slurry is dried; heating the cylindrical blank to 550-700 ℃ at the speed of 1-5 ℃/min, preserving the heat for 2-5 hours, carrying out cold isostatic pressing in oil at the pressure of 200-700 mPa for 5-30 minutes to obtain a green blank, and placing the green blank in N2Heating to 1300-1500 ℃ at the speed of 1-5 ℃/min under the atmosphere, preserving heat for 2-10 hours, then cooling to 500-700 ℃ at the speed of 1-5 ℃/min, cooling along with a furnace, polishing the surface of the obtained ceramic on a polishing machine, coating an electrode, drying at the temperature of 70-120 ℃, and firing the silver electrode at the temperature of 600-800 ℃ to obtain the titanium dioxide-based ceramic.
In the step 1, the raw materials, zirconia balls and absolute ethyl alcohol are preferably ball-milled and mixed for 12-36 hours according to the mass ratio of 1: 10-20: 2-3, and then baked for 4-24 hours at 65-95 ℃.
In the step 1, the TiO2Is rutile phase TiO2。
In the step 2, the titanium dioxide-based ceramic powder is preferably presintered at 1100 ℃ for 2 to 4 hours.
In the step 2, preferably, the secondary ball milling powder, the dispersing agent and deionized water are subjected to third ball milling and mixing for 36-72 hours according to the volume ratio of 1: 0.01-0.015: 2-3, and the pH value is adjusted to 6.5 by using hydrochloric acid during the third ball milling.
In the step 2, the dispersant is any one of a U.S. Dow dispersant of type Acumer Aoo and an ultraoily wetting dispersant of type F420 or F400.
In the step 2, preferably, the slurry obtained by the third ball milling is placed in a magnetic field of 6-12T for standing for 36-48 h, and after the slurry is dried, a cylindrical preform is obtained.
In the step 2, preferably, the cylindrical plastic blank is heated to 650 ℃ at the speed of 2-3 ℃/min and is kept warm for 2 hours, then the cylindrical plastic blank is subjected to cold isostatic pressing in oil at the pressure of 500-600 mPa for 15-20 minutes to obtain a green blank, and the green blank is placed in N2Heating to 1400 ℃ at the speed of 2-3 ℃/min under the atmosphere, preserving heat for 10 hours, then cooling to 500 ℃ at the speed of 2-3 ℃/min, cooling along with a furnace, polishing the surface of the obtained ceramic on a polishing machine, coating an electrode, drying at the temperature of 120 ℃, and firing a silver electrode at the temperature of 650 ℃ to obtain the titanium dioxide-based ceramic.
The invention has the following beneficial effects:
1. according to the invention, trivalent element Al and equal molar mass of pentavalent element Nb are simultaneously added into titanium dioxide, pre-sintering powder is placed in a magnetic field of 3-12T to obtain a green body, and then N is added2Sintering the ceramic at high temperature in the atmosphere to obtain the giant dielectric ceramic, wherein Al is newly added into the material3+Ions increase resistivity, and Nb5+The ions will donate electrons, resulting in Ti4+To Ti3+And transforming to form defect dipoles in small areas of the grains, wherein the huge dielectric properties of the material are mainly derived from the large number of defect dipoles. Standing under a 3-12T magnetic field can enable the dipoles to be oriented by the magnetic field, and movement of free charges is limited, so that resistivity is improved and reduction is achievedDielectric loss.
The invention adopts the method that the embryo is formed under the magnetic field in N2The sintering in (A) to obtain an environmentally friendly titanium dioxide-based ceramic having a giant dielectric constant, a low dielectric loss and a high resistance value and a relative dielectric constant of more than 103Dielectric loss can reach 0.05-0.1, resistivity can reach 107～109Omega cm, has great practical value in the times of miniaturization and light weight of electronic components. Especially, the device prepared by the ceramic has practical application value in various electronic devices such as capacitors and the like.
Drawings
FIG. 1 is an XRD spectrum of ceramics prepared in examples 1 to 3 and comparative example 1.
FIG. 2 is a graph showing the dielectric constant and dielectric loss with respect to the test frequency for the ceramics prepared in examples 1 to 3 and comparative example 1.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Preparation of titanium dioxide-based ceramic powder
According to (Al)0.5Nb0.5)0.005Ti0.995O2Weighing 0.3168g Al according to the stoichiometric ratio2O3、0.8259g Nb2O5、18.8593g TiO2The raw materials are used as raw materials, common ball milling is carried out on the raw materials, zirconia balls and absolute ethyl alcohol according to the mass ratio of 1:15:2 for 24 hours, and then baking is carried out at 80 ℃ for 12 hours to obtain the titanium dioxide based ceramic powder.
2. Preparation of titanium dioxide-based ceramics
Presintering titanium dioxide-based ceramic powder at 1100 ℃ for 2h, grinding the obtained presintered powder into powder, performing secondary ball milling and mixing, drying, performing third ball milling and mixing on the secondary ball milled powder, American Dow dispersant of Acumer Aoo and deionized water according to the volume ratio of 1:0.01:4 for 24h, and adjusting the pH value to 6.5 by using 1mol/L hydrochloric acid during third ball milling. The slurry obtained by the three ball mills was poured into a glass tube having an inner diameter of 10mm per 350. mu.L, and the glass tube was placed at 3TStanding for 48h, drying the slurry to obtain a cylindrical blank with a thickness of 2mm, heating the cylindrical blank to 650 ℃ at a speed of 2 ℃/min, keeping the temperature for 2h, carrying out cold isostatic pressing in oil for 15min at a pressure of 500mPa to obtain a green blank, and placing the green blank in an N atmosphere2Heating to 1400 ℃ at the speed of 3 ℃/min under the atmosphere, preserving heat for 10h, then cooling to 500 ℃ at the speed of 3 ℃/min, then cooling along with the furnace, polishing the flat surface of the obtained ceramic on a polishing machine, coating an electrode, drying at the temperature of 120 ℃, preserving heat for 30min at the temperature of 650 ℃ and firing the silver electrode to obtain the titanium dioxide-based ceramic.
Example 2
2. Preparation of titanium dioxide-based ceramics
In this example, slurry obtained by ball milling three times is poured into a glass tube with an inner diameter of 10mm in an amount of 350 μ L each, the glass tube is placed in a 6T magnetic field and left standing for 48 hours, and a cylindrical green compact with a thickness of 2mm is obtained after the slurry is dried, and other steps are the same as those in example 1, thereby obtaining the titanium dioxide-based ceramic.
Example 3
In this example, slurry obtained by ball milling three times is poured into a glass tube with an inner diameter of 10mm in an amount of 350 μ L each, the glass tube is placed in a 12T magnetic field and left standing for 48 hours, and a cylindrical green compact with a thickness of 2mm is obtained after the slurry is dried, and other steps are the same as those in example 1, thereby obtaining the titanium dioxide-based ceramic.
Comparative example 1
In step 2 of example 1, titanium dioxide-based ceramic powder was preburnt at 1100 ℃ for 2 hours, the preburnt powder was pulverized and then subjected to secondary ball milling and mixing, a 5% by mass aqueous solution of polyvinyl alcohol, 5% by mass of the preburnt powder, was added, granulated, passed through a 80-mesh sieve, and made into a cylindrical preform having a diameter of 10.0mm and a thickness of 1.5mm under a pressure of 200MPa with a powder tablet press, and then subjected to dry-milling in the presence of N2Keeping the temperature of the cylindrical blank at 500 ℃ for 2h in the atmosphere, heating to 1400 ℃ at 3 ℃/min, keeping the temperature for 10h, then cooling to 500 ℃ at 3 ℃/min, and then cooling along with the furnace, wherein other steps are the same as those in the example 1, so as to prepare the titanium dioxide-based ceramic.
XRD characterization was performed on the ceramics prepared in examples 1-3 and comparative example 1, and the results are shown in FIG. 1. As can be seen from the XRD patterns, the ceramics prepared in examples 1-3 and comparative example 1 are all complete rutile phase of titanium dioxide, and no second phase is generated.
The ceramics prepared in examples 1 to 3 and comparative example 1 were further tested for dielectric constant, dielectric loss and resistivity, and the results are shown in FIG. 2, tables 1 and 2.
TABLE 1 Electrical characteristics (test temperature: 25 ℃ C.) of the titania-based ceramics obtained in examples 1 to 3 and comparative example 1
TABLE 2 resistivity of the titania-based ceramics obtained in examples 1 to 3 and comparative example 1 (test temperature: 25 ℃ C.)
| Magnetic field | Direct voltage | Resistivity of | |
| Comparative example 1 | 0T | 10V | 4.0×105Ω·cm |
| Example 1 | 3T | 10V | 5.88×107Ω·cm |
| Example 2 | 6T | 10V | 1.10×108Ω·cm |
| Example 3 | 12T | 10V | 1.05×109Ω·cm |
Through the comparison, the invention obtains Al with high resistance value and giant dielectric constant through the external magnetic field0.0025Nb0.0025Ti0.995O2The dielectric constant of the ceramic is 10 in the frequency range of 1 kHz-100 kHz3The dielectric loss is 0.05-0.1, the ceramic has excellent frequency stability, and the resistivity of the ceramic is 107And the dielectric constant of the ceramic reaches the standard of high dielectric constant and low loss of the insulator under the reducing atmosphere.
Claims (8)
1. A preparation method of titanium dioxide based ceramics with high resistivity, giant dielectric constant and low loss under reducing atmosphere is characterized by comprising the following steps:
(1) preparation of titanium dioxide-based ceramic powder
According to (Al)0.5Nb0.5)0.005Ti0.995O2Weighing raw material Al according to the stoichiometric ratio2O3、Nb2O5And TiO2Ball-milling and mixing the raw materials with zirconia balls and absolute ethyl alcohol, and then drying to obtain titanium dioxide-based ceramic powder;
(2) preparation of titanium dioxide-based ceramics
Presintering titanium dioxide-based ceramic powder at 1050-1150 ℃ for 2-4 hours, grinding the presintered powder into powder, and then carrying out mixing with zirconia balls and absolute ethyl alcoholPerforming secondary ball milling and mixing, drying, performing third ball milling and mixing on the secondary ball milling powder, the dispersing agent and the deionized water according to the volume ratio of 1: 0.005-0.02: 1.5-4, and adjusting the pH value to 6.0-7.0 by using hydrochloric acid during the third ball milling; placing the slurry obtained by the third ball milling in a magnetic field of 3-12T for standing for 24-72 h, and obtaining a cylindrical plastic blank after the slurry is dried; heating the cylindrical blank to 550-700 ℃ at the speed of 1-5 ℃/min, preserving the heat for 2-5 hours, carrying out cold isostatic pressing in oil at the pressure of 200-700 mPa for 5-30 minutes to obtain a green blank, and placing the green blank in N2Heating to 1300-1500 ℃ at the speed of 1-5 ℃/min under the atmosphere, preserving heat for 2-10 hours, then cooling to 500-700 ℃ at the speed of 1-5 ℃/min, cooling along with a furnace, polishing the surface of the obtained ceramic on a polishing machine, coating an electrode, drying at the temperature of 70-120 ℃, and firing the silver electrode at the temperature of 600-800 ℃ to obtain the titanium dioxide-based ceramic.
2. The method of preparing titania-based ceramics according to claim 1, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in step (1), according to (Al)0.5Nb0.5)0.005Ti0.995O2Weighing raw material Al according to the stoichiometric ratio2O3、Nb2O5And TiO2The raw materials, zirconia balls and absolute ethyl alcohol are mixed for 12-36 hours in a ball milling mode according to the mass ratio of 1: 10-20: 2-3, and then the mixture is baked for 4-24 hours at the temperature of 65-95 ℃ to obtain titanium dioxide-based ceramic powder.
3. The method for preparing titania-based ceramics according to claim 1 or 2, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in the step (1), the TiO is2Is rutile phase TiO2。
4. The method of preparing titania-based ceramics according to claim 1, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in the step (2), the titanium dioxide-based ceramic powder is presintered at 1100 ℃ for 2-4 hours.
5. The method of preparing titania-based ceramics according to claim 1, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in the step (2), the secondary ball milling powder, a dispersing agent and deionized water are subjected to third ball milling and mixing for 36-72 hours according to the volume ratio of 1: 0.01-0.015: 2-3, and the pH value is adjusted to 6.5 by using hydrochloric acid during third ball milling.
6. The method for preparing titania-based ceramics according to claim 1 or 5, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in the step (2), the dispersant is any one of American Dow dispersant of type Acumer Aoo and an ultramarine oily wetting dispersant of type F420 or F400.
7. The method of preparing titania-based ceramics according to claim 1, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: and (2) placing the slurry obtained by the third ball milling in a magnetic field of 6-12T for standing for 36-48 h, and obtaining a cylindrical blank after the slurry is dried.
8. The method of preparing titania-based ceramics according to claim 1, having high resistivity, giant dielectric constant and low loss under reducing atmosphere, characterized in that: in the step (2), the cylindrical plastic blank is heated to 650 ℃ at the speed of 2-3 ℃/min and is kept warm for 2 hours, then the cylindrical plastic blank is subjected to cold isostatic pressing in oil at the pressure of 500-600 mPa for 15-20 minutes to obtain a green blank, and the green blank is placed in N2Heating to 1400 ℃ at the speed of 2-3 ℃/min under the atmosphere, preserving heat for 10 hours, then cooling to 500 ℃ at the speed of 2-3 ℃/min, cooling along with a furnace, polishing the surface of the obtained ceramic on a polishing machine, coating an electrode, drying at the temperature of 120 ℃, and firing a silver electrode at the temperature of 650 ℃ to obtain the titanium dioxide-based ceramic.
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