CN113831121A - Complex phase giant dielectric ceramic material with high breakdown field strength and preparation method thereof - Google Patents
Complex phase giant dielectric ceramic material with high breakdown field strength and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 230000015556 catabolic process Effects 0.000 title description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000010936 titanium Substances 0.000 claims abstract description 126
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 30
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 30
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910002971 CaTiO3 Inorganic materials 0.000 claims abstract description 4
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 212
- 239000000919 ceramic Substances 0.000 claims description 198
- 239000002994 raw material Substances 0.000 claims description 60
- 238000001035 drying Methods 0.000 claims description 56
- 238000000498 ball milling Methods 0.000 claims description 55
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 45
- 229910052709 silver Inorganic materials 0.000 claims description 45
- 239000004332 silver Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000005303 weighing Methods 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000005498 polishing Methods 0.000 claims description 30
- 238000003825 pressing Methods 0.000 claims description 28
- 239000011222 crystalline ceramic Substances 0.000 claims description 21
- 229910002106 crystalline ceramic Inorganic materials 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 238000007873 sieving Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 15
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 28
- 239000003990 capacitor Substances 0.000 abstract description 5
- 230000015654 memory Effects 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 106
- 239000000203 mixture Substances 0.000 description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 32
- 238000003801 milling Methods 0.000 description 26
- 239000011230 binding agent Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 13
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 229910001936 tantalum oxide Inorganic materials 0.000 description 13
- 239000012856 weighed raw material Substances 0.000 description 13
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 11
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical group O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 229910003443 lutetium oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910004247 CaCu Inorganic materials 0.000 description 1
- 229910002232 La2−xSrxNiO4 Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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Abstract
The invention relates to a titanium dioxide-based giant dielectric ceramic material and a preparation method thereof, wherein the general formula of the titanium dioxide-based giant dielectric ceramic material is (A)0.5Ta0.5)xTi1‑xO2+y wt%B(x=0.01‑0.1,y=1-10), wherein A is selected from at least one of Ho, Tm, Gd, Lu, La, Al, Ga and In, and B is selected from SiO2、Al3O2、Bi3O2、B3O2、ZrO2、SrTiO3、CaTiO3At least one of (1). The preparation method is a solid-phase sintering method, the method is simple, the repeatability is good, the yield is high, the frequency stability of the obtained giant dielectric ceramic material in the range of 20 Hz-5 MHz is good, and the dielectric constant is 103~105Breakdown field ofThe strength is as high as 322-1985V/cm. Has practical application value in various electronic devices such as capacitors and dynamic memories.
Description
Technical Field
The invention belongs to the technical field of electronic ceramics and manufacturing thereof, and particularly relates to a titanium dioxide-based giant dielectric ceramic material and a preparation method thereof.
Background
In recent years, with the rapid development of microelectronic technology, the integration of electronic components and devices has made the design of miniaturized modules indispensable. Therefore, a giant dielectric material having low dielectric loss and high temperature stability is expected to be used in the research and application of Multi-layer Ceramic Capacitors (MLCCs). In order to meet the application requirements of MLCCs, the development of giant dielectric ceramics with low dielectric loss and good temperature/frequency stability is an important research direction in the material field.
Over the past decade, a novel family of giant dielectric materials, including CaCu, has been discovered3Ti4O12、 Ba(Fe0.5M0.5)O3（M＝Nb, Ta, Sb) Li-doped NiO、 RFe2O4(R ═ Lu, Er) and La2-xSrxNiO4 (x =1/3 and 1/8), although the discovery of these new materials has greatly pushed experimental research and related theoretical development of giant dielectric materials, the overall dielectric properties of these systems do not meet the requirements of practical applications (y. Wang, w. Jie, c. Yang, et al. adv. funct. mater, 29(27):1808118, 2019). High dielectric loss is always accompanied by high dielectric constant, and this phenomenon greatly limits the development of electronic material industry. Therefore, achieving the combined dielectric properties of high dielectric constant, low loss, high temperature and wide frequency stability at the same time is an extremely challenging study.
2013 Liu Yun et al, national university of Australia, discovered (Nb + In) co-doped TiO2The giant dielectric ceramic material has a large dielectric constant (. epsilon.)>104) And the dielectric loss is small (tan delta)<0.05) and good temperature stability/frequency stability (W. Hu, Y. Liu, R.L. Withers, et al. nat. mater, 12(9) 821-826,2013). Subsequently, researchers used different acceptor elements (Al, In, Ga, Al, Co, Cr, Sc, Fe) and donor elements (Nb) to prepare a series of novel TiO2A giga-dielectric ceramic material. Although these TiO compounds are present2The base ceramics all have a high dielectric constant (. epsilon.)r> 104) However, the problems of high dielectric loss and low breakdown field strength are still not solved (CN 110803923A, CN 105906340A and CN 105732020A).
Therefore, it is desirable to provide a novel giant dielectric material having high dielectric constant, low dielectric loss, high breakdown field strength, good temperature and frequency stability, and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a TiO with huge dielectric constant, low dielectric loss, high breakdown field strength and excellent temperature stability2A preparation method of a base complex phase ceramic material.
In order to solve the above technical problems, according to one aspect of the present invention, there is provided a titanium dioxide-based complex phase giant dielectric ceramic material having a composition represented by the formula (A)0.5Ta0.5)xTi1-xO2 +y wt%B (x=0.01-0.1, y =1-10), wherein A is selected from at least one of Ho, Tm, Gd, Lu, La, Al, Ga and In, and B is selected from SiO2、Al3O2、Bi3O2、B3O2、ZrO2、SrTiO3、CaTiO3At least one of (1).
Furthermore, the main phase of the complex phase giant dielectric ceramic material is rutile titanium dioxide codoped with Ta and A, the auxiliary phase is B, and the auxiliary phase is uniformly dispersed in the main phase. The main phase provides giant dielectric property, and the secondary phase has extremely excellent electrical insulation property; the auxiliary phase uniformly distributed at the main phase crystal boundary can effectively block the transmission of weakly bound charges, thereby greatly improving the working voltage and breakdown voltage of the material and not deteriorating the giant dielectric property.
Furthermore, the size range of the crystal grains is 0.5-20 mu m, the microstructure of the titanium dioxide-based complex phase ceramic material is compact, and the high-voltage breakdown resistance is outstanding on the basis of high giant dielectric property, low loss, and good frequency and temperature stability.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned titania-based complex phase giant dielectric ceramic material, comprising:
step one, according to (A)0.5Ta0.5)xTi1-xO2The raw materials, zirconia balls and absolute ethyl alcohol are subjected to ball milling and mixing in a stoichiometric ratio, and then are dried to obtain primary titanium dioxide based ceramic powder; the raw materials are A source and Ta2O5And TiO2；
Step two, presintering the primary titanium dioxide-based ceramic powder to obtain presintering powder, grinding the presintering powder in a mortar for 30min to obtain secondary titanium dioxide-based ceramic powder, adding a B source with the mass of 1-10% into the obtained secondary titanium dioxide ceramic powder, performing ball milling and drying to obtain complex phase ceramic powder, weighing the complex phase ceramic powder, adding a polyvinyl alcohol aqueous solution with the mass percent of 8% of the complex phase ceramic powder, granulating, sieving, and pressing in a powder tablet press under the pressure of 100MPa to obtain sample pieces; spreading a layer of mother powder with the same components and the thickness of 1mm on a crucible cover of alumina, placing a sample piece after the glue removal on the crucible cover, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the crucible in a muffle furnace, heating the crucible to 1300-1400 ℃ at the speed of 2 ℃/min, preserving the heat for 5-15 h, and naturally cooling the crucible to room temperature along with a furnace body to obtain compact crystalline ceramics;
and step three, polishing the flat surface of the compact crystalline ceramic obtained in the step two on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the compact crystalline ceramic, drying, and then placing the compact crystalline ceramic in a resistance furnace to burn silver for 0.5 hour at 800-850 ℃ to obtain the titanium dioxide complex phase giant dielectric ceramic material.
Further, in the step one, the mass ratio of the raw materials to the zirconia balls to the absolute ethyl alcohol is 1:3: 2.
Further, in the second step, the primary titanium dioxide-based ceramic powder is presintered at 1000-1100 ℃ for 2-6 hours to obtain presintered powder.
And further, in the second step, adding a polyvinyl alcohol aqueous solution into the complex-phase ceramic powder, granulating and sieving by a 80-mesh sieve.
Further, in the third step, after silver pastes are respectively coated on the upper surface and the lower surface of the titanium dioxide-based ceramic, the titanium dioxide-based ceramic is dried at 120 ℃.
The complex phase ceramic material has the advantages of simple preparation method, good repeatability, high yield, excellent dielectric property, high breakdown field strength of 322-1985V/cm and strong practicability, can be used for preparing a dielectric material of a dynamic random access memory capacitor to store information, and is expected to be used in the aspects of high-voltage capacitors and the like.
In addition, the invention adopts a solid-phase sintering method, and has the advantages of simple method, good repeatability and high yield. The used raw materials are all oxides, the price is low, the yield is high, and the preparation method is suitable for large-scale industrial production. Has great practical value in the times of miniaturization and light weight of electronic elements. Especially, the device prepared by the ceramic has practical application value in various electronic devices such as capacitors and the like.
Drawings
FIG. 1 shows (Ho)0.5Ta0.5)xTi1-xO2+y wt%SiO2 (x=0.01,y = 1-7) X-ray diffraction pattern of ceramic sample of system.
FIG. 2 is (Ho)0.5Ta0.5)xTi1-xO2+y wt%SiO2 (x=0.01,y = 1-7) microscopic structure of ceramic sample.
FIG. 3 is (Ho)0.5Ta0.5)xTi1-xO2+y wt%SiO2 (x=0.01,y = 1-7) dielectric frequency spectrum of ceramic sample.
FIG. 4 shows (Ho)0.5Ta0.5)xTi1-xO2+y wt%SiO2 (x=0.01,y = 1-7) breakdown field strength of ceramic samples.
Detailed Description
Example 1
In one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y = 1), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+1wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O21wt% of ceramic powder massSiO2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to FIG. 1 and Table 1, FIG. 1 shows the X-ray diffraction pattern obtained for the composition of example 1, from which it can be seen that TiO is the predominant crystalline phase of the sample2And with SiO2Phases exist.
Referring to fig. 2 and table 1, fig. 2(a) is a scanning electron micrograph of the ceramic sample obtained in example 1, and it can be observed that the ceramic sample has a dense structure and an average grain size of 5.12 mm.
Referring to fig. 3 and table 1, x =0.01 in fig. 3 is the dielectric properties of the ceramic sample obtained in example 1, and it can be seen that the ceramic sample has a large dielectric constant (22825) and a low dielectric loss (0.029) at a frequency of 1 kHz.
Referring to fig. 4 and table 1, fig. 4 shows the breakdown field strength of the ceramic sample obtained in example 1. From the figure, it can be derived that the breakdown field strength of the sample is 322V/cm.
Example 2
The multiphase giant dielectricAn example of the ceramic material, the total composition expression of the complex phase giant dielectric ceramic material described in this example is (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =3), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+3wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The ceramic powder crucible is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powderAdding the secondary (Ho) to the body0.5Ta0.5)0.01Ti0.99O2SiO 3wt% of ceramic powder mass2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to FIG. 1 and Table 1, FIG. 1(a) shows the X-ray diffraction pattern obtained for the composition of example 2, from which it can be seen that TiO is the predominant crystalline phase of the sample2And with SiO2Phases exist.
Referring to FIG. 2 and Table 1, FIG. 2(b) is a scanning electron micrograph of the ceramic sample obtained in example 2, and it can be observed that the ceramic sample has a dense structure and an average grain size of 4.13 mm.
Referring to fig. 3 and table 1, x =0.01 in fig. 3 is the dielectric properties of the ceramic sample obtained in example 2, and it can be seen that the ceramic sample has a large dielectric constant (14250) and a low dielectric loss (0.023) at a frequency of 1 kHz.
Referring to fig. 4 and table 1, fig. 4 shows the breakdown field strength of the ceramic sample obtained in example 2. From the figure, the breakdown field strength of the sample is 568V/cm.
Example 3:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =5), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+5wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: the handle is provided with the above-mentioned disposable (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2SiO 5wt% of ceramic powder2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to FIG. 1 and Table 1, FIG. 1(a) shows the X-ray diffraction pattern obtained for the composition of example 3, from which it can be seen that TiO is the predominant crystalline phase of the sample2And with SiO2Phases exist.
Referring to FIG. 2 and Table 1, FIG. 2(c) is a scanning electron micrograph of the ceramic sample obtained in example 3, and it can be observed that the ceramic sample has a dense structure and an average grain size of 3.12 mm.
Referring to FIG. 3 and Table 1, the dielectric properties of the ceramic samples obtained in example 3 are shown in FIG. 3, and it can be seen that the ceramic samples have a large dielectric constant (10662) and a low dielectric loss (0.037) at a frequency of 1 kHz.
Referring to fig. 4 and table 1, fig. 4 shows the breakdown field strength of the ceramic sample obtained in example 3. From the figure, it can be derived that the breakdown field strength of the sample is 931V/cm.
Example 4:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+7wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, placing in a mortarGrinding for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2SiO in the mass of 7wt% of ceramic powder2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to FIG. 1 and Table 1, FIG. 1(a) shows the X-ray diffraction pattern obtained for the composition of example 4, from which it can be seen that TiO is the predominant crystalline phase of the sample2And with SiO2Phases exist.
Referring to FIG. 2 and Table 1, FIG. 2(c) is a scanning electron micrograph of the ceramic sample obtained in example 4, and it can be observed that the ceramic sample has a dense structure and an average grain size of 1.52 mm.
Referring to FIG. 3 and Table 1, in FIG. 3, (c) is the dielectric properties of the ceramic sample obtained in example 4, it can be seen that the ceramic sample has a large dielectric constant (8660) and a low dielectric loss (0.012) at a frequency of 1 kHz.
Referring to fig. 4 and table 1, fig. 4 shows the breakdown field strength of the ceramic sample obtained in example 4. From the figure, the breakdown field strength of the sample is 1861V/cm.
Example 5:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A is Ho, B is Bi2O3。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+7wt%Bi2O3treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Bismuth oxide (Bi)2O3) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2Bi of 7wt% of ceramic powder mass2O3Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 15h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 5, and it can be seen that the ceramic samples have a large dielectric constant (24312) and a low dielectric loss (0.017) at a frequency of 1 kHz. The breakdown field strength was 1621V/cm.
Example 6:
the multiphase giant dielectricAn example of the ceramic material, the total composition expression of the complex phase giant dielectric ceramic material described in this example is (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A is Ho and B is B2O3。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+7wt% B2O3treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Boron oxide (B)2O3) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2B of 7wt% of ceramic powder mass2O3Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 15h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 5, and it can be seen that the ceramic samples have a large dielectric constant (10121) and a low dielectric loss (0.011) at a frequency of 1 kHz. The breakdown field strength is 1321V/cm.
Example 7:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A is Ho, B is Al2O3。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+7wt% Al2O3treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Alumina (Al)2O3) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2Al in an amount of 7wt% based on the mass of the ceramic powder2O3Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 15h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 7, it can be seen that the ceramic samples have a large dielectric constant (7231) and a low dielectric loss (0.009) at a frequency of 1 kHz. The breakdown field strength is 1543V/cm.
Example 8:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A being Ho and B being ZrO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+7wt% ZrO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Zirconium oxide (ZrO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2ZrO of ceramic powder 7wt%2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 7, and it can be seen that the ceramic samples have a large dielectric constant (6012) and a low dielectric loss (0.014) at a frequency of 1 kHz. The breakdown field strength was 1985V/cm.
Example 9:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.05, y =7), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.05Ti0.95O2+7wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.05Ti0.95O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)9.8027g、TiO2(99.99%)78.7335 、Ta2O5(99.99%)11.4639g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, fully milling for 24 hours, and separating the zirconia balls, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2Drying the raw material mixture in a drying oven at 75 deg.C to obtain primary (Ho)0.5Ta0.5)0.05Ti0.95O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.05Ti0.95O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.05Ti0.95O2And (3) putting a crucible of the ceramic powder into a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min, and presintering for 2h to obtain presintering powder. Grinding the pre-sintered powder in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.05Ti0.95O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.05Ti0.95O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.05Ti0.95O2SiO in the mass of 7wt% of ceramic powder2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of 1mm thick mother powder with the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1300 ℃ at the speed of 3 ℃/min, preserving the heat for 10 hours, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 800 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 9, it can be seen that the ceramic samples have a large dielectric constant (25534) and a low dielectric loss (0.025) at a frequency of 1 kHz. The breakdown field strength was 1112V/cm.
Example 10:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =7), A being Lu and B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Lu0.5Ta0.5)0.01Ti0.99O2+7wt% SiO2treatment of raw material powder: lutetium oxide (Lu)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Zirconium oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Lu)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Lu processed in step (1)2O3(99.99%)2.3895g、TiO2(99.99%)94.9570 、Ta2O5(99.99%)2.6535g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Lu)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Lu0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Lu)0.5Ta0.5)0.01Ti0.99O2Placing a crucible of ceramic powder into a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min for pre-sinteringAnd (5) obtaining the calcined powder after 2 h. Grinding the powder to be sintered in a mortar for 30min to obtain a second powder (Lu)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: to two times (Lu)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Lu) into the ceramic powder0.5Ta0.5)0.01Ti0.99O2SiO in the mass of 7wt% of ceramic powder2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of 1mm thick mother powder with the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1300 ℃ at the speed of 3 ℃/min, preserving the heat for 10 hours, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 800 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 10, it can be seen that the ceramic samples have a large dielectric constant (10235) and a low dielectric loss (0.021) at a frequency of 1 kHz. The breakdown field strength is 1675V/cm.
Example 11:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.05, y =7), A being Lu and B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Lu0.5Ta0.5)0.05Ti0.95O2+7wt% SiO2treatment of raw material powder: lutetium oxide (Lu)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Zirconium oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Lu)0.5Ta0.5)0.05Ti0.95O2Stoichiometrically weighing the Lu processed in step (1)2O3(99.99%)10.2699g、TiO2(99.99%)78.3256 、Ta2O5(99.99%)11.4045g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Lu)0.5Ta0.5)0.05Ti0.95O2Ceramic powder;
(4) (Lu0.5Ta0.5)0.05Ti0.95O2synthesis of the complex: is provided with a handle (Lu)0.5Ta0.5)0.05Ti0.95O2And putting the crucible of the ceramic powder into a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min, and burning for 2h to obtain the pre-sintered powder. Grinding the pre-sintered powder in a mortar for 30min to obtain a second powder (Lu)0.5Ta0.5)0.05Ti0.95O2Ceramic powder;
(5) mixing the two phases: to two times (Lu)0.5Ta0.5)0.05Ti0.95O2Adding the secondary (Lu) into the ceramic powder0.5Ta0.5)0.05Ti0.95O2SiO in the mass of 7wt% of ceramic powder2Powder ofUsing absolute ethyl alcohol as a medium, ball-milling for 10 hours, and drying at 75 ℃ to obtain complex phase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of 1mm thick mother powder with the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1300 ℃ at the speed of 3 ℃/min, preserving the heat for 10 hours, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 800 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 11, it can be seen that the ceramic samples have a large dielectric constant (11132) and a low dielectric loss (0.029) at a frequency of 1 kHz. The breakdown field strength was 1455V/cm.
Comparative example 1:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =0), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+0wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, fully milling for 24 hours, separating the zirconia balls, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) granulating, tabletting and discharging rubber: weighing the secondary (Ho) obtained in the step (4)0.5Ta0.5)0.01Ti0.99O20.5g of ceramic powder, adding 8% of polyvinyl alcohol binder by mass, uniformly mixing, sieving by a 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(6) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 10h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(7) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying at 120 ℃, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in comparative example 1, and it can be seen that the ceramic samples have a large dielectric constant (31920) and a low dielectric loss (0.022) at a frequency of 1 kHz.
Referring to Table 1, Table 1 shows the breakdown field strengths of the ceramic samples obtained in comparative example 1. The breakdown field strength of the sample can be found to be 210V/cm.
Comparative example 2:
in one embodiment of the present invention, the total composition of the complex phase giant dielectric ceramic material is expressed as (A)0.5Ta0.5)xTi1-xO2+ y wt% B (x =0.01, y =10), A being Ho, B being SiO2。
The preparation method of the complex phase giant dielectric ceramic material comprises the following steps:
(1) (Ho0.5Ta0.5)0.01Ti0.99O2+10wt%SiO2treatment of raw material powder: holmium oxide (Ho)2O3) Tantalum oxide (Ta)2O5) Titanium oxide (TiO)2) Silicon oxide (SiO)2) Drying at 150 deg.C for 5 hr;
(2) weighing and batching: pressing (Ho)0.5Ta0.5)0.01Ti0.99O2Stoichiometrically weighing the Ho processed in step (1)2O3(99.999%)2.2717g、TiO2(99.99%)95.0716 、Ta2O5(99.99%)2.6567g of raw material powder;
(3) ball milling and mixing: adding the weighed raw materials into a ball milling tank, taking zirconia balls as milling balls and absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material mixture to the zirconia balls to the absolute ethyl alcohol is 1:3:2, and fully milling the raw materials 2Separating zirconia balls for 4 hours, putting the raw material mixture into a drying oven, and drying at 75 ℃ to obtain primary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(4) (Ho0.5Ta0.5)0.01Ti0.99O2synthesis of the complex: is provided with a handle (Ho)0.5Ta0.5)0.01Ti0.99O2The crucible of the ceramic powder is put into a muffle furnace, the temperature is raised to 1100 ℃ at the speed of 2 ℃/min, the temperature is kept for 6h, and the crucible is naturally cooled to about 150 ℃ along with the furnace body. Taking out the pre-synthesized powder, grinding in a mortar for 30min to obtain secondary (Ho)0.5Ta0.5)0.01Ti0.99O2Ceramic powder;
(5) mixing the two phases: towards second order (Ho)0.5Ta0.5)0.01Ti0.99O2Adding the secondary (Ho) into ceramic powder0.5Ta0.5)0.01Ti0.99O2SiO 10wt% of ceramic powder mass2Ball milling the powder for 10 hr in anhydrous alcohol medium, and stoving at 75 deg.c to obtain multiphase ceramic powder;
(6) granulating, tabletting and discharging rubber: weighing 0.5g of the complex phase ceramic powder obtained in the step (5), adding 8% by mass of polyvinyl alcohol binder, uniformly mixing, sieving with an 80-mesh sieve, and pressing into sample tablets in a powder tablet press under the pressure of 100 MPa; then heating to 550 ℃ at the speed of 1 ℃/min in a muffle furnace, and preserving heat for 2h for removing glue;
(7) and (3) sintering: and (3) placing the obtained sample piece on a crucible cover of alumina, paving a layer of mother powder with the thickness of 1mm and the same components to reduce the pollution of the alumina crucible under high-temperature sintering as much as possible, placing the sample piece obtained in the step (6) on the sample piece, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the sample piece in a muffle furnace, heating to 1400 ℃ at the speed of 3 ℃/min, preserving the temperature for 15h, and naturally cooling to room temperature along with the furnace body to obtain the compact crystalline ceramics.
(8) Silver burning: polishing the surface of the sintered giant dielectric complex phase ceramic on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the sintered giant dielectric complex phase ceramic, drying the ceramic, and then placing the ceramic in a resistance furnace to burn silver for 0.5 hour at 850 ℃ to obtain the giant dielectric low-loss titanium dioxide-based giant dielectric ceramic material.
Referring to Table 1, Table 1 shows the dielectric properties of the ceramic samples obtained in example 1, and it can be seen that the ceramic samples have a large dielectric constant (310) and a low dielectric loss (0.142) at a frequency of 1 kHz. It can be concluded that the dielectric properties have deteriorated severely.
Table 1 summarizes the average particle size, dielectric constant, dielectric loss and insulation resistivity of examples 1 to 10 and comparative examples 1 to 2 as follows:
TABLE 1 grain size and dielectric Properties at Room temperature for samples of different compositions
And (4) conclusion: the complex phase giant dielectric ceramic material has a large dielectric constant (>103) And low dielectric loss: (<0.05). And, in the composite SiO2、Al3O2、Bi3O2、B3O2、ZrO2、SrTiO3、CaTiO3And then the breakdown field strength of the giant dielectric ceramic is obviously improved due to the fact that the grain boundary resistance is improved. The invention has practical application value in various electronic devices such as capacitors, dynamic memories and the like.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications belonging to the technical solutions of the present invention are within the scope of the present invention.
Claims (8)
1. A titanium dioxide-based multiphase giant dielectric ceramic material is characterized in that the component expression is (A)0.5Ta0.5)xTi1-xO2 +y wt%B (x=0.01-0.1, y =1-10), wherein A is selected from at least one of Ho, Tm, Gd, Lu, La, Al, Ga and In, and B is selected from SiO2、Al3O2、Bi3O2、B3O2、ZrO2、SrTiO3、CaTiO3At least one of (1).
2. The titanium dioxide-based complex phase giant dielectric ceramic material as claimed in claim 1, wherein: the main phase of the complex phase giant dielectric ceramic material is rutile titanium dioxide codoped with Ta and A, the auxiliary phase is B, and the auxiliary phase is uniformly dispersed in the main phase.
3. The titanium dioxide-based complex phase giant dielectric ceramic material according to claim 2, wherein: the grain size ranges from 0.5 μm to 20 μm.
4. The process for preparing a titania-based complex phase giant dielectric ceramic material as claimed in any one of claims 1 to 3, comprising:
step one, according to (A)0.5Ta0.5)xTi1-xO2The raw materials, zirconia balls and absolute ethyl alcohol are subjected to ball milling and mixing in a stoichiometric ratio, and then are dried to obtain primary titanium dioxide based ceramic powder; the raw materials are A source and Ta2O5And TiO2；
Step two, presintering the primary titanium dioxide-based ceramic powder to obtain presintering powder, grinding the presintering powder in a mortar for 30min to obtain secondary titanium dioxide-based ceramic powder, adding a B source with the mass of 1-10% into the obtained secondary titanium dioxide ceramic powder, performing ball milling and drying to obtain complex phase ceramic powder, weighing the complex phase ceramic powder, adding a polyvinyl alcohol aqueous solution with the mass percent of 8% of the complex phase ceramic powder, granulating, sieving, and pressing in a powder tablet press under the pressure of 100MPa to obtain sample pieces; spreading a layer of mother powder with the same components and the thickness of 1mm on a crucible cover of alumina, placing a sample piece after the glue removal on the crucible cover, covering the sample piece with the mother powder with the same components, inverting the crucible, covering and sealing the crucible, immediately placing the crucible in a muffle furnace, heating the crucible to 1300-1400 ℃ at the speed of 2 ℃/min, preserving the heat for 5-15 h, and naturally cooling the crucible to room temperature along with a furnace body to obtain compact crystalline ceramics;
and step three, polishing the flat surface of the compact crystalline ceramic obtained in the step two on a polishing machine, respectively coating silver paste on the upper surface and the lower surface of the compact crystalline ceramic, drying, and then placing the compact crystalline ceramic in a resistance furnace to burn silver for 0.5 hour at 800-850 ℃ to obtain the titanium dioxide complex phase giant dielectric ceramic material.
5. The method of preparing a titania-based giant dielectric ceramic material according to claim 4, wherein: in the first step, the mass ratio of the raw materials to the zirconia balls and the absolute ethyl alcohol is 1:3: 2.
6. The method of preparing a giant dielectric ceramic material according to claim 4 or 5, wherein: in the second step, the primary titanium dioxide-based ceramic powder is presintered at 1000-1100 ℃ for 2-6 hours to obtain presintered powder.
7. The method of preparing a giant dielectric ceramic material according to claim 6, wherein: and step two, adding a polyvinyl alcohol aqueous solution into the complex phase ceramic powder, granulating and sieving by a 80-mesh sieve.
8. The method of preparing a titania-based giant dielectric ceramic material according to claim 4 or 7, wherein: and in the third step, silver pastes are respectively coated on the upper surface and the lower surface of the titanium dioxide-based ceramic, and then the titanium dioxide-based ceramic is dried at 120 ℃.
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