CN106747411A - The bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material of lithium and preparation method - Google Patents
The bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material of lithium and preparation method Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 55
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 41
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000003179 granulation Effects 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 54
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 36
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 claims description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004677 Nylon Substances 0.000 claims description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 239000004570 mortar (masonry) Substances 0.000 claims description 12
- 229920001778 nylon Polymers 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 229940068984 polyvinyl alcohol Drugs 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910004247 CaCu Inorganic materials 0.000 description 1
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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Abstract
The invention discloses a kind of bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material of lithium, its chemical formula meets below general formula, LixBixCd(1‑x)Cu3Ti4O12, wherein, the span of x is 0 ＜ x≤1, and dielectric constant is high, and sintering temperature is relatively low, and temperature stability is good.The invention also discloses the preparation method of the bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material of the lithium, specifically implement according to following steps：Step 1, calculates and weighs raw material；Step 2, dispensing is simultaneously ground；Step 3, pre-burning；Step 4, secondary ball milling；Step 5, granulation；Step 6, compressing tablet；Step 7, sintering.
Description
Technical field
The invention belongs to technical field of ceramic material, it is related to a kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material,
The invention further relates to the preparation method of the material.
Background technology
CCTO(CaCu3Ti4O12) ceramic material due to its typical dielectric high and low loss performance, in large bulk capacitance
The aspects such as the miniaturization of device, memory and electronic component have potential using value.But the material there is also it is some other
Shortcoming, such as causes that the material favors sintering temperature less high, one pack system in the preparation because the temperature stability of performance is poor
Doping is lifted limited etc. to dielectric properties.In order to overcome these not enough, there is the technology that CCTO is prepared using sol-gel methods.Can be with
Monocrystalline is obtained, but yield is extremely low；Magnetron sputtering method prepares the technology of CCTO, in addition to preparation cost is high, is used only for reality
The preparation of existing large area CCTO films；It is considered as most having the solid phase method technology of preparing of development potentiality then to there is sintering in preparation process
Temperature is higher, and synthesis condition is widely different to cause more than material internal defect the therefore shortcoming of unstable properties；In order to stablize CCTO
Technology of preparing, improves the deficiency of solid phase method, and the research to CCTO at present still mainly includes two parts：(1) relevant its giant dielectric
Property origin research, current internal barriers effect be IBLC theory is recognized extensively.Some disputes are there is also simultaneously, than
The origin of the giant dielectric such as without method interpretation monocrystal material；(2) by reduce loss and the sintering temperatures such as doping, substitution, but effect
Preferably it is mainly single-phase doping techniques.In the research of our same periods, Li and K codopes CaCu is developed3Ti4O12's
Double doped system, reduces sintering temperature, but dielectric constant is only, relatively higher, but preferable not enough.
The content of the invention
It is an object of the invention to provide a kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, dielectric constant is high, burns
Junction temperature is relatively low, and temperature stability is good.
The technical solution adopted in the present invention is, a kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its chemistry
Formula meets below general formula, LixBixCd(1-x)Cu3Ti4O12, wherein, the span of x is 0 ＜ x≤1.
It is a further object of the present invention to provide the lithium and the preparation method of bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material.
Another technical scheme of the invention is, a kind of preparation side of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material
Method, specifically implements according to following steps：
Step 1, calculates and weighs raw material；
Step 2, dispensing is simultaneously ground；
Step 3, pre-burning；
Step 4, secondary ball milling；
Step 5, granulation；
Step 6, compressing tablet；
Step 7, sintering.
The features of the present invention is also resided in,
Step 1 is specifically, press formula LixBixCd(1-x)Cu3Ti4O12, wherein, X values, root are specified in 0 ＜ x≤1 as needed
According to the ceramics amount being actually needed, CdO, CuO, TiO that calculating is respectively necessary for2、Li2CO3And Bi2O3Quality.
CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be 99.5%.
Step 2 is fitted into nylon tank specifically, according to the result calculated in step 1, weigh raw material, and mixed, with
Zirconia ball is abrading-ball, absolute ethyl alcohol is ball-milling medium, and medium cumulative volume is no more than the 1/2 of ball milling tank volume, on ball mill
11~16 hours, zirconium oxide balls are isolated, discharged, mixed slurry is dried at 70~100 DEG C and pack is ground, at the beginning of obtaining
Level powder mixture.
Step 3 specifically, will be prepared in step 2 drying primary powder be placed in alumina crucible, add a cover and stay seam
1-4mm, in 700~850 DEG C of pre-burnings 3~5 hours, furnace cooling obtained precursor powder.
Step 4 specifically, the precursor powder that will be prepared in step 3 is fitted into nylon tank, with zirconia ball as abrading-ball, nothing
Water-ethanol is the half of the volume total amount no more than ball milling tank volume of ball-milling medium, medium and abrading-ball, and ball is continued on ball mill
Mill 3~5 hours, separates zirconia ball, and discharging by mixed slurry at 70~100 DEG C, to be placed into and grind the pre- of acquisition in mortar
Powder is burnt, is then packed standby.
Step 5 specifically, weigh step 4 acquisition pre-burning powder insert aluminum oxide mortar, it is dense to be added dropwise over quality to it
The polyvinyl alcohol water solution for 4%-11% is spent, is sufficiently stirred for, it is finely ground, 80~120 mesh sieves are crossed, the powder pack that will have been granulated.
Wherein, the mass ratio of pre-burning powder and polyvinyl alcohol water solution is 3:0.10~0.4.
Step 6 specifically, the powder that 0.6g~0.8g is granulated is put into the stainless steel mould that internal diameter is 10mm, with 80~
The pressure of 100MPa is compressed into cylindric green compact.The specific requirement for vacuumizing is to be evacuated to 6.6 × 10-3More than Pa.
Step 7 is warming up to 450~850 DEG C, insulation specifically, green compact are put on aluminum oxide flat board with 2~5 DEG C/min
2~6 hours, then 900~1200 DEG C are warming up to 4~6 DEG C/min of heating rate, sinter 14~27 hours, it is then cold with stove
But, lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material is obtained.
The beneficial effects of the invention are as follows, lithium carbonate and bismuth oxide codope CdCu3Ti4O12Giant dielectric ceramic material is
A kind of new giant dielectric ceramic material, dielectric constant is 1.0 × 104More than, can be with other giant dielectrics of document report ceramics material
The dielectric properties performance of material is comparable, can be used to prepare dynamic random storage (DRAM) and dielectric capacitor high (MLCC).This hair
It is bright to have the advantages that method is simple, reproducible, high yield rate.
Brief description of the drawings
Fig. 1 is the X-ray collection of illustrative plates of lithium of the invention-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material；
Fig. 2 is Jie's spectrogram of lithium of the invention-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material；
Fig. 3 is 800 DEG C of pre-burnings when preparing lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material using the inventive method
With dielectric constant, the dielectric loss figure under 1000 degree of sintering lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material 1KHz；
Fig. 4 (a) is that the preparation method of lithium of the present invention-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material is burnt in 1000 DEG C of degree
Tie the impedance spectra of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material；
Fig. 4 (b) be the inventive method under different calcined temperatures and 1000 DEG C of sintering temperature, the lithium of preparation-bismuth co-doped
The impedance spectra of miscellaneous copper titanate cadmium giant dielectric ceramic material.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its chemical formula meets below general formula,
LixBixCd(1-x)Cu3Ti4O12, the wherein span of x is 0 ＜ x≤1.
A kind of preparation method of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, it is characterised in that specifically according to
Lower step is implemented：
Step 1, calculates and weighs raw material,
By formula LixBixCd(1-x)Cu3Ti4O12, wherein, X values are specified, according to actual needs in x=0~1 as needed
Ceramics amount, CdO, CuO, TiO that calculating is respectively necessary for2、Li2CO3And Bi2O3Quality；
Wherein, CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be
99.5%.
Step 2, dispensing is simultaneously ground,
According to the result calculated in step 1, raw material is weighed, and mixed, be fitted into nylon tank, be mill with zirconia ball
Ball, absolute ethyl alcohol are ball-milling medium, and medium cumulative volume 11~16 hours on ball mill, divides no more than the 1/2 of ball milling tank volume
Zirconium oxide balls are separated out, is discharged, mixed slurry is dried at 70~100 DEG C and pack is ground, obtain primary powder mixture.
Step 3, pre-burning,
The drying primary powder that will be prepared in step 2 is placed in alumina crucible, is added a cover and is stayed seam 1-4mm, 700~
850 DEG C of pre-burnings 3~5 hours, furnace cooling obtains precursor powder.
Step 4, secondary ball milling,
The precursor powder that will be prepared in step 3 is fitted into nylon tank, and with zirconia ball as abrading-ball, absolute ethyl alcohol is as ball milling
The volume total amount of medium, medium and abrading-ball continues ball milling 3~5 hours no more than the half of ball milling tank volume on ball mill, point
From zirconia ball, discharging by mixed slurry at 70~100 DEG C, places into the pre-burning powder that acquisition is ground in mortar, then fills
Bag is standby.
Step 5, granulation,
The pre-burning powder for weighing step 4 acquisition inserts aluminum oxide mortar, and mass concentration is added dropwise over for 4%-11% to it
Polyvinyl alcohol water solution, be sufficiently stirred for, it is finely ground, cross 80~120 mesh sieves, the powder that will granulate is packed.Wherein, pre-burning powder
It is 3 with the mass ratio of polyvinyl alcohol water solution:0.10~0.4.
Step 6, compressing tablet,
The powder that 0.6g~0.8g is granulated is put into the stainless steel mould that internal diameter is 10mm, with the pressure of 80~100MPa
It is compressed into cylindric green compact.
Step 7, sintering,
Green compact are put on aluminum oxide flat board, 450~850 DEG C are warming up to 2~5 DEG C/min, be incubated 2~6 hours, then
900~1200 DEG C are warming up to 4~6 DEG C/min of heating rate, are sintered 14~27 hours, then furnace cooling, acquisition lithium-
Bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material.
Lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material to being prepared using the above method carries out dielectric properties detection
When, first, silver ink firing is carried out to the material, it is exactly specifically the lithium and bismuth co-doped miscellaneous CdCu that will be obtained after sintering3Ti4O12
The ceramic surface polishing of giant dielectric ceramic material, is polished to 0.4~0.5mm thickness, upper and lower surface silk screen clearly clean with ultrasonic wave
Silver paste after 0.01~0.03mm of printing, 150 DEG C dry 1-2 hours, obtain electroded lithium and bismuth co-doped miscellaneous CdCu3Ti4O12
Giant dielectric ceramic material.
Then dielectric properties test is carried out to the product after silver ink firing again, is specifically carried out using following tester,
Tester：Precise impedance analyzer, model Agilient4294A is produced by Anjelen Sci. ＆ Tech. Inc；
X-ray diffractometer, model D/max-2200, by Rigaku, company produces；
After test, the result for obtaining is,
(1) can show that the ceramic material that all components are obtained occurs with pure class when sintering for 1000 DEG C by Fig. 1
The main diffraction maximum of Perovskite Phase.
(2) as seen from Figure 2, in the case of 800 DEG C of pre-burnings and 1000 degree of sintering, lithium carbonate and bismuth oxide are common
Doping is to CdCu3Ti4O12Ceramics can obtain giant dielectric performance,
(3) as seen from Figure 3, when 800 DEG C of pre-burnings and 1000 degree are sintered, Li0.0025Bi0.0025Cd0.995Cu3Ti4O12
Ceramics have highest dielectric properties.
(4) can be drawn by Fig. 4 (a) and (b), different temperatures sinters obtained lithium carbonate and bismuth oxide codope
To CdCu3Ti4O12Ceramic material is heterogeneous, internal to lead by insulation crystal boundary and partly crystal grain and constitute, and can be imitated using internal barriers
(IBLC) is answered to explain the giant dielectric origin of ceramic material.
When calcined temperature is 800 DEG C, sintering temperature is 1000 DEG C, and soaking time is 20 hours, and ceramic material obtains optimal
Electrical property, its electrical property is respectively：εr=16181, tan δ=0.1461, obtain a kind of lithium and bismuth co-doped miscellaneous new huge
Dielectric ceramic material.
Embodiment 1
A kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its chemical formula is LixBixCd(1-x)Cu3Ti4O12, its
The value of middle x is 0.1.
A kind of preparation method of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, it is characterised in that specifically according to
Lower step is implemented：
Step 1, calculates and weighs raw material,
By formula LixBixCd(1-x)Cu3Ti4O12, wherein, x=0.1, ceramics amount according to actual needs, calculating is respectively required for
CdO, CuO, the TiO for wanting2、Li2CO3And Bi2O3Quality；
Wherein, CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be
99.5%.
Step 2, dispensing is simultaneously ground,
According to the result calculated in step 1, raw material is weighed, and mixed, be fitted into nylon tank, be mill with zirconia ball
Ball, absolute ethyl alcohol are ball-milling medium, and medium cumulative volume, in ball mill upper 11 hour, is isolated no more than the 1/2 of ball milling tank volume
Mixed slurry is dried at 70 DEG C and grinds pack by zirconium oxide balls, discharging, obtains primary powder mixture.
Step 3, pre-burning,
The drying primary powder that will be prepared in step 2 is placed in alumina crucible, is added a cover and is stayed seam 1mm, at 700 DEG C in advance
Burn 3 hours, furnace cooling, obtain precursor powder.
Step 4, secondary ball milling,
The precursor powder that will be prepared in step 3 is fitted into nylon tank, and with zirconia ball as abrading-ball, absolute ethyl alcohol is as ball milling
The volume total amount of medium, medium and abrading-ball continues ball milling 3 hours no more than the half of ball milling tank volume on ball mill, separates
Zirconia ball, discharging by mixed slurry at 70 DEG C, places into the pre-burning powder that acquisition is ground in mortar, then packs standby.
Step 5, granulation,
The pre-burning powder for weighing step 4 acquisition inserts aluminum oxide mortar, and the poly- second that mass concentration is 4% is added dropwise over to it
The enol aqueous solution, is sufficiently stirred for, finely ground, crosses 80 mesh sieves, the powder pack that will have been granulated.Wherein, pre-burning powder and polyvinyl alcohol
The mass ratio of the aqueous solution is 3:0.10.
Step 6, compressing tablet,
The powder that 0.6g is granulated is put into the stainless steel mould that internal diameter is 10mm, is compressed into the pressure of 80MPa
Cylindric green compact.
Step 7, sintering,
Green compact are put on aluminum oxide flat board, 450 DEG C are warming up to 2 DEG C/min, be incubated 2 hours, then with 4 DEG C/min
Heating rate is warming up to 900 DEG C, sinters 14 hours, then furnace cooling, obtains lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramics
Material.
Embodiment 2
A kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its chemical formula meets below general formula,
LixBixCd(1-x)Cu3Ti4O12, the wherein value of x is 1.
A kind of preparation method of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, it is characterised in that specifically according to
Lower step is implemented：
Step 1, calculates and weighs raw material,
By formula LixBixCd(1-x)Cu3Ti4O12, wherein, x=1, CdO, CuO, TiO that calculating is respectively necessary for2、Li2CO3With
Bi2O3Quality；
Wherein, CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be
99.5%.
Step 2, dispensing is simultaneously ground,
According to the result calculated in step 1, raw material is weighed, and mixed, be fitted into nylon tank, be mill with zirconia ball
Ball, absolute ethyl alcohol are ball-milling medium, and medium cumulative volume, in ball mill upper 16 hour, is isolated no more than the 1/2 of ball milling tank volume
Mixed slurry is dried at 100 DEG C and grinds pack by zirconium oxide balls, discharging, obtains primary powder mixture.
Step 3, pre-burning,
The drying primary powder that will be prepared in step 2 is placed in alumina crucible, is added a cover and is stayed seam 4mm, at 850 DEG C in advance
Burn 5 hours, furnace cooling, obtain precursor powder.
Step 4, secondary ball milling,
The precursor powder that will be prepared in step 3 is fitted into nylon tank, and with zirconia ball as abrading-ball, absolute ethyl alcohol is as ball milling
The volume total amount of medium, medium and abrading-ball continues ball milling 5 hours no more than the half of ball milling tank volume on ball mill, separates
Zirconia ball, discharging by mixed slurry at 100 DEG C, places into the pre-burning powder that acquisition is ground in mortar, then packs standby
With.
Step 5, granulation,
The pre-burning powder for weighing step 4 acquisition inserts aluminum oxide mortar, to its be added dropwise over mass concentration be 11% it is poly-
Vinyl alcohol aqueous solution, is sufficiently stirred for, finely ground, crosses 120 mesh sieves, the powder pack that will have been granulated.Wherein, pre-burning powder and polyethylene
The mass ratio of alcohol solution is 3:0.4.
Step 6, compressing tablet,
The powder that 0.8g is granulated is put into the stainless steel mould that internal diameter is 10mm, is compressed into the pressure of 100MPa
Cylindric green compact.
Step 7, sintering,
Green compact are put on aluminum oxide flat board, 850 DEG C are warming up to 5 DEG C/min, be incubated 6 hours, then with 6 DEG C/min
Heating rate is warming up to 1200 DEG C, sinters 27 hours, then furnace cooling, obtains lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric pottery
Ceramic material.
Embodiment 3
A kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its chemical formula meets below general formula,
LixBixCd(1-x)Cu3Ti4O12, the wherein value of x is 0.5.
A kind of preparation method of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, it is characterised in that specifically according to
Lower step is implemented：
Step 1, calculates and weighs raw material,
By formula LixBixCd(1-x)Cu3Ti4O12, wherein, x=0.5, ceramics amount according to actual needs, calculating is respectively required for
CdO, CuO, the TiO for wanting2、Li2CO3And Bi2O3Quality；
Wherein, CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be
99.5%.
Step 2, dispensing is simultaneously ground,
According to the result calculated in step 1, raw material is weighed, and mixed, be fitted into nylon tank, be mill with zirconia ball
Ball, absolute ethyl alcohol are ball-milling medium, and medium cumulative volume, in ball mill upper 13 hour, is isolated no more than the 1/2 of ball milling tank volume
Mixed slurry is dried at 90 DEG C and grinds pack by zirconium oxide balls, discharging, obtains primary powder mixture.
Step 3, pre-burning,
The drying primary powder that will be prepared in step 2 is placed in alumina crucible, is added a cover and is stayed seam 2mm, at 800 DEG C in advance
Burn 3~5 hours, furnace cooling, obtain precursor powder.
Step 4, secondary ball milling,
The precursor powder that will be prepared in step 3 is fitted into nylon tank, and with zirconia ball as abrading-ball, absolute ethyl alcohol is as ball milling
The volume total amount of medium, medium and abrading-ball continues ball milling 4 hours no more than the half of ball milling tank volume on ball mill, separates
Zirconia ball, discharging by mixed slurry at 80 DEG C, places into the pre-burning powder that acquisition is ground in mortar, then packs standby.
Step 5, granulation,
The pre-burning powder for weighing step 4 acquisition inserts aluminum oxide mortar, and the poly- second that mass concentration is 8% is added dropwise over to it
The enol aqueous solution, is sufficiently stirred for, finely ground, crosses 100 mesh sieves, the powder pack that will have been granulated.Wherein, pre-burning powder and polyvinyl alcohol
The mass ratio of the aqueous solution is 3:0.2.
Step 6, compressing tablet,
The powder that 0.7g is granulated is put into the stainless steel mould that internal diameter is 10mm, is compressed into the pressure of 90MPa
Cylindric green compact.
Step 7, sintering,
Green compact are put on aluminum oxide flat board, 600 DEG C are warming up to 3 DEG C/min, be incubated 4 hours, then with 5 DEG C/min
Heating rate is warming up to 1000 DEG C, sinters 20 hours, then furnace cooling, obtains lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric pottery
Ceramic material.
Claims (10)
1. a kind of lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, it is characterised in that its chemical formula meets below general formula,
LixBixCd(1-x)Cu3Ti4O12, the wherein span of x is 0 ＜ x≤1.
2. a kind of preparation method of the lithium described in claim 1-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature
It is specifically to implement according to following steps：
Step 1, calculates and weighs raw material；
Step 2, dispensing is simultaneously ground；
Step 3, pre-burning；
Step 4, secondary ball milling；
Step 5, granulation；
Step 6, compressing tablet；
Step 7, sintering.
3. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In described step 1 is specially：
By formula LixBixCd(1-x)Cu3Ti4O12, wherein, x values, ceramics according to actual needs are specified in 0 ＜ x≤1 as needed
Amount, CdO, CuO, TiO that calculating is respectively necessary for2、Li2CO3And Bi2O3Quality.
4. the preparation method of lithium according to claim 3-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In described CdO, CuO and Li2CO3Purity be 99%, TiO2Purity be 99.99%, Bi2O3Purity be 99.5%.
5. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In, described step 2 specifically, according to the result calculated in step 1, weighing raw material, and mixed, it is fitted into nylon tank,
With zirconia ball as abrading-ball, absolute ethyl alcohol as ball-milling medium, medium cumulative volume no more than ball milling tank volume 1/2, in ball mill
Upper 11~16 hours, zirconium oxide balls are isolated, discharged, mixed slurry is dried at 70~100 DEG C and pack is ground, obtained
Primary powder mixture.
6. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In, described step 3 specifically, the drying primary powder that will be prepared in step 2 is placed in alumina crucible, add a cover and stay seam
1-4mm, in 700~850 DEG C of pre-burnings 3~5 hours, furnace cooling obtained precursor powder.
7. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In, described step 4 specifically, the precursor powder that will be prepared in step 3 is fitted into nylon tank, with zirconia ball as abrading-ball,
Absolute ethyl alcohol is the half of the volume total amount no more than ball milling tank volume of ball-milling medium, medium and abrading-ball, is continued on ball mill
Ball milling 3~5 hours, separates zirconia ball, and discharging by mixed slurry at 70~100 DEG C, is placed into and grind in mortar what is obtained
Pre-burning powder, then packs standby.
8. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In, described step 5 specifically, the pre-burning powder for weighing step 4 acquisition inserts aluminum oxide mortar, it is dense to be added dropwise over quality to it
The polyvinyl alcohol water solution for 4%-11% is spent, is sufficiently stirred for, it is finely ground, 80~120 mesh sieves are crossed, the powder pack that will have been granulated.
Wherein, the mass ratio of pre-burning powder and polyvinyl alcohol water solution is 3:0.10~0.4.
9. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature exists
In, described step 6 specifically, the powder that 0.6g~0.8g is granulated is put into the stainless steel mould that internal diameter is 10mm, with 80
The pressure of~100MPa is compressed into cylindric green compact.The specific requirement for vacuumizing is to be evacuated to 6.6 × 10-3More than Pa.
10. the preparation method of lithium according to claim 2-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material, its feature
It is that described step 7 is warming up to 450~850 DEG C specifically, green compact are put on aluminum oxide flat board with 2~5 DEG C/min,
Insulation 2~6 hours, then 900~1200 DEG C are warming up to 4~6 DEG C/min of heating rate, sinter 14~27 hours, Ran Housui
Stove is cooled down, and obtains lithium-bismuth co-doped miscellaneous copper titanate cadmium giant dielectric ceramic material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253933A (en) * | 2013-05-09 | 2013-08-21 | 陕西师范大学 | Lithium replaced copper cadmium titanate gigantic dielectric ceramic material and preparation method thereof |
| CN104803664A (en) * | 2015-04-20 | 2015-07-29 | 河南师范大学 | Preparation method of lithium molybdenum-codoped nickel oxide base dielectric ceramic material |
-
2016
- 2016-12-07 CN CN201611112546.1A patent/CN106747411A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253933A (en) * | 2013-05-09 | 2013-08-21 | 陕西师范大学 | Lithium replaced copper cadmium titanate gigantic dielectric ceramic material and preparation method thereof |
| CN104803664A (en) * | 2015-04-20 | 2015-07-29 | 河南师范大学 | Preparation method of lithium molybdenum-codoped nickel oxide base dielectric ceramic material |
Non-Patent Citations (1)
| Title |
|---|
| WATTANA TUICHAI等: "Na0.5Bi0.5Cu3Ti4O12 nanocrystalline powders prepared by a glycine–nitrate process: Preparation, characterization, and their dielectric properties", 《MICROELECTRONIC ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689708A (en) * | 2018-05-17 | 2018-10-23 | 韶关学院 | A kind of bismuth Doped with Titanium tantalic acid copper giant dielectric ceramic material and preparation method |
| CN108689708B (en) * | 2018-05-17 | 2021-04-27 | 韶关学院 | Bismuth-doped copper titanium tantalate giant dielectric ceramic material and preparation method thereof |
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