CN108249918A - Low-temperature sintering huge dielectric constant superfine ceramics material and preparation method and application - Google Patents
Low-temperature sintering huge dielectric constant superfine ceramics material and preparation method and application Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000009766 low-temperature sintering Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000004615 ingredient Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 22
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 25
- 239000011575 calcium Substances 0.000 claims description 22
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LVZCQZOALBUKMO-UHFFFAOYSA-N [Zr].[Ca].[Ba] Chemical compound [Zr].[Ca].[Ba] LVZCQZOALBUKMO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 9
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 231100000701 toxic element Toxicity 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 18
- 230000006872 improvement Effects 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- AMVVEDHCBDQBJL-UHFFFAOYSA-N [Ca][Zr] Chemical compound [Ca][Zr] AMVVEDHCBDQBJL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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Abstract
The invention discloses low-temperature sintering huge dielectric constant superfine ceramics material and preparation method and application, which is made of major ingredient and modifying agent, major ingredient Ba0.98Ca0.02Zr0.12Ti0.88O3, modifying agent MnCO3、Nb2O5、Y2O3、MgO、SiO2In two or more.Dielectric ceramic composition is made by ball milling, drying, grinding and sieving in above-mentioned major ingredient and modifying agent；Dielectric ceramic composition can obtain the high superfine ceramics of consistency through discharge plasma sintering (SPS).The present invention realizes the low-temperature sintering of huge dielectric constant ceramics, obtains the ceramics that consistency is high, crystal grain is tiny；The dielectric ceramic composition has high-k, low-loss, good capacity temperature characteristic and excellent comprehensive electrochemical properties, and the dielectric ceramic composition cost of raw material is cheap, it is a kind of environmentally friendly high Jie's medium ceramic material without toxic elements such as lead, cadmium, mercury, Cr VIs.
Description
Technical field
The invention belongs to ceramic material technical field, it is related to dielectric ceramic material and preparation method more particularly to low
Temperature sintering huge dielectric constant superfine ceramics material and preparation method.
Background technology
Current electronic complete machine is quickly grown, to the miniaturization of electronic component such as ceramic capacitor, Fabrication of High Specific Capacitance, low cost
Strict requirements are proposed with highly reliable etc., corresponding dielectric ceramic material performance is put forward higher requirements.In capacitor knot
In the case that structure and process conditions determine, the size of condenser capacity is mainly determined by the dielectric constant of dielectric ceramic material, because
This dielectric constant for improving material is the key that realize capacitor microminaturization.The room temperature of current existing high dielectric constant material
Dielectric constant is usually less than 5000, it is difficult to continue to improve.And the further development of electronic technology, dielectric constant is needed 10000
Above huge dielectric constant dielectric material.In condenser dielectric ceramic field, a small number of high-k porcelain products are such as in the market
Y5V/Z5U porcelain powder, dielectric constant up to 15000, usual sintering temperature be up to 1300 DEG C and temperature coefficient of capacity variation greatly, make
It is relatively narrow or even leaded material system is in part with warm area, it is only limited to special dimension application.Material development field such as CCTO, Nb-Ln-Ti
System (the positive triad such as Ln Bi, Al, Y) has a huge dielectric constant, but permissive waste is high or insulation resistance is relatively low, to technique
It is very sensitive, still there is segment distance from practical application in conceptual phase at present.
Invention content
Shortcoming present in regarding to the issue above, development environment friendly, sintering temperature are low, comprehensive electrochemical properties are good
High dielectric constant material system it is very necessary.The present invention provides low-temperature sintering huge dielectric constant superfine ceramics material and preparation side
Method can sinter fine and close superfine ceramics at 950 DEG C ± 50 DEG C, and keep very high-k, low-loss and good temperature
Spend characteristic.
To achieve the above object, the present invention provides a kind of low-temperature sintering huge dielectric constant superfine ceramics material, the medium porcelain
Material is made of major ingredient and modifying agent；
The major ingredient is Ba0.98Ca0.02Zr0.12Ti0.88O3；
The modifying agent is MnCO3、Nb2O5、Y2O3、MgO、SiO2In two or more.
As a further improvement on the present invention, the dielectric ceramic composition is with the Ba of 100 parts by weight0.98Ca0.02Zr0.12Ti0.88O3For
Base material, each ingredient and relative amount are as follows：
Major ingredient Ba0.98Ca0.02Zr0.12Ti0.88O3It is 100 parts；
Modifying agent MnCO3It is 0.05~0.50 part；
Modifying agent Nb2O5It is 0.02~0.40 part；
Modifying agent Y2O3It is 0~0.20 part；
Modifying agent MgO is 0~0.20 part；
Modifying agent SiO2It is 0~0.10 part.
The present invention also provides a kind of preparation method of low-temperature sintering huge dielectric constant superfine ceramics material, including：
Step 1 prepares major ingredient Ba using hydro-thermal method0.98Ca0.02Zr0.12Ti0.88O3；
Step 2 weighs major ingredient and modifying agent, is put into the ball grinder equipped with zirconia ball, in addition deionized water ball milling, baking
It does, be ground up, sieved, pack spare, preparation media porcelain.
As a further improvement on the present invention, the step 1 includes：
Step 11 prepares solution：Select deionized water and analysis pure raw material BaCl2、CaCl2、ZrOCl2、TiCl4With
NaOH prepares TiCl respectively after being weighed according to proportioning4Ice water solution, barium calcium zirconium mixed solution and NaOH solution；
Step 12 prepares presoma：By barium calcium zirconium mixed solution and TiCl4Ice water solution measures in proportion, mix after plus
Heat is heated to 80-100 DEG C, then the two kinds of solution heated are uniformly injected into reaction kettle to 60 DEG C~70 DEG C, by NaOH solution
Middle stirring 10~20 minutes obtains presoma as mixing suspension；
Step 13, hydro-thermal process：Mixing suspension is moved in water heating kettle, in 180~240 DEG C of hydro-thermals 3~8 hours, so
Filtering, deionized water are dry after washing to the μ S/cm of conductivity≤100 afterwards, cross 40 mesh sieve, obtain major ingredient
Ba0.98Ca0.02Zr0.12Ti0.88O3。
As a further improvement on the present invention, BaCl in the barium calcium zirconium mixed solution2：CaCl2：ZrOCl2Molar ratio is
98：2：12；TiCl4TiCl in ice water solution, barium calcium zirconium mixed solution and NaOH solution4：(BaCl2+CaCl2+ZrOCl2)：NaOH
Molar ratio 88：112：600.
As a further improvement on the present invention, in step 2, ball milling 12 hours, dry in 120 DEG C 8~12 hours to drying,
Ground 40 mesh sieve, pack are spare.
The present invention also provides a kind of applications of the preparation method of low-temperature sintering huge dielectric constant superfine ceramics material, will be made
Preparation media porcelain be fitted into graphite jig, porcelain is sintered into 950 DEG C ± 50 DEG C using SPS sintering furnaces, then in Muffle furnace
In 650 DEG C of heat treatments, superfine ceramics disks is made.
Compared with prior art, beneficial effects of the present invention are：
The present invention realizes the low-temperature sintering of huge dielectric constant ceramics, obtains the ceramics that consistency is high, crystal grain is tiny.Jie
Matter porcelain has high-k, low-loss, good capacity temperature characteristic and excellent comprehensive electrochemical properties, and the medium
The porcelain cost of raw material is cheap, is a kind of environmentally friendly high Jie's medium pottery without toxic elements such as lead, cadmium, mercury, Cr VIs
Ceramic material.
Description of the drawings
Fig. 1 is major ingredient Ba disclosed in an embodiment of the present invention0.98Ca0.02Zr0.12Ti0.88O3XRD spectra；
Fig. 2 is inventive formulation 7 through the sintered fracture apperance figures of SPS；
Fig. 3 is inventive formulation 7 through the sintered electrical property figures of SPS.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
The part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
Member's all other embodiments obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Raw material selected by the present invention unless otherwise specified, can be purchased by commercial channel.
The present invention is described in further detail below in conjunction with the accompanying drawings：
The present invention provides a kind of low-temperature sintering huge dielectric constant superfine ceramics material, and the dielectric ceramic composition is by major ingredient and modifying agent
Composition；
Major ingredient is Ba0.98Ca0.02Zr0.12Ti0.88O3, Ba0.98Ca0.02Zr0.12Ti0.88O3It is prepared using hydro-thermal method；
Modifying agent is MnCO3、Nb2O5、Y2O3、MgO、SiO2In two or more, select different doping vario-property agents
Improve the comprehensive performance of dielectric ceramic composition.
The dielectric ceramic composition of the present invention is with the Ba of 100 parts by weight0.98Ca0.02Zr0.12Ti0.88O3For base material, each ingredient and opposite
Content is as follows：
Major ingredient Ba0.98Ca0.02Zr0.12Ti0.88O3It is 100 parts；
Modifying agent MnCO3It is 0.05~0.50 part；
Modifying agent Nb2O5It is 0.02~0.40 part；
Modifying agent Y2O3It is 0~0.20 part；
Modifying agent MgO is 0~0.20 part；
Modifying agent SiO2It is 0~0.10 part.
The present invention also provides a kind of preparation method of low-temperature sintering huge dielectric constant superfine ceramics material, including：
Step 1 prepares major ingredient Ba using hydro-thermal method0.98Ca0.02Zr0.12Ti0.88O3；It specifically includes：
Step 11 prepares solution：Select deionized water and analysis pure raw material BaCl2、CaCl2、ZrOCl2、TiCl4With
NaOH prepares TiCl respectively after being weighed according to proportioning4Ice water solution, barium calcium zirconium mixed solution and NaOH solution；Wherein：Barium calcium zirconium
BaCl in mixed solution2：CaCl2：ZrOCl2Molar ratio is 98：2：12.
Step 12 prepares presoma：By barium calcium zirconium mixed solution and TiCl4Ice water solution measures in proportion, mix after plus
Heat is to 60 DEG C~70 DEG C (being preferably heated to 60 DEG C), TiCl4TiCl in ice water solution, barium calcium zirconium mixed solution and NaOH solution4：
(BaCl2+CaCl2+ZrOCl2)：The molar ratio 88 of NaOH：112：600；NaOH solution is heated to 80-100 DEG C (preferably to heat
To 95 DEG C), then the two kinds of solution heated are uniformly injected into reaction kettle and stir 10~20 minutes (preferably stirring 15 minutes),
Presoma is obtained as mixing suspension；
Step 13, hydro-thermal process：Mixing suspension is moved in water heating kettle, it is (excellent in 180~240 DEG C of hydro-thermals 3~8 hours
It is 200~220 DEG C to select hydrothermal temperature, and further preferred hydrothermal temperature is 220 DEG C), then filtering, deionized water are washed to conductance
The μ S/cm of rate≤100 (preferably conductivity≤50 μ S/cm) are dry afterwards, cross 40 mesh sieve, obtain major ingredient
Ba0.98Ca0.02Zr0.12Ti0.88O3。
The method that the present invention prepares major ingredient in step 1 using hydro-thermal method, it is ensured that barium, calcium, zirconium and titanium elements ion level
Ba high-purity, that crystallinity is higher can be made in other hybrid reaction0.98Ca0.02Zr0.12Ti0.88O3Material.
Step 2 weighs major ingredient and modifying agent, is put into the ball grinder equipped with zirconia ball, in addition deionized water ball milling, baking
It does, be ground up, sieved, pack spare, preparation media porcelain；Specially：
Electronic balance weighs major ingredient and each Ingredients Weight of modifying agent, with the Ba of 100 parts by weight0.98Ca0.02Zr0.12Ti0.88O3
For base material, each ingredient and relative amount are as follows：Major ingredient Ba0.98Ca0.02Zr0.12Ti0.88O3It is 100 parts, modifying agent MnCO3It is 0.05
~0.50 part, modifying agent Nb2O5It is 0.02~0.40 part, modifying agent Y2O3It is 0~0.20 part, modifying agent MgO is 0~0.20 part,
Modifying agent SiO2It is 0~0.10 part.The major ingredient weighed and modifying agent are put into the ball grinder equipped with zirconia ball, added up
Ion water for ball milling 12 hours is dried 8~12 hours in 120 DEG C to drying, is ground using agate mortar, crosses 40 mesh sieve, obtained this
Low temperature sintering huge dielectric constant superfine ceramics material, pack are spare.
The present invention can ensure efficient, homogeneous mixture of material using deionized water material by wet type mixing in step 2, and than using wine
Essence is safer, more inexpensive, and preparation can use low-temperature sintering huge dielectric constant superfine ceramics material.
The present invention can be carried out when preparing low-temperature sintering huge dielectric constant superfine ceramics material according to 10 kinds of formulas of table 1
It weighs, unit is parts by weight, and the formula 1 in table 1 is used as a comparative example, and formula 2-10 is specific such as 1 institute of table as embodiment
Show.
Table 1
The dielectric ceramic composition powder sample of above-mentioned 10 kinds formulas is carried out discharge plasma sintering by the present invention in accordance with the following steps
And processing, and test correlated performance：
Step 1 sinters porcelain into：Dielectric ceramic composition powder is fitted into the graphite jig of a diameter of 20mm, then is placed in electric discharge etc.
In ion sintering furnace, in 950 DEG C of ± 50 DEG C of sintering (axially applying pressure about 50MPa on mold), diameter 15mm, thickness is made about
The ceramic disks of 1mm；
Step 2, heat treatment：Ceramic disks removing surface is totally placed on load bearing board of zirconia again, is put into resistance furnace,
It is heat-treated within 8 hours in 650 DEG C of heat preservations；
Step 3, sample treatment：After being heat-treated after disk surfaces polishing, thickness and diameter are measured, then on disk two sides
By silver, silver ink firing, simple wafer capacitance is formed；
Step 4, electric performance test：Capacity, loss, insulation resistance and the capacity of wafer capacitance are tested with the series of temperature
Value, and relative dielectric constant and temperature coefficient of capacity (TC) is calculated, performance parameter is shown in Table 2.The meter of temperature coefficient of capacity
It calculates as follows, wherein Ct and C25℃It is t DEG C and 25 DEG C corresponding capacity of temperature spot respectively：
TC=(Ct-C25℃)/C25℃× 100%
Discharge plasma sintering has the characteristics that hot pressed sintering, prior feature be by electric discharge for instantaneously generating etc. from
Son makes each particle equably self-heating and particle surface activation inside sintered body, thus has the very high thermal efficiency, can be
Sintered body is made to reach fine and close in the extremely short time.
Table 2
| Formula | Sintering temperature (DEG C) | Relative dielectric constant | Loss | Insulation resistance (× 1012Ω) |
| 1 | 1000 | 18926 | 0.22 | 1.7 |
| 2 | 980 | 16110 | 0.17 | 0.8 |
| 3 | 980 | 16433 | 0.13 | 3.5 |
| 4 | 960 | 11802 | 0.10 | 3.1 |
| 5 | 950 | 12554 | 0.07 | 1.4 |
| 6 | 950 | 16012 | 0.04 | 2.3 |
| 7 | 950 | 17900 | 0.03 | 2.7 |
| 8 | 950 | 15053 | 0.05 | 1.8 |
| 9 | 920 | 13648 | 0.03 | 2.0 |
| 10 | 900 | 12542 | 0.04 | 2.1 |
The present invention mainly prepares the higher main composition Ba of activity by hydro-thermal method0.98Ca0.02Zr0.12Ti0.88O3, without addition
Sintering aid selects different doping vario-property elements to improve the comprehensive performance of dielectric ceramic composition, sinters porcelain at 950 DEG C or so, obtains most
The room temperature dielectric constant of good dielectric ceramic composition is up to 17900, loss 0.03, the temperature coefficient of capacity in the range of -55 DEG C to 125 DEG C
It is -7.57%~+21.27%, meets X7S (in -55 DEG C~125 DEG C, the temperature coefficient of capacity ± 22%) requirements of U.S. EIA,
Available for preparing the electronic components such as capacitor, there is great practical value and market value.
The present invention realizes the low-temperature sintering of huge dielectric constant, obtains the ceramics that crystal grain is tiny, consistency is high, the medium porcelain
Material has the features such as high-k, low-loss, high insulation resistance and comparatively ideal temperature coefficient of capacity, which is free of
The toxic elements such as lead, cadmium, mercury, Cr VI, meet environmental requirement.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification for all within the spirits and principles of the present invention, being made,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of low-temperature sintering huge dielectric constant superfine ceramics material, which is characterized in that the dielectric ceramic composition is by major ingredient and modifying agent
Composition；
The major ingredient is Ba0.98Ca0.02Zr0.12Ti0.88O3；
The modifying agent is MnCO3、Nb2O5、Y2O3、MgO、SiO2In two or more.
2. low-temperature sintering huge dielectric constant superfine ceramics material as described in claim 1, which is characterized in that the dielectric ceramic composition with
The Ba of 100 parts by weight0.98Ca0.02Zr0.12Ti0.88O3For base material, each ingredient and relative amount are as follows：
Major ingredient Ba0.98Ca0.02Zr0.12Ti0.88O3It is 100 parts；
Modifying agent MnCO3It is 0.05~0.50 part；
Modifying agent Nb2O5It is 0.02~0.40 part；
Modifying agent Y2O3It is 0~0.20 part；
Modifying agent MgO is 0~0.20 part；
Modifying agent SiO2It is 0~0.10 part.
3. a kind of preparation method of low-temperature sintering huge dielectric constant superfine ceramics material as claimed in claim 2, feature exist
In, including：
Step 1 prepares major ingredient Ba using hydro-thermal method0.98Ca0.02Zr0.12Ti0.88O3；
Step 2 weighs major ingredient and modifying agent, is put into the ball grinder equipped with zirconia ball, and deionized water ball milling, drying,
It is ground up, sieved, packs spare, preparation media porcelain.
4. the preparation method of low-temperature sintering huge dielectric constant superfine ceramics material as claimed in claim 3, which is characterized in that institute
Step 1 is stated to include：
Step 11 prepares solution：Select deionized water and analysis pure raw material BaCl2、CaCl2、ZrOCl2、TiCl4And NaOH, according to
Proportioning prepares TiCl respectively after weighing4Ice water solution, barium calcium zirconium mixed solution and NaOH solution；
Step 12 prepares presoma：By barium calcium zirconium mixed solution and TiCl4Ice water solution measures in proportion, mix after be heated to 60
DEG C~70 DEG C, NaOH solution is heated to 80-100 DEG C, then the two kinds of solution heated are uniformly injected into reaction kettle and are stirred
10~20 minutes, presoma was obtained as mixing suspension；
Step 13, hydro-thermal process：Mixing suspension is moved in water heating kettle, in 180~240 DEG C of hydro-thermals 3~8 hours, then mistake
Filter, deionized water are dry after washing to the μ S/cm of conductivity≤100, cross 40 mesh sieve, obtain major ingredient
Ba0.98Ca0.02Zr0.12Ti0.88O3。
5. the preparation method of low-temperature sintering huge dielectric constant superfine ceramics material as claimed in claim 4, which is characterized in that institute
State BaCl in barium calcium zirconium mixed solution2：CaCl2：ZrOCl2Molar ratio is 98：2：12；TiCl4Ice water solution, the mixing of barium calcium zirconium are molten
TiCl in liquid and NaOH solution4：(BaCl2+CaCl2+ZrOCl2)：The molar ratio 88 of NaOH：112：600.
6. the preparation method of low-temperature sintering huge dielectric constant superfine ceramics material as claimed in claim 3, which is characterized in that
In step 2, ball milling 12 hours is dried 8~12 hours in 120 DEG C and is sieved to drying, ground 40 mesh, and pack is spare.
7. a kind of application of the preparation method of low-temperature sintering huge dielectric constant superfine ceramics material as claimed in claim 3,
It is characterized in that, preparation media porcelain obtained is fitted into graphite jig, sintered into using SPS sintering furnaces in 950 DEG C ± 50 DEG C
Porcelain, then 650 DEG C of heat treatment in Muffle furnace, is made superfine ceramics disk.
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