CN108178626A - A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof - Google Patents
A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof Download PDFInfo
- Publication number
- CN108178626A CN108178626A CN201810056248.8A CN201810056248A CN108178626A CN 108178626 A CN108178626 A CN 108178626A CN 201810056248 A CN201810056248 A CN 201810056248A CN 108178626 A CN108178626 A CN 108178626A
- Authority
- CN
- China
- Prior art keywords
- low
- ceramic capacitor
- capacitor dielectric
- dielectric materials
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003989 dielectric material Substances 0.000 title claims abstract description 45
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract 2
- 239000000919 ceramic Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 20
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000005056 compaction Methods 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 28
- 239000010936 titanium Substances 0.000 description 27
- 244000137852 Petrea volubilis Species 0.000 description 14
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- -1 niobium ion Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The present invention provides a kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof, and chemical formula is (Nd0.5Nb0.5)xTi1‑xO2, the value range of x is 0.005~0.11, and preparation method is by (Nd0.5Nb0.5)xTi1‑xO2Standard stoichiometry take Nd2O3、Nb2O5And TiO2Dispensing is carried out, mixing and ball milling is dried, sieving, pre-burning, secondary wet process ball milling, and cold isostatic compaction sinters porcelain into, and low-loss high-k X9R ceramic capacitor materials are made.This material dielectric constant it is high (>104), dielectric loss it is small (<2.5%), good frequency (20Hz 104) and temperature stability (55~200 DEG C), temperature coefficient of capacitance<± 15%, meet the standard of EIAX9R.Preparation method of the present invention is simple, environmentally safe, is suitble to industrialized production.
Description
Technical field
The invention belongs to electronic ceramic fields, applied to electronic component, are related to a kind of low-loss high-k X9R potteries
Porcelain condenser dielectric material and preparation method thereof.
Background technology
Into 21st century, with the fast development of science and technology, electronic component is to micromation, chip type and integrated hair
Exhibition.Ceramic capacitor is a kind of common electronics, especially appliance component, multilayer ceramic capacitor in electronics, power industry
(MLCC) it is even more to be widely used in the fields such as military project, space flight and aviation, automobile, subsurface investigation.
According to International Electronics Industry Association (EIA, Electronic Industries Association) standard, X9R types
MLCC refers on the basis of 25 DEG C of capacitance, in the range of temperature is from -55 DEG C to 200 DEG C, rate of change of capacitance Δ C/C25<±
15%, dielectric loss<2.5%.At present, the dielectric material of MLCC is mainly barium titanate ceramics, and barium titanate ceramics are a kind of ferroelectricities
Material, dielectric constant is up to 2000-4000 at room temperature, however, when temperature is more than curie point~125 DEG C of barium titanate, dielectric
Constant is remarkably decreased, and seriously affects the temperature stability of ceramic condenser.For this purpose, scientific research personnel has carried out doping vario-property to barium titanate
It is expected to obtain the X9R ceramic capacitor dielectric materials of capacitance stabilization, such as application No. is the patent documents of 201410704138.X
Modification is doped to barium titanate ceramics, however, the barium titanate ceramics component of doping vario-property is extremely complex；For another example Patent No.
201610037683.7 patent document, is also modified barium titanate ceramics, but contains in modified barium titanate ceramics
There is a large amount of bismuth, bismuth is readily volatilized at high temperature, is not suitable for industrialized production.
Therefore, there is still a need for further research, to provide a kind of X9R ceramic capacitor dielectrics of low-loss high-k
Material.
Invention content
X9R ceramic capacitor dielectric materials and its preparation the object of the present invention is to provide a kind of low-loss high-k
Method, the defects of to overcome the above-mentioned prior art.Chemical formula is (Nd0.5Nb0.5)xTi1-xO2, dielectric constant is high, and low, temperature is lost
Stability is good, meets the requirement of X9R, has high reliability.
The present invention is to be achieved through the following technical solutions：
A kind of low-loss high-k X9R ceramic capacitor dielectric materials, low-loss high-k X9R ceramic condensers
The chemical formula of device dielectric material is (Nd0.5Nb0.5)xTi1-xO2, wherein, the value range of x is 0.005~0.11.
Preferably, temperature coefficient of capacitance is no more than ± 15% in -55~200 DEG C of temperature ranges, and dielectric at room temperature is normal
Number reaches 104, dielectric loss is less than 2.5%.
A kind of preparation method of low-loss high-k X9R ceramic capacitor dielectric materials, includes the following steps,
Step 1, by (Nd0.5Nb0.5)xTi1-xO2Standard stoichiometry than weigh Nd2O3, Nb2O5And TiO2, and mixed
It closes, dry and is sieved, form uniformly mixed powder, wherein, the value range of x is 0.005~0.11；
Step 2, the powder that step 1 obtains is obtained into (Nd through calcination, ball milling and drying0.5Nb0.5)xTi1-xO2Powder；
Step 3, (Nd step 2 obtained0.5Nb0.5)xTi1-xO2Ceramic body is made in powder；
Step 4, ceramic body through sintering and surface by silver is handled, prepares low-loss high-k X9R ceramic electricals
Vessel media material.
Preferably, in step 1, drying temperature is 60 DEG C~90 DEG C, and drying time is 15~48h, cross grit number for 40~
120 mesh.
Preferably, in step 2, calcining is specifically to be calcined 2h~3h in air at 1150 DEG C~1200 DEG C.
Preferably, in step 2, ball milling is specifically to use planet using deionized water as medium, by mill Jie of zirconium oxide ballstone
Ball mill carries out wet ball grinding, and the mass ratio of zirconium oxide ballstone, deionized water and powder is (0.5~1):(1~2.2):(1.1
~2), a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling is 250~400r/min, ball milling when
Between be 3~5h.
Preferably, in step 2, drying is specifically to dry 15~48h at 60 DEG C~90 DEG C.
Preferably, in step 3, prepare ceramic body the specific steps are：By (Nd0.5Nb0.5)xTi1-xO2Powder is pressed into circle
Piece reuses the pottery that cold isostatic press obtains even density under conditions of the pressure of 200Mpa and dwell time is 3~5min
Porcelain billet body.
Preferably, in step 4, sintering process is specially：1000 DEG C are warming up to, then with 2~5 DEG C/min with 2~5 DEG C/min
1350 DEG C~1450 DEG C of sintering temperature is warming up to, keeps the temperature 2~4h；400~500 DEG C are cooled to 2~5 DEG C/min later, with stove
It is cooled to room temperature.
Preferably, in step 4, ceramic surface is by the detailed process of silver processing：After polishing and being cleaned by ultrasonic with alcohol, apply
Last layer silver paste fires 15~30min at 720~800 DEG C after drying.
Compared with prior art, the present invention has technique effect beneficial below：
Low-loss high-k X9R ceramic capacitor dielectric materials of the present invention, due to introducing the niobium ion of pentavalent
So that produce free electron in titanium dioxide matrix so that dielectric constant is high.To keep electricity price balance, part is necessarily had
Ti4+Ion becomes Ti3+, the neodymium ion substitution titanium ion of trivalent is introduced, it, must in titanium dioxide matrix to keep the balance of electricity price
Lacking oxygen is so generated, while adulterates niobium and neodymium so that producing a large amount of defects in titanium dioxide, these defects rely on electrostatic attraction
It is attached together, forms defect cluster.Free electron and Lacking oxygen are limited in these defect clusters, can only be interior in a limited space
Short range motion is carried out, and long-range migration cannot be carried out.Therefore dielectric loss is very small, and temperature stability is good.Therefore, this ceramics
Capacitor dielectric material has excellent dielectric properties, and good temperature stability is held within the temperature range of -55~200 DEG C
Warm change rate is no more than ± 15%, and dielectric loss is less than 2.5%, meets the requirement of EIAX9R, in addition, ceramic capacitor of the present invention
Dielectric constant of the dielectric material is up to 104, be far longer than the ceramics that barium titanate system is previously reported, such as application No. is
201110068917.1 patent literature room temperature dielectric constant range 1500~1700.The high dielectric of low-loss of the present invention
Constant X9R ceramic capacitor dielectric materials can be widely applied to the fields such as space flight and aviation, automotive electronics, subsurface investigation.The present invention
Ceramic capacitor dielectric material composition it is simple, without volatile and toxic element element, such as bismuth and lead element, to environment
It is harmless, it is easily prepared, can industrialized production, prepare ceramic capacitor for industrial production and lay a good foundation.
The preparation method of low-loss high-k X9R ceramic capacitor dielectric materials of the present invention uses conventional solid
Method, equipment used is simple, and preparation method is simple, reproducible, and operation is easy；Accurate instrument is not needed to, therefore be at low cost；
Easy control of reaction conditions, therefore can be mass-produced is conducive to the miniaturization of electronic component and integrated.
Further, the zirconium oxide ballstone mixed using major diameter and minor diameter carries out ball milling, and mixing can be made more equal
It is even, make reaction more complete.
Further, the present invention carries out isostatic cool pressing technological forming to ceramic powder, due to isostatic cool pressing so that ceramic blank
Body uniform force so as to improve the consistency of ceramics, optimizes the performance of ceramics.
Description of the drawings
Fig. 1 is that present example 2 prepares (Nd0.5Nb0.5)0.01Ti0.99O2The dielectric constant of ceramic capacitor dielectric material
With frequency variation curve figure.
Fig. 2 is that present example 2 prepares (Nd0.5Nb0.5)0.01Ti0.99O2The dielectric constant of ceramic capacitor dielectric material
Curve graph is varied with temperature with dielectric loss.
Fig. 3 is that present example 2 prepares (Nd0.5Nb0.5)0.01Ti0.99O2The temperature characterisitic of ceramic capacitor dielectric material
Curve graph.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Example 1
(1) according to chemical formula (Nd0.5Nb0.5)0.005Ti0.995O2, with Nd2O3, Nb2O5And TiO2For raw material, by standard chemical
It measures than precise, then carries out wet ball grinding 3h by Media Usage planetary ball mill of water, 15h are dried for 80 DEG C after ball milling,
80 mesh sieve is crossed, obtains uniformly mixed powder.Wherein, the use of planetary ball mill and rotating speed is 250r/min.
(2) obtained powder is calcined 2h at 1150 DEG C in air, then carry out once for when 4h wet ball grinding,
80 DEG C of drying 15h obtain (Nd later0.5Nb0.5)0.002Ti0.998O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go
The mass ratio of ionized water and powder is 1:1:1.1, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling
For 250r/min.
(3) uniformly mixed powder is first passed through into the disk that uniaxial tablet press machine is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 3min under 200MPa.
(4) ceramic body is placed in high temperature resistance furnace, 1000 DEG C is warming up to, then be warming up to 5 DEG C/min with 2 DEG C/min
1450 DEG C of sintering temperature, is sintered 2h at 1450 DEG C, is cooled to 500 DEG C with 5 DEG C/min later, cools to room temperature with the furnace.Then
It is polished ceramic surface with 400 mesh sand paper and 1500 mesh sand paper and is cleaned by ultrasonic with alcohol respectively, finally applied on its surface
Last layer is the silver paste of 0.02mm, and keeping the temperature 20min at 750 DEG C after drying fires so as to prepare low-dielectric loss high-k
X9R ceramic capacitor dielectric materials.
Example 2
(1) according to chemical formula (Nd0.5Nb0.5)0.01Ti0.99O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
Then amount carries out wet ball grinding 4h by Media Usage planetary ball mill of water, 20h, mistake is dried for 75 DEG C after ball milling than precise
120 mesh sieve, and be uniformly mixed powder.Wherein, the use of planetary ball mill and rotating speed is 300r/min.
(2) obtained powder is calcined 2.5h at 1200 DEG C in air, then carry out once for when 3h wet method ball
It grinds, 75 DEG C of drying 20h obtain (Nd later0.5Nb0.5)0.01Ti0.99O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone,
The mass ratio of deionized water and powder is 0.5:1:1.5, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, ball milling
Rotating speed is 300r/min.
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 3.5min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1000 DEG C is warming up to, then be warming up to 2 DEG C/min with 5 DEG C/min
1400 DEG C of sintering temperature, is sintered 2h at 1400 DEG C, is cooled to 500 DEG C with 5 DEG C/min later, cools to room temperature with the furnace.Then
It is polished ceramic surface with 240 mesh sand paper and 1500 mesh sand paper and is cleaned by ultrasonic with alcohol respectively, finally applied on its surface
Last layer is the silver paste of 0.02mm, and keeping the temperature 15min at 800 DEG C after drying fires so as to prepare low-dielectric loss high-k
X9R ceramic capacitor dielectric materials.
Example 3
(1) according to chemical formula (Nd0.5Nb0.5)0.03Ti0.97O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
Then amount carries out wet ball grinding 5h by Media Usage planetary ball mill of water, is dried for 24 hours for 90 DEG C after ball milling, mistake than precise
40 mesh sieve, the powder being uniformly mixed.Wherein, the use of planetary ball mill and rotating speed is 270r/min.
(2) obtained powder is calcined 3h at 1175 DEG C in air, then carry out once for when 5h wet ball grinding,
90 DEG C of drying obtain (Nd for 24 hours later0.5Nb0.5)0.03Ti0.97O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go from
The mass ratio of sub- water and powder is 1:2.2:1.8, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling
For 270r/min.
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 4min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1000 DEG C is warming up to, then be warming up to 2 DEG C/min with 5 DEG C/min
1350 DEG C of sintering temperature, is sintered 3h at 1350 DEG C, is cooled to 500 DEG C with 5 DEG C/min later, cools to room temperature with the furnace.Then
It is polished ceramic surface with 240 mesh sand paper and 800 mesh sand paper and is cleaned by ultrasonic with alcohol respectively, finally coated on its surface
One layer of silver paste for 0.02mm keeps the temperature 25min at 720 DEG C after drying and fires so as to prepare low-dielectric loss high-k X9R
Ceramic capacitor dielectric material.
Example 4
(1) according to chemical formula (Nd0.5Nb0.5)0.05Ti0.95O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
Then amount carries out wet ball grinding 4h by Media Usage planetary ball mill of water, 18h, mistake is dried for 85 DEG C after ball milling than precise
80 mesh sieve, and obtain uniformly mixed powder.Wherein, the use of planetary ball mill and rotating speed is 320r/min.
(2) obtained powder is calcined 2h at 1200 DEG C in air, then carry out once for when 4h wet ball grinding,
85 DEG C of drying 18h obtain (Nd later0.5Nb0.5)0.05Ti0.95O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go from
The mass ratio of sub- water and powder is 0.7:1.8:2, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling
For 350r/min.
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 4.5min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1000 DEG C is warming up to, then be warming up to 3 DEG C/min with 5 DEG C/min
1400 DEG C of sintering temperature, is sintered 3h at 1400 DEG C, is cooled to 500 DEG C with 5 DEG C/min later, cools to room temperature with the furnace.Then
It is polished ceramic surface with 800 mesh sand paper and 2000 mesh sand paper and is cleaned by ultrasonic with alcohol respectively, finally applied on its surface
Last layer is the silver paste of 0.02mm, and keeping the temperature 30min at 780 DEG C after drying fires so as to prepare low-dielectric loss high-k
X9R ceramic capacitor dielectric materials.
Example 5
(1) according to chemical formula (Nd.5Nb0.5)0.07Ti0.93O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
It measures than precise, then carries out wet ball grinding 3.5h by Media Usage planetary ball mill of water, 48h are dried for 60 DEG C after ball milling,
120 mesh sieve is crossed, obtains uniformly mixed powder.Wherein, the use of planetary ball mill and rotating speed is 400r/min.
(2) obtained powder is calcined 3h at 1150 DEG C in air, then carry out once for when 4h wet ball grinding,
60 DEG C of drying 48h later, obtain (Nd.5Nb0.5)0.07Ti0.93O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go from
The mass ratio of sub- water and powder is 1:1.5:2, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling is
400r/min。
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 5min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1350 DEG C of sintering temperature is warming up to 5 DEG C/min, at 1350 DEG C
Lower sintering 4h, is cooled to 450 DEG C with 5 DEG C/min later, cools to room temperature with the furnace.Then respectively with 360 mesh sand paper and 1500 mesh
Sand paper is polished to ceramic surface and is cleaned by ultrasonic with alcohol, and the silver paste that last layer is 0.02mm is finally applied on its surface, is dried
15min is kept the temperature after dry at 760 DEG C to fire so as to prepare low-dielectric loss high-k X9R ceramic capacitor dielectric materials.
Example 6
(1) according to chemical formula (Nd0.5Nb0.5)0.9Ti0.91O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
It measures than precise, then carries out wet ball grinding 4.5h by Media Usage planetary ball mill of water, 36h are dried for 70 DEG C after ball milling,
80 mesh sieve is crossed, obtains powder.Wherein, the use of planetary ball mill and rotating speed is 360r/min.
(2) obtained powder is calcined 2h at 1200 DEG C in air, then carry out once for when 4h wet ball grinding,
70 DEG C of drying 36h obtain (Nd later0.5Nb0.5)0.9Ti0.91O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go from
The mass ratio of sub- water and powder is 0.8:2.2:1.2, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, ball milling turns
Speed is 360r/min.
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 3.5min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1000 DEG C is warming up to, then be warming up to 2 DEG C/min with 3 DEG C/min
1350 DEG C of sintering temperature, is sintered 4h at 1350 DEG C, is cooled to 450 DEG C with 3 DEG C/min later, cools to room temperature with the furnace.Then
It is polished ceramic surface with 360 mesh sand paper and 2000 mesh sand paper and is cleaned by ultrasonic with alcohol respectively, finally applied on its surface
Last layer is the silver paste of 0.02mm, and keeping the temperature 30min at 730 DEG C after drying fires so as to prepare low-dielectric loss high-k
X9R ceramic capacitor dielectric materials.
Example 7
(1) according to chemical formula (Nd0.5Nb0.5)0.11Ti0.89O2, with Nd2O3, Nb2O5And TiO2For raw material, based on standard chemical
It measures than precise, then carries out wet ball grinding 4.5h by Media Usage planetary ball mill of water, 36h are dried for 65 DEG C after ball milling,
80 mesh sieve is crossed, obtains powder.Wherein, the use of planetary ball mill and rotating speed is 380r/min.
(2) obtained powder is calcined 2h at 1200 DEG C in air, then carry out once for when 4h wet ball grinding,
65 DEG C of drying 36h obtain (Nd later0.5Nb0.5)0.11Ti0.89O2Powder.Wherein, wet ball grinding use zirconium oxide ballstone, go from
The mass ratio of sub- water and powder is 0.5:1:1.1, a diameter of 3mm of zirconium oxide ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling
For 380r/min.
(3) uniformly mixed ground powder is first passed through into the disk that uniaxial press is pressed into a diameter of 10mm, thickness is 1.0mm,
By isostatic cool pressing, ceramic body is made in pressurize 4min under 200Mpa.
(4) ceramic body is placed in high temperature resistance furnace, 1350 DEG C of sintering temperature is warming up to 2 DEG C/min, at 1350 DEG C
Lower sintering 4h, is cooled to 400 DEG C with 2 DEG C/min later, cools to room temperature with the furnace.Then respectively with 240 mesh sand paper and 200 mesh sand
Paper is polished to ceramic surface and is cleaned by ultrasonic with alcohol, and the silver paste that last layer is 0.02mm, drying are finally applied on its surface
30min is kept the temperature at 740 DEG C afterwards to fire so as to prepare low-dielectric loss high-k X9R ceramic capacitor dielectric materials.
(the Nd prepared to example 20.5Nb0.5)0.01Ti0.99O2Ceramic capacitor dielectric material carries out following performance test.
Fig. 1 is dielectric constant with frequency variation curve figure, it is seen that (Nd0.5Nb0.5)0.01Ti0.99O2Ceramic capacitor dielectric material
Material in 20-105Dielectric constant maintains 10 always in Hz frequency ranges4More than, illustrate that the dielectric material has good frequency
Stability.
Fig. 2 varies with temperature curve graph for dielectric constant and dielectric loss, it is seen then that (Nd prepared by example 20.5Nb0.5)0.01Ti0.99O2The dielectric constant of ceramic capacitor dielectric material is very high, and dielectric constant is big in -55~200 DEG C of temperature ranges
In 104.Dielectric loss is kept approximately constant in entire temperature range, and under room temperature, 1K Hz, loss is 0.0239.By scheming
3 it is found that this ceramic capacitor dielectric material temperature coefficient of capacitance in -55~200 DEG C of temperature ranges<± 15%, meet
The requirement of EIAX9R.
It can be seen that the ceramic capacitor dielectric material of the present invention has excellent dielectric properties, dielectric constant is up to
104, temperature stability is good, and temperature coefficient of capacitance is no more than ± 15% within the temperature range of -55~200 DEG C, and dielectric loss is less than
2.5%, meet the requirement of EIAX9R.
Preparation method of the present invention is simple to equipment requirement, and experiment condition easily reaches, and the ceramics sample consistency of preparation is good
Good, doping is easy to control, and ceramics can be increased substantially by the appropriate selection and suitable sintering temperature of doping
Dielectric properties.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention and to technical solution of the present invention
Any equivalent transformation taken is that claim of the invention is covered.
Claims (10)
- A kind of 1. low-loss high-k X9R ceramic capacitor dielectric materials, which is characterized in that low-loss high-k The chemical formula of X9R ceramic capacitor dielectric materials is (Nd0.5Nb0.5)xTi1-xO2, wherein, the value range of x for 0.005~ 0.11。
- 2. low-loss high-k X9R ceramic capacitor dielectric materials according to claim 1, which is characterized in that- Temperature coefficient of capacitance is no more than ± 15% in 55~200 DEG C of temperature ranges, and dielectric constant at room temperature reaches 104, dielectric loss Less than 2.5%.
- 3. a kind of preparation method of low-loss high-k X9R ceramic capacitor dielectric materials, which is characterized in that including as follows Step,Step 1, by (Nd0.5Nb0.5)xTi1-xO2Standard stoichiometry than weigh Nd2O3, Nb2O5And TiO2, and mixed, dried Dry and sieving, forms uniformly mixed powder, wherein, the value range of x is 0.005~0.11；Step 2, the powder that step 1 obtains is obtained into (Nd through calcination, ball milling and drying0.5Nb0.5)xTi1-xO2Powder；Step 3, (Nd step 2 obtained0.5Nb0.5)xTi1-xO2Ceramic body is made in powder；Step 4, ceramic body through sintering and surface by silver is handled, prepares low-loss high-k X9R ceramic capacitors Dielectric material.
- 4. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 1, drying temperature is 60 DEG C~90 DEG C, and drying time is 15~48h, and it is 40~120 mesh to cross grit number.
- 5. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 2, calcining is specifically to be calcined 2h~3h in air at 1150 DEG C~1200 DEG C.
- 6. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 2, ball milling be specifically using deionized water as medium, using zirconium oxide ballstone as mill be situated between using planetary ball mill into Row wet ball grinding, the mass ratio of zirconium oxide ballstone, deionized water and powder is (0.5~1):(1~2.2):(1.1~2), oxidation A diameter of 3mm of zirconium ballstone:5mm:8mm=4:2:1, the rotating speed of ball milling is 250~400r/min, and the time of ball milling is 3~5h.
- 7. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 2, drying is specifically to dry 15~48h at 60 DEG C~90 DEG C.
- 8. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 3, prepare ceramic body the specific steps are：By (Nd0.5Nb0.5)xTi1-xO2Powder is pressed into disk, reuses Cold isostatic press obtains the ceramic body of even density under conditions of the pressure of 200Mpa and dwell time is 3~5min.
- 9. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, special Sign is, in step 4, sintering process is specially：1000 DEG C are warming up to, then burning is warming up to 2~5 DEG C/min with 2~5 DEG C/min 1350 DEG C~1450 DEG C of junction temperature keeps the temperature 2~4h；400~500 DEG C are cooled to 2~5 DEG C/min later, cools to room with the furnace Temperature.
- 10. the preparation method of low-loss high-k X9R ceramic capacitor dielectric materials according to claim 3, It is characterized in that, in step 4, ceramic surface is by the detailed process of silver processing：Polishing ceramic body and after being cleaned by ultrasonic with alcohol, Last layer silver paste is applied, fires 15~30min after drying at 720~800 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810056248.8A CN108178626A (en) | 2018-01-20 | 2018-01-20 | A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810056248.8A CN108178626A (en) | 2018-01-20 | 2018-01-20 | A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108178626A true CN108178626A (en) | 2018-06-19 |
Family
ID=62550987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810056248.8A Pending CN108178626A (en) | 2018-01-20 | 2018-01-20 | A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178626A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947522A (en) * | 2018-09-19 | 2018-12-07 | 天津大学 | A kind of ultra-low loss huge dielectric constant dielectric material and preparation method thereof |
| CN109092792A (en) * | 2018-09-25 | 2018-12-28 | 福建毫米电子有限公司 | A kind of ceramic substrate surface processing method |
| CN109133914A (en) * | 2018-11-23 | 2019-01-04 | 陕西师范大学 | A kind of titanium dioxide base ceramic material of high thermal stability and preparation method thereof |
| CN109206133A (en) * | 2018-09-19 | 2019-01-15 | 天津大学 | A kind of ultra-low loss tantalum system huge dielectric constant dielectric material and preparation method thereof |
| CN111205085A (en) * | 2020-02-03 | 2020-05-29 | 河南理工大学 | Preparation method of titanium dioxide-based ceramic with ultrahigh dielectric constant and low dielectric loss |
| CN111410527A (en) * | 2020-03-20 | 2020-07-14 | 广东风华高新科技股份有限公司 | Complex phase giant dielectric ceramic material and preparation method thereof |
| CN116751046A (en) * | 2023-06-19 | 2023-09-15 | 陕西科技大学 | Low-loss microwave dielectric ceramic material, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958414A (en) * | 2011-09-16 | 2014-07-30 | 澳大利亚国立大学 | Giant dielectric constant material |
| CN105036734A (en) * | 2015-06-25 | 2015-11-11 | 武汉理工大学 | High-dielectric-constant X8R type dielectric material for multilayer porcelain capacitor, and preparation method for dielectric material |
| CN105948743A (en) * | 2016-04-29 | 2016-09-21 | 山东大学 | Modified co-doped titanium oxide high-dielectric ceramic material, preparation method and application thereof |
| CN107200576A (en) * | 2017-06-29 | 2017-09-26 | 陕西科技大学 | A kind of high-k europium and niobium are co-doped with titanium dioxide ceramic and preparation method thereof |
-
2018
- 2018-01-20 CN CN201810056248.8A patent/CN108178626A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958414A (en) * | 2011-09-16 | 2014-07-30 | 澳大利亚国立大学 | Giant dielectric constant material |
| CN105036734A (en) * | 2015-06-25 | 2015-11-11 | 武汉理工大学 | High-dielectric-constant X8R type dielectric material for multilayer porcelain capacitor, and preparation method for dielectric material |
| CN105948743A (en) * | 2016-04-29 | 2016-09-21 | 山东大学 | Modified co-doped titanium oxide high-dielectric ceramic material, preparation method and application thereof |
| CN107200576A (en) * | 2017-06-29 | 2017-09-26 | 陕西科技大学 | A kind of high-k europium and niobium are co-doped with titanium dioxide ceramic and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947522A (en) * | 2018-09-19 | 2018-12-07 | 天津大学 | A kind of ultra-low loss huge dielectric constant dielectric material and preparation method thereof |
| CN109206133A (en) * | 2018-09-19 | 2019-01-15 | 天津大学 | A kind of ultra-low loss tantalum system huge dielectric constant dielectric material and preparation method thereof |
| CN109092792A (en) * | 2018-09-25 | 2018-12-28 | 福建毫米电子有限公司 | A kind of ceramic substrate surface processing method |
| CN109133914A (en) * | 2018-11-23 | 2019-01-04 | 陕西师范大学 | A kind of titanium dioxide base ceramic material of high thermal stability and preparation method thereof |
| CN109133914B (en) * | 2018-11-23 | 2021-07-06 | 陕西师范大学 | Titanium dioxide-based ceramic material with high thermal stability and preparation method thereof |
| CN111205085A (en) * | 2020-02-03 | 2020-05-29 | 河南理工大学 | Preparation method of titanium dioxide-based ceramic with ultrahigh dielectric constant and low dielectric loss |
| CN111205085B (en) * | 2020-02-03 | 2021-07-27 | 河南理工大学 | Preparation method of titanium dioxide-based ceramic with ultrahigh dielectric constant and low dielectric loss |
| CN111410527A (en) * | 2020-03-20 | 2020-07-14 | 广东风华高新科技股份有限公司 | Complex phase giant dielectric ceramic material and preparation method thereof |
| CN111410527B (en) * | 2020-03-20 | 2021-06-22 | 广东风华高新科技股份有限公司 | Complex phase giant dielectric ceramic material and preparation method thereof |
| CN116751046A (en) * | 2023-06-19 | 2023-09-15 | 陕西科技大学 | Low-loss microwave dielectric ceramic material, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108178626A (en) | A kind of low-loss high-k X9R ceramic capacitor dielectric materials and preparation method thereof | |
| CN107200576A (en) | A kind of high-k europium and niobium are co-doped with titanium dioxide ceramic and preparation method thereof | |
| CN107698252B (en) | Application of ceramic material as high-temperature stable piezoelectric energy collecting material and preparation method thereof | |
| CN105732020B (en) | A kind of preparation method of giant dielectric, low-loss titanium dioxide base composite ceramic | |
| CN110015894B (en) | Sodium bismuth titanate-based ceramic with high dielectric stability at high temperature and preparation method and application thereof | |
| CN111747740B (en) | Samarium ion doped lead zirconate titanate based high-performance piezoelectric ceramic and preparation method thereof | |
| CN104058741B (en) | Media ceramic that a kind of ultra-wide temperature is stable and preparation method thereof | |
| CN107640970B (en) | The AgNb of low frequency low-dielectric loss is co-doped with titania-based dielectric ceramic material and preparation method thereof | |
| CN108863348A (en) | A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability | |
| CN110015893A (en) | A kind of composite mixed bismuth ferrite-barium titanate binary system Lead-free ferroelectric ceramics material, preparation method and applications | |
| CN109608194A (en) | A kind of lead zirconate titanate thick film ceramics and its preparation method and application | |
| CN113480310A (en) | High-density and high-dielectric-constant tantalum pentoxide-based ceramic and preparation method thereof | |
| CN108218423A (en) | A kind of X8R types ceramic capacitor dielectric material and preparation method thereof | |
| CN104446452B (en) | Lead-free medium-temperature stable dielectric electronic ceramic material and preparation method thereof | |
| CN113045307B (en) | High-dielectric low-loss barium titanate-based ceramic and preparation method thereof | |
| CN113511893B (en) | BNT-based high-energy-density ceramic with three-layer structure and preparation method thereof | |
| JP4789449B2 (en) | Dielectric porcelain and multilayer ceramic capacitor using the same | |
| CN114478006A (en) | KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof | |
| CN108863349A (en) | A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof | |
| CN103880416B (en) | Preparation method for sintering sodium bismuth titanate-based lead-free piezoelectric ceramics at low temperature | |
| CN107500756A (en) | A kind of high-k low-loss SrTiO3Based dielectric material and preparation method thereof | |
| CN104725036B (en) | A kind of barium-strontium titanate-based energy storage ceramic of high temperature low loss and preparation method thereof | |
| CN107226696A (en) | X7R types BaTiO3Based capacitor ceramic material and preparation method thereof | |
| CN107188555A (en) | A kind of preparation method of ceramic target | |
| CN103864416A (en) | Method for preparing barium titanate ceramic capacitor medium at low sintering temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180619 |
|
| RJ01 | Rejection of invention patent application after publication |