CN1362385A - Barium titanate powder and preparation method thereof - Google Patents
Barium titanate powder and preparation method thereof Download PDFInfo
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- CN1362385A CN1362385A CN01143432A CN01143432A CN1362385A CN 1362385 A CN1362385 A CN 1362385A CN 01143432 A CN01143432 A CN 01143432A CN 01143432 A CN01143432 A CN 01143432A CN 1362385 A CN1362385 A CN 1362385A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/188—Barium carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The method for producing barium titanate powder comprises mixing a barium compound producing barium oxide by pyrolysis and titanium dioxide having 99.8 wt.% or more of purity, 5 m not 2/g or more of specific surface area obtained by BET method and 30% or less, preferably 5% or less, rutile ratio obtained by X-ray diffraction method, and calcining preferably under a circumferential pressure of 1x10 not 3 Pa or less in total pressure, wherein the obtained barium titanate powder is microparticle and contains high tetragonal crystallinity.The barium titanate powder to be sintered is provided to obtain a dielectric in a laminated ceramic capacitor, wherein the powder is down-sized and improved in crystal form to enable to improve the temperature characteristic of capacitance in the laminated ceramic capacitor.
Description
Technical field
The present invention relates to barium titanate powder and preparation method thereof, particularly relate to barium titanate powder that has higher square crystallinity and preparation method thereof.
Background technology
Preparation method as in order to the barium titanate powder that obtains dielectric ceramics adopted solid reaction process in the past always, in order to utilize this solid reaction process synthesis of barium titanate, extensively adopted powder mixes, calcining method with barium carbonate and titanium dioxide.In order to adopt this method to obtain the barium titanate powder of particulate, the barium carbonate powder of particulate be mixed as far as possible equably with the titania powder of particulate.
In addition, in aforesaid method,,, be typically, use titanium tetrachloride is carried out the high purity substance that thermolysis obtains in order not make the deterioration in characteristics of gained dielectric ceramics as titanium dioxide.At this moment, the crystal formation of gained titanium dioxide is according to the thermolysis condition and difference, and when being suitable for conventional heat-treat condition, the rutilization rate uprises, and general rutile-type is dominant.
As being used for obtaining dielectric ceramic material powder uses in the laminated ceramic compacitor for example barium titanate powder thin layerization, need littler particulate, and have higher square crystallinity (higher cubic crystallinity) along with ceramic layer between internal electrode.
But, if use the rutile titania powder of particulate, realize the micronize of barium titanate powder, because the reactivity of the titania powder of rutile-type is poor, there is the problem of the square crystallinity step-down of gained barium titanate.And, if the square crystallinity of barium titanate is low, when for example using as the dielectric raw material powder that possesses in the laminated ceramic compacitor, in sintering circuit, the added ingredients that adds in the raw material powder carries out solid solution to barium titanate easily, therefore, behind sintering, be difficult to obtain the sintered compact of core-shell structure, thereby can run into the problem of temperature profile variation of the electrostatic capacitance of gained laminated ceramic compacitor.
In addition, even the square crystallinity height of barium titanate is if the initial size of raw material powder is big, then for the thickness that is positioned at internal electrical interpolar dielectric ceramics layer is reached below the 5 μ m, when realizing the thin layer of dielectric ceramics layer, the credibility of laminated ceramic compacitor reduces.
In addition; in order to improve the square crystallinity of barium titanate; in solid reaction process; barium compounds such as barium carbonate are mixed with titanium dioxide; calcining, the calcining temperature when improving synthesis of barium titanate are effectively, if improve calcining temperature like this; then have condensing between growth that particle occurs or the particle, the barium titanate powder that obtains is difficult to micronized problem.
Summary of the invention
Therefore, the object of the present invention is to provide the barium titanate powder that can address the above problem and preparation method thereof.
In order to solve above-mentioned technical task, barium titanate powder of the present invention is characterised in that, to generate barytic barium compound by thermal degradation mixes with titanium dioxide, calcines and obtain, the rutilization rate that described titanium dioxide is tried to achieve by X-ray diffraction method is below 30%, and is 5m by the specific surface area that the BET method is tried to achieve
2More than/the g.
In addition, the preparation method characteristic of barium titanate powder of the present invention is, comprises that preparation generates the operation of barytic barium compound by thermal degradation; The rutilization rate that preparation is tried to achieve by X-ray diffraction method is below 30% and by the specific surface area that the BET method is tried to achieve to be 5m
2The operation of the titanium dioxide that/g is above; With above-mentioned barium compound and titanium dioxide mix, the incinerating operation.
Like this, according to barium titanate powder of the present invention or the barium titanate powder that adopts preparation method of the present invention to obtain, the median size of observing by scanning electron microscope (SEM) can be decreased to 0.07～0.3 μ m, in addition, can obtain having the powder of high square crystallinity, making its sensing tape by X-ray diffraction (リ-De ベ Le ト) resolve the c axle/a axial ratio of trying to achieve is more than 1.007.
The preparation method of barium titanate powder of the present invention is characterized in that as mentioned above, and using the rutilization rate of trying to achieve by X-ray diffraction method is below 30%, and is 5m by the specific surface area that the BET method is tried to achieve
2The titanium dioxide that/g is above, but the preparation method of barium titanate powder of the present invention is preferably as follows describedly and implements.
That is to say, in the preparation method of barium titanate powder of the present invention, implement following operation: the operation of preparing to generate barytic barium compound by thermal degradation; Prepare the operation of titanium dioxide; For this titanium dioxide, confirm by the rutilization rate that X-ray diffraction method is tried to achieve to be below 30% and by the specific surface area that the BET method is tried to achieve to be 5m
2The operation that/g is above; Use the titanium dioxide of confirming like this, with barium compound and titanium dioxide mix, the incinerating operation.
Among the present invention, the rutilization rate of the titanium dioxide of use is preferred below 5%.Like this, can further improve the square crystallinity of gained barium titanate.
In addition, when the barium compound of calcined mixed and titanium dioxide, be 1 * 10 preferably in total pressure
3The following pressure of ambient gas of Pa is implemented down.Like this, can further improve the square crystallinity of gained barium titanate.
In addition, among the present invention, more than the preferred 99.8 weight % of the purity of the titanium dioxide of use.
If this is that the dielectric characteristics of the dielectric ceramics that the barium titanate powder of its preparation of sintering obtains reduces sometimes because the purity of titanium dioxide is lower than 99.8 weight %.
Embodiment
In order to obtain barium titanate powder of the present invention, at first prepare to generate barytic barium compound powder by thermal degradation.As this barium compound, can use for example barium carbonate (BaCO
3), hydrated barta (Ba (OH)
2) etc., also can use the barium compound more than 2 kinds in addition simultaneously.
In addition, prepare the powder of titanium dioxide.For this titanium dioxide, selecting by the rutilization rate that X-ray diffraction method is tried to achieve is below 30% and by the specific surface area that the BET method is tried to achieve to be 5m
2The material that/g is above.Therefore, for the titanium dioxide of preparing, as mentioned above, preferably confirm by the rutilization rate that X-ray diffraction method is tried to achieve to be below 30% and by the specific surface area that the BET method is tried to achieve to be 5m
2The material that/g is above.
The rutilization rate of above-mentioned titanium dioxide is preferably below 5%.In addition, more than the preferred 99.8 weight % of the purity of titanium dioxide.
In addition, have the titanium dioxide of above-mentioned particular characteristics, for example can obtain, at this moment can control environmental gas in the pyrolosis operation etc., set the thermolysis condition, the rutilization rate is reduced by titanium tetrachloride is carried out thermolysis.
Secondly, with each powder mixes of above-mentioned barium compound and titanium dioxide.Its mixture ratio can be adjusted according to the Ba/Ti mol ratio in the barium carbonate that constitutes the powder that will obtain.
Next, the mixed powder maintenance of barium compound and titanium dioxide for example 950～1100 ℃ top temperature is calcined.Like this, just obtain required barium titanate powder.
Above-mentioned calcining is 1 * 10 in total pressure preferably
3The following pressure of ambient gas of Pa is implemented down.
Secondly, the barium titanate powder after the calcining for example can be pulverized by shredder in case of necessity.
The barium titanate powder that obtains is like this made sintered compact through sintering circuit, thereby for example can use effectively as the dielectric medium in the laminated ceramic compacitor.
Below, be described more specifically the present invention in conjunction with the test example.
(test example 1)
Prepare following sample 1～7.
(1) sample 1 (embodiment)
As barium carbonate, using purity is 99.8 weight %, the specific surface area (specific surface area of trying to achieve according to the BET method.Be 5m down together)
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.The purity of this titanium dioxide is 99.9%, and specific surface area is 12m
2/ g by control thermolysis condition, makes rutilization rate (the rutilization rate that adopts X-ray diffraction method to try to achieve simultaneously.Reach 2% down together).
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1050 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.25 μ m, and c axle/a axial ratio is 1.009.
This sample 1 is a most typical example in the scope of the invention, shows that specific surface area is big by using the purity height, and the titanium dioxide that the rutilization rate is low can access particulate and barium titanate powder that have higher square crystallinity.
(2) sample 2 (embodiment)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 5m
2/ g by control thermolysis condition, makes the rutilization rate reach 30% simultaneously.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1100 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.30 μ m, and c axle/a axial ratio is 1.007.
This sample 2 is under the condition on the border of the rutilization rate of the titanium dioxide of the regulation scope of the invention and two kinds of parameters of specific surface area, the preparation barium titanate powder.
(3) sample 3 (embodiment)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 30m
2/ g by control thermolysis condition, makes the rutilization rate reach 2% simultaneously.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1000 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.07 μ m, and c axle/a axial ratio is 1.007.
This sample 3 uses the bigger titanium dioxide of specific surface area.By this sample 3 as can be known, if titanium dioxide is being carried out the micronized rutilization rate that reduces simultaneously, the c axle/a axial ratio of the barium titanate powder that obtains near the ideal scenario of target 1.007, can micronize make median size reach 0.07 μ m.
(4) sample 4 (embodiment)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 12m
2/ g by control thermolysis condition, makes the rutilization rate reach 2% simultaneously.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1050 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.22 μ m, and c axle/a axial ratio is 1.010.
This sample 4 is compared with sample 1, as barium carbonate, use littler particulate, but the median size of the barium carbonate powder that obtains slightly reduces only.This sample 4 shows that the effect of bringing by the micronize of barium carbonate to barium titanate microparticlesization is very little.
(5) sample 5 (comparative example)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 5m
2/ g is suitable for general condition as the thermolysis condition simultaneously, makes the rutilization rate reach 90%.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1100 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.32 μ m, and c axle/a axial ratio is 1.006.
This sample 5 shows, the rutilization rate of titanium dioxide only compared with sample 2 exceeds the occasion of the scope of the invention.
(6) sample 6 (comparative example)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 30m
2/ g is suitable for general condition as the thermolysis condition simultaneously, makes the rutilization rate reach 90%.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1000 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.17 μ m, and c axle/a axial ratio is 1.004.
This sample 6 shows, even use the fine particulate titanium dioxide same with sample 3, in the high occasion of the rutilization rate of this titanium dioxide, though the barium titanate that obtains is a particulate, square crystallinity is low.
(7) sample 7 (comparative example)
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the material that uses the thermolysis by titanium tetrachloride to obtain.This titanium dioxide purity is 99.9%, and specific surface area is 4m
2/ g by control thermolysis condition, makes the rutilization rate reach 30% simultaneously.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1100 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.50 μ m, and c axle/a axial ratio is 1.007.
This sample 7 shows, even use the low titanium dioxide of rutilization rates equally with sample 2, is lower than 5m in its specific surface area
2The occasion of/g, though its square crystallinity height of the barium titanate that obtains, it is big that particle diameter becomes.
Use the various barium titanate powders of the above-mentioned sample that obtains 1～7, preparation laminated ceramic compacitor as described below.
That is to say,, add Dy respectively with respect to barium titanate powder 100 weight parts
2O
3Powder 1.86 weight parts, MgO powder 0.168 weight part, BaO powder 0.64 weight part, SiO
2Powder 0.37 weight part, MnO
2Powder 0.109 weight part and B
2O
3Powder 0.156 weight part carries out wet mixing, then makes it dry, obtains reducing resistance dielectric ceramics raw material powder.
Secondly, with respect to above-mentioned raw materials powder 150g, the volume ratio that is added in toluene/ethanol is the binding liquid 108g that has dissolved polyvinyl butyral acetal 20 weight % in 1/1 the solvent, and as the dioctyl phthalate (DOP) 6g of softening agent, after the ball mill mixing, use intaglio plate coater (gravurecoater) moulding, obtain the ceramic green sheet that thickness is 5 μ m.
Then,, use the electric conductivity paste contain nickel to form internal electrode for above-mentioned ceramic green sheet, strike out given size after, stacked crimping ceramic green sheet makes the number of the folded effective dielectric ceramics layer of internal electrode reach 50.
Then, the base sheet layered product that obtains as mentioned above of cutting, in the reducing gas environment, 1240 ℃ of following sintering 2 hours obtain the layered product chip behind the sintering with the undressed layered product chip that obtains.And, on the outside surface of this layered product chip, form outer electrode, obtain laminated ceramic compacitor.
For the laminated ceramic compacitor that obtains like this, as shown in table 1, obtain specific inductivity (ε
r), the rate of temperature change of dielectric loss (tan δ), insulation resistance (logIR) and electrostatic capacitance.[table 1]
| The sample sequence number | Specific inductivity (ε r) | Dielectric loss (tan δ) (%) | Insulation resistance (logIR) (Ω) | The rate of temperature change of electrostatic capacitance (%) | |
| ????-55℃ | ????125℃ | ||||
| ????1 | ??2810 | ????2.1 | ????9.8 | ????-1.2 | ????-12.5 |
| ????2 | ??3170 | ????2.3 | ????9.6 | ????-2.5 | ????-14.8 |
| ????3 | ??2390 | ????1.8 | ????9.8 | ????-4.5 | ????-14.2 |
| ????4 | ??2610 | ????2.0 | ????9.9 | ????-2.8 | ????-13.3 |
| ???? *5 | ??3150 | ????2.5 | ????9.7 | ????-7.5 | ????-16.2 |
| ???? *6 | ??3530 | ????2.2 | ????9.8 | ????-21.3 | ????-25.7 |
| ???? *7 | Sintering not | ||||
In the table 1, the sample that the sample sequence number has " * " is equivalent to scope of the invention comparative example in addition.In addition, for sample 7, the layered product chip is unsintered state, can not measure the dielectric characteristics shown in the table 1.
As shown in Table 1, according to the sample 1～4 that is equivalent to the embodiment of the invention, when particularly being conceived to the rate of temperature change of electrostatic capacitance, compare with the sample 5～7 that is equivalent to comparative example, obtained excellent results, sample 1～4 all satisfies ± 15% X7R characteristic with interior this EIA specification.
(test example 2)
For the rutilization rate of the titanium dioxide that uses, implement test example 2 in order to try to achieve preferred scope, in this test example 2, prepare following sample 8～10.
(1) sample 8
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the purity of using the thermolysis by titanium tetrachloride to obtain is 99.9%, and specific surface area is 30m
2/ g, and the rutilization rate is 30% material.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1050 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.11 μ m, and c axle/a axial ratio is 1.007.
(2) sample 9
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the purity of using the thermolysis by titanium tetrachloride to obtain is 99.9%, and specific surface area is 30m
2/ g, and the rutilization rate is 5% material.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 1050 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.10 μ m, and c axle/a axial ratio is 1.008.
(3) sample 10
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the purity of using the thermolysis by titanium tetrachloride to obtain is 99.9%, and specific surface area is 30m
2/ g, and the rutilization rate is 2% material.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, with batch furnace 950 ℃ of top temperatures down maintenance calcined in 2 hours.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.08 μ m, and c axle/a axial ratio is 1.008.
Relatively above sample 8～10, about the c axle/a axial ratio of barium titanate, sample 9 and 10 is 1.008,1.007 big than sample 8, square as can be known crystallinity is higher.This is that the rutilization rate of titanium dioxide is 30% in sample 8 simultaneously, is respectively 5% below 5% and 2% in sample 9 and 10 because in sample 8～10, the particle diameter of titanium dioxide is equal.
If hence one can see that as sample 9 and 10, use rutilization rate is the titanium dioxide below 5%, can further improve the square crystallinity of the barium titanate that obtains.
Secondly, use the various barium titanate powders of sample 8～10, according to the identical method of occasion of test example 1, preparation laminated ceramic compacitor.And, same for the laminated ceramic compacitor that obtains with the occasion of test example 1, obtain specific inductivity (ε
r), the rate of temperature change of dielectric loss (tan δ), insulation resistance (logIR) and electrostatic capacitance.
In addition, in order to estimate credibility, under 150 ℃ temperature, the laminated ceramic compacitor that obtains is applied continuously the volts DS of 10kV/mm, the insulating resistance value of obtaining laminated ceramic compacitor reduces time more than 3 figure places by its initial value, with its mean value as average life time.
These evaluation results are as shown in table 2.[table 2]
| The sample sequence number | Specific inductivity (ε r) | Dielectric loss (tan δ) (%) | Insulation resistance (logIR) (Ω) | The rate of temperature change of electrostatic capacitance (%) | Average life time (hour) | |
| ????-55℃ | ????125℃ | |||||
| ????8 | ????2410 | ????1.8 | ????9.8 | ????-4.0 | ????-14.0 | ????74 |
| ????9 | ????2490 | ????1.9 | ????9.8 | ????-3.0 | ????-13.2 | ????170 |
| ????10 | ????2450 | ????1.9 | ????9.8 | ????-3.1 | ????-13.6 | ????184 |
As shown in Table 2, to resemble sample 9 and 10 be the barium titanate powder that titanium dioxide below 5% has further improved square crystallinity by using the rutilization degree if use, and can obtain the better laminated ceramic compacitor of credibility.
(test example 3)
For the pressure of ambient gas in the operation of calcining barium compound and titanium dioxide blends for synthesis of barium titanate, implement test example 3 in order to try to achieve preferred scope, in this test example 3, prepare following sample 11 and 12.
(1) sample 11
As barium carbonate, using purity is 99.8 weight %, and specific surface area is 10.5m
2The material of/g.In addition, as titanium dioxide, the purity of using the thermolysis by titanium tetrachloride to obtain is 99.9%, and specific surface area is 30m
2/ g, and the rutilization rate is 2% material.
Secondly, according to each powder that waits above-mentioned barium carbonate of molar ratio weighing and titanium dioxide and after mixing, adopt ball mill to carry out wet mixing.Secondly, make the slurry that obtains by this mixing carry out the evaporation drying operation after, in atmospheric environment gas, be adjusted to 1 * 10 with total pressure
3The batch furnace of Pa keeps down for 950 ℃ calcining in 2 hours in top temperature.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.10 μ m, and c axle/a axial ratio is 1.009.
(2) sample 12
Remove and be adjusted to 1 * 10 with total pressure
2The batch furnace of Pa is implemented beyond the calcination process, with the same condition of sample 11 under, obtain barium titanate powder.
Barium titanate powder after the calcining is pulverized with shredder, analyzed its powder characteristics.As a result, the barium titanate powder median size that obtains is 0.09 μ m, and c axle/a axial ratio is 1.009.
In the said sample 11 and 12, used have with above-mentioned test example 2 in the occasion same particle size of sample 10 and the titanium dioxide of rutilization degree, but about the c axle/a axial ratio of gained barium titanate, sample 11 and 12 is 1.009,1.008 big than sample 10, square as can be known crystallinity is higher.This is owing in the sample 11 and 12, be to be 1 * 10 in total pressure
3Calcine under the pressure of ambient gas below the Pa.
In addition, in the sample 1～10 beyond sample 11 and the sample 12, the incinerating pressure of ambient gas is a normal atmosphere.
If hence one can see that as sample 11 and 12, be 1 * 10 in total pressure
3Calcine under the pressure of ambient gas below the Pa, can further improve the square crystallinity of the barium titanate that obtains.
Secondly, use the various barium titanate powders of sample 11 and 12, according to the identical method of occasion of test example 1 and 2, preparation laminated ceramic compacitor.And, same for the laminated ceramic compacitor that obtains with the occasion of test example 1 and 2, obtain specific inductivity (ε
r), the rate of temperature change of dielectric loss (tan δ), insulation resistance (logIR) and electrostatic capacitance.
In addition, in order to estimate the credibility of laminated ceramic compacitor, according to the same method of occasion of test example 2, obtain average life time.
These evaluation results are as shown in table 3.In addition, for the ease of relatively, in table 3, list the evaluation result shown in the above-mentioned table 2 in the lump about " sample 10 ".
[table 3]
| The sample sequence number | Specific inductivity (ε r) | Dielectric loss (tan δ) (%) | Insulation resistance (logIR) (Ω) | The rate of temperature change of electrostatic capacitance (%) | Average life time (hour) | |
| ????-55℃ | ????125℃ | |||||
| ????10 | ????2450 | ????1.9 | ????9.8 | ????-3.1 | ????-13.6 | ????184 |
| ????11 | ????2540 | ????2.0 | ????9.9 | ????-1.0 | ????-11.3 | ????276 |
| ????12 | ????2510 | ????2.0 | ????9.9 | ????-1.4 | ????-11.8 | ????297 |
As shown in Table 3, resemble sample 11 and 12 by being 1 * 10 if use in total pressure
3Calcine the further barium titanate powder that improves square crystallinity under the pressure of ambient gas below the Pa, can obtain credible better laminated ceramic compacitor.
As mentioned above, according to the present invention,, will generate barytic barium compound by thermal degradation and mix, calcine with titanium dioxide in order to obtain barium titanate powder, the rutilization rate that described titanium dioxide is tried to achieve by X-ray diffraction method is below 30%, and is 5m by the specific surface area that the BET method is tried to achieve
2Therefore more than the/g, can obtain particulate, it is 0.07～0.3 μ m by median size that SEM observes, and square crystallinity is high, and it adopts the sensing tape of X-ray diffraction to resolve the c axle/a axial ratio of trying to achieve is the barium titanate powder more than 1.007.
Therefore, if use this barium titanate powder, the dielectric medium of configuration example such as laminated ceramic compacitor, in sintering circuit, added ingredients is difficult to occur solid solution in barium titanate, can easily obtain the sintered compact of core-shell structure, the result makes the temperature profile of electrostatic capacitance of laminated ceramic compacitor good.
Among the present invention,, can further improve the square crystallinity of gained barium titanate,, can make the credibility of this laminated ceramic compacitor better if use its preparation laminated ceramic compacitor if the rutilization rate of the titanium dioxide that uses is below 5%.
In addition, in the present invention, if when the barium compound of calcined mixed and titanium dioxide, be 1 * 10 in total pressure
3The following pressure of ambient gas of Pa is implemented this calcination process down, can further improve the square crystallinity of the barium titanate that obtains, if use its preparation laminated ceramic compacitor, can make the credibility of this laminated ceramic compacitor better.
In addition, in the present invention,, be the above materials of 99.8 weight % if use purity as titanium dioxide, the dielectric characteristics that can keep the dielectric ceramics that the sintering barium titanate powder obtains is higher.
In addition, among the preparation method of barium titanate powder of the present invention,, be below 30% and by the specific surface area that the BET method is tried to achieve to be 5m if confirm by the rutilization rate that X-ray diffraction method is tried to achieve for the titanium dioxide that uses
2More than/the g, can make the barium titanate powder that to give above-mentioned good characteristic really, can improve the effective rate of utilization of making barium titanate powder and make effective rate of utilization with the ceramic electronic components of its formation.
Claims (9)
1, a kind of barium titanate powder, mix with titanium dioxide by thermal degradation being generated barytic barium compound, calcine and obtain, the rutilization rate that described titanium dioxide is tried to achieve according to X-ray diffraction method is below 30%, and is 5m according to the specific surface area that the BET method is tried to achieve
2More than/the g.
2, barium titanate powder as claimed in claim 1, the rutilization rate of above-mentioned titanium dioxide is below 5%.
3, barium titanate powder as claimed in claim 1 or 2, above-mentioned calcining are that total pressure is 1 * 10
3Calcining under the pressure of ambient gas below the Pa.
4, as any described barium titanate powder in the claim 1 to 3, the purity of above-mentioned titanium dioxide is more than the 99.8 weight %.
5, a kind of preparation method of barium titanate powder comprises following each operation,
Preparation generates barytic barium compound by thermal degradation;
The rutilization rate that preparation is tried to achieve according to X-ray diffraction method is below 30% and according to the specific surface area that the BET method is tried to achieve to be 5m
2The titanium dioxide that/g is above;
Above-mentioned barium compound and above-mentioned titanium dioxide are mixed, calcine.
6, a kind of preparation method of barium titanate powder comprises following each operation,
Preparation generates barytic barium compound by thermal degradation;
Prepare titanium dioxide;
For above-mentioned titanium dioxide, confirm according to the rutilization rate that X-ray diffraction method is tried to achieve to be below 30% and according to the specific surface area that the BET method is tried to achieve to be 5m
2More than/the g;
The above-mentioned titanium dioxide that use has been confirmed, with above-mentioned barium compound and above-mentioned titanium dioxide mix, calcining.
7, as the preparation method of claim 5 or 6 described barium titanate powders, the rutilization rate of above-mentioned titanium dioxide is below 5%.
8, as the preparation method of any described barium titanate powder in the claim 5 to 7, above-mentioned calcination process is 1 * 10 in total pressure
3The following pressure of ambient gas of Pa is implemented down.
9, as the preparation method of any described barium titanate powder in the claim 5 to 8, the purity of above-mentioned titanium dioxide is more than the 99.8 weight %.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000397059 | 2000-12-27 | ||
| JP2000397059 | 2000-12-27 | ||
| JP2001342774 | 2001-11-08 | ||
| JP2001342774A JP3835254B2 (en) | 2000-12-27 | 2001-11-08 | Method for producing barium titanate powder |
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| CN1145595C CN1145595C (en) | 2004-04-14 |
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| JP (1) | JP3835254B2 (en) |
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| CN101786656A (en) * | 2010-03-26 | 2010-07-28 | 湘潭大学 | Preparation method of Barium Titanate nano-powder |
| CN102674830A (en) * | 2012-05-25 | 2012-09-19 | 贵州红星发展股份有限公司 | Alkaline earth metal titanate containing low free alkaline earth metal oxide and preparation method for alkaline earth metal titanate |
| CN103030173A (en) * | 2011-09-30 | 2013-04-10 | 深圳光启高等理工研究院 | Preparation method for barium titanate |
| CN108394932A (en) * | 2018-05-16 | 2018-08-14 | 江南大学 | A kind of preparation method of the submicron order barium carbonate powder of good dispersion |
| CN113582681A (en) * | 2021-08-26 | 2021-11-02 | 四川特锐祥科技股份有限公司 | High-dielectric-constant high-dielectric-strength dielectric material and preparation method thereof |
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| JP4660935B2 (en) * | 2001-02-05 | 2011-03-30 | 株式会社村田製作所 | Method for producing barium titanate-based ceramic powder having tetragonal perovskite structure |
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| EP1621519A1 (en) * | 2004-07-28 | 2006-02-01 | SOLVAY (Société Anonyme) | Alkaline - earth metal carbonate core coated with at least one Group IV transition metal compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4764493A (en) * | 1986-06-16 | 1988-08-16 | Corning Glass Works | Method for the production of mono-size powders of barium titanate |
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| CN101786656B (en) * | 2010-03-26 | 2011-05-25 | 湘潭大学 | Preparation method of Barium Titanate nano-powder |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100435165B1 (en) | 2004-06-09 |
| KR20020053749A (en) | 2002-07-05 |
| CN1145595C (en) | 2004-04-14 |
| JP3835254B2 (en) | 2006-10-18 |
| JP2002255552A (en) | 2002-09-11 |
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