CN1338430A - Micro-powders of barium tilanate and of calcium modified barium titanate and manufacture thereof - Google Patents
Micro-powders of barium tilanate and of calcium modified barium titanate and manufacture thereof Download PDFInfo
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Abstract
To provide high-reliability barium titanate fine powder hardly causing insulation failure when used as a dielectric element, calcium-modified barium titanate fine powder and a method for manufacturing the barium titanate fine powder. SOLUTION: This method for manufacturing the barium titanate fine powder comprises a step to prepare a barium hydroxide aqueous solution having 0.20-1.20 mol/l barium hydroxide concentration and a titanium alkoxide alcohol solution having 0.088-1.235 mol/l titanium alkoxide concentration, a step to mix the prepared barium hydroxide solution with the prepared titanium alkoxide alcohol solution so that the Ba/Ti molar ratio is 1.00-1.20 to obtain a mixed solution without incorporating other alkali elements in the mixed solution and a step to subject the obtained mixed solution to reaction at 60-100 deg.C.
Description
Technical field
The present invention relates to as the electronic devices and components barium titanate microparticles sprills of dielectric material, the barium titanate microparticles sprills and the manufacture method thereof of calcium modification, relate in particular to and be applicable to that medium element thickness is that 1 median size to the small-sized large vol laminated type chip capacitor of counting μ m is the barium titanate microparticles sprills of 0.019-0.300 μ m, the barium titanate microparticles sprills and the manufacture method thereof of calcium modification.
Conventional art
The manufacture method of barium titanate microparticles sprills in the past for example has solid phase method, hydrothermal synthesis method and hydrolysis method etc., about hydrolysis method, in the open communique of Japan special permission 1986 No. 146713 and 1992 No. 12020 description is arranged.Specially permit open communique 1986 No. 146713 according to Japan, with oxidizing aqueous titanium, hydrated barta and alkali metal hydroxide the 120-10000 that is equivalent to titanium doubly mole water in the presence of react in 60-110 ℃, can obtain median size is the barium titanate microparticles sprills of 0.07-0.5 μ m.In addition, specially permit open communique 1992 No. 12020 according to Japan, hydrated barta reaches and the mol ratio of this hydrated barta is 1 containing: 1-1: add and the equimolar titan-alkoxide of hydrated barta in 4 at least a alkali metal hydroxide or the aqueous solution of amine, 60-90 ℃ of reaction, and the barium titanate microparticles sprills that generate are carried out roasting under the temperature that does not make its particle growth, can obtain median size is the barium titanate microparticles sprills of 0.06-0.1 μ m.
In recent years, along with the miniaturization of electronic installation and highly integrated, in order to make miniaturization of laminated type chip capacitor and the high capacity as member, medium element thins down.But along with internal electrical interpolar medium layer thins down, if there is a textural defect, then internal electrode will be therefore and short circuit can not be played the effect of medium element.In order to keep high reliability, just must make the pottery that constitutes internal electrical interpolar medium layer have flawless uniform formation.Simultaneously, owing to the high capacity that is undertaken by thin layerization, require the degree of ceramic powder micronize to 0.10-0.25 μ m.
Summary of the invention
The barium titanate microparticles sprills have the tetragonal system crystal formation at normal temperatures, are the strong medium ceramic powder.But generally all know,, then such problem can occur if the median size of ceramic powder is little below 0.25 μ m; that is, owing to micronize causes lattice deformability, the c/a axial ratio diminishes thus; near isometric system, simultaneously strong electric conductivity reduces, and these problems result from dimensional effect.In addition, when the tetragonality of ceramic powder hour, also have such problem, that is, use this ceramic powder and the electrostatic capacitance of the laminated type ceramic condenser that obtains reduces, the electrostatic capacitance temperature profile departs from.
Present commercially available particulate starting material, the barium titanate of hydrothermal synthesis method for example, its finest powder is 0.13-0.20 μ m, the crystallinity index of ceramic powder is that tetragonality (the c/a axial ratio that records with X-ray diffraction) is 1.0055-1.008.Like this, the micronize and the tetragonality of ceramic powder have correlationship, and ceramic powder is fine more, and then tetragonality is more little, and this becomes a problem of ceramic powder miniaturization.
In addition, in hydrolysis method in the past,, use the strong basicity solvent, in reaction soln, add alkaline Na (OH) etc. in order to promote reaction.But so just following problems occurs: the Na of hundreds of ppm remains in the ceramic powder of generation, thereby after being processed into the laminated type chip capacitor, can cause migration, and the insulativity of medium element is worsened.During with the medium layer thin layer, it is remarkable further that this problem becomes.
The problem that produces owing to above-mentioned major cause is, is difficult to obtain electronic device miniaturization and high-density is necessary, be used for medium element thickness is to the ceramic powder of the small-sized large vol laminated type chip capacitor of number μ m about 1 μ m.
The objective of the invention is to solve the above problems, obtain being difficult for causing medium element defective insulation, the barium titanate ceramics powder that reliability is high by hydrolysis method.
In order to achieve the above object, a kind of manufacture method of barium titanate microparticles sprills of the present invention is characterised in that to have following steps:
The alcoholic solution of the baryta water of preparation 0.20-1.20 mol and the titan-alkoxide of 0.088-1.235 mol;
Is that the ratio of 1.00-1.20 is concocted with the alcoholic solution of barium hydroxide solution and titan-alkoxide with the Ba/Ti mol ratio, obtains the mixing solutions that does not have other alkaline element to sneak into;
Allow mixing solutions 60-100 ℃ of reaction.
The another kind of manufacture method of barium titanate microparticles sprills of the present invention is characterised in that, in the manufacture method of above-mentioned barium titanate microparticles sprills, allowing after the step of mixing solutions, also has 850-1000 ℃ of step of heat treatment.
A kind of manufacture method of the barium titanate microparticles sprills of calcium modification of the present invention is characterised in that to have following steps:
The alcoholic solution of the baryta water of preparation 0.20-1.20 mol, the titan-alkoxide of 0.088-1.235 mol and the alcoholic solution of calcium salt;
With the Ba/Ti mol ratio is that the mixing solutions that do not have other alkaline element to sneak into is concocted, obtained to 0.980-1.020 and Ca/Ti mol ratio in the ratio below 0.160;
Allow above-mentioned mixing solutions 60-100 ℃ of reaction.
The another kind of manufacture method of the barium titanate microparticles sprills of calcium modification of the present invention is characterised in that, in the manufacture method of the barium titanate microparticles sprills of above-mentioned calcium modification, allowing after the step of mixing solutions, also have 950-1100 ℃ of step of heat treatment.
A kind of form of barium titanate microparticles sprills of the present invention is that a kind of manufacture method with barium titanate microparticles sprills of the present invention obtains, and it is characterized in that its median size is 0.019-0.056 μ m, and specific surface area is 17.99-52.64m
2/ g, the Ba/Ti mol ratio after synthesizing is 0.9979-1.0060.
The another kind of form of barium titanate microparticles sprills of the present invention is that the another kind of manufacture method with barium titanate microparticles sprills of the present invention obtains, it is characterized in that, its median size is 0.105-0.300 μ m, and the c/a axial ratio that records with X-ray diffraction is 1.008-1.010.
A kind of form of the barium titanate microparticles sprills of calcium modification of the present invention is that a kind of manufacture method with the barium titanate microparticles sprills of calcium modification of the present invention obtains, and it is characterized in that its median size is 0.019-0.025 μ m, and specific surface area is 40.36-54.05m
2/ g, (the Ba+Ca)/Ti mol ratio after synthesizing is 0.994-1.004.
The another kind of form of the barium titanate microparticles sprills of calcium modification of the present invention is that the another kind of manufacture method with the barium titanate microparticles sprills of calcium modification of the present invention obtains, it is characterized in that, its median size is 0.145-0.250 μ m, and the c/a axial ratio that records with X-ray diffraction is 1.008-1.010.
Description of drawings
Fig. 1 is the explanatory view of the synthesizer in the manufacture method of barium titanate microparticles sprills of one embodiment of the present invention.
Fig. 2 is the Photomicrograph of the barium titanate microparticles sprills of the sample C in the embodiment of the invention 1.
Fig. 3 is the Photomicrograph of the barium titanate microparticles sprills of the sample 3 in the embodiment of the invention 1.
Fig. 4 is the Photomicrograph of the barium titanate microparticles sprills of the sample 25 in the embodiment of the invention 1.
Fig. 5 is the Photomicrograph of barium titanate microparticles sprills of the calcium modification of the sample 52 in the embodiment of the invention 2.
Fig. 6 is the Photomicrograph of barium titanate microparticles sprills of the calcium modification of the sample 58 in the embodiment of the invention 2.
Fig. 7 is the graphic representation of the relation of the median size of the barium titanate microparticles sprills of the sample 63-66 of the sample 1-58 that shows the embodiment of the invention and the comparative example that uses hydrothermal synthesis method and c/a axial ratio.
Embodiment
A kind of embodiment to the manufacture method of barium titanate microparticles sprills of the present invention describes below.
At first, the alcoholic solution of the titan-alkoxide of the baryta water of preparation 0.20-1.20 mol and 0.088-1.235 mol.If baryta water is lower than 0.20 mol, then building-up reactions is difficult to carry out, and the median size after synthesizing becomes big.And if baryta water is higher than 1.20 mol, then in building-up process, have barium carbonate to generate the mol ratio instability of gained barium titanate.In addition,, then need a large amount of alcohol, thereby productivity is descended if the alcoholic solution of titan-alkoxide is lower than 0.088 mol.And if the alcoholic solution of titan-alkoxide is higher than 1.235 mol, then easily with airborne moisture generation hydrolysis reaction, generate titanium oxide, and, because it is big that the median size of the barium titanate microparticles sprills after synthetic becomes, cause to make the mol ratio after synthesizing to reach about 1.00.
Then, the alcoholic solution of barium hydroxide solution and titan-alkoxide is concocted, obtained the mixing solutions that the Ba/Ti mol ratio is 1.0-1.2.If the Ba/Ti mol ratio is lower than 1.0, then the Ti surplus is not suitable as the media ceramic powder that uses in the laminated type chip capacitor.And,, therefore also be not suitable as the media ceramic powder that uses in the stacked capacitor then because Ba is superfluous and the c/a axial ratio descends if the Ba/Ti mol ratio is higher than 1.2.
In above-mentioned mixing solutions, must prevent that other alkaline element (as Na etc.) from sneaking into, this is because if sneak into other alkaline element, then alkaline element can remain in the barium titanate microparticles sprills of generation, even the only hundreds of ppm of residual quantity, also will cause migration after being processed into the laminated type chip capacitor, the insulativity of medium element is worsened.Existence does not then hinder but other alkaline element is as unavoidable impurities.
Then, allow above-mentioned mixing solutions, generate the preceding barium titanate microparticles sprills of thermal treatment 60-100 ℃ of reaction.If temperature of reaction is lower than 60 ℃, then building-up reactions is difficult to carry out.On the other hand, the temperature of reaction of the mixing solutions of water and Virahol can be above 100 ℃.Barium titanate microparticles sprills before the thermal treatment that obtains like this, its median size is 0.019-0056 μ m, specific surface area is 17.99-52.64m
2/ g, the Ba/Ti mol ratio after synthesizing is 0.9979-1.0060.
Then, the barium titanate microparticles sprills before the above-mentioned thermal treatment are heat-treated at 850-1000 ℃, obtain the barium titanate microparticles sprills after the thermal treatment.Even having, the barium titanate microparticles sprills before the thermal treatment of the present invention heat-treat the feature that also is not prone to unusual grain growth in the said temperature zone.Barium titanate microparticles sprills after the thermal treatment that obtains like this, its median size are 0.105-0.300 μ m, and the c/a axial ratio that records with X-ray diffraction is 1.008-1.010.
Another kind of embodiment to the manufacture method of the barium titanate microparticles sprills of calcium modification of the present invention describes below.
At first, prepare the baryta water of 0.20-1.20 mol, as the nitrocalcite of the aqueous isopropanol of the titanium isopropoxide of the 0.088-1.235 mol of the alcoholic solution of titan-alkoxide and the amount corresponding with calcium modification amount, earlier nitrocalcite is dissolved in the above-mentioned aqueous isopropanol.If baryta water is lower than 0.20 mol, then building-up reactions is difficult to carry out, and the median size after synthesizing becomes big.And if baryta water is higher than 1.20 mol, then in building-up process, have barium carbonate to generate the mol ratio instability of gained barium titanate.In addition,, then need a large amount of alcohol, thereby productivity is descended if the alcoholic solution of titan-alkoxide is lower than 0.088 mol.And if the alcoholic solution of titan-alkoxide is higher than 1.235 mol, then easy and airborne moisture generation hydrolysis reaction generates titanium oxide, and, because it is big that the median size of the barium titanate microparticles sprills after synthetic becomes, therefore, the mol ratio after synthesizing is reached about 1.00.
Then, the aqueous isopropanol of baryta water, titanium isopropoxide and nitrocalcite is concocted, obtained the Ba/Ti mol ratio and be 0.980-1.020 and Ca/Ti mol ratio at the mixing solutions below 0.160.If the Ba/Ti mol ratio is lower than 0.980, then the Ti surplus is not suitable as the media ceramic powder that uses in the laminated type chip capacitor.And,, therefore also be not suitable as the media ceramic powder that uses in the stacked capacitor then because A side (Ba+Ca) is superfluous and the c/a axial ratio descends if the Ba/Ti mol ratio is higher than 1.020.
In above-mentioned mixing solutions, must prevent that other alkaline element (as Na etc.) from sneaking into, this is because if sneak into other alkaline element, then alkaline element can remain in the barium titanate microparticles sprills of generation, even the only hundreds of ppm of residual quantity, also will cause migration after being processed into the laminated type chip capacitor, the insulativity of medium element is worsened.Existence does not then hinder but other alkaline element is as unavoidable impurities.
Then, allow above-mentioned mixing solutions, generate the preceding barium titanate microparticles sprills of thermal treatment 60-100 ℃ of reaction.If temperature of reaction is lower than 60 ℃, then building-up reactions is difficult to carry out.In addition, the temperature of reaction of the mixing solutions of water and Virahol can be above 100 ℃.The barium titanate microparticles sprills of the calcium modification before the thermal treatment that obtains like this, its median size is 0.019-0.025 μ m, specific surface area is 40.36-54.05m
2/ g, the Ba/Ti mol ratio after synthesizing is 0.994-1.004.
Then, the barium titanate microparticles sprills before the above-mentioned thermal treatment are heat-treated at 950-1100 ℃, obtain the barium titanate microparticles sprills after the thermal treatment.Even having, the barium titanate microparticles sprills of the calcium modification before the thermal treatment of the present invention heat-treat the feature that also is not prone to unusual grain growth in the said temperature zone.The barium titanate microparticles sprills of the calcium modification after the thermal treatment that obtains like this, its median size are 0.145-0.250 μ m, and the c/a axial ratio that records with X-ray diffraction is 1.008-1.010.
Titan-alkoxide and alcoholic solution are not limited to above-mentioned embodiment, can select for example b-oxide, fourth oxide compound and ethanol, butanols etc. aptly.
In addition, above-mentioned calcium salt is not limited to above-mentioned embodiment, also can select for example Calcium Bromide, calcium chloride and nitrocalcite etc. aptly.
In the another kind of manufacture method of the barium titanate microparticles sprills of the invention described above, as mixing solutions, the alcoholic solution of baryta water, titan-alkoxide and the alcoholic solution of calcium salt can be mixed simultaneously, also can limit stirring change each solution be injected the back mixing successively.
Describe synthesizer in a kind of manufacture method of barium titanate microparticles sprills of the present invention in detail according to Fig. 1 below.
Synthesizer 1 is by N
2Jar 2, bubbler 2b and 2d, Ba solution tank 3, Ti solution tank 4, pump 5a, 5b, 5c, static(al) mixing tank 6a and 6b, ageing tank 8, pipeline 2a, 2c, 3a, 4a, 7 constitute.
N
2 Jar 2 is to supply with N to Ba solution tank 3 and ageing tank 8
2The gas holder that gas is used.Bubbler 2b and 2d are used for by N
2The N that jar 2 is supplied with
2The device that gas is emitted with air bubble-shaped in Ba solution tank 3 and in the Ti solution tank 4.Ba solution tank 3 is the containers that inject baryta water.Ti solution tank 4 is the containers that inject the alcoholic solution of titan- alkoxide.Pump 5a, 5b and 5c are respectively the devices of the alcoholic solution of baryta water, titan-alkoxide and barium titanate solution being sent into the static(al) mixing tank.Static(al) mixing tank 6a and 6b are with solution blended mixing machine.Ageing tank 8 is to make synthetic barium titanate microparticles sprills aged container.Pipeline 2a, 2c, 3a, 4a and 7 carry N
2The pipeline of gas and solution.
At first, with N
2Gas by with N
2The pipeline 2a that jar 2 connects are delivered to the bubbler 2b that is arranged in the Ba solution tank 3.Similarly, with N
2Gas is delivered to the bubbler 2d that is arranged in the ageing tank 8 by pipeline 2c.
Then, baryta water is injected Ba solution tank 3,,, respectively solution is sent into pump 5a and 5b by pipeline 3a and 4a with the alcoholic solution injection Ti solution tank 4 of titan-alkoxide.
Then, will in static(al) mixing tank 6a, mix, the common pipeline 7 of mixed solution is delivered to ageing tank 8 by two kinds of solution that pump 5a and 5b send.In order to make lattice stable, ageing tank 8 is being remained in 60-90 ℃, carry out the aging of 1 to a few hours.In ageing tank 8, carry out between aging time, the barium titanate solution in the ageing tank 8 delivered to pump 5c by pipeline 8a, by static(al) mixing tank 6b make its mix aging after, send by pipeline 8b again and return ageing tank 8, wear out again.
Then, behind aging the end, carry out solid-liquid separation, obtain the barium titanate microparticles sprills with separating centrifuge etc.After it is cleaned with boiling pure water, carry out solid-liquid separation.
Then, carry out solid-liquid separation with the displacement of the moisture in the gained barium titanate microparticles sprills, after removing, make its drying again, obtain the barium titanate microparticles sprills before the thermal treatment of regulation mol ratio at last with carrying out the metathetical solvent exchange with the moisture of ethanol etc.Embodiment 1
At first, hydrated barta 8 hydrates are added on to heat to 90 ℃ pure water, stir, it is dissolved fully, obtain baryta water, and titanium isopropoxide is dissolved in the Virahol, obtain the alcohol solution of titan-alkoxide.
Then, baryta water is injected solution tank 3, the alcohol solution of titan-alkoxide is injected Ti solution tank 4, they are pressed Ba molar weight shown in the table 1, Ti molar weight and Ba/Ti mol ratio are concocted, with the method that illustrates in the above-described embodiment, obtain the barium titanate microparticles sprills of the preceding Sample A-K of thermal treatment.In addition, reaction conditions is that ageing tank 8 remains on 80 ℃, and digestion time is 1 hour.
Table 1
| Sample | During blending | Synthetic back (before the thermal treatment) | |||||
| Conversion amount (mol) | Mol ratio Ba/Ti | Mol ratio Ba/Ti | Median size (μ m) | Specific surface area (m 2/g) | |||
| ??Ba | ??Ti | ||||||
| Embodiment | A | ??0.20 | ??0.340 | ??1.150 | ??1.0002 | ??0.048 | ??21.05 |
| B | ??0.40 | ??0.097 | ??1.130 | ??1.0055 | ??0.019 | ??52.64 | |
| C | ??0.40 | ??0.341 | ??1.100 | ??1.0060 | ??0.027 | ??36.76 | |
| D | ??0.40 | ??0.651 | ??1.100 | ??1.0005 | ??0.039 | ??25.34 | |
| E | ??0.40 | ??1.235 | ??1.110 | ??0.9989 | ??0.056 | ??17.99 | |
| F | ??0.60 | ??0.509 | ??1.030 | ??1.0015 | ??0.024 | ??41.24 | |
| G | ??0.60 | ??0.088 | ??1.100 | ??0.9979 | ??0.033 | ??30.10 | |
| H | ??0.80 | ??0.647 | ??1.054 | ??0.9990 | ??0.030 | ??33.56 | |
| I | ??1.20 | ??0.647 | ??1.100 | ??0.9998 | ??0.023 | ??43.64 | |
| J | ??0.20 | ??0.340 | ??1.200 | ??1.0016 | ??0.051 | ??19.64 | |
| K | ??0.50 | ??0.647 | ??1.000 | ??0.9980 | ??0.033 | ??30.63 | |
Then, analyze with the barium titanate microparticles sprills of the Sample A-K of X-ray diffraction before to gained thermal treatment, it is single-phase to determine that it is the isometric system barium titanate.In addition, the Ba/Ti mol ratio after synthesizing is 0.9979-1.0060, and median size (according to the respective diameters of specific surface area calculating) is 0.019-0.056 μ m, narrow particle size distribution and even.The Photomicrograph of the barium titanate microparticles sprills of the sample C before the thermal treatment is seen Fig. 2.
Then, with process furnace respectively 850 ℃, 900 ℃, 950 ℃ and 1000 ℃ to the barium titanate microparticles sprills thermal treatment of the Sample A-K before the thermal treatment 2 hours, obtain barium titanate microparticles sprills into the big sample 1-44 of the tetragonality of strong dielectric.
Then, obtain specific surface area, median size and the c/a axial ratio of the barium titanate microparticles sprills of sample 1-44, it is summarized in table 2.And the Photomicrograph of the barium titanate microparticles sprills of sample 3 and 25 is shown in Fig. 3 and Fig. 4 respectively.
Table 2
| Thermal treatment temp (℃) | Specific surface area (m 2/g) | Median size (μ m) | The c/a axial ratio | |||
| Sample | (table 1) | |||||
| Embodiment | ??1 | ????A | ????850 | ????8.69 | ????0.115 | ????1.008 |
| ??2 | ????B | ????9.29 | ????0.108 | ????1.009 | ||
| ??3 | ????C | ????9.57 | ????0.105 | ????1.009 | ||
| ??4 | ????D | ????7.52 | ????0.133 | ????1.008 | ||
| ??5 | ????E | ????6.53 | ????0.138 | ????1.008 | ||
| ??6 | ????F | ????8.98 | ????0.111 | ????1.008 | ||
| ??7 | ????G | ????6.95 | ????0.14 | ????1.008 | ||
| ??8 | ????H | ????9.24 | ????0.108 | ????1.008 | ||
| ??9 | ????I | ????6.95 | ????0.144 | ????1.008 | ||
| ??10 | ????J | ????8.74 | ????0.114 | ????1.008 | ||
| ??11 | ????K | ????9.06 | ????0.110 | ????1.008 | ||
| ??12 | ????A | ????900 | ????8.07 | ????0.124 | ????1.008 | |
| ??13 | ????B | ????7.76 | ????0.129 | ????1.009 | ||
| ??14 | ????C | ????8.21 | ????0.122 | ????1.009 | ||
| ??15 | ????D | ????6.18 | ????0.162 | ????1.009 | ||
| ??16 | ????E | ????5.51 | ????0.186 | ????1.009 | ||
| ??17 | ????F | ????7.86 | ????0.127 | ????1.008 | ||
| ??18 | ????G | ????4.81 | ????0.208 | ????1.009 | ||
| ??19 | ????H | ????8.25 | ????0.121 | ????1.008 | ||
| ??20 | ????I | ????5.27 | ????0.190 | ????1.009 | ||
| ??21 | ????J | ????7.59 | ????0.132 | ????1.008 | ||
| ??22 | ????K | ????7.71 | ????0.130 | ????1.008 | ||
| ??23 | ????A | ????950 | ????7.36 | ????0.136 | ????1.009 | |
| ??24 | ????B | ????6.83 | ????0.146 | ????1.010 | ||
| ??25 | ????C | ????7.35 | ????0.136 | ????1.010 | ||
| ??26 | ????D | ????5.28 | ????0.189 | ????1.009 | ||
| ??27 | ????E | ????4.66 | ????0.240 | ????1.009 | ||
| ??28 | ????F | ????6.28 | ????0.159 | ????1.008 | ||
| ??29 | ????G | ????3.98 | ????0.252 | ????1.009 | ||
| ??30 | ????H | ????6.77 | ????0.148 | ????1.008 | ||
| ??31 | ????I | ????4.16 | ????0.240 | ????1.009 | ||
| ??32 | ????J | ????6.31 | ????0.158 | ????1.009 | ||
| ??33 | ????K | ????6.09 | ????0.164 | ????1.008 | ||
| Embodiment | ??34 | ????A | ????1000 | ????5.66 | ????0.177 | ????1.009 |
| ??35 | ????B | ????5.62 | ????0.178 | ????1.010 | ||
| ??36 | ????C | ????5.16 | ????0.194 | ????1.009 | ||
| ??37 | ????D | ????4.25 | ????0.235 | ????1.009 | ||
| ??38 | ????E | ????3.34 | ????0.300 | ????1.009 | ||
| ??39 | ????F | ????4.78 | ????0.209 | ????1.008 | ||
| ??40 | ????G | ????3.34 | ????0.300 | ????1.009 | ||
| ??41 | ????H | ????4.39 | ????0.228 | ????1.009 | ||
| ??42 | ????I | ????3.36 | ????0.297 | ????1.009 | ||
| ??43 | ????J | ????5.23 | ????0.191 | ????1.009 | ||
| ??44 | ????K | ????4.13 | ????0.242 | ????1.009 |
As shown in Table 2, the median size of the barium titanate microparticles sprills of sample 1-44 is 0.105-0.300 μ m, and the c/a axial ratio is 1.008-1.010, although be particulate, tetragonality is big.Embodiment 2
At first, hydrated barta 8 hydrates are added on to heat to 90 ℃ pure water, stir, it is dissolved fully, obtain baryta water, and titanium isopropoxide is dissolved in the Virahol, obtain the alcohol solution of titan-alkoxide, calcium chloride is dissolved in the Virahol, obtain the alcoholic solution of calcium salt.
Then, baryta water is injected solution tank 3, the alcohol solution of titan-alkoxide and the alcoholic solution of calcium salt are pre-mixed, mixed solution is injected Ti solution tank 4, they are pressed the Ca/Ti mol ratio blending when of the molar weight of Ba shown in the table 3, Ti molar weight, Ca molar weight, Ba/Ti mole, with the method that illustrates in the above-mentioned embodiment, obtain the barium titanate microparticles sprills of the calcium modification of the preceding sample L-Q of thermal treatment.In addition, reaction conditions is that ageing tank 8 remains on 80 ℃, and digestion time is 1 hour.
Then, analyze with the barium titanate microparticles sprills of the calcium modification of the sample L-Q of X-ray diffraction before to gained thermal treatment, it is single-phase to determine that it is the isometric system barium titanate.In addition, (the Ba+Ca)/Ti mole after synthesizing is 0.994-1.004, and median size (according to the respective diameters of specific surface area calculating) is 0.019-0.025 μ m, narrow particle size distribution and even.
Table 3
| Sample | During blending | Synthetic back (before the thermal treatment) | |||||||||
| Conversion amount (mol) | Mol ratio | Mol ratio | Median size (μ m) | Specific surface area (m 2/g) | |||||||
| ??Ba | ??Ti | ??Ca | Ba/Ti | Ca/Ti | (Ba+Ca)/Ti | Ba/Ti | Ca/Ti | ||||
| Embodiment | L | 0.50 | 0.650 | 0.029 | 1.020 | 0.045 | 1.002 | 0.961 | 0.041 | 0.025 | 40.36 |
| M | 0.50 | 0.650 | 0.036 | 1.010 | 0.055 | 0.996 | 0.945 | 0.051 | 0.023 | 43.54 | |
| N | 0.50 | 0.650 | 0.042 | 1.010 | 0.065 | 1.004 | 0.946 | 0.058 | 0.024 | 42.07 | |
| O | 0.50 | 0.650 | 0.049 | 1.000 | 0.075 | 0.994 | 0.927 | 0.067 | 0.023 | 43.42 | |
| P | 0.50 | 0.650 | 0.065 | 0.980 | 0.100 | 1.004 | 0.906 | 0.098 | 0.019 | 52.65 | |
| Q | 0.50 | 0.650 | 0.128 | 0.986 | 0.160 | 0.998 | 0.846 | 0.152 | 0.019 | 54.05 | |
Then, with process furnace respectively 950 ℃, 1000 ℃, 1050 ℃ and 1100 ℃ with the barium titanate microparticles sprills thermal treatment of the calcium modification of the sample L-Q before the thermal treatment 2 hours, obtain barium titanate microparticles sprills into the calcium modification of the big sample 45-58 of the tetragonality of strong dielectric.
Obtain specific surface area, median size and the c/a axial ratio of barium titanate microparticles sprills of the calcium modification of sample 45-58, it is summarized in table 4.And the Photomicrograph of the barium titanate microparticles sprills of sample 52 and 58 is shown in Fig. 5 and Fig. 6 respectively.
Table 4
| Sample | Thermal treatment temp (℃) | Specific surface area (m 2/g) | Median size (μ m) | The c/a axial ratio | ||
| (table 3) | ||||||
| Embodiment | ??45 | ????M | ????950 | ????5.18 | ????0.179 | ????1.010 |
| ??46 | ????Q | ????7.40 | ????0.145 | ????1.008 | ||
| ??47 | ????M | ????1000 | ????4.43 | ????0.209 | ????1.009 | |
| ??48 | ????N | ????5.23 | ????0.167 | ????1.010 | ||
| ??49 | ????Q | ????4.85 | ????0.221 | ????1.009 | ||
| ??50 | ????L | ????1050 | ????4.88 | ????0.166 | ????1.008 | |
| ??51 | ????M | ????3.11 | ????0.250 | ????1.010 | ||
| ??52 | ????N | ????5.14 | ????0.174 | ????1.009 | ||
| ??53 | ????O | ????4.65 | ????0.174 | ????1.009 | ||
| ??54 | ????P | ????5.59 | ????0.157 | ????1.009 | ||
| ??55 | ????L | ????1100 | ????3.71 | ????0.194 | ????1.008 | |
| ??56 | ????N | ????4.15 | ????0.193 | ????1.010 | ||
| ??57 | ????O | ????3.89 | ????0.219 | ????1.009 | ||
| ??58 | ????P | ????4.63 | ????0.250 | ????1.010 | ||
As shown in Table 4, the median size of the barium titanate microparticles sprills of the calcium modification of sample 45-58 is 0.145-0.250 μ m, and the c/a axial ratio is 1.008-1.010, although be particulate, tetragonality is big.Embodiment 3
At first, the alcoholic solution of the baryta water of preparation 0.20-1.20 mol and the titan-alkoxide of 0.088-1.235 mol, is the ratio blending of 1.00-1.20 with the alcoholic solution of barium hydroxide solution and titan-alkoxide in the Ba/Ti mol ratio, and other alkaline element is sneaked into.Allow mixing solutions 60-100 ℃ of reaction, make the preceding barium titanate microparticles sprills of thermal treatment, it is heat-treated at 850 ℃ with process furnace, make have specific surface area shown in the table 5, median size and the sample 59 of c/a axial ratio and 60 barium titanate microparticles sprills.
Table 5
| Sample | Thermal treatment temp (℃) | Specific surface area (m 2/g) | Median size (μ m) | The c/a axial ratio | |
| Embodiment | ??59 | ????850 | ????5.29 | ????0.189 | ??1.010 |
| ??60 | ????4.43 | ????0.226 | ??1.009 | ||
| Comparative example | ??61 | ????7.68 | ????0.130 | ??1.007 | |
| ??62 | ????3.11 | ????0.322 | ??1.010 | ||
Then, prepare above-mentioned volumetric molar concentration scope baryta water and above-mentioned volumetric molar concentration scope titan-alkoxide solution in addition in addition, allow the mixing solutions that forms of blending 60-100 ℃ of reaction, make the preceding barium titanate microparticles sprills of thermal treatment, 850 ℃ of thermal treatments, obtain having the sample as a comparative example 61 of specific surface area shown in the table 5, median size and c/a axial ratio and 62 barium titanate microparticles sprills with process furnace.The c/a axial ratio of the barium titanate microparticles sprills of sample 61 is less than 1.008, and outside scope of the present invention, and the median size of the barium titanate microparticles sprills of sample 62 is greater than 0.300 μ m, also outside scope of the present invention.
Then, preparation is that the thickness of main component is the ceramic green bed of material of 1.5 μ m with the barium titanate microparticles sprills of sample 59-62, printing becomes the electrode film of internal electrode on the surface of the ceramic green bed of material of regulation sheet number, make the one end margin be exposed to arbitrary end face side of the ceramic green bed of material, these ceramic raw materials of regulation sheet number are folded layer by layer, compressed and roasting, obtain the ceramic duplexer of sample 59-62, the electrode film area is 1.23mm
2
Then, in the both ends of the surface of the ceramic duplexer of sample 59-62, dip coated is used to form the conduction of terminal electrode and sticks with paste, and is dried, roasting, forms and is electrically connected the also pair of terminal electrode of mechanical engagement with internal electrode.Then, form the Ni plated film by electroplating processes on to terminal electrode, on the Ni plated film, form the Sn plated film again, obtain the laminated type ceramic condenser of sample 59-62 by electroplating processes at this.
Measure specific inductivity, dielectric loss, electrostatic capacity, electrostatic capacity velocity of variation and the mean failure rate time of origin of the laminated type ceramic condenser of sample 59-62, obtain n=75 mean value, it is summarized in table 6.In addition, specific inductivity, dielectric loss, electrostatic capacity velocity of variation and electrostatic capacity all are to measure under the condition of 1kHz, 0.5Vrms/ μ m.The electrostatic capacity velocity of variation is that the electrostatic capacity during with 20 ℃ is a benchmark, calculates the electrostatic capacity velocity of variation-55 ℃ ,-25 ℃, 85 ℃ and 125 ℃.In addition, mean failure rate time of origin (MTTF) is to measure by accelerated life test (HALT) under 150 ℃, the condition of 10V/ μ m.
Table 6
| Sample | Specific inductivity | Dielectric loss (%) | Electrostatic capacity (nF) | Electrostatic capacity velocity of variation (Δ C/C 20/％) | The mean failure rate time of origin (hour) | ||||
| -55℃ | ??-25℃ | 85℃ | ??125℃ | ||||||
| Embodiment | ??59 | ??2617 | ??9.90 | ??1906 | -7.0 | ??-3.0 | -2.1 | ??-21.6 | ????56 |
| ??60 | ??3224 | ??10.70 | ??2349 | -4.0 | ??0.0 | -4.7 | ??-20.5 | ????59 | |
| Comparative example | ??61 | ??4325 | ??11.20 | ??3150 | 12.1 | ??22.1 | 19.9 | ??-52.3 | Do not survey |
| ??62 | ??4310 | ??10.40 | ??3140 | -3.0 | ??1.0 | -7.6 | ??-20.4 | ????19 | |
As shown in Table 6, specific inductivity, dielectric loss and the electrostatic capacity of the laminated type ceramic condenser of sample 59-62 are all very good.
In addition, adopting the sample 59 of the barium titanate microparticles sprills in the scope of the invention and 60 laminated type ceramic condenser, is-7.0%～-2.1% at the electrostatic capacity velocity of variation of-55 ℃ ,-25 ℃ and 85 ℃, and absolute value is little, and is very excellent.In addition, even at 125 ℃, its electrostatic capacity velocity of variation also only is-21.6%～-20.5%.And the laminated type ceramic condenser of sample 61 as a comparative example is 12.1-22.1%, and absolute value is big, and is relatively poor.In addition, be-52.3% at 125 ℃ electrostatic capacity velocity of variation, extreme difference.
In addition, adopt the sample 59 of the barium titanate microparticles sprills in the scope of the invention and 60 laminated type ceramic condenser, its mean failure rate time of origin is 56-59 hour, and is longer, very excellent.And the laminated type ceramic condenser of sample 62 as a comparative example, its mean failure rate time of origin is 19 hours, and is very short, very poor.In addition, as the sample 59 of the embodiment of the invention and 60 laminated type ceramic condenser, its specific inductivity and electrostatic capacity liken little into the sample 61 of comparative example and 62 to, this is mainly because of the median size and the c/a axial ratio of barium titanate microparticles sprills, in addition, sample 59 and 60 specific inductivity and electrostatic capacity are no problem in practicality.Embodiment 4
Below, as a comparative example, prepare the barium titanate microparticles sprills with hydrothermal synthesis method.That is, stir 15 ℃ titanium sulfate (Ti (SO
4)
2) (120g/L in the time of 1L), remains on 15 ℃ with the liquid temperature to the aqueous solution, and adds sodium peroxide (Na slowly
2O
2) 117g.After adding end, add the 10N aqueous sodium hydroxide solution, produce precipitation, continue to stir 30 minutes after adding.Then, when stirring obtained aqueous solution, be warming up to 50 ℃, and kept 5 hours, obtain throw out.With its filtration, washing, with gained filter cake and bariumchloride 2 hydrate (BaCl
22H
2O) 244g is scattered in the water, is modulated into the slurry of 2L, and the airtight then nitrogen replacement that carries out was 150 ℃ of reactions 10 hours.Cool off after reaction finishes, with gained slurries filtration, washing and drying, obtain the Ba/Ti mol ratio and be 0.996, particle diameter is that 0.065 μ m, specific surface area are 15.3m
2Barium titanate microparticles sprills before the thermal treatment of/g.Then, the barium titanate microparticles sprills before the thermal treatment are heat-treated at 800 ℃, 850 ℃, 900 ℃ and 1000 ℃ respectively, obtain the barium titanate microparticles sprills of sample 63-66 as a comparative example.
Measure specific surface area, median size and the c/a axial ratio of the barium titanate microparticles sprills of sample 63-66, the result is summarized in table 7.
Table 7
| Sample | Thermal treatment temp (℃) | Specific surface area (m 2/g) | Median size (μ m) | The c/a axial ratio | |
| Comparative example | ??63 | ????800 | ????7.69 | ????0.130 | ??1.0055 |
| ??64 | ????850 | ????5.62 | ????0.178 | ??1.0075 | |
| ??65 | ????900 | ????4.48 | ????0.223 | ??1.0086 | |
| ??66 | ????1000 | ????2.57 | ????0.389 | ??1.0102 | |
As shown in Table 7, sample 63,64 and 66 barium titanate microparticles sprills, its c/a axial ratio outside the scope of 1.008-1.010, the barium titanate microparticles sprills of sample 66, its median size is greater than 0.300 μ m.
Here, the barium titanate microparticles sprills of within the scope of the present invention the sample 1-58 that makes with hydrolysis method and the median size of the barium titanate microparticles sprills of as a comparative example the sample 63-66 that makes with hydrothermal synthesis method and the relation of c/a axial ratio are shown in Fig. 7.
As shown in Figure 7, though the barium titanate microparticles sprills of sample 65 with ▲ expression, its specific surface area, median size and c/a axial ratio be in the scope that becomes barium titanate microparticles sprills of the present invention (in the rectangular extent shown in Fig. 7) all, but with equally carried out the heat treated sample of the present invention that shows with oral thermometer and compared at 900 ℃, in median size is under the situation of same degree, barium titanate microparticles sprills with hydrolysis method barium titanate microparticles sprills of the present invention that make and the prior art that makes with hydrothermal synthesis method are compared, and exist the tendency that the c/a axial ratio increases; And be under the situation of same degree in the c/a axial ratio, compare with the barium titanate microparticles sprills of hydrolysis method barium titanate microparticles sprills of the present invention that make and the prior art that makes with hydrothermal synthesis method, exist the tendency that median size reduces.Embodiment 5
The barium titanate microparticles sprills of the sample as a comparative example 64 that preparation is made with the barium titanate microparticles sprills of the sample of the present invention 25 made with hydrolysis method with hydrothermal synthesis method in the past respectively are the ceramic green bed of material of the thick 1.5 μ .m of main component, printing becomes the electrode film of internal electrode on the ceramic raw material laminar surface of regulation sheet number, make the one end margin be exposed to arbitrary end face side of the ceramic green bed of material, with these ceramic raw material layer laminate of regulation sheet number, compress, and, obtain the ceramic duplexer of sample 25 and 64 1200 ℃ of roastings.Making the electrode film area is 1.23mm
2, size is 2mm * 1.25mm * 1.2mm.
Then, the ceramic duplexer both ends of the surface in sample 25 and 64, dip coated are used to form the conduction of terminal electrode and stick with paste, and are dried, roasting, form and are electrically connected the also pair of terminal electrode of mechanical engagement with internal electrode.Then, form the Ni plated film by electroplating processes on to terminal electrode, on the Ni plated film, form the Sn plated film again, obtain the laminated type ceramic condenser of sample 25,64 by electroplating processes at this.
Measure specific inductivity, dielectric loss, electrostatic capacity, electrostatic capacity velocity of variation and the mean failure rate time of origin of the laminated type ceramic condenser of sample 25,64, obtain n=75 mean value, it is summarized in table 7.Identical in the condition determination of specific inductivity, dielectric loss, electrostatic capacity velocity of variation, electrostatic capacity and average time of failure and the foregoing description 3.
Table 8
| Sample | Specific inductivity | Dielectric loss (%) | Electrostatic capacity (nF) | Electrostatic capacity velocity of variation (Δ C/C 20/％) | The mean failure rate time of origin (hour) | ||||
| -55℃ | -25℃ | 85℃ | ??125℃ | ||||||
| Embodiment | 25 | 1510 | 1.15 | 1100 | 1.3 | 2.6 | -7.2 | ??-14.5 | ????428 |
| Comparative example | 64 | 2320 | 4.41 | 1720 | -12.8 | -7.2 | 17.9 | ??-37.9 | ????81 |
As shown in Table 8, adopt the laminated type ceramic condenser of the sample 25 of the barium titanate microparticles sprills in the scope of the invention, its dielectric loss is 1.15%, very little, very excellent, be-7.2%～1.3% at the electrostatic capacity velocity of variation of-55 ℃ ,-25 ℃ and 85 ℃, absolute value is little, and is very excellent.In addition, the mean failure rate time of origin is 428 hours, and is longer, very excellent.Also only be-14.5% at 125 ℃ electrostatic capacity velocity of variation, less, very excellent.And the dielectric loss of the laminated type ceramic condenser of sample 64 as a comparative example is 4.41%, and is bigger, is-17.9%～-7.2% at the electrostatic capacity velocity of variation of-55 ℃ ,-25 ℃ and 85 ℃, absolute value is big, the mean failure rate time of origin is 81 hours, and is very short, and these results are very poor.In addition, be-37.9% at 125 ℃ electrostatic capacity velocity of variation, extreme difference.Though liken little into the sample 64 of comparative example to as the specific inductivity of the sample 25 of the embodiment of the invention and electrostatic capacity, but this is mainly because of the median size and the c/a axial ratio of barium titanate microparticles sprills, in addition, the specific inductivity of sample 25 and electrostatic capacity are no problem in practicality.
As mentioned above, the manufacture method of barium titanate microparticles sprills of the present invention concoct, obtain not having the step of the mixed solution that other alkaline element sneaks into the step of the alcoholic solution of the alkoxytitanium of baryta water with preparation 0.20-1.20 mol/L and 0.088-1.235 mol/L, with the ratio of alcoholic solution take the Ba/Ti mol ratio as 1.00-1.20 of barium hydroxide solution and alkoxytitanium and allow mixed solution in the step of 60-100 ℃ of reactions as feature. Its effect is, can obtain being not easy the barium titanate microparticles sprills that cause that the bad reliability of interlayer element insulating is high, and can obtain realizing the laminated type ceramic electronic component of small-sized highly integrated and high capacity.
The feature of said method also is, after the step that allows above-mentioned mixed solution react, heat-treats at 850-1000 ℃, reclaims ceramic powders. Its effect is, can obtain the growth of crystal grain appropriateness and without the barium titanate microparticles sprills of unusual grain growth, and such barium titanate microparticles sprills are fit to make the laminated ceramic electronic components and parts that can realize small-sized highly integrated and high capacity very much.
The manufacture method of the barium titanate microparticles sprills of calcium modification of the present invention with the step of the alcoholic solution of the alcoholic solution of the alkoxytitanium of baryta water with preparation 0.20-1.20 mol/L, 0.088-1.235 mol/L and calcium salt, take the Ba/Ti mol ratio as 0.980-1.020 and the Ca/Ti mol ratio concoct, obtain not having the step of the mixed solution that other alkaline element sneaks in the ratio below 0.160 and allow above-mentioned mixed solution in the step of 60-100 ℃ of reaction as feature. Its effect is, the barium titanate microparticles sprills of the calcium modification that can obtain being not easy causing that the bad reliability of interlayer element insulating is high, and can obtain realizing the laminated type ceramic electronic component of small-sized highly integrated and high capacity.
The feature of said method also is, after the step that allows above-mentioned mixed solution react, heat-treats at 950-1100 ℃, reclaims ceramic powders. Its effect is, can obtain crystal grain appropriateness growth and without the barium titanate microparticles sprills of the calcium modification of unusual grain growth, the barium titanate microparticles sprills of such calcium modification are fit to make the laminated ceramic electronic components and parts that can realize small-sized highly integrated and high capacity very much.
In addition, the barium titanate microparticles sprills that manufacturing method according to the invention obtains and the barium titanate microparticles sprills of calcium modification, wet type is synthetic in to liquid need not to add in reactant liquor the alkaline elements such as Na, K owing to can be in reaction system, therefore has free from admixture, purity height, effect that tetragonality is large.
Claims (8)
1. the manufacture method of barium titanate microparticles sprills is characterized in that, has following steps:
The alcoholic solution of the baryta water of preparation 0.20-1.20 mol and the titan-alkoxide of 0.088-1.235 mol;
Is that the ratio of 1.00-1.20 is concocted with the alcoholic solution of barium hydroxide solution and titan-alkoxide with the Ba/Ti mol ratio, obtains the mixing solutions that does not have other alkaline element to sneak into;
Allow mixing solutions 60-100 ℃ of reaction.
2. the manufacture method of barium titanate microparticles sprills as claimed in claim 1 is characterized in that, after the step that allows above-mentioned mixing solutions react, also has the step of heat-treating, reclaim ceramic powder at 850-1000 ℃.
3. the manufacture method of the barium titanate microparticles sprills of calcium modification is characterized in that having following steps:
The alcoholic solution of the baryta water of preparation 0.20-1.20 mol, the titan-alkoxide of 0.088-1.235 mol and the alcoholic solution of calcium salt;
With the Ba/Ti mol ratio is that the mixing solutions that do not have other alkaline element to sneak into is concocted, obtained to 0.980-1.020 and Ca/Ti mol ratio in the ratio below 0.160;
Allow above-mentioned mixing solutions 60-100 ℃ of reaction.
4. the manufacture method of the barium titanate microparticles sprills of calcium modification as claimed in claim 3 is characterized in that, after the step that allows above-mentioned mixing solutions react, also has 950-1100 ℃ of step of heat treatment.
5. the barium titanate microparticles sprills obtain with the described manufacture method of claim 1, it is characterized in that, its median size is 0.019-0.056 μ m, and specific surface area is 17.99-52.64m
2/ g, the Ba/Ti mol ratio after synthesizing is 0.9979-1.0060.
6. the barium titanate microparticles sprills obtain with the described manufacture method of claim 2, it is characterized in that, its median size is 0.105-0.300 μ m, and the c/a axial ratio that records with X-ray diffraction is 1.008-1.010.
7. the barium titanate microparticles sprills of calcium modification obtain with the described manufacture method of claim 3, it is characterized in that, its median size is 0.019-0.025 μ m, and specific surface area is 40.36-54.05m
2/ g, (the Ba+Ca)/Ti mol ratio after synthesizing is 0.994-1.004.
8. the barium titanate microparticles sprills of calcium modification obtain with the described manufacture method of claim 4, it is characterized in that, its median size is 0.145-0.250 μ m, and the a/c axial ratio that records with X-ray diffraction is 1.008-1.010.
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| JP2000244885A JP3780405B2 (en) | 2000-08-11 | 2000-08-11 | Fine barium titanate powder, calcium-modified fine barium titanate powder, and method for producing the same |
| JP244885/00 | 2000-08-11 | ||
| JP244885/2000 | 2000-08-11 |
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| US5087437A (en) * | 1988-01-15 | 1992-02-11 | E. I. Du Pont De Nemours And Company | Process for preparing crystalline mixed metal oxides |
| US5445806A (en) * | 1989-08-21 | 1995-08-29 | Tayca Corporation | Process for preparing fine powder of perovskite-type compound |
-
2000
- 2000-08-11 JP JP2000244885A patent/JP3780405B2/en not_active Expired - Lifetime
-
2001
- 2001-08-01 TW TW090118794A patent/TW539649B/en not_active IP Right Cessation
- 2001-08-09 KR KR10-2001-0047911A patent/KR100435073B1/en active IP Right Grant
- 2001-08-10 CN CNB011249935A patent/CN1202014C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675005B (en) * | 2007-02-20 | 2011-08-31 | 日本化学工业株式会社 | Amorphous fine-particle powder, process for production thereof and perovskite-type barium titanate powder made by using the same |
| CN112830512A (en) * | 2014-06-13 | 2021-05-25 | 户田工业株式会社 | Barium titanate fine particle powder, dispersion, and method for producing coating film |
| CN106430295A (en) * | 2016-09-12 | 2017-02-22 | 天津城建大学 | Micro-nano hierarchy BaTiO3 crystal and preparation method thereof |
| CN106430295B (en) * | 2016-09-12 | 2017-12-26 | 天津城建大学 | A kind of micro-nano hierarchy BaTiO3Crystal and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020013740A (en) | 2002-02-21 |
| KR100435073B1 (en) | 2004-06-09 |
| JP3780405B2 (en) | 2006-05-31 |
| JP2002060219A (en) | 2002-02-26 |
| CN1202014C (en) | 2005-05-18 |
| TW539649B (en) | 2003-07-01 |
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