CN115806311B - Barium titanate material composition, barium titanate material, and method for producing same - Google Patents
Barium titanate material composition, barium titanate material, and method for producing same Download PDFInfo
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- CN115806311B CN115806311B CN202111078779.5A CN202111078779A CN115806311B CN 115806311 B CN115806311 B CN 115806311B CN 202111078779 A CN202111078779 A CN 202111078779A CN 115806311 B CN115806311 B CN 115806311B
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 117
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 127
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 127
- 239000000843 powder Substances 0.000 claims abstract description 125
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 62
- 239000002270 dispersing agent Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 150000004820 halides Chemical class 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 10
- 239000010936 titanium Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 8
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- -1 diallyl ammonium halide Chemical class 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Capacitors (AREA)
Abstract
The invention relates to a barium titanate material composition, a barium titanate material and a manufacturing method thereof. The barium titanate material composition comprises barium carbonate powder (A), titanium dioxide powder (B), solvent (C) and dispersant (D). The barium atoms of the barium carbonate powder (A) and the titanium atoms of the titanium dioxide powder (B) have a specific molar ratio, and the dispersant (D) comprises a polymer of dialkyldiallylammonium halide. The method for manufacturing barium titanate material can manufacture barium titanate material with high composition uniformity by the specific mole ratio, the specific kind of polymer and the specific weight of dispersing agent (D), so that the method can be applied to dielectric ceramic material.
Description
Technical Field
The present invention relates to a barium titanate material composition, a barium titanate material and a method for producing the same, and more particularly, to a barium titanate material having high composition uniformity, a composition thereof and a method for producing the same.
Background
The multilayer ceramic capacitor has the advantages of high rated voltage resistance and high temperature operating environment, so that the multilayer ceramic capacitor is suitable for being applied to the fields of high-density displays of electronic circuits and power supplies. With the electrical properties, high temperature resistance and miniaturization of laminated ceramic capacitors, the requirements for the composition uniformity of barium titanate materials in dielectric ceramic materials for manufacturing laminated ceramic capacitors are becoming more stringent. The aforementioned compositional uniformity can be evaluated from the ratio of the molar number of barium to titanium (Ba/Ti molar ratio), specific surface area, the ratio of a-axis to c-axis (c/a-axis ratio) at different points (e.g., three points) in the barium titanate material, and the relative standard deviation of the test results of the particle diameters. The barium titanate material has good composition uniformity only when the relative standard deviation of the molar ratio of Ba/Ti is less than 0.15%, the relative standard deviation of the specific surface area is less than 10%, the relative standard deviation of the c/a axis ratio is less than 0.05%, and the relative standard deviation of the particle diameter is less than 5.0%.
The conventional process for barium titanate materials uses a filter pressing method to separate a solvent and oxide powder from a suspension containing two or more oxide powders, so as to facilitate the subsequent heat treatment. However, the composition uniformity of the barium titanate material produced is poor, and the aforementioned requirement for composition uniformity cannot be met.
In view of the foregoing, there is a need to develop a new barium titanate material composition, barium titanate material and manufacturing method thereof to improve the disadvantages of the barium titanate materials.
Disclosure of Invention
In view of the foregoing, an aspect of the present invention provides a barium titanate composition. The composition comprises barium carbonate powder (A), titanium dioxide powder (B), solvent (C) and dispersing agent (D), wherein the barium atoms of the barium carbonate powder (A) and the titanium atoms of the titanium dioxide powder (B) have specific mole ratio, and the dispersing agent (D) comprises specific polymer and specific weight, so that the composition uniformity of the prepared barium titanate material is improved, and the barium titanate material can be applied to dielectric ceramic materials.
Another aspect of the present invention is to provide a method for manufacturing a barium titanate material. The manufacturing method uses the barium titanate material composition to manufacture the barium titanate material with high composition uniformity.
Yet another aspect of the present invention is to provide a barium titanate material. The barium titanate material is produced by the aforementioned method for producing a barium titanate material.
According to one aspect of the present invention, a barium titanate material composition is provided. The composition comprises barium carbonate (BaCO) 3 ) Powder (A), titanium dioxide (TiO) 2 ) Powder (B), solvent (C) and dispersant (D). The molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is 0.99 to 1.01, andand the dispersant (D) comprises a polymer of dialkyldiallylammonium halide. The dispersant (D) is present in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (A), the titanium dioxide powder (B) and the solvent (C).
According to an embodiment of the present invention, the specific surface area of the barium carbonate powder (A) is not more than 20m 2 /g。
According to another embodiment of the present invention, the specific surface area of the titanium dioxide powder (B) is not more than 30m 2 /g。
According to still another embodiment of the present invention, the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) is 50 to 60 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C).
According to another aspect of the present invention, a method for manufacturing a barium titanate material is provided. In this production method, barium carbonate (BaCO) 3 ) Powder (A), titanium dioxide (TiO) 2 ) The powder (B) and the solvent (C) are subjected to a first grinding treatment to obtain a suspension in which the molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is from 0.99 to 1.01. Adding a dispersant (D) to the suspension to obtain a slurry, wherein the dispersant (D) comprises a polymer of dialkyldiallylammonium halide and the weight of the dispersant (D) is 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C). And sequentially performing drying treatment and second grinding treatment on the slurry to obtain mixed powder. Sequentially performing heat treatment and third grinding treatment on the mixed powder to obtain barium titanate material, wherein the temperature of the heat treatment is 900-1200deg.C, and the atmosphere of the heat treatment is not more than 3×10 4 Oxygen partial pressure of Pa.
According to still another embodiment of the present invention, the specific surface area of the barium carbonate powder (A) is not more than 20m 2 /g。
According to still another embodiment of the present invention, the specific surface area of the titanium dioxide powder (B) is not more than 30m 2 /g。
According to still another embodiment of the present invention, the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) is 50 to 60 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C).
According to still another aspect of the present invention, a barium titanate material is provided. The barium titanate material is prepared by the method for preparing the barium titanate material, wherein the ratio of the c axis to the a axis (c/a axis ratio) of the barium titanate material is not less than 1.0070, and the relative standard deviation is less than 0.05%.
According to still another embodiment of the present invention, the particle size of the powder of the barium titanate material is 0.25 μm to 0.60 μm.
The barium titanate material composition, the barium titanate material and the manufacturing method thereof are applied, wherein the composition comprises barium carbonate powder (A), titanium dioxide powder (B), solvent (C) and dispersing agent (D). The method for manufacturing barium titanate materials can manufacture barium titanate materials having high composition uniformity by a specific molar ratio between barium atoms of the barium carbonate powder (a) and titanium atoms of the titanium dioxide powder (B), a specific kind of polymer contained in the dispersant (D), and a specific weight of the dispersant (D), so that the barium titanate materials can be applied to dielectric ceramic materials.
Drawings
For a more complete understanding of embodiments of the present invention and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only.
The relevant drawings are described as follows:
fig. 1 is a flowchart illustrating a method for manufacturing a barium titanate material according to an embodiment of the present invention.
Detailed Description
The making and using of the embodiments of the present invention are discussed in detail below. However, it is to be understood that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The particular embodiments discussed are merely illustrative and are not meant to limit the scope of the invention.
The barium titanate material composition of the present invention comprises barium carbonate powder (A), titanium dioxide powder (B), solvent (C) and dispersant (D). The molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is 0.99 to 1.01, so that the molar ratio of the barium atoms to the titanium atoms in the prepared barium titanate material is close to 1, and the barium titanate material with a perovskite structure is manufactured, thereby improving the tetragonality of the barium titanate material and reducing the particle size of the barium titanate material, and the manufactured barium titanate material can be used as a dielectric ceramic material.
In addition, the dispersant (D) comprises a polymer of dialkyldiallylammonium halide, which comprises a homopolymer (D1) and a copolymer (D2), and the positive charges carried by the ammonium groups thereof neutralize (or attract) the negative charges coated on the surfaces of the barium carbonate powder (a) and the titanium dioxide powder (B), so that the polymer can wind the barium carbonate powder (a) and the titanium dioxide powder (B) to form a network structure, i.e., the suspension forms a colloidal solution. The viscosity of the formed colloidal solution can limit the movement of the barium carbonate powder (A) and the titanium dioxide powder (B) and prevent the two from precipitating so as to uniformly disperse the two, thereby improving the composition uniformity of the prepared barium titanate material and being suitable for being applied to dielectric ceramic materials.
The term "uniformity of composition of barium titanate material" as used herein means that the molar ratio of barium to titanium (expressed as "Ba/Ti molar ratio"), specific surface area, ratio of c-axis to a-axis (expressed as "c/a-axis ratio") and relative standard deviation of test results of particle diameter were measured from three places in the barium titanate material according to the following evaluation methods. The barium titanate material has good composition uniformity when the relative standard deviation of the Ba/Ti molar ratio is less than 0.15%, the relative standard deviation of the specific surface area is less than 10%, the relative standard deviation of the c/a axis ratio is less than 0.05%, and the relative standard deviation of the particle diameter is less than 5.0%. The foregoing relative standard deviation may be used to represent the distribution range of the corresponding test results.
Referring to fig. 1, a method 100 for manufacturing barium titanate material includes providing barium carbonate (BaCO 3 ) Powder (A), titanium dioxide (TiO) 2 ) Powder (B) and solvent (C), and subjected to a grinding process to obtain a suspension, as shown in operation 110. In some embodiments, the specific surface area of the barium carbonate powder (A) is no greater than 20m 2 /gAnd may preferably be 4m 2 /g to 15m 2 And/g. When the specific surface area of the barium carbonate powder (a) is in the aforementioned range, the barium carbonate powder (a) and the titanium dioxide powder (B) are uniformly mixed, and the particle size distribution of the produced barium titanate material is narrow, thereby improving the uniformity of the particle size of the barium titanate material.
In some embodiments, the particle size of the barium carbonate powder (A) may be 0.05 μm to 0.40 μm, and preferably may be 0.10 μm to 0.35 μm. When the particle diameter of the barium carbonate powder (a) is within the above-mentioned range, the particle diameter distribution range of the barium titanate material to be produced can be reduced, so that the uniformity of the particle diameter of the barium titanate material can be improved.
In some embodiments, the specific surface area of the titanium dioxide powder (B) is no greater than 30m 2 /g, and may preferably be 5m 2 /g to 25m 2 And/g. When the specific surface area of the titanium dioxide powder (B) is in the above-described range, the barium carbonate powder (a) and the titanium dioxide powder (B) can be uniformly mixed, and the particle size distribution of the produced barium titanate material is narrow, so that the uniformity of the particle size of the barium titanate material is improved.
In some embodiments, the particle size of the titanium dioxide powder (B) may be 0.03 μm to 0.35 μm, and preferably may be 0.05 μm to 0.30 μm. When the particle diameter of the titanium dioxide powder (B) is in the aforementioned range, the particle diameter distribution range of the produced barium titanate material can be reduced, so that the composition uniformity of the barium titanate material can be improved.
The molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is 0.99 to 1.01. If the molar ratio of barium atoms to titanium atoms is not in the above range, it is unfavorable to produce a barium titanate material having a perovskite structure, and tetragonality (ratio of c-axis to a-axis (c/a-axis ratio)) of the barium titanate material is reduced, and the particle size distribution range of the barium titanate material is increased, so that the produced barium titanate material has poor composition uniformity and is not useful as a dielectric ceramic material. The molar ratio of the barium atom to the titanium atom is preferably 1.00.
In some embodiments, the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) may be 50 to 60 parts by weight, and preferably may be 55 parts by weight, based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B), and the solvent (C). When the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) is in the above range, the surface charges of the colloidal particles formed by the barium carbonate powder (a) and the titanium dioxide powder (B) are neutralized by the dispersant (D) to increase the viscosity of the suspension, so that the uniformity of the composition of the barium titanate material is improved.
In some embodiments, solvent (C) comprises water, an organic acid having a carbon number less than 10. In some embodiments, the weight of the solvent (C) may be 40 to 50 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B), and the solvent (C). The polishing treatment with the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C) is not particularly limited, and for example, wet polishing treatment with zirconia balls is performed.
After operation 110 described above, a dispersant (D) is added to the suspension to obtain a slurry, as shown in operation 120. The dispersant (D) comprises a polymer of dialkyldiallylammonium halide, which in some embodiments may comprise a homopolymer (D1). The homopolymer (D1) is completely soluble in water, and the positive charges carried by the ammonium groups thereof neutralize (or attract) the negative charges coated on the surfaces of the barium carbonate powder (a) and the titanium dioxide powder (B), so that the barium carbonate powder (a) and the titanium dioxide powder (B) can be entangled by the attraction to form a network structure, thereby changing the suspension into a colloidal solution.
The viscosity of the colloidal solution can limit the movement of the barium carbonate powder (A) and the titanium dioxide powder (B) and prevent the two from precipitating so as to uniformly disperse the two, thereby improving the composition uniformity of the prepared barium titanate material. If the dispersant (D) does not use a polymer of dialkyldiallylammonium halide, the dispersant (D) does not have a high charge density and cannot generate the aforementioned attraction effect, so that the viscosity of the suspension cannot be increased, thereby reducing the composition uniformity of the produced barium titanate material.
In some embodiments, the homopolymer of dialkyldiallylammonium halide (D1) has a structure represented by the following formula (I).
In formula (I), R 1 R is R 2 Each independently represents a methyl group or an ethyl group, X represents a halogen atom, and n is an integer of 1 to 6. Preferably, X may be a chlorine or bromine atom, and n may be an integer of 3 to 4. When R is 1 R is R 2 When representing methyl or ethyl, the steric hindrance of methyl and ethyl is smaller than other groups, and the positive charge of the ammonium group of the homopolymer (D1) of dialkyl diallyl ammonium halide and the negative charge of the surfaces of the barium carbonate powder (A) and the titanium dioxide powder (B) are helped to attract each other, so that the viscosity of the suspension is effectively increased, and the composition uniformity of the prepared barium titanate material is further improved. When n is an integer of 3 to 5 (i.e., a molecular weight of 368.3g/mole to 613.9 g/mole), the chain length of the homopolymer (D1) of dialkyldiallylammonium halide is advantageous in increasing the viscosity of the suspension, thereby improving the compositional uniformity of the barium titanate material produced.
In other words, in some embodiments, the dispersant (D) may exclude polymers containing hydroxyl groups and ether groups, and the two groups are not able to achieve the attraction effect because they are not able to carry positive charges, and thus, the uniformity of composition of the barium titanate material is not improved. In addition, the dispersant (D) may exclude polymers containing functional groups such as carboxylic acid groups, phosphoric acid groups, sulfuric acid groups and nitric acid groups, and since the charges carried by these functional groups are negative, the above-mentioned attraction effect cannot be achieved, and the above-mentioned attraction effect due to the ammonium groups of the dispersant (D) is disturbed, and further the uniformity of the composition of the barium titanate material produced cannot be improved.
The dispersant (D) is present in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (A), the titanium dioxide powder (B) and the solvent (C). If the weight of the dispersant (D) is not within the above range, insufficient dispersant (D) cannot increase the viscosity of the suspension to become a colloidal solution, and the particle size distribution of the barium titanate material produced is too broad, so that the composition uniformity thereof cannot be improved. Preferably, the weight of the dispersant (D) is 0.55 to 5.5 parts by weight.
After adding the dispersant (D) to the suspension, the two are uniformly mixed to cause the aforementioned suction effect, and the suspension is thickened to become a colloidal solution, which is a slurry. The mixing method is not particularly limited, but the purpose is to achieve the suspension into a colloidal solution. For example, the dispersant (D) and the suspension may be mixed using a mechanical stirrer.
After the aforementioned operation 120, the slurry is sequentially subjected to a drying process and a second grinding process to obtain powder, as shown in operation 130. In some embodiments, the drying process may be heating at a temperature greater than the boiling point of solvent (C) for several hours to remove solvent (C). For example, drying is carried out at 120℃for 2 hours. If the method 100 for manufacturing barium titanate material does not perform the drying process and the second polishing process, the distribution range of the specific surface area of the manufactured barium titanate material is increased, and the composition uniformity of the barium titanate material is reduced.
In some embodiments, the second grinding process may be performed using a planetary mill (planetary mill) or bead mill (beads mill) and screened with a screen, such as a 50 mesh screen, to obtain a mixed powder. In some embodiments, the particle size of the mixed powder may be 0.30 μm to 0.60 μm to facilitate the production of barium titanate materials of suitable particle sizes (e.g., 0.25 μm to 0.60 μm).
After the foregoing operation 130, the mixed powder is heat-treated to obtain a barium titanate material, as shown in operation 140. The heat treatment is carried out at a temperature of 900 ℃ to 1200 ℃ and in a specific atmosphere comprising not more than 3 x 10 4 Oxygen partial pressure of Pa. If the temperature and atmosphere of the heat treatment are not the conditions described above, organic matters or other metal oxides remain in the barium titanate material, so that the composition uniformity of the barium titanate material is reduced. Preferably, the temperature of the heat treatment may be 1100 ℃. The atmosphere may preferably comprise not more than 2X 10 4 Oxygen partial pressure of Pa. In some embodiments, the heat treatment may be performed in a calciner.
Another aspect of the present invention provides a barium titanate material manufactured by the above manufacturing method, wherein the ratio of c-axis to a-axis (c/a-axis ratio) of the barium titanate material is not less than 1.0070. If the c/a axis ratio of the barium titanate material is less than 1.0070, the dielectric constant of the ceramic material is low, and thus the ceramic material is not suitable for a multilayer ceramic capacitor. Preferably, the c/a axis ratio may be greater than 1.0070.
In some embodiments, the particle size of the barium titanate material may be 0.25 μm to 0.60 μm, and preferably may be 0.30 μm to 0.60 μm. When the particle size of the barium titanate material is within the above range, the tetragonality of the barium titanate material can be improved, so that the barium titanate material is more suitable for being applied to a laminated ceramic capacitor.
The following examples are set forth to illustrate the practice of the invention and are not intended to limit the invention thereto, as various modifications and variations may be made by those skilled in the art without departing from the spirit and scope of the invention.
Production of barium titanate material
Example 1
The barium titanate material of example 1 was wet-milled for 24 hours with respect to the total weight of barium carbonate powder (a), titanium oxide powder (B) and water, wherein the total weight of barium carbonate powder (a) and titanium oxide powder (B) was 55 parts by weight and the weight of water was 45 parts by weight, based on the total weight of barium carbonate powder (a), titanium oxide powder (B) and water, to obtain a suspension. To this suspension, 0.55 to 5.5 parts by weight of polydiallyl dimethyl ammonium chloride was added, and stirred for 1 hour, and dried at 120℃for 2 hours, and after grinding, it was sieved with a 50-mesh sieve to obtain a mixed powder having a particle diameter of 0.30 to 0.60. Mu.m. The mixed powder is not more than 2×10 4 The calcination treatment was carried out at a temperature of 1100℃and an oxygen partial pressure of Pa.
Example 2 and comparative examples 1 to 2
Example 2 and comparative examples 1 to 2 were each produced in a similar manner to example 1. Except that the amounts of barium carbonate powder (a), titanium dioxide powder (B) and dispersant (D) were changed in example 2 and comparative examples 1 to 2, the specific conditions thereof are shown in table 1.
Evaluation method
1. Test of molar ratio of barium to titanium (Ba/Ti molar ratio)
The molar ratio of barium to titanium was measured by quantitatively analyzing the barium element and the titanium element of barium titanate material using an X-ray fluorescence spectrometer (XRF, manufactured by Bruker (Bruker) company, model S8 Tiger) and obtaining the molar ratio of the two, wherein the test conditions and the calculation method are those conventionally used by those skilled in the art.
2. Specific surface area test
Specific surface area test the specific surface area of the barium titanate material was measured using a specific surface area meter (Macsorb (registered trademark), manufactured by makroot technology (mount tech), model HM-1220).
Test of ratio of 3.c axis to a axis (c/a axis ratio)
The test of the ratio of a-axis to c-axis (c/a-axis ratio) was performed by collecting an X-ray diffraction (XRD) spectrum of a barium titanate material using an X-ray diffractometer (manufactured by Bruker, model D2 Phaser), wherein parameters were set to 20 DEG to 80 DEG 2 theta, a scanning speed of 0.35 seconds/step, and an operating voltage of 30 KV. The crystal structure of the barium titanate material was then refined by TOPAS software (total pattern analysis solutions software, developed by Bruker) to obtain values of a-axis and c-axis in the unit cell, and the c/a-axis ratio was calculated, and the tetragonality of the barium titanate material was evaluated by the c/a-axis ratio. When the c/a axis ratio is not less than 1.0070, the barium titanate material has high tetragonality.
4. Particle size test
Particle size test the particle size of the barium titanate material was measured using an electron microscope, wherein the test conditions are those conventionally used by those skilled in the art to which the present invention pertains.
TABLE 1
Referring to table 1, the barium titanate materials prepared in examples 1 to 2 have a more uniform Ba/Ti molar ratio, specific surface area and c/a axis ratio than those of comparative examples 1 to 2 in which the dispersant (D) was not used, so that the dispersant (D) can improve the composition uniformity of the prepared barium titanate materials. In addition, according to the results of the Ba/Ti molar ratio of examples 1 to 2, decreasing the Ba/Ti molar ratio increases the specific surface area and increases the c/a axis ratio, so that the tetragonality of the barium titanate material produced is improved, making it more suitable for application to multilayer ceramic capacitors.
In summary, the barium titanate material composition of the present invention comprises a barium carbonate powder (a), a titanium dioxide powder (B), a solvent and a dispersant (D), wherein the barium atoms of the barium carbonate powder (a) and the titanium atoms of the titanium dioxide powder (B) have a specific molar ratio, and the dispersant (D) comprises a polymer of dialkyldiallylammonium halide. The method for manufacturing barium titanate material can manufacture barium titanate material with high composition uniformity by the specific mole ratio, specific type of polymer and specific amount of dispersant (D), so that the barium titanate material can be applied to dielectric ceramic material.
While the present invention has been described with reference to the above embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and the scope of the invention is defined by the appended claims.
[ symbolic description ]
100 method
110,120,130, 140.
Claims (10)
1. A barium titanate material composition, comprising:
barium carbonate (BaCO) 3 ) A powder (A);
titanium dioxide (TiO) 2 ) A powder (B) wherein the molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is 0.99 to 1.01;
a solvent (C); and
a dispersant (D), wherein the dispersant (D) comprises a polymer of dialkyldiallylammonium halide;
wherein the weight of the dispersant (D) is 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (A), the titanium dioxide powder (B) and the solvent (C).
2. The barium titanate material composition according to claim 1, wherein the specific surface area of the barium carbonate powder (a) is not more than 20m 2 /g。
3. The barium titanate material composition according to claim 1, wherein the specific surface area of the titanium dioxide powder (B) is not more than 30m 2 /g。
4. The barium titanate material composition according to claim 1, wherein the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) is 50 to 60 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C).
5. A method for producing a barium titanate material, comprising:
for barium carbonate (BaCO) 3 ) Powder (A), titanium dioxide (TiO) 2 ) Carrying out a first grinding treatment of the powder (B) and the solvent (C) to obtain a suspension, wherein the molar ratio of the barium atoms of the barium carbonate powder (A) to the titanium atoms of the titanium dioxide powder (B) is 0.99 to 1.01;
adding a dispersant (D) to the suspension to obtain a slurry, wherein the dispersant (D) comprises a polymer of dialkyldiallylammonium halide and is 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C);
sequentially performing drying treatment and second grinding treatment on the slurry to obtain mixed powder; and
sequentially performing a heat treatment and a third grinding treatment on the mixed powder to obtain the barium titanate material, wherein the temperature of the heat treatment is 900-1200 ℃, and the heat treatmentIs not more than 3 x 10 4 Oxygen partial pressure of Pa.
6. The method of producing a barium titanate material according to claim 5, wherein the specific surface area of the barium carbonate powder (A) is not more than 20m 2 /g。
7. The method of producing a barium titanate material according to claim 5, wherein the specific surface area of the titanium dioxide powder (B) is not more than 30m 2 /g。
8. The method according to claim 5, wherein the total weight of the barium carbonate powder (a) and the titanium dioxide powder (B) is 50 to 60 parts by weight based on 100 parts by weight of the total weight of the barium carbonate powder (a), the titanium dioxide powder (B) and the solvent (C).
9. A barium titanate material produced by the method for producing a barium titanate material according to any one of claims 5 to 8, wherein the ratio of the c-axis to the a-axis (c/a-axis ratio) of the barium titanate material is not less than 1.0070, and the relative standard deviation is less than 0.05%.
10. The barium titanate material of claim 9, wherein the particle size of the powder of the barium titanate material is 0.25 μm to 0.60 μm.
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