WO2010140868A2 - Barium titanate powder coated with an oxide layer, and a production method therefor - Google Patents
Barium titanate powder coated with an oxide layer, and a production method therefor Download PDFInfo
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- WO2010140868A2 WO2010140868A2 PCT/KR2010/003613 KR2010003613W WO2010140868A2 WO 2010140868 A2 WO2010140868 A2 WO 2010140868A2 KR 2010003613 W KR2010003613 W KR 2010003613W WO 2010140868 A2 WO2010140868 A2 WO 2010140868A2
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- barium titanate
- titanate powder
- oxide layer
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- 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 132
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 132
- 239000000843 powder Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- 239000000243 solution Substances 0.000 claims description 74
- 239000002002 slurry Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 47
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910052727 yttrium Inorganic materials 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000003985 ceramic capacitor Substances 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 229910052720 vanadium Inorganic materials 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000002003 electrode paste Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 12
- 239000007858 starting material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 86
- 238000004448 titration Methods 0.000 description 50
- 238000010992 reflux Methods 0.000 description 25
- 239000000654 additive Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910007926 ZrCl Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052692 Dysprosium Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000002075 main ingredient Substances 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 229910009523 YCl3 Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- 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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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
Definitions
- the present invention provides a ceramic raw material powder having an oxide layer composed of a minor ingredient additive on the surface of particles of a main ingredient raw material powder composed of barium titanate (BaTiO 3 ) (hereinafter referred to as 'main ingredient particles'), and the raw material powder.
- the present invention relates to a method of manufacturing a ceramic raw material powder which can be easily manufactured when forming a dielectric ceramic composition such as a dielectric layer of a multilayer ceramic capacitor (MLCC).
- MLCC multilayer ceramic capacitor
- Multilayer Ceramic Capacitors are widely used as small, large-capacity, high-reliability electronic components, and many types and quantities are used in one electronic device.
- a multilayer ceramic capacitor is usually produced by laminating and baking a paste for an internal electrode layer and a paste for a dielectric layer by using a sheet method or a printing method.
- the conductive material of the internal electrode layer As the conductive material of the internal electrode layer, a relatively inexpensive base metal such as Ni or Ni alloy is used. In the case of using a nonmetal as the conductive material for the internal electrode layer, since the internal electrode layer oxidizes when firing in the air, it is necessary to perform simultaneous firing of the dielectric layer and the internal electrode layer in a reducing atmosphere. However, when firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance is lowered. Therefore, a non-reducing dielectric material has been proposed.
- X7R characteristics As a non-reducing dielectric material, X7R characteristics (currently defined by EIAJ (Japan Electromechanical Association)) (with a capacitance change rate of less than ⁇ 15% based on 25 ° C in a temperature range of -55 ° C to 125 ° C), or It is mainstream that the temperature stability of the electrostatic capacity which satisfies the B characteristic prescribed
- This problem is a cause of serious defects in the dielectric constant and insulation resistance of the multilayer ceramic capacitor, characteristics related to load life, quality and reliability. For this reason, in order to ensure the characteristic, quality, and reliability of the above-mentioned ceramic electronic components, uniform dispersion of the main component BaTiO 3 and the subcomponent additives is indispensable.
- the temperature stability of the capacitance that satisfies both the X7R characteristics defined by the EIAJ standard and the B characteristics specified by the JIS standard is satisfactory, the characteristics such as insulation resistance value and relative dielectric constant are good, and the accelerated life of the insulation resistance is good.
- a main raw material used to obtain an electronic product such as a long laminated ceramic capacitor (MLCC)
- additives capable of exerting the above functions are formed on the surface of the metal oxide coated layer. It is an object of the present invention to provide a barium titanate powder coated with a metal oxide capable of improving dispersibility and a method of manufacturing the same.
- Barium titanate powder according to the present invention is an oxide layer formed by uniformly dispersing at least one material selected from Si, Y, V, Dy, Mg, Mn, Ni, Co and Zr on the surface of the barium titanate (BaTiO 3 ) particles 1 It is characterized by being coated over a layer.
- the particle radius (r) of the barium titanate particles is characterized in that 40 to 400nm
- the oxide layer is characterized in that consisting of 0.01 to 15% by weight relative to the weight of the barium titanate particles
- the oxide layer is characterized in that 0.01 ⁇ 30nm
- the oxide layer is characterized in that formed by hydrothermal hydrolysis reaction.
- the barium titanate powder according to an embodiment of the present invention is characterized in that the SiO 2 layer is coated on the surface of the barium titanate (BaTiO 3 ) particles.
- an oxide layer formed by uniformly dispersing one or more materials selected from Y, V, Dy, Mg, Mn, Ni, Co, and Zr is further coated on the SiO 2 layer.
- the SiO 2 layer and the oxide layer are each formed by hydrothermal hydrolysis.
- the multilayer ceramic capacitor (MLCC) according to the present invention is characterized in that the barium titanate powder described above.
- the method for producing a barium titanate powder coated with an oxide layer comprises the steps of adding a barium titanate powder to a reactor containing water and stirring to form a first slurry, and the Si, Y, Titrating a diluent in which a compound composed of at least one selected from V, Dy, Mg, Mn, Ni, Co, and Zr is dissolved to form a second slurry, and dehydrating (concentrating) and washing the second slurry. And removing the foreign matter and heat-treating the remaining solids.
- the first slurry is characterized in that it further comprises the step of heating to 70 ⁇ 90 °C, pH of the second slurry when titrating a diluent in which the oxide composed of Si in the second slurry is titrated Is maintained at 5.0 to 14.0, and the diluent in which the oxide made of Si is dissolved is used as water glass, and Si, Y, V, Dy, Mg, and Mn are used in the second slurry.
- the titration of the second slurry is maintained at 5.0 to 14.0 when titrating a dilution solution of an oxide composed of at least one selected from Ni, Co, and Zr, wherein the Y, V, Dy,
- the diluent in which an oxide composed of at least one material selected from Mg, Mn, Ni, Co, and Zr is dissolved is used as an aqueous solution composed of one selected from chloride, nitrate and sulfate.
- the pH is maintained by using one selected from HCl, H 2 SO 4 , HNO 3 , NaOH and KOH, and further comprising the step of stirring for 10 to 60 minutes after the composition of the second slurry Characterized in that, the heat treatment step comprises the step of maintaining for 20 to 120 minutes at a temperature of 125 ⁇ 1300 °C, the thickness of the oxide layer is Si, Y, V, Dy, Mg, Mn It is characterized by determining by adjusting the addition amount of Ni, Co and Zr compounds.
- the method for manufacturing a multilayer ceramic capacitor raw material is performed by dispersing an oxide layer-coated barium titanate powder in water as an internal electrode layer paste or a dielectric layer paste. It is characterized by forming.
- the present invention is to prepare a barium titanate powder composed of an oxide layer (Si, Y, V, Dy, Mg, Mn, Ni, Co and Zr) oxide layer on the surface of the barium titanate (BaTiO 3 ) particles of the main component, the secondary component oxide
- the thickness of the layer within the range of 0.01 to 30 nm, it satisfies both the X7R characteristic defined by the EIAJ standard and the B characteristic defined by the JIS standard, the temperature stability of the capacitance is good, and characteristics such as insulation resistance value and relative dielectric constant. This provides an effect of making it possible to manufacture a raw material for an electronic component having a good and long life of accelerated insulation resistance.
- the barium titanate powder coated with the oxide layer to easily form an electronic material such as a multilayer ceramic capacitor (MLCC), it provides an effect of improving the production efficiency and cost.
- MLCC multilayer ceramic capacitor
- FIG. 1 is a cross-sectional view schematically showing a barium titanate powder coated with an oxide layer according to the present invention.
- FIG. 2 is a TEM photograph showing a barium titanate powder coated with an oxide layer according to the present invention.
- FIG. 3 is a TEM photograph showing an enlarged surface of an oxide layer-coated barium titanate powder according to the present invention.
- FIG. 5 is a graph illustrating the line scan results of FIG. 4.
- FIG. 6 is a TEM photograph showing a barium titanate powder coated with a Dy 2 O 3 metal oxide layer according to the present invention.
- FIG. 7 is a graph illustrating the line scan results of FIG. 6.
- FIG. 10 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Dy 2 O 3 oxide layer according to the present invention.
- FIG. 11 is a graph illustrating a line scan result of FIG. 10.
- FIG. 12 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Y 2 O 3 oxide layer according to the present invention.
- FIG. 13 is a graph illustrating a line scan result of FIG. 12.
- 16 and 17 are E-SEM photographs showing the results of heat treatment on SiO 2 coated barium titanate powder according to an embodiment of the present invention.
- 22 and 23 are E-SEM photographs showing the results of heat treatment on the MgO-coated barium titanate powder according to an embodiment of the present invention.
- a coating layer made of subcomponent elements is formed on the surface of each ceramic main component particle, and the subcomponent elements are also homogeneously distributed so as to form a coating layer.
- a liquid solution containing the sub ingredient additive is precipitated in the main ingredient powder, and a liquid method is used so that the sub ingredient is directly and uniformly coated on the surface of the main ingredient.
- an oxide layer composed of subsidiary additives is coated on the surface of a main component particle composed of barium titanate.
- FIG. 1 is a cross-sectional view schematically showing a barium titanate powder coated with an oxide layer according to the present invention.
- the average radius of the barium titanate (BaTiO 3 ) particles 100 as the main component particles constituting the ceramic raw material powder is r.
- r is set to 40 to 400 nm, and ⁇ r is controlled within a range of 0.01 to 30 nm. At this time, more preferably, r is formed in the range of 50 to 200 nm, and ⁇ r is preferably formed in the range of 0.1 to 10 nm.
- the thickness of the oxide layer 110 when the thickness of the oxide layer 110 is formed to be less than 0.01 nm, the dispersion characteristics may be degraded.
- the thickness of the oxide layer 110 is formed to be greater than 30 nm, the temperature stability is good, and the characteristics such as insulation resistance and relative dielectric constant decrease. As such, it is desirable to comply with the scope provided by the present invention.
- the coating amount of the oxide layer 110 is preferably in the range of 0.01 to 15% by weight relative to the barium titanate particles. Most suitably 0.05 to 5% by weight is preferred. When the coating amount is added in less than 0.01% by weight, the oxide layer 110 of the desired thickness cannot be obtained. When the coating amount is more than 15% by weight, the thickness of the oxide layer 110 may be non-uniformly provided. It is desirable to comply with the range.
- FIG. 2 is a TEM photograph showing a barium titanate powder coated with an oxide layer according to the present invention.
- barium titanate powders are shown, and when one of the barium titanate particles is examined, an oxide layer is transparently formed on the outside.
- FIG. 3 is a TEM photograph showing an enlarged surface of an oxide layer-coated barium titanate powder according to the present invention.
- an SiO 2 layer is formed as an oxide layer on the surface of one barium titanate (BaTiO 3 ) particles included in the barium titanate powder.
- the barium titanate powder as described above has a process of coating the main component particles in a hydroxide state, a process of dehydrating, washing with water, and heat treating the solution, and having a process of forming a hydroxide into an oxide layer in the form of a solid by heat treatment.
- the dielectric properties of the barium titanate powder is adjusted.
- At least one selected from Si, Dy, Y, Mg, V, Mn, Ni, Co and Zr is dispersed on the surface of the barium titanate to form an oxide layer.
- an oxide layer By forming such an oxide layer, it is possible to compensate the barium titanate, which has been miniaturized and whose dispersion characteristics are reduced.
- additives that can improve temperature stability, insulation resistance, relative dielectric constant, accelerated life of insulation resistance, and the like as subcomponent elements, depending on the dispersion state of barium titanate particles, Their dispersion characteristics can also be adjusted.
- SiO 2 is formed on the surface of the barium titanate particles as a first layer, and a coating for laminating at least one metal oxide selected from Dy, Y, Mg, V, Mn, Ni, Co, and Zr materials
- a method may be used, and as another embodiment, a method of mixing 2 to 8 materials to form an oxide and coating the same may be used.
- the total thickness of the oxide layer is 0.01 to 30 nm. It is desirable to.
- Si may be used as Water Glass
- Dy is DyCl 3 , Dy (NO 3 ) 3 and Dy 2 (SO 4 ) 3
- Y is YCl 3 and Y ( NO 3 ) 3
- Mg is MgCl 2 , Mg (NO 3 ) 2 and Mg (SO 4 )
- V is VO (SO 4 ) and VOCl 2
- Mn is MnCl 2 , Mn (NO 3 ) 2 and Mn (SO 4)
- Ni is NiCl 2 , Ni (NO 3 ) 2 and Ni (SO 4 )
- Co is CoCl 2 , Co (NO 3 ) 2 and Co (SO 4 )
- Zr is ZrCl 2 , Zr (NO 3 ) 2 and Zr (SO 4 ) can be used.
- Si sodium silicate
- Dy is DyCl 3
- Y is YCl 3
- Mg is MgCl 2
- V is VO (SO 4 )
- Ni NiCl 2
- Co Co (SO 4 )
- Zr is easy to use ZrCl 2 .
- pH adjusting solutions include HCl, H 2 SO 4 , H (NO 3 ) 3 as acidic solutions, and NaOH and KOH as alkaline solutions.
- the oxide-coated barium titanate powder according to the present invention and a manufacturing method thereof are made of compositions of Si, Dy, Y, Mg, V, Mn, Ni, Co, and Zr on the surface of spherical barium titanate particles.
- the coating layer on which the oxide layer is formed and various methods for improving the physical properties of the dielectric are presented.
- the present invention is different from the conventional method of coating using a hydrothermal hydrolysis method, unlike the dry and wet mixing (mixing) method, it is possible to apply a uniform surface and to stack or simultaneously coat several different metal oxides in multiple layers. It is a new technology.
- the oxide layer-coated barium titanate powder is easy to be used to make an ultra-small, high capacity, high efficiency multilayer ceramic capacitor (MLCC).
- MLCC multilayer ceramic capacitor
- the aqueous solution of sodium hydroxide was added to raise the pH of the slurry to 5.0 to 10.0, and 100 g of sodium silicon solution (5.0% of SiO 2 content) was weighed and then fixed over about 1 hour. Titrate at speed. At this time, pH 5.0 to 10.0 is kept constant with a dilution solution of 10 to 30% HCl.
- the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range.
- the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor.
- [Formula 1] shows the reaction that the pH is adjusted as HCl is added.
- Forma 2 shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
- calcination was performed at a temperature increase rate of 200 ° C./hour, a holding temperature of 650 ° C., a holding time of 30 minutes, a temperature reduction time of 150 ° C./hour, and a treatment atmosphere.
- the pH is kept constant with 10-50% sodium hydroxide solution.
- the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor.
- ZrO 2 -coated barium titanate powder was synthesized by treating the slurry in which titration was completed in the same manner as in Example 1.
- [Formula 4] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
- the pH is kept constant with 10-50% sodium hydroxide solution.
- the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor.
- DyCl 3 solution is titrated rather than the basis weight after the YCl 3 solution (YCl 3 50.0g / L) 100g .
- the pH was kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred for 30 minutes to reflux.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with V 2 O 5 .
- NiCl 2 solution instead of DyCl 3 solution after the same treatment as in Example 2 (NiCl 2 50.0 g / L)
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with NiO.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with CoO.
- the coated SiO 2 may be eluted, so it is slowly increased at a constant rate.
- ZrCl 2 solution 100 g of ZrCl 2 solution (ZrCl 2 50.0 g / L) is titrated in basis weight. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and ZrO 2 .
- the coated SiO 2 may be eluted, so it is slowly increased at a constant rate.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and Dy 2 O 3 .
- Example 11 and treated in the same manner and, DyCl 3 solution is titrated rather than the basis weight after the YCl 3 solution (YCl 3 50.0g / L) 100g . During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and Y 2 O 3 .
- Example 11 The same treatment as in Example 11 was carried out, followed by titration of 100 g of MgCl 2 solution (MgCl 2 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and MgO.
- Example 11 The same treatment as in Example 11 was carried out after the basis weight of 100 g of VO (SO 4 ) solution (VO (SO 4 ) 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with SiO 2 and V 2 O 5 .
- Example 11 The same treatment as in Example 11 was carried out, followed by titration of 100 g of NiCl 2 solution (NiCl 2 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and NiO 2 .
- Example 11 The same treatment as in Example 11 was carried out after the basis weight of 100 g of MnCl 2 solution (NiCl 2 50.0 g / L) instead of the DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with SiO 2 and MnO 2 .
- Example 11 The same treatment as in Example 11 was carried out after the basis weight of 100 g of Co (SO 4 ) solution (Co (SO 4 ) 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- ZrCl 2 solution (ZrCl 2 50.0 g / L), which is the treatment method of Example 2, is weighed and titrated at a constant rate over 1 hour. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with ZrO 2 and SiO 2 .
- Example 2 After the same treatment as in Example 2, the pH was raised to 6.0 to 12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder sequentially coated with ZrO, Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. .
- Example 2 After the same treatment as in Example 2, the pH was raised to 6.0 to 12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
- the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO.
- the rest may be mixed to form a coating layer.
- Example 18 After the same treatment as in Example 18, the pH was raised to 6.0-12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
- Example 2 the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, SiO 2 , Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. It was. At this time, ZrO, SiO 2 is first coated, and then the remaining materials are sequentially coated.
- Example 18 After the same treatment as in Example 18, the pH was raised to 6.0-12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
- the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, SiO 2 , Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. It was. At this time, ZrO, SiO 2 may be coated first, and then the remainder may be mixed to form a coating layer.
- the barium titanate powder coated with the oxide layer according to the present invention includes various embodiments that can improve the physical properties of the dielectric.
- the oxide layer according to the present invention is uniformly formed by hydrothermal hydrolysis, thereby further improving the dispersibility of the barium titanate powder.
- FIG. 4 is a TEM photograph showing a barium titanate powder coated with SiO 2 according to the present invention
- FIG. 5 is a graph showing the line scan result of FIG. 4.
- FIG. 6 is a TEM photograph showing a barium titanate powder coated with a Dy 2 O 3 metal oxide layer according to the present invention
- FIG. 7 is a graph showing the line scan result of FIG. 6.
- FIG. 6 a barium titanate powder coated with a single layer of Dy 2 O 3 metal oxide layer is shown, and FIG. 7 shows a distribution of Dy while scanning along a cross section of barium titanate particles of one of the powders. Referring to FIG. 7, it can be seen that Dy is evenly distributed.
- FIG. 8 illustrates the number of Dy detected at one point of the cross section of FIG. 7, and FIG. 9 illustrates the number of Dy detected at two points. It can be seen that the detection result is uniformly shown as shown.
- FIG. 10 is a TEM photograph showing a barium titanate powder coated with SiO 2 and Dy 2 O 3 oxide layers according to the present invention
- FIG. 11 is a graph showing the line scan results of FIG. 10.
- FIG. 10 SiO 2 , Dy 2 O 3 A barium titanate powder coated with a double layer of a metal oxide layer is shown, and FIG. 11 shows a distribution of Dy and Si while scanning along a cross section of barium titanate particles of one of the powders.
- FIG. 12 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Y 2 O 3 oxide layer according to the present invention
- FIG. 13 is a graph showing the line scan result of FIG. 12.
- FIG. 12 a barium titanate powder coated with a double layer of SiO 2 and Y 2 O 3 oxide layers is shown, and FIG. 13 shows a distribution of Y and Si while scanning along a cross section of barium titanate particles of one of the powders.
- Y and Si are evenly distributed.
- Figure 15 is a photograph taken after the heat treatment of the barium titanate powder in the form of a bulk without an oxide layer for 30 minutes at a temperature of 125 °C
- Figure 15 is a photograph taken after the heat treatment for 30 minutes at a temperature of 1250 °C.
- the boundary between particles is distinct and has a regular distribution.
- FIG. 16 and 17 show the results of heat treatment on SiO 2 coated barium titanate powder according to an embodiment of the present invention
- Figures 18 and 19 is a titanic acid coated Dy 2 O 3 according to an embodiment of the present invention
- FIG. 20 and FIG. 21 show the results of the heat treatment on the barium titanate powder coated with Y 2 O 3 according to the embodiment of the present invention
- FIGS. 22 and 23 show the results of the heat treatment on the barium powder.
- Eg shows the results of the heat treatment to the MgO-coated barium titanate powder
- Figures 24 and 25 is a heat treatment to the V 2 O 5 -coated barium titanate powder according to an embodiment of the present invention SEM pictures.
- the barium titanate powder according to the present invention has a uniform oxide coating layer, and thus the powder distribution can be uniform.
- the powders of the uniform particles are also improved in properties such as temperature stability, insulation resistance, relative dielectric constant and accelerated life of the insulation resistance in proportion to the uniformity.
- a paste for internal electrode layers or a paste for dielectric layers used to make an ultra-small, high-capacity, high-efficiency multilayer ceramic capacitor (MLCC) can be obtained. It can be formed easily.
- the present invention can be utilized in manufacturing a more versatile and highly efficient multilayer ceramic capacitor (MLCC).
- MLCC multilayer ceramic capacitor
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Abstract
The present invention relates to a barium titanate powder coated with an oxide layer and to a production method therefor, wherein the barium titanate powder consists of an auxiliary component oxide layer coated onto the surface of a barium titanate particle constituting the main component, and in which the thickness of the oxide layer constituting the auxiliary component is adjusted to be in a range of from 0.01 to 30 nm, in order to produce a starting material for electronic products which satisfy both the X7R characteristics stipulated in the EIAJ standards and the B characteristics stipulated in the JIS standards, which have good temperature stability capacitance and insulation resistance values, good relative dielectric constants, and the insulation resistance has a lengthy accelerated lifetime.
Description
본 발명은 티탄산바륨(BaTiO3)으로 이루어지는 주성분 원료 분체의 입자(이하, ‘주성분 입자’라고 한다)의 표면에, 부성분 첨가물로 이루어지는 산화물층을 가지는 세라믹(Ceramic) 원료 분말과, 상기 원료 분말을 이용하여 적층세라믹콘덴서(Multi Layer Ceramic Condenser; MLCC)의 유전체층과 같은 유전체 자기 조성물 형성 시 제조가 용이해 질 수 있도록 하는 세라믹 원료 분말 제조 방법에 관한 것이다.The present invention provides a ceramic raw material powder having an oxide layer composed of a minor ingredient additive on the surface of particles of a main ingredient raw material powder composed of barium titanate (BaTiO 3 ) (hereinafter referred to as 'main ingredient particles'), and the raw material powder. The present invention relates to a method of manufacturing a ceramic raw material powder which can be easily manufactured when forming a dielectric ceramic composition such as a dielectric layer of a multilayer ceramic capacitor (MLCC).
적층세라믹콘덴서(MLCC)는 소형, 대용량, 고 신뢰성의 전자 부품으로서 널리 이용되고 있고, 한 대의 전자기기에 사용되는 종류 및 수량도 다수에 이른다. Multilayer Ceramic Capacitors (MLCC) are widely used as small, large-capacity, high-reliability electronic components, and many types and quantities are used in one electronic device.
전자기기의 소형화 및 고성능화가 진행됨에 따라서, 고용량의 적층세라믹콘덴서가 필요하게 되었다. 이와 같은 필요성이 증가됨에 따라 고용량 적층세라믹콘덴서를 제조하기 위하여, 주성분인 BaTiO3의 입경이 300nm이상에서 200nm이하로 감소될 것을 요구하고 있다.As miniaturization and high performance of electronic devices progress, high capacity multilayer ceramic capacitors are required. As such a necessity increases, in order to manufacture a high capacity multilayer ceramic capacitor, it is required that the particle diameter of the main component BaTiO 3 be reduced from 300 nm or more to 200 nm or less.
그러나, 입경이 작아질 경우 부성분의 균질 분산이 더욱 어려워지므로, 부성분의 균질혼합에 의한 규격에 부합되는 적층세라믹콘덴서(MLCC)를 제조하기 위한 방법들이 새롭게 제시되고 있다.However, since the homogeneous dispersion of the subcomponents becomes more difficult when the particle size is small, new methods for manufacturing a multilayer ceramic capacitor (MLCC) that meet the specifications by homogeneous mixing of the subcomponents have been newly proposed.
적층세라믹콘덴서(MLCC)는 통상 내부 전극층 용의 페이스트(paste)와 유전체 층용의 페이스트(paste)를, 시트(sheet)법이나 인쇄법을 이용하여 적층하고, 소성가공하여 제조된다. A multilayer ceramic capacitor (MLCC) is usually produced by laminating and baking a paste for an internal electrode layer and a paste for a dielectric layer by using a sheet method or a printing method.
내부 전극층의 도전재에는 비교적 값싼 Ni이나 Ni합금과 같은 비금속이 사용 되어있다. 내부 전극층의 도전재용으로서 비금속을 이용하는 경우, 대기 중에서 소성을 진행하게 되면 내부 전극층이 산화해 버리기 때문에, 유전체층과 내부 전극 층과의 동시 소성을, 환원성 분위기속에서 행할 필요가 있다. 그러나, 환원성 분위기속에서 소성한다면, 유전체 층이 환원되고, 비저항이 낮아져 버리기 때문에, 비환원성의 유전체 재료가 제안되어 있다.As the conductive material of the internal electrode layer, a relatively inexpensive base metal such as Ni or Ni alloy is used. In the case of using a nonmetal as the conductive material for the internal electrode layer, since the internal electrode layer oxidizes when firing in the air, it is necessary to perform simultaneous firing of the dielectric layer and the internal electrode layer in a reducing atmosphere. However, when firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance is lowered. Therefore, a non-reducing dielectric material has been proposed.
비환원성의 유전체 재료로서, 현재 EIAJ(일본 전자 기계 공업 회 규약)으로 규정하는 X7R 특성(-55℃ ∼ 125℃의 온도 범위에서, 25℃를 기준에 정전 용량 변화율이 ±15% 이내), 또는 JIS 규격으로 규정하는 B 특성(-25 ∼ 85℃의 온도 범위에서, 20℃를 기준에 정전 용량 변화율이 ±10% 이내)을 만족한다고 한 정전 용량의 온도 안정성의 양호한 것이 주류로 되어 있다.As a non-reducing dielectric material, X7R characteristics (currently defined by EIAJ (Japan Electromechanical Association)) (with a capacitance change rate of less than ± 15% based on 25 ° C in a temperature range of -55 ° C to 125 ° C), or It is mainstream that the temperature stability of the electrostatic capacity which satisfies the B characteristic prescribed | regulated by the JIS standard (the capacitance change rate within ± 10% based on 20 degreeC in the temperature range of -25-85 degreeC) is the mainstream.
그러나, 고용량의 적층세라믹콘덴서를 제조하기 위하여 유전체층의 박층화가 절실히 요구되고 이에 따라 주성분인 BaTiO3 입자의 나노화가 진행되고 있으며, 이에 따라, 유전체층을 구성하는 부성분 첨가물의 분산 불균일성이 저하되는 문제가 발생하고 있다.However, in order to manufacture a high capacity multilayer ceramic capacitor, there is an urgent need for thinning of the dielectric layer, and accordingly, the nanomaterialization of BaTiO 3 particles as a main component is progressing, and thus, a problem of deterioration in dispersion non-uniformity of subsidiary additives constituting the dielectric layer occurs. Doing.
상기 문제는 적층세라믹콘덴서의 유전율 및 절연 저항치, 부하 수명에 관한 특성, 품질, 신뢰성 등에 중대한 결함을 가져오는 원인이 된다. 이 때문에, 상기와 같은 세라믹스(Ceramics) 전자부품의 특성, 품질, 신뢰성을 확보하기 위해서는, 주성분 BaTiO3와 부성분 첨가물의 균일한 분산이 필수 불가결하다. This problem is a cause of serious defects in the dielectric constant and insulation resistance of the multilayer ceramic capacitor, characteristics related to load life, quality and reliability. For this reason, in order to ensure the characteristic, quality, and reliability of the above-mentioned ceramic electronic components, uniform dispersion of the main component BaTiO 3 and the subcomponent additives is indispensable.
종래기술로 부성분 첨가물의 불균일 혼합을 억제하는 방법으로서, 미세한 부성분 첨가물을 이용하는 방법이나, 복수의 부성분 첨가물을 미리 열처리하여 화합물화 한 후에 미세하게 분쇄하고, 첨가하는 방법이 제안 되고 있다. 이러한 방법으로 제조되는 유전체층을 이용하면, 어느 정도는 특성, 품질, 신뢰성 저하 문제를 억제할 수 있다.As a method of suppressing nonuniform mixing of subsidiary ingredient additives in the prior art, a method of using fine subsidiary ingredient additives, or a method of finely grinding and adding a plurality of subsidiary ingredient additives in advance after heat treatment has been proposed. By using the dielectric layer produced in this way, the problem of deterioration in characteristics, quality and reliability can be suppressed to some extent.
그러나, 부성분 첨가물의 입경을 미세화 하는 것 자체가 어렵고, 입경이 미세해질 경우 응집이 생기기 쉽기 때문에, 근본적인 해결 방법으로 인정되고 있지 않는 실정이다.However, it is difficult to refine the particle size of the subsidiary ingredient additive itself, and when the particle size becomes fine, coagulation tends to occur, which is not recognized as a fundamental solution.
본 발명에서는 EIAJ 규격으로 규정하는 X7R 특성 및 JIS 규격으로 규정하는 B 특성이 모두 만족하는 정전 용량의 온도 안정성이 양호하고, 절연 저항치, 비유전율 등의 특성이 양호하고, 또한 절연 저항의 가속 수명이 긴 적층세라믹콘덴서(MLCC)등의 전자제품을 얻기 위하여 사용되는 주원료인 BaTiO3표면에 상기 각각의 기능을 발휘 할 수 있는 첨가제들이 균일하게 분산된 금속산화물이 코팅된층을 형성함으로써, 주원료 분체의 분산성을 향상시킬 수 있도록 하는 금속산화물이 코팅된 티탄산바륨 분말 및 이를 제조하는 방법을 제공하는 것을 그 목적으로 한다.In the present invention, the temperature stability of the capacitance that satisfies both the X7R characteristics defined by the EIAJ standard and the B characteristics specified by the JIS standard is satisfactory, the characteristics such as insulation resistance value and relative dielectric constant are good, and the accelerated life of the insulation resistance is good. On the surface of BaTiO 3 , a main raw material used to obtain an electronic product such as a long laminated ceramic capacitor (MLCC), additives capable of exerting the above functions are formed on the surface of the metal oxide coated layer. It is an object of the present invention to provide a barium titanate powder coated with a metal oxide capable of improving dispersibility and a method of manufacturing the same.
본 발명에 따른 티탄산바륨 분말은 티탄산바륨(BaTiO3) 입자의 표면에 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질이 균일하게 분산되어 이루어지는 산화물층이 1층 이상 코팅되어 있는 것을 특징으로 한다.Barium titanate powder according to the present invention is an oxide layer formed by uniformly dispersing at least one material selected from Si, Y, V, Dy, Mg, Mn, Ni, Co and Zr on the surface of the barium titanate (BaTiO 3 ) particles 1 It is characterized by being coated over a layer.
여기서, 상기 티탄산바륨 입자의 입자반경(r)은 40 ~ 400nm인 것을 특징으로 하고, 상기 산화물층은 상기 티탄산바륨 입자의 중량대비 0.01 ~ 15중량%로 이루이지는 것을 특징으로 하고, 상기 산화물층의 총 두께(△r)는 0.01 ~ 30nm인 것을 특징으로 하고, 상기 산화물층은 수열가수분해반응에 의해 형성되는 것을 특징으로 한다.Here, the particle radius (r) of the barium titanate particles is characterized in that 40 to 400nm, the oxide layer is characterized in that consisting of 0.01 to 15% by weight relative to the weight of the barium titanate particles, the oxide layer The total thickness of △ r is characterized in that 0.01 ~ 30nm, the oxide layer is characterized in that formed by hydrothermal hydrolysis reaction.
아울러, 본 발명의 일실시예에 따른 티탄산바륨 분말은 티탄산바륨(BaTiO3) 입자의 표면에 SiO2층이 코팅되어 있는 것을 특징으로 한다.In addition, the barium titanate powder according to an embodiment of the present invention is characterized in that the SiO 2 layer is coated on the surface of the barium titanate (BaTiO 3 ) particles.
여기서, 상기 SiO2층의 상부에는 Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질이 균일하게 분산되어 이루어지는 산화물층이 1층 이상 더 코팅되어 있는 것을 특징으로 하고, 상기 SiO2층 및 상기 산화물층은 각각 수열가수분해반응에 의해 형성되는 것을 특징으로 한다.Here, an oxide layer formed by uniformly dispersing one or more materials selected from Y, V, Dy, Mg, Mn, Ni, Co, and Zr is further coated on the SiO 2 layer. The SiO 2 layer and the oxide layer are each formed by hydrothermal hydrolysis.
아울러, 본 발명에 따른 적층세라믹콘덴서(MLCC)는 상술한 티탄산바륨 분말로 이루어지는 것을 특징으로 한다.In addition, the multilayer ceramic capacitor (MLCC) according to the present invention is characterized in that the barium titanate powder described above.
아울러, 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말 제조방법은 물이 담겨있는 반응기에 티탄산바륨 분말을 투입한 후 교반하여 제 1 슬러리를 조성하는 단계와, 상기 제 1 슬러리에 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질로 이루어지는 화합물을 용해시킨 희석액을 적정(滴定)하여 제 2 슬러리를 조성하는 단계 및 상기 제 2 슬러리를 탈수(농축) 및 수세(이물질 제거)하고, 잔류하는 고화물을 열처리하는 단계를 포함하는 것을 특징으로 한다.In addition, the method for producing a barium titanate powder coated with an oxide layer according to the present invention comprises the steps of adding a barium titanate powder to a reactor containing water and stirring to form a first slurry, and the Si, Y, Titrating a diluent in which a compound composed of at least one selected from V, Dy, Mg, Mn, Ni, Co, and Zr is dissolved to form a second slurry, and dehydrating (concentrating) and washing the second slurry. And removing the foreign matter and heat-treating the remaining solids.
여기서, 상기 제 1 슬러리는 70 ~ 90℃까지 가열하는 단계를 더 포함하는 것을 특징으로 하고, 상기 제 2 슬러리에 Si로 이루어지는 산화물을 용해시킨 희석액을 적정(滴定)하는 경우 상기 제 2 슬러리의 pH는 5.0 ~ 14.0으로 유지시키는 것을 특징으로 하고, 상기 Si로 이루어지는 산화물을 용해시킨 희석액은 물유리(Water Glass)를 이용하는 것을 특징으로 하고, 상기 제 2 슬러리에 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질로 이루어지는 산화물을 용해시킨 희석액을 적정(滴定)하는 경우 상기 제 2 슬러리의 pH는 5.0 ~ 14.0로 유지시키는 것을 특징으로 하고, 상기 Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질로 이루어지는 산화물을 용해시킨 희석액은 염화물, 질산염 및 황산염 중 선택된 하나로 이루어지는 수용액을 이용하는 것을 특징으로 하고, 상기 pH는 HCl, H2SO4, HNO3, NaOH 및 KOH 중 선택된 하나를 이용하여 유지시키는 것을 특징으로 하고, 상기 제 2 슬러리를 조성한 후 10 ~ 60분 동안 교반하는 단계를 더 포함하는 것을 특징으로 하고, 상기 열처리 단계는 125 ~ 1300℃의 온도에서 20 ~ 120분 동안 유지시키는 단계를 포함하는 것을 특징으로 하고, 상기 산화물층의 두께는 상기 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr화합물의 첨가량을 조절하여 결정하는 것을 특징으로 한다.Here, the first slurry is characterized in that it further comprises the step of heating to 70 ~ 90 ℃, pH of the second slurry when titrating a diluent in which the oxide composed of Si in the second slurry is titrated Is maintained at 5.0 to 14.0, and the diluent in which the oxide made of Si is dissolved is used as water glass, and Si, Y, V, Dy, Mg, and Mn are used in the second slurry. The titration of the second slurry is maintained at 5.0 to 14.0 when titrating a dilution solution of an oxide composed of at least one selected from Ni, Co, and Zr, wherein the Y, V, Dy, The diluent in which an oxide composed of at least one material selected from Mg, Mn, Ni, Co, and Zr is dissolved is used as an aqueous solution composed of one selected from chloride, nitrate and sulfate. The pH is maintained by using one selected from HCl, H 2 SO 4 , HNO 3 , NaOH and KOH, and further comprising the step of stirring for 10 to 60 minutes after the composition of the second slurry Characterized in that, the heat treatment step comprises the step of maintaining for 20 to 120 minutes at a temperature of 125 ~ 1300 ℃, the thickness of the oxide layer is Si, Y, V, Dy, Mg, Mn It is characterized by determining by adjusting the addition amount of Ni, Co and Zr compounds.
아울러, 본 발명에 따른 적층세라믹콘덴서 원료 제조방법은 상술한 방법으로 제조된 산화물층이 코팅된 티탄산바륨 분말을 물(Aqua)에 분산시켜 내부 전극층용 페이스트(Paste) 또는 유전체층용 페이스트(Paste)로 형성하는 것을 특징으로 한다.In addition, according to the present invention, the method for manufacturing a multilayer ceramic capacitor raw material is performed by dispersing an oxide layer-coated barium titanate powder in water as an internal electrode layer paste or a dielectric layer paste. It is characterized by forming.
본 발명은 주성분인 티탄산바륨(BaTiO3) 입자의 표면에 부성분(Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr) 산화물층으로 구성되어지는 티탄산바륨 분말을 제조하되, 부성분 산화물층의 두께를 0.01 ~ 30nm의 범위 내에 제어함으로써, EIAJ 규격으로 규정하는 X7R 특성 및 JIS 규격으로 규정하는 B 특성을 모두 만족시키고, 정전 용량의 온도 안정성이 양호하고, 절연 저항치, 비유전율 등의 특성이 양호하고, 절연 저항의 가속 수명이 긴 전자부품용 원료를 제조할 수 있도록 하는 효과를 제공한다.The present invention is to prepare a barium titanate powder composed of an oxide layer (Si, Y, V, Dy, Mg, Mn, Ni, Co and Zr) oxide layer on the surface of the barium titanate (BaTiO 3 ) particles of the main component, the secondary component oxide By controlling the thickness of the layer within the range of 0.01 to 30 nm, it satisfies both the X7R characteristic defined by the EIAJ standard and the B characteristic defined by the JIS standard, the temperature stability of the capacitance is good, and characteristics such as insulation resistance value and relative dielectric constant. This provides an effect of making it possible to manufacture a raw material for an electronic component having a good and long life of accelerated insulation resistance.
아울러, 상기 산화물층이 코팅된 티탄산바륨 분말을 사용하여 적층세라믹콘덴서(MLCC)와 같은 전자 소재를 용이하게 형성함으로써, 생산 효율 향상 및 원가를 절감시킬 수 있는 효과를 제공한다.In addition, by using the barium titanate powder coated with the oxide layer to easily form an electronic material such as a multilayer ceramic capacitor (MLCC), it provides an effect of improving the production efficiency and cost.
도 1은 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말을 모식적으로 나타낸 단면도.1 is a cross-sectional view schematically showing a barium titanate powder coated with an oxide layer according to the present invention.
도 2는 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진.2 is a TEM photograph showing a barium titanate powder coated with an oxide layer according to the present invention.
도 3은 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말의 표면을 확대하여 나타낸 TEM 사진.3 is a TEM photograph showing an enlarged surface of an oxide layer-coated barium titanate powder according to the present invention.
도 4는 본 발명에 따라서 SiO2가 코팅된 티탄산바륨 분말을 나타낸 TEM 사진.4 is a TEM photograph showing a barium titanate powder coated with SiO 2 according to the present invention.
도 5는 상기 도 4의 라인 스캔 결과를 나타낸 그래프.5 is a graph illustrating the line scan results of FIG. 4.
도 6은 본 발명에 따라서 Dy2O3 금속산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진.6 is a TEM photograph showing a barium titanate powder coated with a Dy 2 O 3 metal oxide layer according to the present invention.
도 7은 상기 도 6의 라인 스캔 결과를 나타낸 그래프.7 is a graph illustrating the line scan results of FIG. 6.
도 8 및 도 9는 상기 도 7의 라인 스캔 결과 중 Dy 분포를 분석한 그래프들.8 and 9 are graphs analyzing Dy distribution among the line scan results of FIG. 7.
도 10은 본 발명에 따라서 SiO2 및 Dy2O3 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진.10 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Dy 2 O 3 oxide layer according to the present invention.
도 11은 상기 도 10의 라인 스캔 결과를 나타낸 그래프.FIG. 11 is a graph illustrating a line scan result of FIG. 10. FIG.
도 12는 본 발명에 따라서 SiO2 및 Y2O3 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진.12 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Y 2 O 3 oxide layer according to the present invention.
도 13은 상기 도 12의 라인 스캔 결과를 나타낸 그래프.FIG. 13 is a graph illustrating a line scan result of FIG. 12. FIG.
도 14 및 도 15는 본 발명의 비교예에 따른 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.14 and 15 are E-SEM photographs showing the results of heat treatment to the barium titanate powder according to a comparative example of the present invention.
도 16 및 도 17은 본 발명의 실시예에 따른 SiO2가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.16 and 17 are E-SEM photographs showing the results of heat treatment on SiO 2 coated barium titanate powder according to an embodiment of the present invention.
도 18 및 도 19는 본 발명의 실시예에 따른 Dy2O3가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.18 and 19 are E-SEM photographs showing the results of heat treatment on Dy 2 O 3 -coated barium titanate powder according to an embodiment of the present invention.
도 20 및 도 21은 본 발명의 실시예에 따른 Y2O3가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.20 and 21 are E-SEM photographs showing the results of the heat treatment to the Y 2 O 3 -coated barium titanate powder according to an embodiment of the present invention.
도 22 및 도 23은 본 발명의 실시예에 따른 MgO가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.22 and 23 are E-SEM photographs showing the results of heat treatment on the MgO-coated barium titanate powder according to an embodiment of the present invention.
도 24 및 도 25는 본 발명의 실시예에 따른 V2O5가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들.24 and 25 are E-SEM photographs showing the results of heat treatment on the V 2 O 5 -coated barium titanate powder according to an embodiment of the present invention.
본 발명에서는 보다 근본적인 세라믹 입자의 균질화를 실현하기 위해서, 각각의 세라믹(Ceramic) 주성분 입자 표면에 부성분 원소로 이루어지는 코팅층을 형성하되, 부성분 원소들 또한 균질하게 분포되어 코팅층이 이루어지도록 한다.In the present invention, in order to realize a more fundamental homogenization of the ceramic particles, a coating layer made of subcomponent elements is formed on the surface of each ceramic main component particle, and the subcomponent elements are also homogeneously distributed so as to form a coating layer.
이를 위하여, 주성분과 부성분을 습식 혼합하는 방법을 사용하지 않고, 주성분 분말에 부성분 첨가제가 포함된 액상용액을 침전시켜, 부성분이 주성분의 표면에 직접 균일하게 코팅되도록 하는 액상법을 이용한다.To this end, without using a method of wet mixing the main ingredient and the sub ingredient, a liquid solution containing the sub ingredient additive is precipitated in the main ingredient powder, and a liquid method is used so that the sub ingredient is directly and uniformly coated on the surface of the main ingredient.
이하에서는 상술한 본 발명의 기술에 근거하여 산화물이 코팅된 티탄산바륨 분말 및 이를 제조하는 방법에 대해 상세히 설명하는 것으로 한다.Hereinafter, the barium titanate powder coated with an oxide and a method of preparing the same will be described in detail based on the technology of the present invention described above.
본 발명에 따른 바람직한 실시예로 먼저 티탄산바륨으로 구성되어 지는 주성분 입자의 표면에 부성분 첨가물로 구성되어지는 산화물층을 코팅한다. According to a preferred embodiment of the present invention, first, an oxide layer composed of subsidiary additives is coated on the surface of a main component particle composed of barium titanate.
도 1은 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말을 모식적으로 나타낸 단면도이다.1 is a cross-sectional view schematically showing a barium titanate powder coated with an oxide layer according to the present invention.
도 1을 참조하면, 세라믹(ceramic) 원료 분체를 구성하는 상기 주성분 입자로서 티탄산바륨(BaTiO3) 입자(100)의 평균 반경을 r로 한다.Referring to FIG. 1, the average radius of the barium titanate (BaTiO 3 ) particles 100 as the main component particles constituting the ceramic raw material powder is r.
다음에는, 산화물층(110)의 평균 두께를 △r로 했을 때에, r을 40 ~ 400nm로 하고, △r을 0.01 ~ 30nm의 범위 내에 제어한다. 이때, 더 바람직하게는 r을 50 ~ 200nm의 범위로 형성하고, △r을 0.1 ~ 10nm의 범위로 형성하는 것이 바람직하다. Next, when the average thickness of the oxide layer 110 is Δr, r is set to 40 to 400 nm, and Δr is controlled within a range of 0.01 to 30 nm. At this time, more preferably, r is formed in the range of 50 to 200 nm, and Δr is preferably formed in the range of 0.1 to 10 nm.
여기서, 산화물층(110)의 두께가 0.01nm 미만으로 형성될 경우 분산특성이 저하될 수 있고, 30nm를 초과하는 두께로 형성될 경우 온도 안정성이 양호하고, 절연 저항치, 비유전율 등의 특성이 저하될 수 있으므로, 본 발명에서 제공하는 범위를 준수하는 것이 바람직하다.In this case, when the thickness of the oxide layer 110 is formed to be less than 0.01 nm, the dispersion characteristics may be degraded. When the thickness of the oxide layer 110 is formed to be greater than 30 nm, the temperature stability is good, and the characteristics such as insulation resistance and relative dielectric constant decrease. As such, it is desirable to comply with the scope provided by the present invention.
여기서, 산화물층(110)의 코팅량은 티탄산바륨입자 대비 0.01 ~ 15중량%의 범위가 바람직하다. 가장 적합하게는 0.05 ~ 5중량%가 바람직하다. 코팅량이 0.01중량% 미만으로 첨가될 경우 원하는 두께의 산화물층(110)을 얻을 수 없고, 15중량%를 초과할 경우 산화물층(110)의 두께가 불균일하게 형성될 우려가 있으므로, 본 발명에서 제공하는 범위를 준수하는 것이 바람직하다.Here, the coating amount of the oxide layer 110 is preferably in the range of 0.01 to 15% by weight relative to the barium titanate particles. Most suitably 0.05 to 5% by weight is preferred. When the coating amount is added in less than 0.01% by weight, the oxide layer 110 of the desired thickness cannot be obtained. When the coating amount is more than 15% by weight, the thickness of the oxide layer 110 may be non-uniformly provided. It is desirable to comply with the range.
도 2는 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진이다.2 is a TEM photograph showing a barium titanate powder coated with an oxide layer according to the present invention.
도 2를 참조하면, 티탄산바륨 분말들이 나타나 있으며, 그 중 하나의 티탄산바륨 입자를 살펴보면 외부에 투명하게 산화물층이 형성된 것을 볼 수 있다.Referring to FIG. 2, barium titanate powders are shown, and when one of the barium titanate particles is examined, an oxide layer is transparently formed on the outside.
도 3은 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말의 표면을 확대하여 나타낸 TEM 사진이다.3 is a TEM photograph showing an enlarged surface of an oxide layer-coated barium titanate powder according to the present invention.
도 3을 참조하면, 티탄산바륨 분말 중에 포함된 하나의 티탄산바륨(BaTiO3) 입자의 표면에 산화물층으로서 SiO2층이 형성된 것을 볼 수 있다.Referring to FIG. 3, it can be seen that an SiO 2 layer is formed as an oxide layer on the surface of one barium titanate (BaTiO 3 ) particles included in the barium titanate powder.
상기와 같은 티탄산바륨 분말은 주성분 입자에 수산화물 상태로 코팅하는 공정과, 상기 용액을 탈수, 수세 및 열처리하는 공정을 가지며, 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되도록 하는 공정을 가진다. The barium titanate powder as described above has a process of coating the main component particles in a hydroxide state, a process of dehydrating, washing with water, and heat treating the solution, and having a process of forming a hydroxide into an oxide layer in the form of a solid by heat treatment.
이때, 산화물층을 구성하는 원소의 사용량 및 열처리 온도와 처리시간을 변화 시키고, 산화물층의 평균 두께를 0.01 ~ 30nm 범위 내에 제어함으로써, 티탄산바륨 분말의 유전특성을 조절한다.At this time, by changing the amount of use of the elements constituting the oxide layer, the heat treatment temperature and the treatment time, and controlling the average thickness of the oxide layer within the range of 0.01 ~ 30nm, the dielectric properties of the barium titanate powder is adjusted.
본 발명에서는 티탄산바륨의 표면에 Si, Dy, Y, Mg, V, Mn, Ni, Co 및 Zr 각 물질 중 선택된 하나 이상의 물질을 분산시켜 산화물층으로 형성한다. 이와 같은 산화물층을 형성함으로써, 미세화되어 분산 특성이 저하된 티탄산바륨을 보완할 수 있다. 아울러, 각 티탄산바륨 입자의 표면에, 온도 안정성, 절연 저항치, 비유전율 및 절연 저항의 가속 수명 등을 향상시킬 수 있는 첨가물들을 부성분 원소로서 코팅함으로써, 티탄산바륨 입자의 분산 상태에 따라서, 자연스럽게 부성분 원소들의 분산 특성도 조절될 수 있도록 한다.In the present invention, at least one selected from Si, Dy, Y, Mg, V, Mn, Ni, Co and Zr is dispersed on the surface of the barium titanate to form an oxide layer. By forming such an oxide layer, it is possible to compensate the barium titanate, which has been miniaturized and whose dispersion characteristics are reduced. In addition, by coating the surface of each barium titanate particles with additives that can improve temperature stability, insulation resistance, relative dielectric constant, accelerated life of insulation resistance, and the like as subcomponent elements, depending on the dispersion state of barium titanate particles, Their dispersion characteristics can also be adjusted.
코팅층에 대한 일 실시예로서 SiO2를 티탄산바륨 입자의 표면에 제 1 층으로 형성하고, Dy, Y, Mg, V, Mn, Ni, Co 및 Zr 각 물질 중 선택된 하나 이상의 금속산화물을 적층하는 코팅 방법을 사용할 수 있으며, 다른 실시예로서 2 ~ 8가지 물질들을 혼합하여 산화물을 형성하고, 이를 코팅하는 방법도 사용될 수 있다.As an example of the coating layer, SiO 2 is formed on the surface of the barium titanate particles as a first layer, and a coating for laminating at least one metal oxide selected from Dy, Y, Mg, V, Mn, Ni, Co, and Zr materials A method may be used, and as another embodiment, a method of mixing 2 to 8 materials to form an oxide and coating the same may be used.
먼저, 티탄산바륨 표면에 제 1 층으로 SiO2를 코팅하고, 제 2 층에 Dy, Y, Mg, V, Mn, Ni, Co 및 Zr등을 코팅하는 경우 산화물층의 총 두께는 0.01 ~ 30nm가 되도록 하는 것이 바람직하다. 이때, 사용되는 각 산화물의 전구물질로는 Si는 물유리(Water Glass)를 사용될 수 있고, Dy는 DyCl3, Dy(NO3)3 및 Dy2(SO4)3, Y은 YCl3 및 Y(NO3)3, Mg는 MgCl2, Mg(NO3)2 및 Mg(SO4), V는 VO(SO4) 및 VOCl2, Mn는 MnCl2, Mn(NO3)2 및 Mn(SO4), Ni는 NiCl2, Ni(NO3)2 및 Ni(SO4), Co는 CoCl2, Co(NO3)2 및 Co(SO4), Zr는 ZrCl2, Zr(NO3)2 및 Zr(SO4)가 사용될 수 있다. 그리고, 더 바람직하게 Si는 규산나트륨(Sodium Silicate), Dy는 DyCl3, Y은 YCl3, Mg는 MgCl2, V는 VO(SO4), Ni는 NiCl2, Co는 Co(SO4), Zr는 ZrCl2를 사용하는 것이 용이하다.First, when SiO 2 is coated on the surface of barium titanate as a first layer and Dy, Y, Mg, V, Mn, Ni, Co, and Zr are coated on the second layer, the total thickness of the oxide layer is 0.01 to 30 nm. It is desirable to. In this case, as precursors of the oxides used, Si may be used as Water Glass, Dy is DyCl 3 , Dy (NO 3 ) 3 and Dy 2 (SO 4 ) 3 , and Y is YCl 3 and Y ( NO 3 ) 3 , Mg is MgCl 2 , Mg (NO 3 ) 2 and Mg (SO 4 ), V is VO (SO 4 ) and VOCl 2, Mn is MnCl 2 , Mn (NO 3 ) 2 and Mn (SO 4) ) , Ni is NiCl 2 , Ni (NO 3 ) 2 and Ni (SO 4 ), Co is CoCl 2 , Co (NO 3 ) 2 and Co (SO 4 ), Zr is ZrCl 2 , Zr (NO 3 ) 2 and Zr (SO 4 ) can be used. More preferably, Si is sodium silicate, Dy is DyCl 3 , Y is YCl 3 , Mg is MgCl 2 , V is VO (SO 4 ), Ni is NiCl 2 , Co is Co (SO 4 ), Zr is easy to use ZrCl 2 .
여기서, 각 첨가물의 종류에 따라서 pH를 조절하는 것이 바람직한데, Si의 경우 pH 5.0 ~ 14.0, Zr의 경우 pH 1.0 ~ 5.0으로 조절하고, 나머지 화합물의 경우 pH 6.0 ~ 14.0으로 조절하는 것이 바람직하다. pH 조절 용액은 산성용액으로는 HCl, H2SO4, H(NO3)3가 있으며, 알카리 용액으로는 NaOH 및 KOH이 있다.Here, it is preferable to adjust the pH according to the type of each additive, in the case of Si pH 5.0 ~ 14.0, in the case of Zr it is adjusted to pH 1.0 ~ 5.0, it is preferable to adjust the pH to 6.0 ~ 14.0. pH adjusting solutions include HCl, H 2 SO 4 , H (NO 3 ) 3 as acidic solutions, and NaOH and KOH as alkaline solutions.
상기와 같이, 본 발명에 따른 산화물이 코팅된 티탄산바륨 분말 및 그의 제조 방법은 구상의 티탄산바륨 입자 표면에 Si, Dy, Y, Mg, V, Mn, Ni, Co 및 Zr 등의 조성물들로 이루어지는 산화물층을 형성한 코팅층과 이 코팅층에 대하여 유전체의 물성을 향상 시킬 수 있는 다양한 제법을 제시한 것이다. 여기서, 본 발명이 종래와 다른 점은 수열 가수분해 방법을 이용한 코팅법으로 건식, 습식 혼합(Mixing) 방법과는 다르게 균일한 표면 도포가 가능하고 여러 개의 다른 금속 산화물들을 다층으로 적층하거나 동시에 코팅 할 수 있는 새로운 기술이다.As described above, the oxide-coated barium titanate powder according to the present invention and a manufacturing method thereof are made of compositions of Si, Dy, Y, Mg, V, Mn, Ni, Co, and Zr on the surface of spherical barium titanate particles. The coating layer on which the oxide layer is formed and various methods for improving the physical properties of the dielectric are presented. Here, the present invention is different from the conventional method of coating using a hydrothermal hydrolysis method, unlike the dry and wet mixing (mixing) method, it is possible to apply a uniform surface and to stack or simultaneously coat several different metal oxides in multiple layers. It is a new technology.
이렇게 만들어진 산화물층이 코팅된 티탄산바륨 분말은 초소형, 고용량, 고효율 적층세라믹 콘덴서(MLCC)를 만드는데 사용되기가 용이하다.The oxide layer-coated barium titanate powder is easy to be used to make an ultra-small, high capacity, high efficiency multilayer ceramic capacitor (MLCC).
본 발명에 사용된 수열 가수분해 반응의 구체적인 실시예는 이하에서 상술하는 것으로 한다.Specific examples of the hydrothermal hydrolysis reaction used in the present invention will be described in detail below.
실시예 1Example 1
입자 크기가 40 ~ 400nm인 티탄산바륨 100g을 2L 탈미네랄수 속에서 투입 후 교반하여 슬러리를 형성한다. 다음에는, 슬러리를 70 ~ 90℃까지 가열한다. 100 g of barium titanate having a particle size of 40 to 400 nm was added to 2 L demineralized water and stirred to form a slurry. Next, the slurry is heated up to 70-90 degreeC.
상기 온도에 도달했을 때, 수산화나트륨 수용액을 첨가하여, 슬러리의 pH를 5.0 ~ 10.0으로 상승시키고, 규소나트륨(Sodium Silicate) 용액(SiO2 함량 5.0%) 100g을 평량하고, 약 1시간에 걸쳐 일정한 속도로 적정한다. 이때, 10 ~ 30% HCl 희석액으로 pH 5.0 ~ 10.0를 일정하게 유지시킨다.When the temperature was reached, the aqueous solution of sodium hydroxide was added to raise the pH of the slurry to 5.0 to 10.0, and 100 g of sodium silicon solution (5.0% of SiO 2 content) was weighed and then fixed over about 1 hour. Titrate at speed. At this time, pH 5.0 to 10.0 is kept constant with a dilution solution of 10 to 30% HCl.
여기서, pH를 일정하게 유지시키는 이유는 특정 온도 및 pH 영역 대에서 반응이 미세하고, 균일하게 잘 이루어지기 때문이다. 아울러, 적정 속도가 너무 빠를 경우 산화물층이 불균일하게 될 수 있으며, 천천히 적정할 경우 반응에서는 차이가 없으나 작업성이 떨어진다. 하기 [화학식 1]은 HCl이 첨가되면서 pH가 조절되는 반응을 나타낸 것이다.Here, the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range. In addition, if the titration rate is too fast, the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor. [Formula 1] shows the reaction that the pH is adjusted as HCl is added.
[화학식 1][Formula 1]
Na2O SiO2 + 2HCl → SiO(OH)2 + 2NaCl + H↑Na 2 O SiO 2 + 2HCl → SiO (OH) 2 + 2NaCl + H ↑
상기와 같은 적정 후, 추가로 30분 동안 교반하여 환류한다.After the above titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 교반까지 마친 최종 슬러리를 여과하고, 탈미네랄수로 세척하고, 110℃에서 10시간 동안 건조시켜 분말을 얻는다. Next, the final slurry completed until stirring is filtered, washed with demineralized water and dried at 110 ° C. for 10 hours to obtain a powder.
최종적으로, 상기 분말을 650℃에서 30분 동안 하소 시켜, SiO2가 코팅된 티탄산바륨 분말을 합성하였다. 하기 [화학식 2]는 상기 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되는 과정을 나타낸 것이다.Finally, the powder was calcined at 650 ° C. for 30 minutes to synthesize SiO 2 coated barium titanate powder. [Formula 2] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
[화학식 2] [Formula 2]
SiO(OH)2 → SiO2 + H2O↑SiO (OH) 2 → SiO 2 + H 2 O ↑
상기 열처리 조건 중 하소는 승온 속도 200℃/시간, 유지 온도 650℃, 유지 시간 30분, 감온 시간 150℃/시간, 처리 분위기는 공기 분위기의 조건으로 하였다.Among the heat treatment conditions, calcination was performed at a temperature increase rate of 200 ° C./hour, a holding temperature of 650 ° C., a holding time of 30 minutes, a temperature reduction time of 150 ° C./hour, and a treatment atmosphere.
실시예 2Example 2
입자 크기가 40 ~ 400nm인 티탄산바륨 100g을 2L 탈미네랄수 속에서 투입 후 교반하여 슬러리화 한다. 다음에는, 슬러리를 70 ~ 90℃까지 가열한다. 100 g of barium titanate having a particle size of 40 to 400 nm is introduced into 2 L demineralized water, followed by stirring to slurry. Next, the slurry is heated up to 70-90 degreeC.
상기 온도에 도달했을 때, 염산 수용액으로 pH를 1.0 ~ 5.0으로 하강시키고, ZrCl2 용액(ZrCl2 50.0g/L) 100g을 평량하고, 1시간에 걸쳐 일정한 속도로 적정한다. When the temperature is reached, the pH is lowered to 1.0 to 5.0 with aqueous hydrochloric acid solution, and 100 g of ZrCl 2 solution (ZrCl 2 50.0 g / L) is weighed and titrated at a constant rate over 1 hour.
이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.During this addition, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다. After titration, the mixture is stirred for 30 minutes to reflux.
여기서, pH를 일정하게 유지시키는 이유는 특정 온도 및 pH 영역 대에서 반응이 미세하고, 균일하게 잘 이루어지기 때문이다. 하기 [화학식 3]은 수산화나트륨이 첨가되면서 pH가 조절되는 반응을 나타낸 것이다.Here, the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range. [Formula 3] shows a reaction in which the pH is adjusted while the sodium hydroxide is added.
[화학식 3][Formula 3]
ZrCl2 + 3NaOH → Zr(OH)2 + 3NaCl + H↑ZrCl 2 + 3NaOH → Zr (OH) 2 + 3NaCl + H ↑
이때, 적정 속도가 너무 빠를 경우 산화물층이 불균일하게 될 수 있으며, 천천히 적정할 경우 반응에서는 차이가 없으나 작업성이 떨어진다.At this time, if the titration rate is too fast, the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor.
다음으로, 적정이 완료된 슬러리를 실시예 1과 동일하게 처리하여 ZrO2가 코팅된 티탄산바륨 분말을 합성하였다. 하기 [화학식 4]는 상기 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되는 과정을 나타낸 것이다.Next, ZrO 2 -coated barium titanate powder was synthesized by treating the slurry in which titration was completed in the same manner as in Example 1. [Formula 4] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
[화학식 4] [Formula 4]
Zr(OH)2 → ZrO + H2O↑Zr (OH) 2 → ZrO + H 2 O ↑
실시예 3Example 3
입자 크기가 40 ~ 400nm인 티탄산바륨 100g을 2L 탈미네랄수 속에서 투입 후 교반하여 슬러리화 한다. 다음에는, 슬러리를 70 ~ 90℃까지 가열한다. 100 g of barium titanate having a particle size of 40 to 400 nm is introduced into 2 L demineralized water, followed by stirring to slurry. Next, the slurry is heated up to 70-90 degreeC.
상기 온도에 도달했을 때, 수산화나트륨 수용액으로 pH를 6.0 ~ 14.0으로 상승시키고, DyCl3 용액(DyCl3 50.0g/L) 100g을 평량하고, 1시간에 걸쳐 일정한 속도로 적정한다. When the temperature is reached, the pH is raised to 6.0 to 14.0 with aqueous sodium hydroxide solution, and 100 g of DyCl 3 solution (DyCl 3 50.0 g / L) is weighed and titrated at a constant rate over 1 hour.
이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.During this addition, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다. After titration, the mixture is stirred for 30 minutes to reflux.
여기서, pH를 일정하게 유지시키는 이유는 특정 온도 및 pH 영역 대에서 반응이 미세하고, 균일하게 잘 이루어지기 때문이다. 하기 [화학식 5]은 수산화나트륨이 첨가되면서 pH가 조절되는 반응을 나타낸 것이다.Here, the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range. [Formula 5] shows the reaction in which the pH is adjusted while the sodium hydroxide is added.
[화학식 5][Formula 5]
DyCl3 + 3NaOH → Dy(OH)3 + 3NaCl + H↑DyCl 3 + 3NaOH → Dy (OH) 3 + 3NaCl + H ↑
이때, 적정 속도가 너무 빠를 경우 산화물층이 불균일하게 될 수 있으며, 천천히 적정할 경우 반응에서는 차이가 없으나 작업성이 떨어진다.At this time, if the titration rate is too fast, the oxide layer may be non-uniform, and if titration slowly, there is no difference in the reaction, but workability is poor.
다음으로, 적정이 완료된 슬러리를 실시예 1과 동일하게 처리하여 Dy2O3가 코팅된 티탄산바륨 분말을 합성하였다. 하기 [화학식 6]는 상기 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되는 과정을 나타낸 것이다.Next, the slurry was titrated and treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with Dy 2 O 3 . [Formula 6] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
[화학식 6] [Formula 6]
2Dy(OH)3 → Dy2O3 + 3H↑2Dy (OH) 3 → Dy 2 O 3 + 3H ↑
실시예 4Example 4
실시예 3와 동일한 처리 후 DyCl3 용액 대신 YCl3 용액(YCl3 50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정 하게 유지시켰다. 적정 후, 추가로 30분 동안 교반하여 환류한다.Carried out after the same treatment as in Example 3 DyCl 3 solution is titrated rather than the basis weight after the YCl 3 solution (YCl 3 50.0g / L) 100g . During this titration, the pH was kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred for 30 minutes to reflux.
여기서, pH를 일정하게 유지시키는 이유는 특정 온도 및 pH 영역 대에서 반응이 미세하고, 균일하게 잘 이루어지기 때문이다. 하기 [화학식 7]은 수산화나트륨이 첨가되면서 pH가 조절되는 반응을 나타낸 것이다.Here, the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range. [Formula 7] shows the reaction that the pH is adjusted while the sodium hydroxide is added.
[화학식 7][Formula 7]
YCl3 + 3NaOH → Y(OH)3 + 3NaCl + H↑YCl 3 + 3NaOH → Y (OH) 3 + 3NaCl + H ↑
다음으로, 상기 슬러리를 실시예 1과 동일하게 처리하여 Y2O3가 코팅된 티탄산바륨 분말을 합성하였다. 하기 [화학식 8]은 상기 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되는 과정을 나타낸 것이다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with Y 2 O 3 . [Formula 8] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
[화학식 8] [Formula 8]
2Y(OH)3 → Y2O3 + 3H↑2Y (OH) 3 → Y 2 O 3 + 3H ↑
실시예 5Example 5
실시예 2와 동일한 처리 후 DyCl3 용액 대신 MgCl2 용액(MgCl2 50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정 하게 유지시켰다. After the same treatment as in Example 2, 100 g of MgCl 2 solution (MgCl 2 50.0 g / L) instead of DyCl 3 solution is titrated after basis weight. During this titration, the pH was kept constant with 10-50% sodium hydroxide solution.
여기서, pH를 일정하게 유지시키는 이유는 특정 온도 및 pH 영역 대에서 반응이 미세하고, 균일하게 잘 이루어지기 때문이다. 하기 [화학식 9]은 수산화나트륨이 첨가되면서 pH가 조절되는 반응을 나타낸 것이다. Here, the reason for keeping the pH constant is that the reaction is fine and uniformly well at a specific temperature and pH range. [Formula 9] shows the reaction that the pH is adjusted while the sodium hydroxide is added.
[화학식 9][Formula 9]
MgCl2 + 2NaOH → Mg(OH)2 + 2NaCl + H↑MgCl 2 + 2NaOH → Mg (OH) 2 + 2NaCl + H ↑
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음으로, 상기 슬러리를 실시예 1과 동일하게 처리하여 MgO가 코팅된 티탄산바륨 분말을 합성하였다. 하기 [화학식 10]은 상기 열처리에 의하여 수산화물이 고화물 형태의 산화물층으로 형성되는 과정을 나타낸 것이다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with MgO. [Formula 10] shows a process in which the hydroxide is formed as an oxide layer of the solid form by the heat treatment.
[화학식 10] [Formula 10]
Mg(OH)2 → MgO + H2O↑Mg (OH) 2 → MgO + H 2 O ↑
실시예 6Example 6
실시예 2와 동일한 처리 후 DyCl3 용액 대신 VO(SO4) 용액 (VO(SO4)50.0g/L)VO (SO 4 ) solution (VO (SO 4 ) 50.0 g / L) instead of DyCl 3 solution after the same treatment as in Example 2
100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시켰다. After weighing 100g, titrate. During this titration, the pH was kept constant with 10-50% sodium hydroxide solution.
2VO(SO4) + 2NaOH → 2VO(OH)2 + Na2(SO4) + H↑2VO (SO 4 ) + 2NaOH → 2VO (OH) 2 + Na 2 (SO 4 ) + H ↑
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 V2O5가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with V 2 O 5 .
2VO(OH)2 → V2O5 + H2O + 2H↑2VO (OH) 2 → V 2 O 5 + H 2 O + 2H ↑
실시예 7Example 7
실시예 2와 동일한 처리 후 DyCl3 용액 대신 NiCl2 용액 (NiCl2 50.0g/L)NiCl 2 solution instead of DyCl 3 solution after the same treatment as in Example 2 (NiCl 2 50.0 g / L)
100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정 하게 유지시켰다. After weighing 100g, titrate. During this titration, the pH was kept constant with 10-50% sodium hydroxide solution.
NiCl2 + 2NaOH → 2Ni(OH)2 + 2NaCl + H↑NiCl 2 + 2NaOH → 2Ni (OH) 2 + 2NaCl + H ↑
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 NiO가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with NiO.
Ni(OH)2 → NiO + H2O↑Ni (OH) 2 → NiO + H 2 O ↑
실시예 8Example 8
실시예 2와 동일한 처리 후 DyCl3 용액 대신 MnCl2 용액 (MnCl2 50.0g/L)MnCl 2 solution instead of DyCl 3 solution after the same treatment as in Example 2 (MnCl 2 50.0 g / L)
100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정 하게 유지시켰다. After weighing 100g, titrate. During this titration, the pH was kept constant with 10-50% sodium hydroxide solution.
MnCl2 + 2NaOH → 2Mn(OH)2 + 2NaCl + H↑MnCl 2 + 2NaOH → 2Mn (OH) 2 + 2NaCl + H ↑
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 MnO가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with MnO.
Mn(OH)2 → MnO + H2O↑ Mn (OH) 2 → MnO + H 2 O ↑
실시예 9Example 9
실시예 2와 동일한 처리 후 DyCl3 용액 대신 CoSO4 용액 (CoSO4 50.0g/L)CoSO 4 solution (CoSO 4 50.0 g / L) instead of DyCl 3 solution after the same treatment as in Example 2
100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정 하게 유지시켰다. After weighing 100g, titrate. During this titration, the pH was kept constant with 10-50% sodium hydroxide solution.
CoSO4 + 2NaOH → 2Co(OH)2 + 2NaCl + H↑CoSO 4 + 2NaOH → 2Co (OH) 2 + 2NaCl + H ↑
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 CoO가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with CoO.
CoSO4(OH)2 → CoO + H2O↑ CoSO 4 (OH) 2 → CoO + H 2 O ↑
실시예 10Example 10
실시예 1의 처리 방법인 규소나트륨(Sodium Silicate) 용액 (SiO2 함량 3.0%) 166g을 평량하고, 1시간에 걸쳐 일정한 속도로 적정한다. 이때, 10 ~ 30% HCl 희석액으로 pH 5.0 ~ 10.0를 일정하게 유지시킨다.166 g of a sodium Silicate solution (3.0% of SiO 2 ), which is the treatment method of Example 1, was weighed out and titrated at a constant rate over 1 hour. At this time, pH 5.0 to 10.0 is kept constant with a dilution solution of 10 to 30% HCl.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 염산 수용액으로 pH를 1.0 ~ 5.0까지 하강시킨 후, 추가로 15분 동안 교반하여 환류한다.Next, the pH was lowered to 1.0 to 5.0 with an aqueous hydrochloric acid solution, followed by further stirring for 15 minutes to reflux.
pH를 급격히 상승시킬 경우 코팅된 SiO2가 용출될 가능성이 있으므로, 천천히 일정한 속도로 상승시킨다.If the pH is sharply increased, the coated SiO 2 may be eluted, so it is slowly increased at a constant rate.
ZrCl2 용액(ZrCl2 50.0g/L) 100g을 평량 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.100 g of ZrCl 2 solution (ZrCl 2 50.0 g / L) is titrated in basis weight. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 15분 동안 교반하여 환류한다.After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, ZrO2가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and ZrO 2 .
실시예 11Example 11
실시예 1의 처리 방법인 규소나트륨(Sodium Silicate) 용액 (SiO2 함량 3.0%) 166g을 평량하고, 1시간에 걸쳐 일정한 속도로 적정한다. 이때, 10 ~ 30% HCl 희석액으로 pH 5.0 ~ 10.0를 일정하게 유지시킨다.166 g of a sodium Silicate solution (3.0% of SiO 2 ), which is the treatment method of Example 1, was weighed out and titrated at a constant rate over 1 hour. At this time, pH 5.0 to 10.0 is kept constant with a dilution solution of 10 to 30% HCl.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 수산화나트륨 수용액으로 pH를 6.0 ~ 12.0까지 상승시킨 후, 추가로 15분 동안 교반하여 환류한다.Next, the pH was raised to 6.0-12.0 with an aqueous sodium hydroxide solution, followed by stirring for further 15 minutes to reflux.
pH를 급격히 상승시킬 경우 코팅된 SiO2가 용출될 가능성이 있으므로, 천천히 일정한 속도로 상승시킨다.If the pH is sharply increased, the coated SiO 2 may be eluted, so it is slowly increased at a constant rate.
DyCl3 용액(DyCl3 50.0g/L) 100g을 평량 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.Titrate 100 g of DyCl 3 solution (DyCl 3 50.0 g / L). During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 15분 동안 교반하여 환류한다.After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, Dy2O3가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and Dy 2 O 3 .
실시예 12Example 12
실시예 11과 동일하게 처리하며, DyCl3 용액 대신 YCl3 용액(YCl3 50.0g/L)100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.Example 11 and treated in the same manner and, DyCl 3 solution is titrated rather than the basis weight after the YCl 3 solution (YCl 3 50.0g / L) 100g . During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2,Y2O3가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and Y 2 O 3 .
실시예 13Example 13
실시예 11과 동일한 처리를 하며, DyCl3 용액 대신 MgCl2 용액(MgCl2 50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.The same treatment as in Example 11 was carried out, followed by titration of 100 g of MgCl 2 solution (MgCl 2 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2,MgO가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and MgO.
실시예 14Example 14
실시예 11과 동일한 처리를 하며, DyCl3 용액 대신 VO(SO4) 용액(VO(SO4)50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. The same treatment as in Example 11 was carried out after the basis weight of 100 g of VO (SO 4 ) solution (VO (SO 4 ) 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, V2O5가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with SiO 2 and V 2 O 5 .
실시예 15Example 15
실시예 11과 동일한 처리를 하며, DyCl3 용액 대신 NiCl2 용액(NiCl2 50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. The same treatment as in Example 11 was carried out, followed by titration of 100 g of NiCl 2 solution (NiCl 2 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, NiO2가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with SiO 2 and NiO 2 .
실시예 16Example 16
실시예 11과 동일한 처리를 하며, DyCl3 용액 대신 MnCl2 용액(NiCl2 50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. The same treatment as in Example 11 was carried out after the basis weight of 100 g of MnCl 2 solution (NiCl 2 50.0 g / L) instead of the DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, MnO2가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with SiO 2 and MnO 2 .
실시예 17Example 17
실시예 11과 동일한 처리를 하며, DyCl3 용액 대신 Co(SO4) 용액(Co(SO4)50.0g/L) 100g을 평량 후 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. The same treatment as in Example 11 was carried out after the basis weight of 100 g of Co (SO 4 ) solution (Co (SO 4 ) 50.0 g / L) instead of DyCl 3 solution. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 SiO2, CoO가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize SiO 2 , CoO-coated barium titanate powder.
실시예 18Example 18
실시예 2의 처리 방법인 ZrCl2 용액(ZrCl2 50.0g/L) 100g을 평량하고, 1시간에 걸쳐 일정한 속도로 적정한다. 이렇게 적정하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다.100 g of ZrCl 2 solution (ZrCl 2 50.0 g / L), which is the treatment method of Example 2, is weighed and titrated at a constant rate over 1 hour. During this titration, the pH is kept constant with 10-50% sodium hydroxide solution.
적정 후, 추가로 30분 동안 교반하여 환류한다.After titration, the mixture is stirred for 30 minutes to reflux.
다음에는, 수산화나트륨 수용액으로 pH를 5.0 ~ 10.0까지 상승시킨 후, 추가로 15분 동안 교반하여 환류한다.Next, the pH was raised to 5.0 to 10.0 with an aqueous sodium hydroxide solution, followed by stirring for further 15 minutes to reflux.
규소나트륨(Sodium Silicate) 용액(SiO2 함량 5.0%) 100g을 평량하고, 약 1시간에 걸쳐 일정한 속도로 적정한다. 이때, 10 ~ 30% HCl 희석액으로 pH 5.0 ~ 10.0를 일정하게 유지시킨다.Weigh 100 g of a sodium silicon solution (5.0% SiO 2 ) and titrate at a constant rate over about 1 hour. At this time, pH 5.0 to 10.0 is kept constant with a dilution solution of 10 to 30% HCl.
적정 후, 추가로 15분 동안 교반하여 환류한다.After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 ZrO2, SiO2가 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize a barium titanate powder coated with ZrO 2 and SiO 2 .
실시예 19Example 19
실시예 2과 동일한 처리 후 수산화나트륨 수용액으로 pH를 6.0 ~ 12.0까지 상승시킨 후, 추가로 30분 동안 교반하여 환류한다. After the same treatment as in Example 2, the pH was raised to 6.0 to 12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
DyCl3 (DyCl3 50.0g/L) 40.0g, YCl3 (YCl3 50.0g/L) 40.0g, MgCl2 (MgCl2 50.0g/L) 40.0g, VO(SO4) (VO(SO4) 50.0g/L) 40.0g, MnCl2, (MnCl2 50.0g/L) 40.0g, NiCl2 (NiCl2 50.0g/L) 40.0g, Co(SO4) (Co(SO4) 50.0g/L) 40.0g을 순서대로 평량하고, 2시간에 걸쳐 일정한 속도(2.33g/min)로 적정한다. 이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. 적정 후, 추가로 15분 동안 교반하여 환류한다.DyCl3 (DyCl350.0g / L) 40.0g, YCl3(YCl350.0g / L) 40.0g, MgCl2 (MgCl250.0 g / L) 40.0 g, VO (SO4) (VO (SO4) 50.0g / L) 40.0g, MnCl2, (MnCl250.0g / L) 40.0g, NiCl2 (NiCl250.0 g / L) 40.0 g, Co (SO4) (Co (SO4) 50.0 g / L) 40.0 g are weighed in order and titrated at a constant rate (2.33 g / min) over 2 hours. During this addition, the pH is kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 ZrO, Dy2O3, Y2O3, MgO, V2O5, MnO, NiO, CoO가 순차적으로 코팅된 티탄산바륨 분말을 합성하였다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder sequentially coated with ZrO, Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. .
실시예 20Example 20
실시예 2과 동일한 처리 후 수산화나트륨 수용액으로 pH를 6.0 ~ 12.0까지 상승시킨 후, 추가로 30분 동안 교반하여 환류한다. After the same treatment as in Example 2, the pH was raised to 6.0 to 12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
혼합용액 {DyCl3 20.0g, YCl3 20.0g, MgCl2 20.0g, VO(SO4) 20.0g, MnCl2, 20.0g, NiCl2 20.0g, Co(SO4) 20.0g Total 140.0g/3L)} 280g을 평량하고, 2시간에 걸쳐 일정한 속도(2.33g/min)로 적정한다. 이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. 적정 후, 추가로 15분 동안 교반하여 환류한다.Mixed Solution (DyCl 3 20.0g, YCl 3 20.0g, MgCl 2 20.0g, VO (SO 4 ) 20.0g, MnCl 2 , 20.0g, NiCl 2 20.0g, Co (SO 4 ) 20.0g Total 140.0g / 3L) } Weigh 280 g and titrate at a constant rate (2.33 g / min) over 2 hours. During this addition, the pH is kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 ZrO, Dy2O3, Y2O3, MgO, V2O5, MnO, NiO, CoO가 코팅된 티탄산바륨 분말을 합성하였다. 이때, ZrO 코팅층을 먼저형성 한 후, 나머지를 믹싱(Mixing)하여 코팅층을 형성할 수 있다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. At this time, after forming the ZrO coating layer first, the rest may be mixed to form a coating layer.
실시예 21Example 21
실시예 18과 동일한 처리 후 수산화나트륨 수용액으로 pH를 6.0 ~ 12.0까지 상승시킨 후, 추가로 30분 동안 교반하여 환류한다. After the same treatment as in Example 18, the pH was raised to 6.0-12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
DyCl3 (DyCl3 50.0g/L) 40.0g, YCl3 (YCl3 50.0g/L) 40.0g, MgCl2 (MgCl2 50.0g/L) 40.0g, VO(SO4) (VO(SO4) 50.0g/L) 40.0g, MnCl2, (MnCl2 50.0g/L) 40.0g, NiCl2 (NiCl2 50.0g/L) 40.0g, Co(SO4) (Co(SO4) 50.0g/L) 40.0g을 순서대로 평량하고, 2시간에 걸쳐 일정한 속도(2.33g/min)로 적정한다. 이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. 적정 후, 추가로 15분 동안 교반하여 환류한다.DyCl3 (DyCl350.0g / L) 40.0g, YCl3(YCl350.0g / L) 40.0g, MgCl2 (MgCl250.0 g / L) 40.0 g, VO (SO4) (VO (SO4) 50.0g / L) 40.0g, MnCl2, (MnCl250.0g / L) 40.0g, NiCl2 (NiCl250.0 g / L) 40.0 g, Co (SO4) (Co (SO4) 50.0 g / L) 40.0 g are weighed in order and titrated at a constant rate (2.33 g / min) over 2 hours. During this addition, the pH is kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 ZrO, SiO2, Dy2O3, Y2O3, MgO, V2O5, MnO, NiO, CoO가 코팅된 티탄산바륨 분말을 합성하였다. 이때, ZrO, SiO2 를 먼저 코팅한 후 나머지 물질들은 순차적으로 코팅한다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, SiO 2 , Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. It was. At this time, ZrO, SiO 2 is first coated, and then the remaining materials are sequentially coated.
실시예 22Example 22
실시예 18과 동일한 처리 후 수산화나트륨 수용액으로 pH를 6.0 ~ 12.0까지 상승시킨 후, 추가로 30분 동안 교반하여 환류한다. After the same treatment as in Example 18, the pH was raised to 6.0-12.0 with an aqueous sodium hydroxide solution, followed by stirring for 30 minutes to reflux.
혼합용액 {DyCl3 20.0g, YCl3 20.0g, MgCl2 20.0g, VO(SO4) 20.0g, MnCl2, 20.0g, NiCl2 20.0g, Co(SO4) 20.0g Total 140.0g/3L)} 280g을 평량하고, 2시간에 걸쳐 일정한 속도(2.33g/min)로 적정한다. 이렇게 첨가하는 동안, 10 ~ 50% 수산화나트륨 용액으로 pH를 일정하게 유지시킨다. 적정 후, 추가로 15분 동안 교반하여 환류한다.Mixed Solution (DyCl 3 20.0g, YCl 3 20.0g, MgCl 2 20.0g, VO (SO 4 ) 20.0g, MnCl 2 , 20.0g, NiCl 2 20.0g, Co (SO 4 ) 20.0g Total 140.0g / 3L) } Weigh 280 g and titrate at a constant rate (2.33 g / min) over 2 hours. During this addition, the pH is kept constant with 10-50% sodium hydroxide solution. After titration, the mixture is stirred and refluxed for an additional 15 minutes.
다음에는, 상기의 슬러리를 실시예 1과 동일하게 처리하여 ZrO, SiO2, Dy2O3, Y2O3, MgO, V2O5, MnO, NiO, CoO가 코팅된 티탄산바륨 분말을 합성하였다. 이때, ZrO, SiO2 를 먼저 코팅한 후 나머지를 믹싱(Mixing)하여 코팅층을 형성할 수 있다.Next, the slurry was treated in the same manner as in Example 1 to synthesize barium titanate powder coated with ZrO, SiO 2 , Dy 2 O 3 , Y 2 O 3 , MgO, V 2 O 5 , MnO, NiO, and CoO. It was. At this time, ZrO, SiO 2 may be coated first, and then the remainder may be mixed to form a coating layer.
상술한 바와 같이, 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말은 유전체의 물성을 향상 시킬 수 있는 다양한 실시예를 포함한다. 아울러, 본 발명에 따른 산화물층은 수열가수분해반응에 의해 균일하게 형성됨으로써, 티탄산바륨 분말의 분산성을 더 향상시킬 수 있다. As described above, the barium titanate powder coated with the oxide layer according to the present invention includes various embodiments that can improve the physical properties of the dielectric. In addition, the oxide layer according to the present invention is uniformly formed by hydrothermal hydrolysis, thereby further improving the dispersibility of the barium titanate powder.
도 4는 본 발명에 따라서 SiO2가 코팅된 티탄산바륨 분말을 나타낸 TEM 사진이고, 도 5는 상기 도 4의 라인 스캔 결과를 나타낸 그래프이다.4 is a TEM photograph showing a barium titanate powder coated with SiO 2 according to the present invention, and FIG. 5 is a graph showing the line scan result of FIG. 4.
도 4에 나타난 티탄산바륨 입자의 중심부를 가로지르는 라인을 따라서 각 원소들의 분포 상태를 조사하였다. 그 결과, 도 5에 나타난 바와 같이 Si 및 BT(BaTiO3) 모두 균일하게 분포되고 있음을 알 수 있다.The distribution state of each element was examined along the line across the center of the barium titanate particles shown in FIG. 4. As a result, it can be seen that both Si and BT (BaTiO 3 ) are uniformly distributed as shown in FIG. 5.
도 6은 본 발명에 따라서 Dy2O3 금속산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진이고, 도 7은 상기 도 6의 라인 스캔 결과를 나타낸 그래프이다.FIG. 6 is a TEM photograph showing a barium titanate powder coated with a Dy 2 O 3 metal oxide layer according to the present invention, and FIG. 7 is a graph showing the line scan result of FIG. 6.
도 6을 참조하면, Dy2O3 금속산화물층이 단일층으로 코팅된 티탄산바륨 분말이 나타나며, 도 7은 상기 분말 중 하나의 티탄산바륨 입자 단면을 따라 스캔하면서, Dy의 분포를 조사한 것이다. 도 7을 참조하면, Dy 가 고르게 분포되고 있는 것을 알 수 있다.Referring to FIG. 6, a barium titanate powder coated with a single layer of Dy 2 O 3 metal oxide layer is shown, and FIG. 7 shows a distribution of Dy while scanning along a cross section of barium titanate particles of one of the powders. Referring to FIG. 7, it can be seen that Dy is evenly distributed.
도 8 및 도 9는 상기 도 7의 라인 스캔 결과 중 Dy 분포를 분석한 그래프들이다.8 and 9 are graphs analyzing Dy distribution among the line scan results of FIG. 7.
도 8은 상기 도 7의 단면 중 1 지점에서 검출되는 Dy 개수를 나타낸 것이고, 도 9는 2 지점에서 검출되는 Dy 개수를 나타낸 것이다. 검출 결과는 도시된 바와 같이 균일하게 나타남을 알 수 있다.FIG. 8 illustrates the number of Dy detected at one point of the cross section of FIG. 7, and FIG. 9 illustrates the number of Dy detected at two points. It can be seen that the detection result is uniformly shown as shown.
도 10은 본 발명에 따라서 SiO2 및 Dy2O3 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진이고, 도 11은 상기 도 10의 라인 스캔 결과를 나타낸 그래프이다.FIG. 10 is a TEM photograph showing a barium titanate powder coated with SiO 2 and Dy 2 O 3 oxide layers according to the present invention, and FIG. 11 is a graph showing the line scan results of FIG. 10.
도 10을 참조하면, SiO2, Dy2O3 금속산화물층이 이중층으로 코팅된 티탄산바륨 분말이 나타나며, 도 11은 상기 분말 중 하나의 티탄산바륨 입자 단면을 따라 스캔하면서, Dy 및 Si의 분포를 조사한 것이다. Referring to FIG. 10, SiO2, Dy2O3 A barium titanate powder coated with a double layer of a metal oxide layer is shown, and FIG. 11 shows a distribution of Dy and Si while scanning along a cross section of barium titanate particles of one of the powders.
도 11을 참조하면, Dy, Si 가 고르게 분포되고 있는 것을 알 수 있다.Referring to FIG. 11, it can be seen that Dy and Si are evenly distributed.
도 12는 본 발명에 따라서 SiO2 및 Y2O3 산화물층이 코팅된 티탄산바륨 분말을 나타낸 TEM 사진이고, 도 13은 상기 도 12의 라인 스캔 결과를 나타낸 그래프이다.12 is a TEM photograph showing a barium titanate powder coated with an SiO 2 and Y 2 O 3 oxide layer according to the present invention, and FIG. 13 is a graph showing the line scan result of FIG. 12.
도 12를 참조하면, SiO2 및 Y2O3 산화물층이 이중층으로 코팅된 티탄산바륨 분말이 나타나며, 도 13은 상기 분말 중 하나의 티탄산바륨 입자 단면을 따라 스캔하면서, Y 및 Si의 분포를 조사한 것이다. 도 12를 참조하면, Y, Si 가 고르게 분포되고 있는 것을 알 수 있다.Referring to FIG. 12, a barium titanate powder coated with a double layer of SiO 2 and Y 2 O 3 oxide layers is shown, and FIG. 13 shows a distribution of Y and Si while scanning along a cross section of barium titanate particles of one of the powders. will be. 12, it can be seen that Y and Si are evenly distributed.
도 14 및 도 15는 본 발명의 비교예에 따른 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들이다.14 and 15 are E-SEM photographs showing the results of heat treatment on the barium titanate powder according to the comparative example of the present invention.
도 14는 산화물층이 코팅되지 않은 벌크형태의 티탄산바륨 분말을 125℃의 온도에서 30분간 열처리한 후 촬영한 사진이고, 도 15는 1250℃의 온도에서 30분가 열처리한 후 촬영한 사진이다.14 is a photograph taken after the heat treatment of the barium titanate powder in the form of a bulk without an oxide layer for 30 minutes at a temperature of 125 ℃, Figure 15 is a photograph taken after the heat treatment for 30 minutes at a temperature of 1250 ℃.
도 14 및 도 15를 참조하면, 티탄산바륨 분말의 분산성이 좋지 못해서 입자의 경계가 뚜렷하지 못하고, 불규칙하게 분포되어 있는 것을 볼 수 있다.14 and 15, it can be seen that the dispersion of the barium titanate powder is not good, so the boundary of the particles is not clear and irregularly distributed.
그러나, 반면에 하기의 본 발명에 따른 산화물층이 코팅된 티탄산바륨 분말의 경우 입자간 경계가 뚜렷하고, 규칙적인 분포를 갖는 것을 알 수 있다.However, in the case of the barium titanate powder coated with the oxide layer according to the present invention, it can be seen that the boundary between particles is distinct and has a regular distribution.
도 16 및 도 17은 본 발명의 실시예에 따른 SiO2가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 것이고, 도 18 및 도 19는 본 발명의 실시예에 따른 Dy2O3가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 것이고, 도 20 및 도 21은 본 발명의 실시예에 따른 Y2O3가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 것이고, 도 22 및 도 23은 본 발명의 실시예에 따른 MgO가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 것이고, 도 24 및 도 25는 본 발명의 실시예에 따른 V2O5가 코팅된 티탄산바륨 분말에 열처리한 결과를 나타낸 E-SEM 사진들이다.16 and 17 show the results of heat treatment on SiO 2 coated barium titanate powder according to an embodiment of the present invention, Figures 18 and 19 is a titanic acid coated Dy 2 O 3 according to an embodiment of the present invention FIG. 20 and FIG. 21 show the results of the heat treatment on the barium titanate powder coated with Y 2 O 3 according to the embodiment of the present invention, and FIGS. 22 and 23 show the results of the heat treatment on the barium powder. Eg shows the results of the heat treatment to the MgO-coated barium titanate powder, Figures 24 and 25 is a heat treatment to the V 2 O 5 -coated barium titanate powder according to an embodiment of the present invention SEM pictures.
상기 실시예들을 통하여 알 수 있는 바와 같이 본 발명에 따른 티탄산바륨 분말은 그 균일한 산화물 코팅층을 갖고, 이에 따라서 분말의 분포도 균일하게 될 수 있다. As can be seen from the above examples, the barium titanate powder according to the present invention has a uniform oxide coating layer, and thus the powder distribution can be uniform.
아울러 이와 같이, 균일한 입자의 분말들은 그 균일성에 비례하여 온도 안정성, 절연 저항치, 비유전율 및 절연 저항의 가속 수명 등의 특성도 향상된다.In addition, the powders of the uniform particles are also improved in properties such as temperature stability, insulation resistance, relative dielectric constant and accelerated life of the insulation resistance in proportion to the uniformity.
따라서, 본 발명에 따라 제조된 산화물층이 코팅된 티탄산바륨 분말을 이용하면, 초소형, 고용량, 고효율 적층세라믹콘덴서(MLCC)를 만드는데 사용되는 내부 전극층용 페이스트(Paste) 또는 유전체층용 페이스트(Paste)를 용이하게 형성할 수 있다. Therefore, when the barium titanate powder coated with the oxide layer prepared according to the present invention is used, a paste for internal electrode layers or a paste for dielectric layers used to make an ultra-small, high-capacity, high-efficiency multilayer ceramic capacitor (MLCC) can be obtained. It can be formed easily.
이때, 종래의 경우 티탄산바륨 분말 및 기타 첨가물을 유기 용매에 분산시키는 불편함이 있었으나, 본 발명에서와 같이 분산성이 향상된 티탄산바륨 분말을 이용하는 경우 물(Aqua)과 같은 용액에도 용이하게 분산되므로, 그 제조 단가를 절약할 수 있게 된다.In this case, in the conventional case, there was an inconvenience in dispersing the barium titanate powder and other additives in an organic solvent, but when using the barium titanate powder with improved dispersibility as in the present invention, it is easily dispersed in a solution such as water (Aqua), The manufacturing cost can be saved.
따라서, 본 발명은 더 다양하고, 고효율의 적층세라믹콘덴서(MLCC) 제작에 활용될 수 있다.Therefore, the present invention can be utilized in manufacturing a more versatile and highly efficient multilayer ceramic capacitor (MLCC).
Claims (23)
- 티탄산바륨(BaTiO3) 입자의 표면에 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질이 균일하게 분산되어 이루어지는 산화물층이 1층 이상 코팅되어 있는 것을 특징으로 하는 티탄산바륨 분말.At least one oxide layer formed by uniformly dispersing at least one selected from Si, Y, V, Dy, Mg, Mn, Ni, Co, and Zr is coated on the surface of the barium titanate (BaTiO 3 ) particles. Barium titanate powder.
- 제 1 항에 있어서,The method of claim 1,상기 티탄산바륨 입자의 입자반경(r)은 40 ~ 400nm인 것을 특징으로 하는 티탄산바륨 분말.Particle radius (r) of the barium titanate particles are barium titanate powder, characterized in that 40 ~ 400nm.
- 제 1 항에 있어서,The method of claim 1,상기 산화물층은 상기 티탄산바륨 입자의 중량대비 0.01 ~ 15중량%로 이루이지는 것을 특징으로 하는 티탄산바륨 분말.The oxide layer is barium titanate powder, characterized in that consisting of 0.01 to 15% by weight relative to the weight of the barium titanate particles.
- 제 1 항에 있어서,The method of claim 1,상기 산화물층의 총 두께(△r)는 0.01 ~ 30nm인 것을 특징으로 하는 티탄산바륨 분말.The total thickness (Δr) of the oxide layer is barium titanate powder, characterized in that 0.01 ~ 30nm.
- 제 1 항에 있어서,The method of claim 1,상기 산화물층은 수열가수분해반응에 의해 형성되는 것을 특징으로 하는 티탄산바륨 분말.The oxide layer is barium titanate powder, characterized in that formed by hydrothermal hydrolysis.
- 티탄산바륨(BaTiO3) 입자의 표면에 SiO2층이 코팅되어 있는 것을 특징으로 하는 티탄산바륨 분말.Barium titanate powder, characterized in that the SiO 2 layer is coated on the surface of the barium titanate (BaTiO 3 ) particles.
- 제 6 항에 있어서,The method of claim 6,상기 티탄산바륨 입자의 입자반경(r)은 40 ~ 400nm인 것을 특징으로 하는 티탄산바륨 분말.Particle radius (r) of the barium titanate particles are barium titanate powder, characterized in that 40 ~ 400nm.
- 제 6 항에 있어서,The method of claim 6,상기 SiO2층의 총 두께(△r)는 0.01 ~ 30nm인 것을 특징으로 하는 티탄산바륨 분말.The total thickness (Δr) of the SiO 2 layer is barium titanate powder, characterized in that 0.01 ~ 30nm.
- 제 6 항에 있어서, The method of claim 6,상기 SiO2층의 상부에는 Y, V, Dy, Mg, Mn, Ni, Co 및 Zr중 선택된 하나 이상의 물질이 균일하게 분산되어 이루어지는 산화물층이 1층 이상 더 코팅되어 있는 것을특징으로 하는 티탄산바륨 분말.Barium titanate powder, characterized in that at least one layer of an oxide layer formed by uniformly dispersing at least one selected from Y, V, Dy, Mg, Mn, Ni, Co, and Zr is further coated on the SiO 2 layer. .
- 제 9 항에 있어서,The method of claim 9,상기 SiO2층 및 상기 산화물층은 각각 수열가수분해반응에 의해 형성되는 것을 특징으로 하는 티탄산바륨 분말.The SiO 2 layer and the oxide layer, respectively, barium titanate powder, characterized in that formed by hydrothermal hydrolysis reaction.
- 제 1 항 내지 제 10 항 중 선택된 어느 한 항의 티탄산바륨 분말로 이루어지는 것을 특징으로 하는 적층세라믹콘덴서(MLCC).A multilayer ceramic capacitor (MLCC) comprising the barium titanate powder of any one of claims 1 to 10.
- 물이 담겨있는 반응기에 티탄산바륨 분말을 투입한 후 교반하여 제 1 슬러리를 조성하는 단계;Adding a barium titanate powder to a reactor containing water, followed by stirring to form a first slurry;상기 제 1 슬러리에 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질로 이루어지는 화합물을 용해시킨 희석액을 적정(滴定)하여 제 2 슬러리를 조성하는 단계 및 상기 제 2 슬러리를 탈수(농축) 및 수세(이물질 제거)하고, 잔류하는 고화물을 열처리하는 단계를 포함하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.Preparing a second slurry by titrating a diluent in which a compound composed of at least one material selected from Si, Y, V, Dy, Mg, Mn, Ni, Co, and Zr is dissolved in the first slurry; Dehydration (concentration) and washing with water (removal of foreign substances), and the method for producing an oxide layer coated barium titanate powder, characterized in that it comprises the step of heat-treating the remaining solids.
- 제 12 항에 있어서,The method of claim 12,상기 제 1 슬러리는 70 ~ 90℃까지 가열하는 단계를 더 포함하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.The first slurry is a method for producing an oxide layer coated barium titanate powder, characterized in that it further comprises the step of heating up to 70 ~ 90 ℃.
- 제 12 항에 있어서,The method of claim 12,상기 제 2 슬러리에 Si로 이루어지는 산화물을 용해시킨 희석액을 적정(滴定)하는 경우 상기 제 2 슬러리의 pH는 5.0 ~ 14.0으로 유지시키는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.When titrating a diluent in which an oxide of Si is dissolved in the second slurry, the pH of the second slurry is maintained at 5.0 to 14.0, wherein the oxide layer is coated with barium titanate powder.
- 제 14 항에 있어서,The method of claim 14,상기 Si로 이루어지는 산화물을 용해시킨 희석액은 물유리(Water Glass)를 이용하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.The dilution solution in which the oxide made of Si is dissolved is a method of manufacturing barium titanate powder coated with an oxide layer, characterized in that water glass is used.
- 제 12 항에 있어서,The method of claim 12,상기 제 2 슬러리에 Zr로 이루어지는 산화물을 용해시킨 희석액을 적정(滴定)하는 경우 상기 제 2 슬러리의 pH는 1.0 ~ 5.0으로 유지시키는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.When titrating a dilution solution in which an oxide of Zr is dissolved in the second slurry, the pH of the second slurry is maintained at 1.0 to 5.0.
- 제 12 항에 있어서,The method of claim 12,상기 제 2 슬러리에 Y, V, Dy, Mg, Mn, Ni 및 Co 중 선택된 하나 이상의 물질로 이루어지는 산화물을 용해시킨 희석액을 적정(滴定)하는 경우 상기 제 2 슬러리의 pH는 5.0 ~ 14.0로 유지시키는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.When titrating a diluent in which an oxide composed of at least one of Y, V, Dy, Mg, Mn, Ni, and Co is dissolved in the second slurry, the pH of the second slurry is maintained at 5.0 to 14.0. Method for producing a barium titanate powder coated with an oxide layer, characterized in that.
- 제 17 항에 있어서,The method of claim 17,상기 Y, V, Dy, Mg, Mn, Ni, Co 및 Zr 중 선택된 하나 이상의 물질로 이루어지는 산화물을 용해시킨 희석액은 염화물, 질산염 및 황산염 중 선택된 하나로 이루어지는 수용액을 이용하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.The oxide layer is coated with an oxide layer, characterized in that the dilution of an oxide made of at least one selected from Y, V, Dy, Mg, Mn, Ni, Co, and Zr uses an aqueous solution made of one selected from chloride, nitrate, and sulfate. Barium titanate powder production method.
- 제 14 항 또는 제 16 항에 있어서,The method according to claim 14 or 16,상기 pH는 HCl, H2SO4, HNO3, NaOH 및 KOH 중 선택된 하나를 이용하여 유지시키는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.Wherein the pH is maintained using one selected from HCl, H 2 SO 4 , HNO 3 , NaOH and KOH oxide layer-coated barium titanate powder manufacturing method.
- 제 12 항에 있어서,The method of claim 12,상기 제 2 슬러리를 조성한 후 10 ~ 60분 동안 교반하는 단계를 더 포함하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.After the composition of the second slurry, the method for preparing an oxide layer-coated barium titanate powder, further comprising the step of stirring for 10 to 60 minutes.
- 제 12 항에 있어서,The method of claim 12,상기 열처리 단계는 125 ~ 1300℃의 온도에서 20 ~ 120분 동안 유지시키는 단계를 포함하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.The heat treatment step is an oxide layer coated barium titanate powder manufacturing method comprising the step of maintaining for 20 to 120 minutes at a temperature of 125 ~ 1300 ℃.
- 제 12 항에 있어서,The method of claim 12,상기 산화물층의 두께는 상기 Si, Y, V, Dy, Mg, Mn, Ni, Co 및 Zr의 첨가량을 조절하여 결정하는 것을 특징으로 하는 산화물층이 코팅된 티탄산바륨 분말 제조방법.The thickness of the oxide layer is a method for producing an oxide layer coated barium titanate powder, characterized in that determined by adjusting the addition amount of the Si, Y, V, Dy, Mg, Mn, Ni, Co and Zr.
- 제 12 항 내지 제 21 항 중 선택된 어느 한 항의 방법으로 제조된 산화물층이 코팅된 티탄산바륨 분말을 물(Aqua)에 분산시켜 내부 전극층용 페이스트(Paste) 또는 유전체층용 페이스트(Paste)로 형성하는 것을 특징으로 하는 적층세라믹콘덴서 원료 제조방법.A method of dispersing a barium titanate powder coated with an oxide layer prepared by the method of any one of claims 12 to 21 in water to form an internal electrode paste or a dielectric layer paste. Laminated ceramic capacitor raw material manufacturing method characterized in that.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010800247131A CN102459083A (en) | 2009-06-05 | 2010-06-04 | Barium titanate powder coated with an oxide layer, and a production method therefor |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20090050124 | 2009-06-05 | ||
| KR10-2009-0050124 | 2009-06-05 | ||
| KR10-2010-0052641 | 2010-06-04 | ||
| KR1020100052641A KR101142251B1 (en) | 2009-06-05 | 2010-06-04 | Barium titanate powder coated oxide layer and method for fabricating the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010140868A2 true WO2010140868A2 (en) | 2010-12-09 |
| WO2010140868A3 WO2010140868A3 (en) | 2011-03-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2010/003613 WO2010140868A2 (en) | 2009-06-05 | 2010-06-04 | Barium titanate powder coated with an oxide layer, and a production method therefor |
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| Country | Link |
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| WO (1) | WO2010140868A2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977006A (en) * | 1997-05-06 | 1999-11-02 | Taiyo Yuden Co., Ltd. | Barium titanate-magnesium ceramic for use in capacitors or the like |
| US6071842A (en) * | 1997-09-05 | 2000-06-06 | Tdk Corporation | Barium titanate-based semiconductor ceramic |
| US20020090335A1 (en) * | 2000-11-13 | 2002-07-11 | Toshiharu Harada | Spherical tetragonal barium titanate particles and process for producing the same |
-
2010
- 2010-06-04 WO PCT/KR2010/003613 patent/WO2010140868A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977006A (en) * | 1997-05-06 | 1999-11-02 | Taiyo Yuden Co., Ltd. | Barium titanate-magnesium ceramic for use in capacitors or the like |
| US6071842A (en) * | 1997-09-05 | 2000-06-06 | Tdk Corporation | Barium titanate-based semiconductor ceramic |
| US20020090335A1 (en) * | 2000-11-13 | 2002-07-11 | Toshiharu Harada | Spherical tetragonal barium titanate particles and process for producing the same |
Non-Patent Citations (2)
| Title |
|---|
| CHRISTOPHE HUBER ET AL. JOURNAL OF MATERIAL CHEMISTRY vol. 13, 2003, pages 650 - 653 * |
| RENZHENG CHEN ET AL. MATERIAL LETTERS vol. 54, 2002, pages 314 - 317 * |
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| Publication number | Publication date |
|---|---|
| WO2010140868A3 (en) | 2011-03-31 |
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