WO2007007587A1 - POLYCRISTAL D’OXYDE DE Co A ORIENTATION CONTRÔLÉE - Google Patents

POLYCRISTAL D’OXYDE DE Co A ORIENTATION CONTRÔLÉE Download PDF

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WO2007007587A1
WO2007007587A1 PCT/JP2006/313288 JP2006313288W WO2007007587A1 WO 2007007587 A1 WO2007007587 A1 WO 2007007587A1 JP 2006313288 W JP2006313288 W JP 2006313288W WO 2007007587 A1 WO2007007587 A1 WO 2007007587A1
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crystal
coo
temperature
oxide
crystal structure
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PCT/JP2006/313288
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Japanese (ja)
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Hiroshi Fukutomi
Eisuke Iguchi
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National University Corporation Yokohama National University
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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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
    • C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
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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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/787—Oriented grains
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9623—Ceramic setters properties

Definitions

  • the present invention relates to ceramics manufactured by controlling crystal orientation, and more specifically, (00
  • Ceramics generally cause plastic deformation even when a large force is applied for the purpose of plastic deformation because the number of independent slip systems necessary for plastic deformation of a polycrystalline body having a high Peierls potential cannot be secured sufficiently. It is normal to destroy without. Therefore, unlike metal materials, ceramics did not have an orientation control technology by plastic working.
  • thermoelectric conversion ceramics by orientation control, a method has been proposed in which a part of the raw material is partially melted while being uniaxially pressed and then gradually cooled (Patent Document 1).
  • anisotropically shaped powders such as needles and plates are present in the molded body at a relatively high degree of orientation, and this anisotropically shaped powder is used as a template or a reactive template for the growth and oxidation of oxides. It is also possible to adjust the orientation by synthesis and / or sintering. The usefulness of rolling in a slurry state is also presented (Non-Patent Literature)
  • thermoelectric characteristic a ceramic represented by the general formula Bi Pb Sr Y Co O as a thermoelectric characteristic.
  • Non-Patent Document 1 (Non-Patent Document 1).
  • Patent Document 1 JP 2001-19544 (Patent No. 3089301)
  • Patent Document 2 JP 2003-282965 A
  • Patent Document 3 J. Phys. D: Appl. Phys. 34 (2001) 1017-1024
  • An object of the present invention is to provide a method for controlling the crystal orientation of a ceramic and a ceramic produced by controlling the crystal orientation.
  • the ceramic orientation whose crystal orientation is controlled has anisotropy, and in the case of thermoelectric conversion ceramics, it can be used as thermoelectric conversion ceramics with improved performance index by utilizing the direction of low electrical resistance.
  • the present invention relates to a polycrystalline body of cobalt oxide having an incommensurate crystal structure, and the crystals are oriented in a certain direction due to slip deformation in the (001) plane of the polycrystalline crystal. It is a Co acid complex polycrystal.
  • the polycrystal is compressed at a strain rate of 1.0 X 10 _5 to 1.0 X 10 _3 s _1 at a temperature range of 800 ° C or higher and a temperature of 30 ° C below the melting point of the crystal.
  • This slip deformation can be caused by performing the above.
  • plastic processing methods such as uniaxial compression processing, plane strain compression processing, rolling, and extrusion processing may be used.
  • the present invention is, 1. 0 X 10 _5 at a temperature range up to a temperature of 30 ° C under the melting point of the Co Sani ⁇ of polycrystalline whether we said crystals 800 ° C or higher with a mismatched crystal structure ⁇ 1.0 X 10 " 3 s"
  • This is a process for producing Co oxides with a mismatched crystal structure with slip deformation in the (001) plane consisting of compression processing at a strain rate of 1 .
  • the present invention has made it possible to provide a ceramic in which the orientation is aligned in a certain direction by plastically deforming a polycrystalline ceramic having a crystal grain force whose orientation direction is random.
  • the Co oxide having an incommensurate crystal structure of the present invention undergoes plastic deformation by high-temperature processing, realizing densification and texture formation, and as a result, improved thermoelectric properties.
  • the material of the present invention is a high-temperature thermoelectric conversion material that can be used up to around 700 ° C.
  • heat generated by combustion in factories and garbage incinerators can be removed.
  • the highly oriented polycrystalline ceramic of the present invention is a Co oxide having a mismatch crystal structure.
  • “Incommensurate crystal structure” refers to C composed of multiple layers including CoO electron conducting layers.
  • o Oxide is a stack of layers in the c-axis direction, with the a and b axes in the vertical direction, and the ratio of the lattice constant of the CoO layer in the b-axis direction to the lattice constant of the other layers in contact with this layer above and below Is an irrational number
  • This ceramic has a layered crystal structure and is more than 10 times the maximum value of the average density in the positive pole figure measured by the Schulz reflection method.
  • the layered crystal structure includes a first sublattice made of a Co 2 O layer and a layer different from Co 2 O.
  • the incommensurate crystal structure can be confirmed by X-ray diffractometry, but can be confirmed more accurately by neutron beam analysis.
  • composition can be confirmed by the EDX measurement method, and more accurately, it is generally difficult to determine the amount of oxygen that can be confirmed by wet analysis using either method.
  • Bi Pb Sr Y Co O (wherein x
  • Polycrystal is a collection of a large number of the above single crystals having a size of about 1 to about L0 m in various directions. This polycrystal can be obtained by assembling and sintering powders of this composition.
  • compression processing is a plastic processing method in which a shape is changed by applying a compression force to a target object.
  • Single-axis compression processing is a plastic processing method in which a uniaxial compression force is applied.
  • ⁇ Plane strain compression processing '' prevents deformation in one direction among deformations in the direction perpendicular to the compression force of the target object when a uniaxial compression force is applied, and deformation in only one direction. This is a compression processing method that allows
  • the temperature of this compressive force is over 800 ° C.
  • the temperature range is up to 30 ° C below the melting point of the crystal.
  • the temperature 30 ° C below the melting point of the crystal indicates the temperature at which the crystal close to the melting point of the crystal is in a solid state.
  • the melting point of the crystal is measured by thermal analysis.
  • the strain rate of the compression processing is obtained by dividing the compression rate by the height of the object to be compressed, and is 1.0 X 10 _5 to 1.0 X 10 _3 s _1 , preferably 2.0 X 10 _5 to 8 OX 10 _5 s _1 .
  • distortion If the speed is less than 1.0 X 10 _5 s _1 , the main deformation mechanism, which takes a long time to give sufficient strain, changes to crystal slip deformation force diffusion creep, and the crystal orientation is sufficiently aligned. If the strain rate is greater than 1.0 X 10 _4 s _1 , the contribution of diffusion to alleviate the lack of the slip system is insufficient.
  • Annealing is performed to remove lattice defects such as dislocations that have proliferated during crystal slip deformation, and in a temperature range of 800 ° C or higher up to 30 ° C below the melting point of the crystal. Heat. By annealing after the processing, recovery of dislocations and the like occurs, and the electrical resistance can be further reduced.
  • the measurement method was the Schulz reflection method, using CuKo; wire, tube voltage 40 kV, tube current 30 mA.
  • Tissue photographs were taken using a scanning electron microscope (SEM). The unsintered specimen was thinly cut with a diamond cutter and the surface of the specimen was also observed, and the finished specimen was observed on a surface perpendicular to the compression surface of the specimen.
  • SEM scanning electron microscope
  • the electrical resistance was measured by a four-terminal method after attaching an electrode to the sample, connecting a copper wire to the sample with a silver paste.
  • the measurement procedure was as follows. Place the prepared sample in a single bottle (manufactured by OXFORD), draw a vacuum with an oil rotary pump, and apply a current of 10 mA when rising from about 80 K to 340 K using liquid nitrogen as a medium. The voltage value of the hour (workpiece is 100mA) was measured under GP-IB control at a temperature interval of 1K. The temperature was measured using a copper-constantan thermocouple.
  • Bi 0 purity 99.9%, Wako Pure Chemical Industries, Ltd.
  • PbO purity 97%, Nakarai Desk Co., Ltd.
  • Sr 0 purity 99.9%, Wako Pure Chemical Industries, Ltd.
  • PbO purity 97%, Nakarai Desk Co., Ltd.
  • Sr 0 purity 97%, Nakarai Desk Co., Ltd.
  • this mixture was dry-mixed for 60 minutes using an agate ball mill and a milling machine (SPEX, CertiPrep).
  • the sample was put in an alumina boat and calcined at 790 ° C for 12 hours in a pine furnace.
  • the powder was refined by dry grinding using an agate mortar.
  • the obtained powder was formed into a cylinder having a diameter of about 11 mm and a height of about 4 mm, placed in an alumina boat, and baked in air at 840 ° C for 24 hours in a Matsufur furnace.
  • the resulting crystal is a Co oxide with a mismatch crystal structure with a composition of Bi Pb Sr Y Co O.
  • the sample produced in Production Example 1 was sandwiched between magnesia plates at right angles to the axial direction of the cylinder using a 2t autograph (manufactured by Shimadzu Corporation) and heated in an infrared image furnace. While the temperature rose to 840 ° C, the temperature of the sample was measured using a thermocouple. Even after the target temperature was reached, the jig continued to expand, so the temperature was held for about 70 minutes until it stopped.
  • Fig. 4 and Fig. 4 show the diffraction pattern of the plane perpendicular to the cylinder axis of the test specimen and the positive dot diagram. Shown in 5.
  • Imax was measured by taking a positive point map of this peak. From this positive pole figure, it can be seen that the (001) plane is oriented parallel to the compression plane and rotated around the normal of the (001) plane by various angles.
  • a cross-sectional photograph (SEM) in the direction parallel to the cylinder axis of the obtained specimen is shown in FIG. From this photograph, it can be seen that the dimensions of the crystal grains differ between the direction perpendicular to the compression direction (longitudinal direction in the figure) and the direction parallel to the direction, and plastic deformation occurred in the compression direction.
  • the maximum value of the pole density in the (001) pole figure (Fig. 8) determined by Schulz's reflection method was 1.0 before calorie, but increased to 11.7 as the amount of strain increased. As shown in Fig. 9, the resistance decreases monotonously with increasing strain ( ⁇ ) due to processing up to true strain of 1.87. In addition, materials manufactured by plane strain compression show a lower specific resistance than workpieces with true strains up to 1.87. Furthermore, the electrical resistance of the material created by this method remains low even at high temperatures.
  • Example 4 The sample that had been subjected to the compression check in Example 2 (with a strain of 1.87) was annealed in air at 840 ° C for 24 hours in a Matsufur furnace. Figure 9 shows the resistivity. Annealing further reduced the electrical resistance, down to a maximum of 20: 1. That is, by realizing high orientation by the orientation control technology of the present invention, the figure of merit of thermoelectric characteristics has been dramatically improved by 20 times.
  • a magnesia plate used for uniaxial compression was cut into a strip of 5 mm width, which was then manufactured
  • a high-temperature plane strain compressive force test was performed by applying a pressure vertically from the axial direction of the cylinder of the sample prepared in 1.
  • Example 2 As in Example 1, at 840 ° C along the axial direction of the sample cylinder at 2t autograph cross-head speed constant (5.0 X 10- 3 mm / min , the strain rate 2.0 X 10- 5 s-1 High-temperature plane strain compression processing was performed. The results are shown in Table 2.
  • a cylindrical base material was made by press molding and then sintered at 920 ° C for 24 hours.
  • Example 6 The electrical resistance of Example 6 was measured by a four-terminal method after attaching an electrode to the sample and then connecting a copper wire to the sample with a silver paste. The results are shown in Figs.
  • Figure 14 shows the measurement results of the specific resistance of [Ca CoO] CoO. b Sr Y Co O results in low resistivity, -1.87 force-working material and plane strain compression material
  • CoO is the result of heating and cooling.
  • the result of 0 is shown enlarged.
  • the electrical resistivity reaches a minimum of 2 m ⁇ cm or less.
  • Example 2 (Bi-Sr-Co-O) and Example 5 and Example 6 (Ca-Co-0), which are layered oxides having a misfit structure, are also shown in FIG. Shown in
  • Figure 17 shows the results of confirming the crystal structure of [Ca CoO] CoO by X-ray diffraction.
  • CoO is a material in which Ca in [Ca CoO] CoO is partially substituted with Sr.
  • the crystal structure is the same as [Ca CoO] CoO.
  • Example 2 four layers of insulation between CoO layers
  • the crystal orientation can be controlled by this method even when V, V, and misalignment.
  • FIG. 1 is a diagram showing a crystal structure of Bi Pb Sr Y Co 2 O. In the figure, vertical direction (crystal c
  • the atomic plane whose normal is (axial direction) is the (001) plane.
  • FIG. 2 is a diagram showing a diffraction pattern of a polycrystal prepared in Production Example 1.
  • FIG. 3 is a cross-sectional photograph (SEM) of a polycrystal prepared in Production Example 1.
  • FIG. 4 is a diagram showing a diffraction pattern of a crystal subjected to high-temperature uniaxial compression processing in Example 1.
  • FIG. 5 is a diagram showing a positive electrode dot diagram of a crystal subjected to high-temperature uniaxial compression processing in Example 1.
  • the concentric curve indicates the position where the average pole density is 1, 2, 3, 4, 5 or 6 times higher from the outside.
  • FIG. 6 is a cross-sectional photograph (SEM) of a crystal subjected to high-temperature uniaxial compression processing in Example 1.
  • the vertical direction in the figure is the compression direction.
  • FIG. 7 is a graph showing changes in density of crystals subjected to high-temperature uniaxial compression processing in Example 2.
  • the vertical axis represents density (g / cm 2 ), and the horizontal axis represents strain.
  • FIG. 8 is a diagram showing a positive electrode dot diagram of a crystal subjected to high-temperature uniaxial compression processing in Example 2.
  • FIG. 9 is a graph showing the resistivity of crystals subjected to high-temperature uniaxial compression processing in Example 2.
  • FIG. 10 is a diagram showing a diffraction pattern of a crystal subjected to high-temperature plane strain compression processing in Example 4.
  • FIG. 11 is a diagram showing a positive electrode dot diagram of a crystal subjected to high-temperature plane strain compression processing in Example 4. Concentric curves indicate the positions where the average pole density is 1, 2, 3, 4, 5, 6, 7 times as many as the order from the outside.
  • FIG. 12 is a diagram showing a positive electrode dot diagram of a crystal subjected to high-temperature uniaxial compression processing in Example 5.
  • FIG. 13 is a diagram showing a positive electrode dot diagram of a crystal subjected to high-temperature uniaxial compression processing in Example 6.
  • FIG. 14 is a graph showing the results of measuring electrical resistance of the crystal prepared in Example 6.
  • FIG. 15 is a diagram showing the results of measuring electrical resistance of the crystal prepared in Example 6.
  • FIG. 1 A first figure.
  • FIG. 17 A diagram showing an X-ray diffraction pattern of a polycrystal prepared in Production Example 3.

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  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

La présente invention concerne un polycristal d’oxyde de Co, comprenant un polycristal d’un oxyde de Co ayant une structure cristalline non appariée, provoquant une déformation de glissement sur le plan (001) du polycristal, et ayant subi une rotation de cristal dans une direction donnée. En outre, un polycristal d’oxyde de Co soumis à une rotation de cristal dans une direction donnée peut être obtenu en comprimant un polycristal d’oxyde de Co ayant une structure cristalline non appariée à 800 - 930ºC et à un taux de contrainte de 1,0 × 10-5 à 1,0 × 10-3 s-1 pour provoquer une déformation de glissement. Selon la constitution ci-dessus, on peut contrôler l’orientation cristalline de céramiques et alors produire des céramiques soumises à un contrôle d’orientation cristalline, ayant une résistance électrique anisotrope et pouvant être utilisées comme céramiques de conversion thermoélastique.
PCT/JP2006/313288 2005-07-07 2006-07-04 POLYCRISTAL D’OXYDE DE Co A ORIENTATION CONTRÔLÉE WO2007007587A1 (fr)

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WO2013004630A2 (fr) 2011-07-01 2013-01-10 Alzchem Ag Procédé de production d'ammoniac à partir d'une substance précurseur d'ammoniac pour la réduction d'oxydes d'azote dans des gaz de combustion

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