WO2013094346A1 - Procédé de production d'un composé de mayénite conducteur et électrode destinée à des lampes fluorescentes - Google Patents

Procédé de production d'un composé de mayénite conducteur et électrode destinée à des lampes fluorescentes Download PDF

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WO2013094346A1
WO2013094346A1 PCT/JP2012/079433 JP2012079433W WO2013094346A1 WO 2013094346 A1 WO2013094346 A1 WO 2013094346A1 JP 2012079433 W JP2012079433 W JP 2012079433W WO 2013094346 A1 WO2013094346 A1 WO 2013094346A1
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mayenite compound
sintered body
powder
conductive mayenite
titanium
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PCT/JP2012/079433
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English (en)
Japanese (ja)
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伊藤　和弘
俊成 渡邉
暁 渡邉
宮川　直通
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旭硝子株式会社
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Priority to JP2013550183A priority Critical patent/JP5971258B2/ja
Publication of WO2013094346A1 publication Critical patent/WO2013094346A1/fr

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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/164—Calcium aluminates
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    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
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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
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
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    • 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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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
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    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/652—Reduction treatment
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    • C04B2235/658—Atmosphere during thermal treatment
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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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/04—Electrodes; Screens; Shields
    • H01J61/06—Main electrodes
    • H01J61/067—Main electrodes for low-pressure discharge lamps
    • H01J61/0675—Main electrodes for low-pressure discharge lamps characterised by the material of the electrode

Definitions

  • the present invention relates to a method for producing a conductive mayenite compound.
  • the mayenite compound has a typical crystal structure having a representative composition represented by 12CaO ⁇ 7Al 2 O 3 and having three-dimensionally connected voids (cages) having a diameter of about 0.4 nm.
  • the skeleton constituting this cage is positively charged and forms 12 cages per unit cell. Since 1/6 of this cage satisfies the electrical neutrality condition of the crystal, the inside is occupied by oxygen ions. However, the oxygen ions in the cage have characteristics that are chemically different from the other oxygen ions constituting the skeleton. Therefore, the oxygen ions in the cage are particularly called free oxygen ions. .
  • the mayenite compound is also expressed as [Ca 24 Al 28 O 64 ] 4 + ⁇ 2O 2 ⁇ (Non-patent Document 1).
  • Such a conductive mayenite compound is particularly referred to as a “conductive mayenite compound”.
  • the conductive mayenite compound When the conductive mayenite compound is used as an electrode material such as a fluorescent lamp, for example, the conductive mayenite compound is required to have a high electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more. This is because when a conductive mayenite compound having an electron density lower than this is used as an electrode, Joule heat is generated in the electrode during use, which may cause a problem that the electrode becomes high temperature. Further, when such Joule heat is generated in the electrode every time the lamp is lit, as a result of repeatedly applying thermal stress to the electrode, the electrode may be cracked or broken, and the electrode may be damaged.
  • Patent Document 2 discloses that a silica glass tube is used as a container and a single crystal of the mayenite compound is heat-treated in a vacuum atmosphere containing metallic titanium. , It is disclosed that a member made of a conductive mayenite compound having an electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more can be produced.
  • a member made of a conductive mayenite compound having a high electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more is obtained by heat-treating a single crystal of a mayenite compound in a vacuum atmosphere containing metallic titanium. Can be manufactured.
  • the member made of the conductive mayenite compound obtained by this method is characterized by having a relatively thick “surface layer” on the surface.
  • the “surface layer” is formed by the reaction of the surface of the object to be processed with free oxygen ions in the environment component or in the cage of the mayenite compound in the course of the heat treatment of the object. It is a generic term for layers having a phase composition different from that of a mayenite compound.
  • Fluorescent lamp electrodes must exhibit stable characteristics as soon as possible after use of the fluorescent lamp.
  • the “surface layer” of the member made of the conductive mayenite compound is removed by processing before the member is assembled to the fluorescent lamp.
  • a “surface layer” is firmly fixed to the member.
  • an electrode often has a complicated shape, and it is extremely difficult to remove the “surface layer” of the electrode in advance by processing. Therefore, it is necessary to remove the “surface layer” of the member while using the fluorescent lamp by utilizing the discharge phenomenon of the fluorescent lamp.
  • the “surface layer” formed on the surface of the conductive mayenite compound member needs to be as thin as possible for the rapid and stable operation of the fluorescent lamp.
  • This invention is made
  • a method for producing a conductive mayenite compound (1) preparing a powder of a mayenite compound; (2) The object to be treated containing the mayenite compound powder prepared in the step (1) is placed in the presence of carbon monoxide gas and titanium vapor supplied from a titanium source in a state not in contact with the titanium source. Holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment; The manufacturing method characterized by including is provided.
  • the object to be treated containing the mayenite compound powder may be a molded body containing the mayenite compound powder.
  • the object to be treated may be configured by attaching a compact containing the powder of the mayenite compound to a conductive member.
  • a method for producing a conductive mayenite compound (1) preparing a sintered body containing a mayenite compound; (2) The to-be-processed object containing the sintered compact containing the mayenite compound prepared in the step (1) is not in contact with the titanium source in the presence of carbon monoxide gas and titanium vapor supplied from the titanium source. Holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment; The manufacturing method characterized by including is provided.
  • a method for producing a conductive mayenite compound (1) a step of preparing a calcined powder compact, (2) A state in which the object to be processed including the calcined powder formed body prepared in the step (1) is not in contact with the titanium source in the presence of carbon monoxide gas and titanium vapor supplied from the titanium source. And holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment;
  • the manufacturing method characterized by including is provided.
  • the step (2) may be performed in a state where the object to be processed and the titanium source are placed in a container containing carbon.
  • the conductive mayenite compound obtained after the step (2) may have an electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more.
  • the said to-be-processed object contains a fluorine (F)
  • a conductive mayenite compound containing fluorine may be obtained.
  • the present invention provides an electrode for a fluorescent lamp containing the highly conductive mayenite compound manufactured by the above-described manufacturing method.
  • the present invention provides a method for producing a film-forming target containing a conductive mayenite compound using the production method as described above.
  • a method for producing a highly conductive mayenite compound (1) preparing a powder of a mayenite compound; (2) The object to be treated containing the mayenite compound powder prepared in the step (1) is placed in the presence of carbon monoxide gas and titanium vapor supplied from a titanium source in a state not in contact with the titanium source. Holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment; The manufacturing method characterized by including is provided.
  • the second aspect of the present invention is a method for producing a highly conductive mayenite compound, (1) preparing a sintered body containing a mayenite compound; (2) The to-be-processed object containing the sintered compact containing the mayenite compound prepared in the step (1) is not in contact with the titanium source in the presence of carbon monoxide gas and titanium vapor supplied from the titanium source. Holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment; The manufacturing method characterized by including is provided.
  • the third aspect of the present invention is a method for producing a highly conductive mayenite compound, (1) a step of preparing a calcined powder compact, (2) A state in which the object to be processed including the calcined powder formed body prepared in the step (1) is not in contact with the titanium source in the presence of carbon monoxide gas and titanium vapor supplied from the titanium source. And holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment;
  • the manufacturing method characterized by including is provided.
  • the “mayenite compound” is a general term for 12CaO ⁇ 7Al 2 O 3 (hereinafter also referred to as “C12A7”) having a cage ( ⁇ ) structure and a compound having the same crystal structure as C12A7 (same type compound).
  • the “conductive mayenite compound” means an electron density of 1.0 ⁇ 10 18 cm ⁇ 3 or more in which a part or all of “free oxygen ions” contained in the cage is replaced with electrons. Represents a mayenite compound. The electron density when all the free oxygen ions are replaced with electrons is 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the “mayenite compound” includes a “conductive mayenite compound” and a “non-conductive mayenite compound”.
  • the manufactured “conductive mayenite compound” has an electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more, and a “conductive mayenite compound” that can be used as an electrode of a lamp can be obtained.
  • a conductive mayenite compound having an electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more is particularly referred to as a “highly conductive mayenite compound”.
  • the electron density of the conductive mayenite compound is measured by two methods according to the electron density of the mayenite compound.
  • the electron density is 1.0 ⁇ 10 18 cm ⁇ 3 to less than 3.0 ⁇ 10 20 cm ⁇ 3
  • the electron density is 2 of the absorption spectrum obtained by measuring the diffuse reflection of the conductive mayenite compound powder and subjected to Kubelka-Munk conversion. It is calculated from the absorbance (Kuberkunk conversion value) of .8 eV (wavelength 443 nm). This method utilizes the fact that the electron density and the Kubelka-Munk conversion value are in a proportional relationship.
  • a method for creating a calibration curve will be described.
  • ESR electron spin resonance
  • n (-(E sp -2.83) /0.199) 0.782
  • n represents the electron density (cm ⁇ 3 )
  • E sp represents the peak energy (eV) of the absorption spectrum obtained by Kubelka-Munk transformation.
  • the highly conductive mayenite compound has a C12A7 crystal structure composed of calcium (Ca), aluminum (Al) and oxygen (O), calcium (Ca), aluminum (Al) and oxygen
  • a part of at least one atom selected from (O) may be substituted with another atom or atomic group.
  • a part of calcium (Ca) is magnesium (Mg), strontium (Sr), barium (Ba), lithium (Li), sodium (Na), chromium (Cr), manganese (Mn), cerium (Ce).
  • Cobalt (Co), nickel (Ni) and copper (Cu) may be substituted with one or more atoms selected from the group consisting of.
  • a part of aluminum (Al) is silicon (Si), germanium (Ge), boron (B), gallium (Ga), titanium (Ti), manganese (Mn), iron (Fe), cerium (Ce).
  • Praseodymium (Pr), scandium (Sc), lanthanum (La), yttrium (Y), europium (Eu), yttrium (Yb), cobalt (Co), nickel (Ni) and terbium (Tb) May be substituted with one or more atoms. Further, the oxygen in the cage skeleton may be substituted with nitrogen (N) or the like.
  • the conductive mayenite compound is such that at least a part of free oxygen ions in the cage is H ⁇ , H 2 ⁇ , H 2 ⁇ , O ⁇ , O 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , and S 2. It may be substituted with an anion such as 2- or an anion of nitrogen (N).
  • a member made of a highly conductive mayenite compound obtained by a conventional method is characterized by having a relatively thick “surface layer” on the surface.
  • Such a “surface layer” has a phase composition different from the inside of the member, and is composed of a phase different from the mayenite compound. Therefore, when a member made of a conductive mayenite compound having such a “surface layer” is used as an electrode of a fluorescent lamp, for example, for stable operation of the fluorescent lamp, the “surface layer” is formed by sputtering during discharge. It is necessary to remove it promptly.
  • the inventors of the present application conducted an experiment for producing a conductive mayenite compound under various conditions, and earnestly influenced the influence of the production conditions on the aspect of the “surface layer” of the conductive mayenite compound. I have been considering it.
  • the inventors of the present application when heat-treating the object to be treated containing the powder of the mayenite compound in a predetermined temperature range, when coexisting a carbon monoxide gas and a titanium source that becomes titanium vapor in the environment, It has been found that a highly conductive mayenite compound can be produced without growing the surface layer too much.
  • the object to be treated is placed in the presence of a carbon source and a titanium source that becomes titanium vapor, and an inert gas atmosphere excluding nitrogen or a reduced pressure environment.
  • the first feature is that the object to be processed is maintained at a temperature in the range of 1230 ° C. to 1380 ° C.
  • titanium oxide is deposited on the surface of the mayenite compound that is the object to be processed.
  • the mayenite compound which comprises a to-be-processed object is an oxide, it has high affinity with the deposited titanium oxide. For this reason, the titanium oxide deposited on the surface of the object to be processed is firmly bonded to the surface of the object to be processed. Thereafter, deposition of titanium oxide is continued on the surface of the object to be processed, and finally a thick “surface layer” is formed.
  • titanium carbide when titanium vapor and carbon monoxide gas coexist in the environment, the titanium vapor reacts with the carbon monoxide gas in the environment to produce titanium carbide. Since this titanium carbide is a non-oxide, its affinity with the mayenite compound constituting the object to be processed is not so high. Therefore, even if titanium carbide is deposited on the surface of the object to be processed, the titanium carbide easily falls off the surface without being fixed to the surface of the object to be processed. Therefore, it is significantly suppressed that the titanium carbide deposit adheres to the surface of the object to be processed or grows on the surface of the object to be processed. As a result, it is considered that a thin “surface layer” is finally formed.
  • the object to be processed of the mayenite compound when the object to be processed of the mayenite compound is brought into direct contact with the titanium source, titanium metal adheres to the surface of the object to be processed during the heat treatment.
  • the temperature is lowered to room temperature in such a state, the metal titanium solid is fixed to the surface of the conductive mayenite compound.
  • Such a fixed substance is firmly adhered to the conductive mayenite compound, and it is not easy to peel or remove the fixed substance from the conductive mayenite compound in a subsequent process.
  • the second feature of the present invention is that the object to be processed is disposed so as not to contact the titanium source, and the object to be processed is heat-treated in this state. Thereby, the problem that metal titanium adheres firmly to the surface of the object to be processed can be solved.
  • a conductive mayenite compound having a high electron density without growing a “surface layer” too thick is obtained. It can be manufactured.
  • the thickness of the “surface layer” can be set to 40 ⁇ m or less, for example.
  • FIG. 1 schematically shows a flow of a method for producing a highly conductive mayenite compound according to an embodiment of the present invention.
  • a step of preparing a mayenite compound powder (step S110); (2) The object to be treated containing the mayenite compound powder prepared in the step (1) is placed in the presence of carbon monoxide gas and titanium vapor supplied from a titanium source in a state not in contact with the titanium source. Holding the object to be treated at a temperature in the range of 1230 ° C. to 1380 ° C. in an inert gas atmosphere excluding nitrogen or a reduced pressure environment (step S120); Have Hereinafter, each process will be described.
  • Step S110 Mayenite Compound Powder Preparation Step
  • a powder of mayenite compound is prepared.
  • the mayenite compound powder is synthesized and manufactured by heating the raw material powder to a high temperature as shown below.
  • a raw material powder for synthesizing a mayenite compound powder is prepared.
  • the ratio of calcium (Ca) to aluminum (Al) is preferably in the range of 13: 6 to 10: 9 in terms of molar ratio converted to CaO: Al 2 O 3 , and 12.6: 6.4 to
  • the range of 11.7: 7.3 is more preferable, the range of 12.3: 6.7 to 11.5: 7.5 is more preferable, and the range of 12.2: 6.8 to 11.8: 7.2.
  • a range is more preferred, with about 12: 7 being particularly preferred.
  • the number of moles of calcium and other atoms is regarded as the number of moles of calcium.
  • the number of moles of aluminum and the other atoms is regarded as the number of moles of aluminum.
  • the compound used for the raw material powder is not particularly limited as long as the ratio is maintained.
  • the raw material powder preferably contains calcium aluminate or at least two selected from the group consisting of calcium compounds, aluminum compounds, and calcium aluminates.
  • the raw material powder may be, for example, a mixed powder containing a calcium compound and an aluminum compound.
  • the raw material powder may be, for example, a mixed powder containing a calcium compound and calcium aluminate.
  • the raw material powder may be a mixed powder containing, for example, an aluminum compound and calcium aluminate.
  • the raw material powder may be a mixed powder containing, for example, a calcium compound, an aluminum compound, and calcium aluminate.
  • the raw material powder may be, for example, a mixed powder containing only calcium aluminate.
  • Examples of calcium compounds include calcium carbonate, calcium oxide, calcium hydroxide, calcium hydrogen carbonate, calcium sulfate, calcium metaphosphate, calcium oxalate, calcium acetate, calcium nitrate, and calcium halide. Of these, calcium carbonate, calcium oxide, and calcium hydroxide are preferred.
  • Examples of the aluminum compound include aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum nitrate, and aluminum halide. Of these, aluminum hydroxide and aluminum oxide are preferred.
  • Examples of aluminum oxide (alumina) include ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, with ⁇ -aluminum oxide (alumina) being preferred.
  • the raw material powder may further contain a fluorine (F) component.
  • a fluorine (F) component examples include calcium fluoride (CaF 2 ).
  • a fluorine (F) component is added to the raw material powder, a high electron density conductive mayenite compound in which fluorine ions are introduced into the cage can be finally produced (after step S120).
  • the raw material powder containing the fluorine (F) component is not limited to this, but may be prepared, for example, by adding calcium fluoride to the mixed powder of the calcium compound and the aluminum compound as described above.
  • the content of fluorine (F) in the raw material powder is not particularly limited.
  • the fluorine (F) content is, for example, the chemical formula of the finally obtained conductive mayenite compound.
  • (12-x) CaO ⁇ 7Al 2 O 3 ⁇ xCaF 2 (1) formula
  • the range of x may be selected to be in the range of 0 to 0.60.
  • the prepared raw material powder is kept at a high temperature, and a mayenite compound is synthesized.
  • the synthesis may be performed under an inert gas atmosphere or under vacuum, but is preferably performed under air.
  • the synthesis temperature is not particularly limited, but is, for example, in the range of 1200 ° C to 1415 ° C, preferably in the range of 1250 ° C to 1400 ° C, and more preferably in the range of 1300 ° C to 1350 ° C.
  • a mayenite compound containing a large amount of C12A7 crystal structure is easily obtained. If the synthesis temperature is too low, the C12A7 crystal structure may be reduced. On the other hand, if the synthesis temperature is too high, since the melting point of the mayenite compound is exceeded, the crystal structure of C12A7 may be reduced.
  • the holding time at high temperature is not particularly limited, and it varies depending on the amount of synthesis and the holding temperature.
  • the holding time is, for example, 1 hour to 12 hours.
  • the holding time is, for example, preferably 2 hours to 10 hours, and more preferably 4 hours to 8 hours.
  • the mayenite compound obtained by synthesis is a lump that is partially or entirely sintered.
  • the massive mayenite compound is pulverized to a size of, for example, about 5 mm by a stamp mill or the like. Further, pulverization is performed with an automatic mortar or a dry ball mill until the average particle size is about 10 ⁇ m to 100 ⁇ m.
  • average particle diameter means a value obtained by measurement by a laser diffraction scattering method.
  • the average particle diameter of the powder means a value measured by the same method.
  • a wet ball mill using an alcohol for example, isopropyl alcohol represented by C n H 2n + 1 OH (n is an integer of 3 or more) as a solvent, or a circulation type
  • an alcohol for example, isopropyl alcohol
  • n is an integer of 3 or more
  • the average particle size of the powder can be reduced to 0.5 ⁇ m to 50 ⁇ m.
  • Water cannot be used as the solvent. This is because the mayenite compound is a component of alumina cement and easily reacts with water to form a hydrate.
  • the powder of mayenite compound is prepared by the above process.
  • the mayenite compound prepared as a powder may be a conductive mayenite compound. This is because the conductive mayenite compound is more pulverizable than the non-conductive compound.
  • the method for synthesizing the conductive mayenite compound is not particularly limited, and the following method is exemplified.
  • a method in which a mayenite compound is placed in a carbon container with a lid and heat-treated at 1600 ° C. see International Publication No. 2005/000741
  • a mayenite compound is placed in a carbon container with a lid and 1300 ° C. in nitrogen.
  • a method of manufacturing by heat treatment see International Publication No. 2006/129674
  • a powder made of calcium carbonate powder and aluminum oxide powder, such as calcium aluminate is placed in a carbon crucible with a lid and heat treated at 1300 ° C. in nitrogen.
  • a method in which a powder obtained by mixing calcium carbonate powder and aluminum oxide powder is put in a carbon crucible with a lid and heat-treated in nitrogen at 1300 ° C. 2010-132467).
  • the method for pulverizing the conductive mayenite compound is the same as the method for pulverizing the mayenite compound.
  • the conductive mayenite compound powder is prepared.
  • a mixed powder of a mayenite compound and a conductive mayenite compound may be used.
  • the powder prepared in step S110 may be used as it is.
  • a molded body containing the mayenite compound powder prepared in step S110 is used as the object to be processed.
  • the formation method of the molded body is not particularly limited, and the molded body may be formed using various conventional methods.
  • the molded body may be prepared by pressure molding of a molding material made of the powder prepared in step S110 or a kneaded product containing the powder.
  • the molding material includes a binder, a lubricant, a plasticizer, or a solvent as necessary.
  • a binder for example, polystyrene, polyethylene, polyvinyl butyral, EVA (ethylene vinyl acetate) resin, EEA (ethylene ethyl acrylate) resin, acrylic resin, cellulose resin (nitrocellulose, ethyl cellulose), polyethylene oxide, and the like can be used.
  • Waxes and stearic acid can be used as the lubricant.
  • Phthalate esters can be used as plasticizers.
  • a molded product can be obtained by sheet molding, extrusion molding, or injection molding of the molding material. Near-net shape molding is possible, that is, injection molding is preferred because a shape close to the final product can be produced with high productivity.
  • a powder of a mayenite compound and a binder are previously heated and kneaded to prepare a molding material, and the molding material is charged into an injection molding machine to obtain a molded body having a desired shape.
  • a mayenite compound powder is heated and kneaded with a binder and cooled to obtain pellets or powdery molding material having a size of about 1 mm to 10 mm.
  • a lab plast mill or the like is used, and the aggregation of the powder is loosened by the shearing force, and the binder is coated on the primary particles of the powder.
  • This molding material is put into an injection molding machine and heated to 120 ° C. to 250 ° C. to cause the binder to exhibit fluidity.
  • the mold is preliminarily heated at 50 ° C. to 80 ° C., and a desired molded product can be obtained by injecting the material into the mold at a pressure of 3 MPa to 10 MPa.
  • an isotropic hydrostatic press (CIP) process may be used.
  • the pressure during the CIP process is not particularly limited. It is in the range of 50 MPa to 200 MPa.
  • the molded body when a molded body is prepared and the molded body contains a solvent, the molded body is previously held at a temperature range of 50 ° C. to 200 ° C. for about 20 minutes to 2 hours, and the solvent is volatilized and removed. May be.
  • the molded body contains a binder, it is preferable to hold the molded body in the temperature range of 200 ° C. to 800 ° C. for about 30 minutes to 6 hours in advance, or raise the temperature at 50 ° C./hour to remove the binder. .
  • both processes may be performed simultaneously.
  • the object to be treated may be configured by attaching the molded body prepared by the above-described method to a conductive member such as metal.
  • a conductive member such as metal.
  • the conductive member may be made of, for example, metallic nickel, nickel alloy, molybdenum, tungsten, or the like. Further, the shape of the conductive member is not particularly limited. For example, the conductive member may have a linear shape, a rod shape, a cup shape, a strip shape, or the like.
  • titanium vapor is present in the heat treatment environment.
  • titanium is a metal having an extremely low vapor pressure, and therefore there is little possibility of reacting with other metals during the heat treatment of the object to be processed to form a brittle intermetallic compound. Therefore, even when a conductive member is included in the object to be processed, the risk of the conductive member becoming brittle or damaged after heat treatment is significantly suppressed.
  • a carbon container since it is difficult to produce a compound with titanium having a low vapor pressure, deterioration of the carbon container can be suppressed.
  • an object to be treated such as a molded body is subjected to high temperature treatment in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment.
  • an inert gas atmosphere excluding nitrogen or in a reduced pressure environment.
  • the object to be processed is disposed in the presence of carbon monoxide gas and titanium vapor supplied from a titanium vapor source.
  • the high temperature treatment of the object to be processed is performed in an inert gas atmosphere excluding nitrogen or in a reduced pressure environment.
  • the “depressurized environment” may be an environment having a pressure of 100 Pa or less, for example.
  • the oxygen partial pressure is preferably 10 ⁇ 5 Pa or less, more preferably 10 ⁇ 10 Pa or less, and even more preferably 10 ⁇ 15 Pa or less.
  • the titanium vapor source is not particularly limited, but may be a layer of titanium particles, for example. Note that, as described above, the object to be processed is disposed in the presence of titanium vapor so as not to be in direct contact with the titanium vapor source.
  • the carbon monoxide gas may be supplied from the outside to the environment where the object to be processed is placed, but it is preferable to arrange the object to be processed in a container containing carbon.
  • Carbon containers may be used, and carbon sheets may be placed in the environment.
  • the heat treatment may be performed in a state where the object to be processed and the titanium layer are arranged in a carbon container with a lid.
  • the method of adjusting the reaction environment to an inert gas atmosphere or a reduced pressure environment during high temperature treatment of the workpiece is not particularly limited.
  • a container containing carbon may be placed in a vacuum atmosphere having a pressure of 100 Pa or less.
  • the pressure is preferably 60 Pa or less, more preferably 20 Pa or less, still more preferably 5 Pa or less, and particularly preferably 0.1 Pa or less.
  • an inert gas having an oxygen partial pressure of 1000 Pa or less may be supplied to a container containing carbon.
  • the oxygen partial pressure of the inert gas to be supplied is preferably 100 Pa or less, more preferably 10 Pa or less, still more preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
  • the inert gas atmosphere may be an argon gas atmosphere or the like.
  • the treatment temperature is in the range of 1230 ° C to 1380 ° C, preferably in the range of 1280 ° C to 1340 ° C, and more preferably in the range of 1290 ° C to 1320 ° C.
  • the treatment temperature is lower than 1230 ° C., a lot of different phases are precipitated, and there is a possibility that sufficient conductivity cannot be imparted. Further, when the processing temperature is higher than 1380 ° C., the melting point of the highly conductive mayenite compound is exceeded, so that the crystal structure is decomposed and the electron density is lowered.
  • the high temperature holding time of the object to be treated is preferably in the range of 5 minutes to 48 hours, more preferably in the range of 30 minutes to 24 hours, still more preferably in the range of 1 hour to 12 hours, Most preferred is 4 to 8 hours.
  • the retention time of the object to be processed is less than 5 minutes, there is a possibility that a conductive mayenite compound having a sufficiently high electron density cannot be obtained, and sintering is insufficient. May be fragile.
  • the “surface layer” tends to be thicker when the holding time is lengthened, the holding time is preferably within 24 hours, and more preferably within 12 hours.
  • FIG. 2 schematically shows a configuration diagram of an apparatus used for high-temperature processing of an object to be processed.
  • the entire apparatus 100 is constituted by a heat-resistant airtight container, and an exhaust port 170 is connected to an exhaust system.
  • the apparatus 100 includes a carbon container 120 having an open top in a heat-resistant sealed container, a carbon lid 130 disposed on the carbon container 120, and a partition plate 140 disposed in the carbon container 120 (for example, An alumina plate).
  • a titanium metal powder layer 150 placed on a heat-resistant dish (for example, an alumina dish) 145 is disposed as a titanium vapor source.
  • a workpiece 160 is disposed on the upper part of the partition plate 140.
  • the partition plate 140 has a configuration in which titanium vapor from the layer 150 is not hindered from reaching the object to be processed 160. Moreover, the partition plate 140 needs to be comprised with the material which does not react with a titanium vapor
  • the partition plate 140 is composed of an alumina plate having a large number of through holes.
  • the carbon container 120 and the carbon lid 130 serve as a supply source of carbon monoxide gas when the object 160 is subjected to high temperature processing. That is, carbon monoxide gas is generated from the carbon container 120 and the carbon lid 130 side while the object to be processed 160 is held at a high temperature.
  • This carbon monoxide gas suppresses oxidation of the surface of the mayenite compound powder contained in the object 160 to form a titanium oxide layer.
  • free oxygen ions in the cage of the mayenite compound contained in the object to be processed 160 are reduced by the following reaction by titanium vapor generated from the layer 150 of the titanium metal powder: 2O 2 + + Ti ⁇ 4e ⁇ + TiO 2 (2)
  • Titanium oxide generated by the reaction of formula (2) is generated by the following reaction when the titanium carbide is titanium carbide (TiC), for example, by carbon monoxide gas in the atmosphere.
  • Titanium carbide has poor affinity with the mayenite compound and does not stick. Furthermore, since it does not sinter in this heat treatment temperature range, it is considered to be easily excluded.
  • the powder of the mayenite compound contained in the object to be processed 160 is sintered, and further, electrons are contained in the cage of the mayenite compound sintered body. Can be introduced.
  • FIG. 2 is an example, and it will be apparent to those skilled in the art that other objects may be used to treat the object to be processed at a high temperature.
  • an object to be processed containing powder of mayenite compound instead of an object to be processed containing powder of mayenite compound, an object to be processed containing a sintered body of mayenite compound may be used.
  • Such a sintered body of mayenite compound is obtained by, for example, sintering the mayenite compound produced through the above-described (mayenite compound powder preparation step) or heat-treating a molded body containing the mayenite compound powder. Can be prepared.
  • the heat treatment condition is not particularly limited as long as the compact is sintered.
  • the heat treatment may be performed in the temperature range of 300 ° C. to 1450 ° C., for example, in the atmosphere.
  • the temperature is 300 ° C. or higher, the organic components are volatilized and the number of powder contacts increases, so that the sintering process is likely to proceed.
  • the temperature is 1450 ° C. or lower, the shape of the sintered body is easily maintained.
  • the maximum temperature of the heat treatment is in the range of approximately 1000 ° C. to 1420 ° C., preferably 1050 ° C. to 1415 ° C., more preferably 1100 ° C. to 1380 ° C., and particularly preferably 1250 ° C. to 1350 ° C.
  • the holding time at the maximum temperature of the heat treatment is in the range of about 1 hour to 50 hours, preferably 2 hours to 40 hours, more preferably 3 hours to 30 hours. Further, even if the holding time is increased, there is no particular problem in terms of characteristics, but the holding time is preferably within 48 hours in view of manufacturing cost. You may implement in inert gas, such as argon, helium, neon, nitrogen, oxygen gas, or these mixed atmosphere, or in a vacuum.
  • inert gas such as argon, helium, neon, nitrogen, oxygen gas, or these mixed atmosphere, or in a vacuum.
  • a sintered body of the mayenite compound may be prepared by various methods.
  • the mayenite compound contained in the sintered body may be a conductive mayenite compound or a non-conductive mayenite compound. Further, the mayenite compound contained in the sintered body may be a mayenite compound containing fluorine or a mayenite compound not containing fluorine.
  • an object to be processed including a calcined powder compact may be used instead of the object to be processed containing the mayenite compound powder.
  • the “calcined powder” is a powder prepared through heat treatment, and (i) a mixed powder containing at least two selected from calcium oxide, aluminum oxide, and calcium aluminate, or (Ii) Means a mixed powder of two or more types of calcium aluminate.
  • Examples of calcium aluminate include CaO ⁇ Al 2 O 3 , 3CaO ⁇ Al 2 O 3 , 5CaO ⁇ 3Al 2 O 3 , CaO ⁇ 2Al 2 O 3 , CaO ⁇ 6Al 2 O 3 , C12A7, and the like.
  • the ratio of calcium (Ca) to aluminum (Al) in the “calcined powder” is 9.5: 9.5 to 13: 6 in terms of a molar ratio converted to CaO: Al 2 O 3 .
  • the ratio of calcium (Ca) to aluminum (Al) is such that the molar ratio in terms of CaO: Al 2 O 3 is in the range of 10: 9 to 13: 6.
  • CaO: Al 2 O 3 (molar ratio) is preferably in the range of 11: 8 to 12.5: 6.5, more preferably in the range of 11.5: 7.5 to 12.3: 6.7, 11
  • the range of .8: 7.2 to 12.2: 6.8 is more preferred, and about 12: 7 is particularly preferred.
  • the calcined powder can be prepared as follows. First, raw material powder is prepared.
  • the raw material powder includes at least a raw material to be a calcium oxide source and an aluminum oxide source.
  • the raw material powder preferably contains two or more kinds of calcium aluminate, or at least two selected from the group consisting of calcium compounds, aluminum compounds, and calcium aluminates.
  • the raw material powder may be, for example, the following raw material powder: raw material powder containing calcium compound and aluminum compound, raw material powder containing calcium compound and calcium aluminate, raw material powder containing aluminum compound and calcium aluminate , Raw material powder containing calcium compound, aluminum compound and calcium aluminate, raw material powder containing only calcium aluminate.
  • the raw material powder includes at least a raw material A serving as a calcium oxide source and a raw material B serving as an aluminum oxide source.
  • Examples of the raw material A include calcium carbonate, calcium oxide, calcium hydroxide, calcium hydrogen carbonate, calcium sulfate, calcium metaphosphate, calcium oxalate, calcium acetate, calcium nitrate, and calcium halide. Of these, calcium carbonate, calcium oxide, and calcium hydroxide are preferred.
  • Examples of the raw material B include aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum nitrate, and aluminum halide. Of these, aluminum hydroxide and aluminum oxide are preferred.
  • Examples of aluminum oxide (alumina) include ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, with ⁇ -aluminum oxide (alumina) being preferred.
  • the calcined powder may contain substances other than the raw material A and the raw material B.
  • the calcined powder may contain a fluorine component or may not contain a fluorine component.
  • the raw material powder containing the raw material A and the raw material B is heat-treated. Thereby, the calcined powder containing calcium and aluminum is obtained.
  • the ratio of calcium (Ca) to aluminum (Al) in the calcined powder is in the range of about 10: 9 to 13: 6 in terms of a molar ratio converted to CaO: Al 2 O 3 .
  • the maximum temperature of the heat treatment is approximately in the range of 600 ° C to 1250 ° C, preferably 900 ° C to 1200 ° C, more preferably 1000 ° C to 1100 ° C.
  • the holding time at the maximum temperature of the heat treatment is in the range of about 1 hour to 50 hours, preferably 2 hours to 40 hours, more preferably 3 hours to 30 hours. Further, even if the holding time is lengthened, there is no particular problem in terms of characteristics, but the holding time is preferably within 48 hours in view of manufacturing cost.
  • the heat treatment may be performed in the air.
  • the heat treatment may be performed in an inert gas such as argon, helium, neon, nitrogen, an oxygen gas, an atmosphere in which these gases are mixed, or in a vacuum.
  • the calcined powder obtained after the heat treatment is usually a lump that is partially or entirely sintered. For this reason, if necessary, a pulverization treatment (coarse pulverization and / or refinement) as shown in the above-mentioned column (Preparation of mayenite compound powder) may be performed.
  • the calcined powder is prepared by the above steps.
  • a molded body is formed using the calcined powder prepared as described above. Since the formation method of a molded object can apply the method similar to the formation method of the above-mentioned molded object containing the powder of a mayenite compound, it does not explain here any more.
  • Example 1 A highly conductive mayenite compound was produced by the following method.
  • this white lump was pulverized into pieces having a size of about 5 mm with an alumina stamp mill, and then coarsely pulverized with an alumina automatic mortar to obtain white particles (hereinafter referred to as particles “A1”). )
  • particles A1 white particles
  • SALD-2100 laser diffraction scattering method
  • the molded body C1 was placed in an electric furnace in a state of being placed on an alumina plate, and heated to 200 ° C. in the air for 40 minutes. Furthermore, after heating to 600 degreeC in 8 hours, it was made to cool to room temperature in 2 hours. The degreased shaped body was white and maintained the rod shape.
  • FIG. 3 shows an apparatus used for the firing treatment of the compact C1 after degreasing.
  • the apparatus 300 includes an alumina container 310 and a carbon container 330 with a carbon lid 335.
  • a titanium layer 320 formed by spreading 0.8 g of metal titanium powder is disposed on the bottom of the alumina container 310.
  • the titanium layer 320 serves as a titanium vapor source that generates titanium vapor when the apparatus 300 reaches a high temperature.
  • the alumina container 310 has a substantially cylindrical shape with an outer diameter of 20 mm, an inner diameter of 18 mm, and a height of 10 mm, and has been subjected to a rough cutting process so that titanium vapor diffuses throughout the carbon container 330.
  • the carbon container 330 has a substantially cylindrical shape with an outer diameter of 50 mm, an inner diameter of 40 mm, and a height of 60 mm.
  • This device 300 was used as follows.
  • an alumina plate 315 was placed on top of an alumina container 310 having a titanium layer 320.
  • a plurality of the degreased compacts C1 described above were placed on the alumina plate 315. In this state, the molded body C1 is not in direct contact with the titanium layer 320.
  • this apparatus 300 was installed in an electric furnace capable of adjusting the atmosphere.
  • the furnace was evacuated using a rotary pump and a diffusion pump. Then, after the pressure in the furnace became 0.1 Pa or less, heating of the apparatus 300 was started and the temperature was raised to 1300 ° C. in 2 hours. The apparatus 300 was kept in this state for 6 hours, and then cooled to room temperature in 2 hours.
  • the molded body C1 was sintered, and a sintered body having a black surface (hereinafter referred to as a sintered body “D1”) was obtained.
  • the relative density of the sintered body D1 was 96.6%.
  • the sintered body D1 was roughly pulverized with an alumina automatic mortar. Coarse pulverization was performed using an alumina mortar and an alumina automatic mortar.
  • the obtained powder had a dark brown color. As a result of X-ray diffraction analysis, this powder was found to have only a C12A7 structure. Further, the electron density obtained from the peak position of the light diffuse reflection spectrum of the obtained powder was 1.6 ⁇ 10 21 cm ⁇ 3 , and the electric conductivity was 16 S / cm. From this, it was confirmed that the sintered compact D1 is a highly conductive mayenite compound.
  • the cross section of the sintered compact D1 was observed using SEM (scanning electron microscope). From the result of the cross-sectional observation, it was confirmed that the sintered body D1 was in a dense state with few pores. The thickness of the surface layer was about 5 ⁇ m to about 10 ⁇ m, and it was confirmed that the surface layer was extremely thin.
  • Example 2 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in this Example 2, the heat treatment temperature was set to 1320 ° C. in the above-described step (production of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D2”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D2 was 96.6%.
  • the sintered body D2 had only the C12A7 structure.
  • the sintered body D2 had an electron density of 1.6 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 16 S / cm.
  • the sintered body D2 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D2 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 3 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 3, the heat treatment temperature was set to 1280 ° C. in the above-described process (manufacturing the highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D3”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D3 was 98.5%.
  • the sintered body D3 had only the C12A7 structure.
  • the sintered body D3 had an electron density of 1.7 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 17 S / cm.
  • the sintered body D3 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D3 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 4 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in this Example 4, the heat treatment time was set to 12 hours in the above-described process (preparation of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D4”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D4 was 97.5%.
  • the sintered body D4 had only the C12A7 structure.
  • the sintered body D4 had an electron density of 1.7 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 17 S / cm.
  • the sintered body D4 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D4 is about 5 ⁇ m to about 15 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 5 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in this Example 5, the heat treatment time was set to 48 hours in the above-described process (preparation of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D5”) was obtained after the above-described step (production of a highly conductive mayenite compound).
  • the relative density of the sintered body D5 was 96.0%.
  • the sintered body D5 had only the C12A7 structure.
  • the sintered body D5 had an electron density of 1.4 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 14 S / cm.
  • the sintered body D5 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D5 is about 5 ⁇ m to about 15 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 6 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in this Example 6, the heat treatment time was set to 96 hours in the above-described (preparation of highly conductive mayenite compound) step. Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D6”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D6 was 96.7%.
  • the sintered body D6 had only the C12A7 structure.
  • the sintered body D6 had an electron density of 1.5 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 15 S / cm.
  • the sintered body D6 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D6 is about 5 ⁇ m to about 20 ⁇ m, and the surface layer is extremely thin. confirmed.
  • the holding time is preferably within about 50 hours from the viewpoint of suppressing the growth of the surface layer.
  • Example 7 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in this Example 7, the heat treatment time was set to 0.5 hours in the above-described step (preparation of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D7”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D7 was 95.2%.
  • the sintered body D7 had only the C12A7 structure.
  • the sintered body D7 had an electron density of 1.0 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 10 S / cm.
  • the sintered body D7 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D7 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Example 8 A highly conductive mayenite compound was produced by the same method as in Example 1 described above. However, in this Example 8, what was used once on the same conditions as Example 1 was used as the metal titanium layer 320 in the above-mentioned process (production of a highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D8”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D8 was 97.2%.
  • the sintered body D8 had only the C12A7 structure.
  • the sintered body D8 had an electron density of 1.5 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 16 S / cm.
  • the sintered body D8 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D8 was evaluated by the same method as in Example 1. As a result, the thickness of the surface layer was about 5 ⁇ m to about 10 ⁇ m, and the surface layer was extremely thin. confirmed.
  • the metal titanium layer 320 can be reused. Incidentally, it has been confirmed from the subsequent experiments that even if the metal titanium layer 320 is repeatedly used five times in the apparatus 300, almost the same highly conductive mayenite compound can be obtained.
  • Example 9 A highly conductive mayenite compound was produced by the same method as in Example 1 described above. In Example 9, however, the powder used in the above-mentioned step (manufacturing the mayenite compound) was not a mayenite compound, but a conductive mayenite compound having an electron density of 5.0 ⁇ 10 19 cm ⁇ 3 . Of powder was used. Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D9”) was obtained after the above-described (manufacturing the highly conductive mayenite compound) step.
  • the relative density of the sintered body D9 was 96.5%.
  • the sintered body D9 had only the C12A7 structure.
  • the sintered body D9 had an electron density of 1.6 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 17 S / cm.
  • the sintered body D9 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D9 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Example 10 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 10, a diffusion pump was not used during the vacuum treatment in the above-described process (production of a highly conductive mayenite compound). Therefore, in Example 10, the pressure in the furnace was about 50 Pa. Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D10”) was obtained after the above-described step (production of a highly conductive mayenite compound).
  • the relative density of the sintered body D10 was 96.3%.
  • the sintered body D5 had only the C12A7 structure.
  • the sintered body D10 had an electron density of 1.1 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 11 S / cm.
  • the sintered body D10 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D10 is about 20 ⁇ m to about 40 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 11 A highly conductive mayenite compound was produced by the same method as in Example 1 described above. However, in this Example 11, in the above-mentioned step (manufacturing the highly conductive mayenite compound), the mayenite compound molded body C1 was not prepared, and the mayenite compound powder was fired. Other conditions are the same as in the first embodiment.
  • the sintered body D11 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D11 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 12 A highly conductive mayenite compound was produced by the same method as in Example 1 described above. However, in this Example 12, in the above-described process (production of a molded body of a mayenite compound), Instead of the molded product C1, a product obtained by inserting a nickel wire into the molded product C1 was produced and used as a workpiece.
  • the object to be processed was prepared as follows.
  • a hole having a diameter of about 0.7 mm and a depth of about 2.5 mm was formed in the center of one bottom surface of the molded body C1 by using a router.
  • a nickel wire having a wire diameter of 0.7 mm and a length of 10 mm heated to 150 ° C. was inserted into the hole. Since the nickel wire is heated, the resin in the contact portion with the molded body C1 is softened, and the nickel wire can be easily inserted.
  • a black sintered body (hereinafter referred to as a sintered body “D12”) bonded to the nickel wire was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the portion excluding the nickel wire of sintered body D12 was 96.7%.
  • the sintered body D12 had only the C12A7 structure.
  • the sintered body D12 had an electron density of 1.6 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 16 S / cm.
  • the sintered body D12 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D12 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Example 13 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 13, the heat treatment temperature was set to 1360 ° C. in the above-described step (preparation of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D13”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D13 was 97.8%.
  • the sintered body D13 had only the C12A7 structure.
  • the sintered body D13 had an electron density of 1.5 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 15 S / cm.
  • the sintered body D13 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D13 was about 5 ⁇ m to about 20 ⁇ m and the surface layer was thin. It was.
  • Example 14 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 14, the heat treatment temperature was set to 1250 ° C. in the above-described process (manufacturing the highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D14”) was obtained after the above-described step (production of a highly conductive mayenite compound).
  • the relative density of the sintered body D14 was 96.0%.
  • the sintered body D14 had only the C12A7 structure.
  • the sintered body D14 had an electron density of 1.0 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 10 S / cm.
  • the sintered body D13 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D13 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 15 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 15, the time for heating from room temperature to 1300 ° C. in the above-described (preparation of highly conductive mayenite compound) process was 4 hours, and the time for cooling from 1300 ° C. to room temperature was 4 hours. did. Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D15”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D15 was 97.0%.
  • the sintered body D15 had only the C12A7 structure.
  • the sintered body D15 had an electron density of 1.5 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 15 S / cm.
  • the sintered body D15 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D15 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Comparative Example 1 An attempt was made to produce a highly conductive mayenite compound by the same method as in Example 1 described above. However, in Comparative Example 1, the heat treatment temperature was 1200 ° C. in the above-described process (manufacturing the highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D51”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • Comparative Example 2 An attempt was made to produce a highly conductive mayenite compound by the same method as in Example 1 described above. However, in Comparative Example 2, the heat treatment temperature was set to 1400 ° C. in the above-described process (manufacturing the highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D52”) was obtained after the above-described step (production of a highly conductive mayenite compound).
  • the sintered body D52 was severely deformed and did not maintain its original shape. For this reason, the relative density could not be measured.
  • the sintered body D52 had a different phase in addition to the C12A7 structure. Since the sintered body D52 has a different phase, the exact electron density and electrical conductivity are unknown, but the electron density of the sintered body D52 was estimated to be approximately 7.7 ⁇ 10 19 cm ⁇ 3 .
  • the sintered body D52 does not have a high electron density.
  • Comparative Example 3 An attempt was made to produce a highly conductive mayenite compound by the same method as in Example 10 above. However, in Comparative Example 3, in the apparatus 300 used in the above-described process (production of a highly conductive mayenite compound), only the alumina container 310 and the alumina plate 315 are used, and the carbon container 330 with the lid 335 is Not used. Other conditions are the same as those in the tenth embodiment.
  • a sintered body having a white surface (hereinafter referred to as a sintered body “D53”) was obtained after the above-described (manufacturing the highly conductive mayenite compound) step.
  • the relative density of the sintered body D53 was 92.0%.
  • Comparative Example 4 An attempt was made to produce a highly conductive mayenite compound by the same method as in Example 1 described above. However, in this comparative example 4, the metal titanium layer 320 was not used in the apparatus 300 used in the above-described process (production of a highly conductive mayenite compound). That is, in Comparative Example 5, the compact C1 was fired in an environment where no titanium vapor was present. Other conditions are the same as in the first embodiment.
  • a sintered body having a black surface (hereinafter referred to as a sintered body “D54”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D54 was 99.7%.
  • the sintered body D54 had only the C12A7 structure.
  • the electron density determined by Kubelka-Munk conversion from the light diffuse reflection spectrum of the obtained powder was 4.0 ⁇ 10 19 cm ⁇ 3
  • the electric conductivity was 0.04 S / cm.
  • the sintered body D54 does not have a high electron density.
  • Comparative Example 5 An attempt was made to produce a highly conductive mayenite compound by the same method as in Example 1 described above. However, in this comparative example 5, the alumina plate 315 is not used in the apparatus 300 used in the above-described (preparation of highly conductive mayenite compound), and the compact C1 of the mayenite compound is directly formed on the metal titanium layer 320. Installed on top of. Other conditions are the same as in the first embodiment.
  • a sintered body (hereinafter referred to as a sintered body “D55”) was obtained after the above-described (manufacturing the highly conductive mayenite compound) step.
  • the surface of the sintered body D55 in contact with the metal titanium layer 320 was white.
  • the relative density of the sintered body D55 from which the white material was removed was 94.4%.
  • the sintered body D55 had only the C12A7 structure.
  • the sintered body D55 had an electron density of 1.6 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 16 S / cm.
  • the surface form of the sintered body D55 was observed by the same method as in Example 1. As a result, a white layer having a thickness of about 10 ⁇ m was present on the surface of the sintered body D55, and another layer was observed immediately below. This other layer had the same form as the surface layer in another sintered body (for example, sintered body D1). The thickness of this other layer was about 40 ⁇ m to about 50 ⁇ m, and was confirmed to be thick.
  • Comparative Example 6 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Comparative Example 6, the atmosphere for the heat treatment was the nitrogen atmosphere in the above-described process (preparation of highly conductive mayenite compound). Other conditions are the same as in the first embodiment.
  • sintered body“ D56 ” a sintered body having a cream-colored surface
  • the relative density of the sintered body D56 was 97.8%.
  • the sintered body D56 had only the C12A7 structure.
  • the electron density of the sintered body D56 is below the measurement limit. From this, it was confirmed that the sintered body D56 is not a highly conductive mayenite compound.
  • Table 1 shows the types of objects to be processed in Examples 1 to 15 and Comparative Examples 1 to 6, presence / absence of CO source and titanium source, processing temperature, processing time, and electron density and relative density of the obtained sintered body. And the thickness of the surface layer are shown together.
  • Example 21 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in Example 21, a sintered body E21 of a mayenite compound (non-conductive) was used in place of the degreased molded body C1 in the above-described (preparation of highly conductive mayenite compound) step. Other conditions are the same as in the first embodiment.
  • the sintered body E21 of the mayenite compound was produced as follows.
  • the molded body C1 obtained through the process of the above-described Example 1 production of a molded body of mayenite compound
  • the heating rate was 300 ° C./hour.
  • the compact C1 at 1100 ° C. for 2 hours it was cooled to room temperature at a temperature decrease rate of 300 ° C./hour.
  • the sintered compact E21 of the nonelectroconductive mayenite compound was obtained.
  • the above-described process production of a highly conductive mayenite compound
  • a sintered body having a black surface hereinafter referred to as a sintered body “D21”
  • the relative density of the sintered body D21 was 95.8%.
  • the sintered body D21 had only the C12A7 structure.
  • the sintered body D21 had an electron density of 1.6 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 16 S / cm.
  • the sintered body D21 is a highly conductive mayenite compound.
  • the thickness of the surface layer of the sintered body D21 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 22 A conductive mayenite compound was produced in the same manner as in Example 1 described above. However, in the step of (production of a mayenite compound compact), a compact C22 was prepared using a mixed powder containing a fluorine component instead of the powder B1. Other conditions are the same as in the first embodiment.
  • the mixed powder F22 was produced by the following process.
  • sintered body“ D22 ”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D22 was 97.2%.
  • the sintered body D22 had only the C12A7 structure.
  • the sintered body D22 had an electron density of 1.1 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 12 S / cm.
  • the lattice constant of the sintered body D22 was smaller than the value of the sintered body D1 in Example 1. From this, in the sintered compact D22, it is thought that the mayenite compound contains fluorine.
  • the black material D22 was fractured, and the composition analysis of the fracture surface was performed by energy dispersive X-ray analysis (EDX). From the analysis results, it was found that the ratio of detected fluorine was close to the mixing ratio of the mixed powder F22.
  • EDX energy dispersive X-ray analysis
  • the sintered body D22 was a sintered body of a highly conductive mayenite compound containing fluorine.
  • the thickness of the surface layer of the sintered body D22 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Example 23 A conductive mayenite compound was produced in the same manner as in Example 22 described above. However, in Example 23, in the above-mentioned step (preparation method of mixed powder), 39.78 g of powder B1 was mixed with 0.12 g of calcium fluoride (CaF 2 , manufactured by Kanto Chemical Co., Ltd., special grade) powder and oxidized. 0.09 g of aluminum ( ⁇ -Al 2 O 3 , manufactured by Kanto Chemical Co., Ltd., special grade) powder was added and mixed well to obtain a mixed powder F23.
  • CaF 2 calcium fluoride
  • Al ⁇ -Al 2 O 3
  • sintered body“ D23 ”) was obtained after the above-described step (manufacturing the highly conductive mayenite compound).
  • the relative density of the sintered body D23 was 96.0%.
  • the sintered body D23 had only the C12A7 structure.
  • the sintered body D23 had an electron density of 1.1 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 11 S / cm.
  • the lattice constant of the sintered body D23 was smaller than the value of the sintered body D1 in Example 1. From this, in the sintered compact D23, it is thought that the mayenite compound contains fluorine.
  • the black material D23 was fractured, and the composition analysis of the fracture surface was performed by energy dispersive X-ray analysis (EDX). From the analysis results, it was found that the detected proportion of fluorine was close to the mixing ratio of the mixed powder F23.
  • EDX energy dispersive X-ray analysis
  • the sintered body D23 was a sintered body of a highly conductive mayenite compound containing fluorine.
  • the thickness of the surface layer of the sintered body D23 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is extremely thin. confirmed.
  • Example 24 A conductive mayenite compound was produced in the same manner as in Example 22 described above. However, in Example 24, 38.11 g of powder B1 was added to 1.07 g of calcium fluoride (CaF 2 , manufactured by Kanto Chemical Co., Ltd., special grade) powder and oxidized in the above-described (mixed powder preparation method) step. 0.82 g of aluminum ( ⁇ -Al 2 O 3 , manufactured by Kanto Chemical Co., Ltd., special grade) powder was added and mixed well to obtain mixed powder F24.
  • CaF 2 calcium fluoride
  • Al ⁇ -Al 2 O 3
  • sintered body“ D24 ”) a sintered body having a black surface
  • the lattice constant of the sintered body D24 was smaller than the value of the sintered body D1 in Example 1. From this, in the sintered compact D24, it is thought that the mayenite compound contains fluorine.
  • the black material D24 was broken, and composition analysis of the fracture surface was performed by energy dispersive X-ray analysis (EDX). From the analysis results, it was found that the ratio of detected fluorine was close to the mixing ratio of the mixed powder F24.
  • EDX energy dispersive X-ray analysis
  • the sintered body D24 was a sintered body of a highly conductive mayenite compound containing fluorine.
  • the thickness of the surface layer of the sintered body D24 is about 5 ⁇ m to about 10 ⁇ m, and the surface layer is very thin. confirmed.
  • Example 25 A conductive mayenite compound was produced in the same manner as in Example 22 described above. However, in Example 25, a sintered body E25 of a mayenite compound containing fluorine (non-conductive) was used in place of the compact C22 in the above-described step (production of a highly conductive mayenite compound). Other conditions are the same as in the case of Example 22.
  • the sintered body E25 of the mayenite compound was produced as follows.
  • the compact C22 of Example 22 described above was placed on an alumina plate and heated to 1100 ° C. in the atmosphere. The heating rate was 300 ° C./hour.
  • the molded body C22 was held at 1100 ° C. for 2 hours, and then cooled to room temperature at a temperature decrease rate of 300 ° C./hour. Thereby, the sintered compact E25 of the nonelectroconductive mayenite compound containing a fluorine was obtained.
  • sintered body“ D25 ”) a sintered body having a black surface
  • the relative density of the sintered body D25 was 95.6%.
  • the sintered body D25 had only the C12A7 structure.
  • the sintered body D25 had an electron density of 1.0 ⁇ 10 21 cm ⁇ 3 and an electric conductivity of 10 S / cm.
  • the lattice constant of the sintered body D25 was smaller than the value of the sintered body D1 in Example 1. From this, it is considered that the mayenite compound contains fluorine.
  • the black material D25 was fractured, and the composition analysis of the fracture surface was performed by energy dispersive X-ray analysis (EDX). From the analysis results, it was found that the ratio of detected fluorine was close to the mixing ratio of the mixed powder F22.
  • EDX energy dispersive X-ray analysis
  • the sintered body D25 was a sintered body of a highly conductive mayenite compound containing fluorine.
  • the thickness of the surface layer of the sintered body D25 was evaluated by the same method as in Example 1. As a result, the thickness of the surface layer was about 5 ⁇ m to about 10 ⁇ m, and the surface layer was extremely thin. confirmed.
  • Table 2 shows the types of objects to be processed in Examples 21 to 25, the presence or absence of a CO source and a titanium source, the processing temperature, the processing time, and the electron density, relative density, and thickness of the surface layer of the obtained sintered body. This is summarized.
  • the present invention can be applied to a method for manufacturing a member made of a conductive mayenite compound that can be used for a sputtering target, a fluorescent lamp, or the like necessary for forming a thin film of an electron injection layer of an organic EL element.

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Abstract

L'invention concerne un procédé de production d'un composé de mayénite conducteur, caractérisé en ce qu'il comprend : (1) une étape au cours de laquelle une poudre de composé de mayénite est préparée ; et (2) une étape au cours de laquelle un matériau à traiter, qui contient la poudre de composé de mayénite préparée dans l'étape (1), est agencé de manière à ne pas être en contact avec une source de titane en présence de monoxyde de carbone gazeux et de vapeur de titane alimentée à partir de la source de titane, et le matériau à traiter est maintenu à une température dans la plage de 1230˚C à 1380˚C dans une atmosphère de gaz inerte autre qu'une atmosphère d'azote ou dans un environnement à pression réduite.
PCT/JP2012/079433 2011-12-20 2012-11-13 Procédé de production d'un composé de mayénite conducteur et électrode destinée à des lampes fluorescentes WO2013094346A1 (fr)

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WO2014050899A1 (fr) * 2012-09-28 2014-04-03 旭硝子株式会社 Procédé de production de composé mayénite conducteur ayant une densité électronique élevée
WO2014050900A1 (fr) * 2012-09-28 2014-04-03 旭硝子株式会社 Procédé de production de composé mayénite conducteur ayant une densité électronique élevée
CN107954709A (zh) * 2016-10-17 2018-04-24 旭硝子株式会社 导电性钙铝石化合物的制造方法和导电性钙铝石化合物的烧结体

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WO2006129675A1 (fr) * 2005-05-30 2006-12-07 Asahi Glass Company, Limited Processus de production de compose mayenite conducteur
WO2007060890A1 (fr) * 2005-11-24 2007-05-31 Japan Science And Technology Agency COMPOSÉ MÉTALLIQUE ÉLECTROCONDUCTEUR 12Caoû7Al2O3 ET SON PROCÉDÉ DE FABRICATION

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KR101160131B1 (ko) * 2010-05-11 2012-06-26 한국세라믹기술원 도데카칼슘 헵타-알루미네이트계 전자화물의 제조방법

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WO2006129675A1 (fr) * 2005-05-30 2006-12-07 Asahi Glass Company, Limited Processus de production de compose mayenite conducteur
WO2007060890A1 (fr) * 2005-11-24 2007-05-31 Japan Science And Technology Agency COMPOSÉ MÉTALLIQUE ÉLECTROCONDUCTEUR 12Caoû7Al2O3 ET SON PROCÉDÉ DE FABRICATION

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014050899A1 (fr) * 2012-09-28 2014-04-03 旭硝子株式会社 Procédé de production de composé mayénite conducteur ayant une densité électronique élevée
WO2014050900A1 (fr) * 2012-09-28 2014-04-03 旭硝子株式会社 Procédé de production de composé mayénite conducteur ayant une densité électronique élevée
US9428827B2 (en) 2012-09-28 2016-08-30 Asahi Glass Company, Limited Method of manufacturing electrically conductive mayenite compound with high electron density
US9879338B2 (en) 2012-09-28 2018-01-30 Asahi Glass Company, Limited Method of manufacturing electrically conductive mayenite compound with high electron density
CN107954709A (zh) * 2016-10-17 2018-04-24 旭硝子株式会社 导电性钙铝石化合物的制造方法和导电性钙铝石化合物的烧结体
JP2018065706A (ja) * 2016-10-17 2018-04-26 旭硝子株式会社 導電性マイエナイト化合物の製造方法および導電性マイエナイト化合物の焼結体

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