WO2015186656A1 - 透明セラミックスの製造方法及び透明セラミックス、磁気光学デバイス並びに焼結用希土類酸化物粉末 - Google Patents
透明セラミックスの製造方法及び透明セラミックス、磁気光学デバイス並びに焼結用希土類酸化物粉末 Download PDFInfo
- Publication number
- WO2015186656A1 WO2015186656A1 PCT/JP2015/065756 JP2015065756W WO2015186656A1 WO 2015186656 A1 WO2015186656 A1 WO 2015186656A1 JP 2015065756 W JP2015065756 W JP 2015065756W WO 2015186656 A1 WO2015186656 A1 WO 2015186656A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- rare earth
- terbium
- transparent ceramic
- group
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/0009—Materials therefor
- G02F1/0036—Magneto-optical materials
-
- 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
- C01F17/00—Compounds of rare earth metals
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/626—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
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/626—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
- C04B35/6303—Inorganic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/645—Pressure sintering
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/28—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect
- G02F1/093—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect used as non-reciprocal devices, e.g. optical isolators, circulators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Definitions
- the present invention relates to a method for producing a transparent ceramic for a magneto-optical device used as a material constituting a magneto-optical device such as an optical isolator, and the transparent ceramic.
- the present invention also relates to magneto-optical devices such as a Faraday rotator and an optical isolator, and a rare earth oxide powder for sintering.
- the optical isolator has three parts: a Faraday rotator, a polarizer disposed on the light incident side of the Faraday rotator, and an analyzer disposed on the light emitting side of the Faraday rotator.
- the optical isolator utilizes the so-called Faraday effect that the plane of polarization rotates in the Faraday rotator when light is incident on the Faraday rotator while a magnetic field is applied to the Faraday rotator in parallel with the traveling direction of light. To do. That is, of the incident light, light having the same polarization plane as the polarizer passes through the polarizer and is incident on the Faraday rotator. This light is rotated by plus 45 degrees with respect to the traveling direction of the light in the Faraday rotator and emitted.
- the Faraday rotation angle ⁇ is represented by the following formula (A).
- ⁇ V ⁇ H ⁇ L (A)
- V is a Verde constant determined by the material of the Faraday rotator
- H is the magnetic flux density
- L is the length of the Faraday rotator.
- the Faraday rotator of the optical isolator As described above, it is important that the Faraday effect is large and the transmittance is high at the wavelength used. Further, when a polarized component different from the incident light is generated in the outgoing light, the different polarized component is transmitted through the polarizer, so that the return light is not sufficiently blocked.
- Patent Document 1 As a material having a large Verde constant, (Tb x Re 1-x ) 2 O 3 : 0.4 ⁇ x ⁇ 1.0 Oxide single crystals and transparent oxide ceramics are disclosed.
- Patent Document 2 the rare earth oxide represented by the general formula R 2 O 3 (R: rare earth element) has a cubic crystal structure and no birefringence. Therefore, it is described that a sintered body having excellent transparency can be obtained by completely removing pores and segregation of impurities.
- Patent Document 3 it is effective to add a sintering aid to remove pores.
- Patent Document 4 a method of removing pores by performing re-sintering after the hot isostatic pressing step is disclosed.
- a sintering aid one or more sintering aids disclosed in Patent Document 3 are added, mixed, molded, calcined, sintered under vacuum, and further subjected to HIP (Hot Isostatic Pressing) treatment. Manufacturing.
- the transparent oxide ceramics of (Tb x Re 1-x ) 2 O 3 : 0.4 ⁇ x ⁇ 1.0 basically has a cubic crystal structure,
- the sintering aid reacts with the main component and a phase different from the cubic crystal precipitates in the crystal grains or at the grain boundaries, which may cause slight birefringence.
- the ratio may decrease.
- the precipitate has a minute size of 1 ⁇ m or less, when irradiated with laser light, the laser light is scattered there, and this scattering sometimes reduces the insertion loss.
- the composition of the main component (Tb x Re 1-x ) 2 O 3 and the concentration of the sintering aid are segregated in the ceramic inner and outer peripheral parts, and the ceramic surface There were variations in extinction ratio and insertion loss.
- Patent Document 5 yttrium oxide, scandium containing terbium oxide (chemical formula: Tb 2 O 3 ) in a molar ratio of 40% or more and having almost no absorption at a wavelength of 1064 nm.
- a ceramic comprising a compound of at least one oxide of an oxide and a lanthanide rare earth oxide, (1) Using a starting material having a specific particle size distribution excellent in sinterability, (2) Using a sintering aid that is excellent in sinterability and that can maintain the crystal structure of the ceramic in cubic form, (3) Vacuum sintering at an optimum temperature or sintering in an oxygen-free atmosphere, and performing HIP treatment, (4) The sintered body obtained above is heat-treated in an oxygen-free atmosphere.
- optical ceramics mainly composed of optically uniform rare earth oxides with little composition variation, with an insertion loss of 1.0 dB or less can be obtained. It has been described.
- the output of a laser beam machine has been increased from 10 W to higher output, and from 20 W to several hundred W has come to be obtained.
- the high-power laser beam passes through the Faraday optical material of the isolator that is a component of the laser processing machine, even if the insertion loss is about 1.0 dB, the decrease in the laser output after passing through cannot be ignored. It was. Further, when the irradiated light is absorbed by the Faraday optical material, the density and refractive index of the portion where the light absorption occurs and the peripheral portion thereof change.
- the Faraday optical material when the Faraday optical material is irradiated with light having a high intensity such as laser light, a temperature distribution is generated in the center where heat is likely to accumulate in the Faraday optical material and on the outside where the heat is radiated. Since the refractive index of the passing part changes more greatly than the refractive index of the peripheral part, a lens action occurs. As a result, the laser beam that should be emitted in parallel is focused. This is called a thermal lens and has become an unstable element for stably oscillating laser light. Further, if there is a defect that causes light absorption in the optical material, the light absorbed by the defect is converted into heat.
- defects include heterogeneous precipitates, pores that enter grain boundaries or grains, oxygen defects, or ion defects.
- JP 2010-285299 A Japanese Patent No. 4033451 JP-A-5-330913 Japanese Patent No. 2638669 JP 2012-206935 A
- ceramics mainly composed of oxides of terbium oxide and other rare earth elements (scandium, yttrium, lanthanum, europium, gadolinium, ytterbium, thulium, holmium, and lutetium) are likely to scatter and have insertion loss. Since the extinction ratio becomes smaller and the extinction ratio becomes smaller, efforts have been made to improve it, but it has been extremely difficult to apply to optical materials such as optical isolators whose optical requirements have become more stringent. .
- the present invention has been made in view of the above circumstances, and the transparent ceramics of a rare earth oxide containing terbium oxide having a large Verde constant in a wavelength range of 1.06 ⁇ m (1,064 ⁇ 40 nm) are uniform and transparent in the plane.
- the present invention provides the following transparent ceramic production method, transparent ceramic, magneto-optical device, and rare earth oxide powder for sintering.
- Main components of terbium oxide (chemical formula: Tb 2 O 3 ) and at least one other rare earth oxide selected from oxides of yttrium oxide, scandium oxide, and lanthanide rare earth elements (excluding terbium) (A) at least one other rare earth ion selected from (a) terbium ion, (b) yttrium ion, scandium ion and lanthanide rare earth ion (excluding terbium ion),
- the components (a), (b), and (c) are co-precipitated in an aqueous solution containing ions of at least one element selected from Group 2 elements and Group 4 elements, and the co-precipitates are separated by filtration and heat dehydrated Terbium oxide, yttrium oxide, scandium oxide, and lanthanide rare earth elements (excluding terbium)
- a method for producing a transparent ceramic characterized by pressure firing.
- the component (c) is at least one ion selected from titanium ion, zirconium ion, hafnium ion, calcium ion, and magnesium ion.
- a transparent ceramics comprising a material and a sintering aid comprising an oxide of at least one element selected from Group 2 elements and Group 4 elements.
- the transparent ceramic according to [6], wherein the content of the sintering aid is more than 0.5 parts by mass and not more than 5 parts by mass with respect to 100 parts by mass of the rare earth oxide.
- the insertion loss at a wavelength of 1064 nm including the reflection loss of the end face on the inner surface of 90% or more of the measurement surface in the thickness direction of the 10 mm thick sample is 0.97 dB or less [6]
- a magneto-optical device comprising the transparent ceramic according to any one of [6] to [9].
- the optical characteristics of the transparent ceramic can be improved as compared with the conventional manufacturing method reported in JP 2012-206935 A (Patent Document 5).
- a single crystal material such as an existing terbium gallium garnet that exhibits excellent optical properties in the visible to infrared region, which could not be obtained by a conventional manufacturing method by setting the sintering aid to a predetermined content.
- Transparent ceramics with performance equal to or better than that can be provided.
- optical loss and optical uniformity are superior to conventional ceramic materials, so light in a 1.06 ⁇ m wavelength region (1,064 ⁇ 40 nm) with very little birefringence component and very little scattering.
- a suitable magneto-optical device for an isolator can be provided.
- the method for producing a transparent ceramic according to the present invention includes terbium oxide (chemical formula: Tb 2 O 3 ) and at least one other selected from oxides of yttrium oxide, scandium oxide, and lanthanide rare earth elements (excluding terbium).
- a method for producing a transparent ceramic mainly comprising a rare earth oxide of (1) (a) terbium ion, (B) at least one other rare earth ion selected from yttrium ions, scandium ions, and lanthanide rare earth ions (excluding terbium ions); (C) In an aqueous solution containing ions of at least one element selected from Group 2 elements and Group 4 elements, the components (a), (b), and (c) are coprecipitated, and the coprecipitate is filtered off.
- Dehydrating (and firing) by heating and comprising terbium oxide and at least one other rare earth oxide selected from oxides of yttrium oxide, scandium oxide and lanthanide rare earth elements (excluding terbium), A sintering aid comprising a rare earth oxide having a terbium oxide ratio of 40 mol% or more and the remaining rare earth oxide as the balance, and an oxide of at least one element selected from Group 2 elements and Group 4 elements;
- At least one other rare earth selected from (a) terbium ions and (b) yttrium ions, scandium ions and lanthanide rare earth ions (excluding terbium ions) having little absorption at a wavelength of 1.064 ⁇ m.
- Components (a) to (c) are prepared by a so-called coprecipitation method using an aqueous solution containing ions of various elements, for example, at least one ion selected from titanium ions, zirconium ions, hafnium ions, calcium ions, and magnesium ions.
- a raw material powder (sintering rare earth oxide powder) containing a rare earth oxide and a sintering aid comprising an oxide of at least one element selected from Group 2 elements and Group 4 elements is prepared. This production method is referred to as a three-component coprecipitation method.
- a predetermined raw material is dissolved so that the components (a), (b), and (c) are contained in an acidic aqueous solution, for example, a 5N nitric acid aqueous solution.
- an acidic aqueous solution for example, a 5N nitric acid aqueous solution.
- the resulting hydroxides are heated and dehydrated to 500 ° C. or higher.
- an oxide raw material powder is preferably produced.
- the method for generating the precipitate is not limited to the method of adding the alkaline aqueous solution, and the above components (a), (b), and (c) may not be disproportionated when the precipitate is generated.
- a method of precipitation as a salt can also be suitably used.
- an alkaline aqueous solution such as aqueous ammonia is dropped into an acidic aqueous solution containing three component ions, and then a hydroxide is prepared.
- a salt containing carbonate ions is dropped and once substituted with a carbonate from a hydroxide and matured, and then ammonia water is dropped again to re-substituted with a hydroxide.
- the particles are precipitated in a stable particle shape without agglomeration.
- the raw material for the component (a) is preferably terbium oxide powder (Tb 2 O 3 ) having a purity of 99% by mass or more, more preferably 99.9% by mass or more, or Tb 4 O having the same purity.
- Tb 2 O 3 terbium oxide powder
- Tb 4 O Tb 4 O having the same purity.
- Powders or powders of other compounds such as terbium fluoride or nitride may be used as long as they are dissolved in an acidic aqueous solution and do not form complex ions and become terbium ions.
- terbium oxide powder is more preferable because impurity ions may affect the reaction or firing.
- the raw material for component (b) is at least one rare earth oxide powder selected from yttrium, scandium and lanthanide rare earths (excluding terbium) having a purity of 99% by mass or more, more preferably 99.9% by mass or more. preferable.
- powders of other compounds such as fluorides or nitrides of these rare earth elements may be used as long as they are dissolved in an acidic aqueous solution and do not form complex ions and become those rare earth ions.
- yttrium oxide, scandium, and lanthanide rare earth powder are more preferable because impurity ions may affect the reaction or firing.
- the raw material for component (c) is preferably an oxide powder of at least one element selected from Group 2 and Group 4 elements having a purity of 99% by mass or more, more preferably 99.9% by mass or more. .
- the raw material for component (a) and the raw material for component (b) are each weighed as a rare earth oxide in a predetermined molar ratio, and then oxidized relative to the total mass of the rare earth oxide.
- the raw material for component (c) is weighed so that it becomes a predetermined amount as a product.
- the ratio of the amounts weighed as the raw materials is the same as the three-component coprecipitation. It becomes the mass ratio (parts by mass) in the raw material powder obtained by the method.
- this mixed powder may be dissolved in an acidic aqueous solution, or each raw material is dissolved in turn. May be.
- the acidic aqueous solution to be used is not particularly limited as long as it dissolves without forming complex ions with the raw materials for the above three components and can contain ions of the components (a) to (c).
- Nitric acid aqueous solution, sulfuric acid aqueous solution, hydrochloric acid aqueous solution and the like can be mentioned.
- an acidic aqueous solution that dissolves all of the three component raw materials is preferable, and a nitric acid solution is more preferable.
- a nitric acid solution is used, the residual amount of inorganic salt after firing is small.
- the precipitant is not particularly limited as long as it can be added to an acidic aqueous solution containing three component ions to coprecipitate all the three component ions, and can be removed from the coprecipitate by washing with water and filtering.
- ammonia water is more preferable in order to minimize impurity ions.
- the oxide raw material obtained by the above method is selected from (A) terbium oxide and (B) yttrium oxide, scandium oxide, and lanthanide rare earth oxides (excluding terbium oxide) that hardly absorb at a wavelength of 1.064 ⁇ m.
- a raw material powder containing a sintering aid made of an oxide of at least one element selected from group elements.
- This raw material powder itself is not significantly different from conventional powders in physical aspects such as grain shape and orientation, but is characterized in that the reaction in sintering is performed uniformly even at the micro level.
- a reflection electron image of an electron microscope is seen on a transparent ceramic that has been subjected to vacuum sintering, HIP (Hot Isostatic Press) using a conventional powder, white spots remain on the crystal grains (FIG. 2 (b)).
- the backscattered electron image has large and small atomic numbers, and the difference in reflection intensity can be seen. Elements with heavy atomic numbers appear white. Therefore, the above-mentioned white spots indicate that elements with heavy atomic numbers remain segregated at the micro level even after the reaction.
- the raw material powder of this time since white spots are not seen, it can be reacted even at the micro level (FIG. 2 (a)).
- the purity of the prepared raw material powder is preferably 99% by mass or more, but is preferably 99.9% by mass or more, and more preferably 99.99% by mass or more for use as an optical application.
- the oxide raw material powder is composed of the components (A) and (B) and the sintering aid of the component (C).
- the main components (A) and (B) means that the total of oxides of components (A) and (B) is contained by 50% by mass or more of the raw material powder.
- the total content of the component oxides (A) and (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
- the sintering aid is an oxide of at least one element selected from Group 2 elements and Group 4 elements.
- terbium oxide alone is said to undergo a phase transition from cubic to monoclinic at around 1400 to 1600 ° C. Therefore, when sintering rare earth oxide ceramics containing terbium oxide, the ceramic is heated to 1400 to 1600 ° C., so that a phase transition from monoclinic to cubic is unavoidable during sintering or cooling. Therefore, if a part of monoclinic crystal remains without undergoing this phase transition, the part becomes a precipitate as a different phase, which causes scattering. Further, the monoclinic crystal has anisotropy and therefore exhibits birefringence.
- a sintering aid capable of smoothly phase transition from monoclinic to cubic.
- sintering aids include oxides of Group 4 elements such as titanium, zirconium and hafnium, and oxides of Group 2 elements such as magnesium and calcium.
- a Group 4 element oxide and a Group 2 element oxide may be used at the same time. These oxides do not absorb near the wavelength of 1.06 ⁇ m and are suitable for the transparent ceramic of the present invention.
- Group 4 element oxides are known as stabilizers for sintering yttria, but are also effective as stabilizers in the transparent ceramics of the present invention.
- Group 2 elements such as magnesium and calcium have strong ionicity and thus have high reaction activity and are easily dissolved in rare earth oxides.
- a sintering aid that does not precipitate a different phase other than the cubic crystal of the crystal structure of the terbium oxide ceramic of component (C) for example, an oxide of a Group 4 element such as titanium, zirconium, hafnium and / or It is preferable to contain an oxide of a Group 2 element such as magnesium or calcium with respect to 100 parts by mass of the total of the (A) and (B) components, and more than 0.5 parts by mass and 5 parts by mass or less.
- the content is more preferably 8 parts by mass to 5 parts by mass, and particularly preferably 1 part by mass to 4.8 parts by mass.
- magneto-optics such as the insertion loss at a wavelength of 1064 nm including the reflection loss of the end face on the inner surface of 90% or more of the measurement surface in the thickness direction of the 10 mm thick sample as a transparent ceramic exceeds 0.97 dB.
- the required characteristics as a material for a device may not be satisfied. That is, if it is 0.5 parts by mass or less, a stable effect as a sintering aid may not be obtained, and if it exceeds 5 parts by mass, it may not be solid-dissolved and may precipitate alone, which may cause scattering. There is.
- Group 4 element oxide alone or a Group 2 element oxide may be used alone as a sintering aid, or these Group 4 element oxides and Group 2 element oxides may be used. May be contained at the same time. Since Group 4 elements are tetravalent ions and Group 2 elements are divalent ions, they are added simultaneously to compensate for the valence of the total amount of ions. Can be suppressed.
- the primary particle diameter of the raw material powder used in the first step is preferably 100 to 2000 nm, and more preferably 200 to 1000 nm.
- the primary particle diameter is less than 100 nm, handling is difficult, for example, molding is difficult, the density of the green compact is low, the shrinkage rate during sintering is large, and cracks may easily occur.
- the said primary particle diameter exceeds 2000 nm, the sinterability of a raw material is scarce and it may be difficult to obtain a high-density and transparent sintered compact.
- the measurement of this primary particle diameter is an average value of the long diameter of 100 primary particles in arbitrary visual fields by observation with a scanning electron microscope or an optical microscope.
- Step 2 At least one of a dispersing agent such as ammonium polyacrylate and ammonium polycarboxylate, a binder such as methylcellulose and polyvinyl alcohol, etc., as necessary, in order to make the obtained raw material powder (coprecipitation raw material) uniform in particle size
- a dispersing agent such as ammonium polyacrylate and ammonium polycarboxylate
- a binder such as methylcellulose and polyvinyl alcohol, etc.
- general mixing and grinding such as a ball mill is performed for several to several tens of hours.
- the obtained slurry is subjected to solvent removal and granulation by a spray drying apparatus, and after molding a granule of several tens of ⁇ m, the produced granule is first molded with a predetermined mold, and CIP (Cold Isostatic Press: cold).
- CIP Cold Isostatic Press: cold.
- the calcined body is obtained by calcining the molded body at 400 to 1000 ° C. for the purpose of removing the added organic components (dispersant and binder).
- the calcining atmosphere may be generally in the air or an oxidizing atmosphere.
- the calcination time is generally about 60 to 180 minutes, although it depends on the calcination temperature.
- the calcined body is fired at 1400 to 1800 ° C., more preferably 1400 to 1600 ° C., to obtain a fired body.
- the firing atmosphere is not particularly limited as long as it is an atmosphere in which Tb 4 O 7 of terbium oxide changes to Tb 2 O 3 , that is, a non-oxidizing atmosphere.
- a reducing atmosphere It may be either inside or in an inert gas atmosphere.
- the pressure can be reduced from 10 2 Pa to 10 ⁇ 5 Pa.
- the firing time is generally about 30 to 480 minutes although it depends on the firing temperature. In this step, it is desirable that the relative density of the fired body is 90% or more.
- the fired body is preferably fired at 1400 to 1800 ° C., more preferably 1400 to 1600 ° C., to obtain a pressure fired body.
- the method for performing the pressure firing is not particularly limited, and may be any one of, for example, an HP (Hot Press) method, an HIP (Hot Isostatic Press) method, and the like.
- HP Hot Press
- HIP Hot Isostatic Press
- argon gas as a pressure medium and pressure firing within a range of 19 to 196 MPa for 1 hour or more at 1400 to 1800 ° C.
- a transparent ceramic pressure transparent fired body
- the pressure fired body obtained above may be further heat-treated at 1500 to 2000 ° C. in a non-oxidizing atmosphere (an atmosphere not containing oxygen) (referred to as an annealing step).
- the transparent ceramic thus obtained is heated on the outer periphery of the ceramic in the third calcination step, the fourth step calcination step, the fifth step pressure calcination step, and the sixth step annealing step. Since carbon and tungsten, which are heater materials, and aluminum, silicon, and calcium, which are heat insulating materials, adhere as impurities and devitrify the transparent ceramics, both end faces in the thickness direction are chemically etched, mechanically ground or polished Need to be removed.
- the chemical etching may be an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, or an organic acid such as malic acid and citric acid as long as it is an acidic aqueous solution.
- hydrochloric acid the outer peripheral surface can be etched away by several hundred ⁇ m by heating to 60 ° C. or higher.
- a centerless grinding device or a cylindrical grinding device may be used as long as it is an outer peripheral surface, and a surface grinding device may be used to cut several hundred ⁇ m to several mm if it is at both end surfaces.
- polishing rough polishing using a diamond slurry, SiC slurry or the like, followed by precision polishing such as colloidal silica may be performed to polish several hundred ⁇ m to several mm.
- precision polishing such as colloidal silica
- optical defects of Tb-rich phase and ZrO 2 can be reduced as the ceramic crystal structure, the uniformity of the crystal structure is improved, and the material properties as a magneto-optical device are improved. It is possible to improve.
- the transparent ceramic according to the present invention is a transparent ceramic manufactured by the above-described method for manufacturing a transparent ceramic according to the present invention, and includes terbium oxide (chemical formula: Tb 2 O 3 ), yttrium oxide, scandium oxide, and lanthanide.
- a rare earth oxide composed of at least one other rare earth oxide selected from oxides of rare earth elements (excluding terbium), with a molar ratio of terbium oxide of 40 mol% or more and the remaining rare earth oxide remaining
- a sintering aid comprising an oxide of at least one element selected from Group 2 elements and Group 4 elements.
- the transparent ceramic of the present invention contains an oxide represented by the following formula (I) as a main component rare earth oxide.
- (Tb x R 1-x ) 2 O 3 (I) (In the formula (I), x is 0.4 ⁇ x ⁇ 1.0, and R is at least one other rare earth element selected from yttrium, scandium, and lanthanide rare earth elements (excluding terbium). )
- R is not particularly limited as long as it contains at least one rare earth element selected from the group consisting of yttrium, scandium, lanthanum, europium, gadolinium, ytterbium, holmium and lutetium, Other elements such as erbium and thulium may be contained. However, it is most preferable that other elements are not included and only the rare earth element selected from the group consisting of yttrium, scandium, lanthanum, europium, gadolinium, ytterbium, holmium, and lutetium is used.
- R may be one kind alone, or a plurality of R may be contained in any ratio. Of these, yttrium, scandium, and lutetium are preferred as R from the viewpoint of easy availability of raw materials.
- x is 0.4 or more and less than 1.0. That is, the rare earth oxide represented by the formula (I) contains 40 mol% or more of Tb 2 O 3 in terms of molar ratio.
- x is preferably 0.4 or more and 0.8 or less, and more preferably 0.45 or more and 0.75 or less. It is preferable that x is in the above range because a high Verde constant is obtained and the transparency is further excellent. In particular, it is preferable that x is 0.8 or less because cracking during cooling after crystal growth is suppressed and white turbidity of the crystal is suppressed.
- the transparent ceramic of the present invention includes a sintering aid composed of an oxide of at least one element selected from Group 2 elements and Group 4 elements together with the rare earth oxide.
- This sintering aid is preferably an oxide of at least one element selected from titanium, zirconium, hafnium, calcium and magnesium.
- the content of the sintering aid composed of these oxides is preferably more than 0.5 parts by mass and not more than 5 parts by mass with respect to 100 parts by mass of the rare earth oxide, and not less than 0.8 parts by mass and not more than 5 parts by mass. It is more preferable that it is 1 part by mass or more and 4.8 parts by mass or less. If it is 0.5 parts by mass or less, a stable effect as a sintering aid cannot be obtained, and the insertion loss may exceed 0.97 dB. On the other hand, in the case of more than 5 parts by mass, the sintering aid component cannot be dissolved, but is precipitated alone, which causes laser light scattering, and in this case, the insertion loss may exceed 0.97 dB. is there.
- the transparent ceramic of the present invention is selected from (A) terbium oxide, (B) yttrium oxide, scandium oxide, and lanthanide rare earth oxide (excluding terbium oxide) prepared by the above-described three-component coprecipitation method. It is produced using a raw material powder containing at least one other rare earth oxide and (C) a sintering aid comprising an oxide of at least one element selected from Group 2 elements and Group 4 elements. It will be. This suppresses generation of Tb-rich phases and optical defects of ZrO 2 in the ceramic crystal structure as compared with ceramics produced by a conventional manufacturing method, and improves material properties for a magneto-optical device.
- the transparent ceramic of the present invention preferably has an insertion loss at a wavelength of 1,064 nm including an end surface reflection loss of 90% or more in terms of the area ratio of the measurement surface in the thickness direction of a 10 mm thick sample. 97 dB or less, more preferably 0.96 dB or less. When this insertion loss exceeds 0.97 dB, light scattering at crystal grains or grain boundaries is very large, or light absorption at crystal grains is very large, and a thermal lens is assumed. It is difficult to use for a high power (for example, output 20 W) laser processing machine.
- a high power for example, output 20 W
- the measured values include surface reflections at both end faces of the sample.
- Rms Root-mean-square
- Rms is the root mean square roughness obtained as the square root of the mean of the square values of deviations relative to the arithmetic mean value of the cross-sectional profile at the reference length.
- the V-shaped block on which the ceramic is placed can move in the direction perpendicular to the incident light, and thereby the in-plane distribution of the ceramic can be measured. Therefore, the in-plane distribution of 90% or more of the measurement surface is a result of measurement at each measurement point while moving the V-shaped block to 95% of the sample diameter.
- the extinction ratio at a wavelength of 1064 nm in a plane of 90% or more of the measurement surface in the thickness direction of a sample having a thickness of 10 mm is preferably 35 dB or more, more preferably 36 dB or more.
- the transparent ceramic of the present invention has a maximum incident power of a laser beam that does not generate a thermal lens when a laser beam having a wavelength of 1,064 nm is incident at a beam diameter of 1.6 mm in the thickness direction of a sample having a thickness of 10 mm.
- the value is preferably 15 W or more, more preferably 20 W or more, and further preferably 25 W or more.
- the thermal lens emits light having a predetermined incident power as a spatial light of 1.6 mm, and the transparent ceramic is inserted as a Faraday rotator there. This is obtained by reading the maximum incident power when the change in focal length is 0.1 m or less.
- the transparent ceramic of the present invention is suitable for magneto-optical device applications.
- the transparent ceramic of the present invention is suitably used as a Faraday rotator of an optical isolator having a wavelength of 1.06 ⁇ m (1,064 ⁇ 40 nm).
- FIG. 1 is a schematic cross-sectional view showing an example of an optical isolator which is a magneto-optical device having a Faraday rotator as an optical element.
- the optical isolator 100 includes a Faraday rotator 110, and a polarizer 120 and an analyzer 130 that are polarizing materials are provided before and after the Faraday rotator 110.
- a polarizer 120, a Faraday rotator 110, and an analyzer 130 are arranged on the optical axis 112 in this order, and a magnet 140 is placed on at least one of the side surfaces. Is preferably housed inside the housing 150.
- the isolator is preferably used for a fiber laser for a processing machine. That is, it is suitable for preventing the reflected light of the laser light emitted from the laser element from returning to the element and causing oscillation to become unstable.
- Example 1 First, as raw materials for rare earth oxides, terbium oxide powder (Tb 2 O 3 , purity 99.9% by mass or more) manufactured by Shin-Etsu Chemical Co., Ltd., and yttrium oxide powder (Y 2 O 3 , purity 99.9% by mass) are used. The above were prepared and weighed so that Tb 2 O 3 : Y 2 O 3 was a molar ratio of 60:40. Furthermore, as a raw material for the sintering aid, zirconium oxide (ZrO 2 ) powder (purity of 99.9% by mass or more) manufactured by Daiichi Rare Element Chemical Co., Ltd. is used as a total of 100 parts by mass of the rare earth oxide.
- ZrO 2 zirconium oxide
- an aqueous ammonium hydrogen carbonate solution (NH 4 HCO 3 ) was added dropwise thereto and aged for 1 hour. Thereafter, ammonia water was further added to cause complete precipitation, followed by filtration and washing with ultrapure water, followed by drying.
- the obtained dry powder was put in an alumina crucible and subjected to heat dehydration in the atmosphere at 700 ° C. for 3 hours to obtain a raw material powder.
- a mixture is obtained by mixing them with a pot mill, and then the mixture is spray-dried to produce granules.
- Granules with a diameter of several tens of ⁇ m were obtained. Molding was performed as a primary molding using the granules, and then a molded body was obtained by a cold isostatic (CIP) method at a pressure of 200 MPa as a secondary molding. The obtained molded body was calcined at 1000 ° C. in an oxygen atmosphere, and then fired in a vacuum furnace at 1700 to 1750 ° C. for 8 hours in a vacuum of 5 ⁇ 10 ⁇ 2 Pa. Furthermore, the obtained sintered body was processed by a hot isostatic pressing (HIP) method at 1800 ° C., a pressure of 100 MPa, and 10 hours to obtain six kinds of ceramic samples having a diameter of 6 mm.
- CIP cold isostatic
- a polarizing element is set before and after each of the obtained ceramic samples, and then a hollow cylindrical neodymium-iron-boron magnet is covered so that the ceramic sample is arranged at the center of the cylinder.
- a high power laser beam diameter: 1.6 mm
- a high power laser beam with a wavelength of 1064 nm is incident from both end faces, insertion loss, total transmittance, scattering transmittance, extinction ratio
- the maximum of the Verde constant and the incident power not generated by the thermal lens were measured.
- the total transmittance was measured using a UV-visible spectrophotometer V-670 manufactured by JASCO Corporation.
- the light was uniformly reflected by integrating the light with an integrating sphere coated with a high reflectivity material on the inner wall, and the light scattered by the turbidity of the sample was also measured by the intensity of the captured light, and obtained based on the following equation.
- the wavelength at this time is 1,064 nm.
- Total transmittance I / I 0 ⁇ 100 (In the formula, I represents transmitted light intensity (intensity of light transmitted through a sample having a length of 10 mm), and I 0 represents incident light intensity.)
- the scattering transmittance was measured using a UV-visible spectrophotometer V-670 manufactured by JASCO Corporation.
- the above integrating sphere is inserted and measured. At this time, by opening the part of the integrating sphere that hits the measurement optical path, the light that has been linearly transmitted passes through the integrating sphere, but is scattered by the turbidity of the sample. Light is captured by an integrating sphere. It measured by the intensity
- the wavelength at this time is 1,064 nm.
- Scattering transmittance I / I 0 ⁇ 100 (In the formula, I represents scattered light intensity (intensity of light scattered by a sample having a length of 10 mm), and I 0 represents incident light intensity.)
- the extinction ratio is such that ceramics are placed on a V-shaped block, 20 mW coherent light having a wavelength of 1.064 ⁇ m is converged to a diameter of 0.3 mm by a 10 ⁇ objective lens, and vertically incident on the ceramics through a polarizer. .
- the light at this time is linearly polarized light.
- the light transmitted through the ceramic is put into a polarizer rotated 90 degrees with respect to the polarizer, and the light intensity is measured with a semiconductor light receiver.
- the Verde constant V was determined based on the following equation.
- the magnitude (H) of the magnetic field applied to the sample was a value calculated by simulation from the dimensions of the measurement system, the residual magnetic flux density (Br), and the holding force (Hc).
- ⁇ V ⁇ H ⁇ L (Where, ⁇ is the Faraday rotation angle (min), V is the Verde constant, H is the magnitude of the magnetic field (Oe), and L is the length of the Faraday rotator (in this case, 1 cm).)
- a high power laser beam having a wavelength of 1,064 nm is emitted as a spatial beam having a beam diameter of 1.6 mm, and a beam waist position F0 (m) is measured by a beam profiler. Thereafter, a measurement sample is placed in the spatial optical system, and the beam waist position F1 (m) of the emitted light is measured similarly.
- the change amount ( ⁇ F) of the beam waist position at this time is expressed by the following equation.
- ⁇ F (m) F0 ⁇ F1
- terbium oxide powder (Tb 2 O 3 , purity 99.9% by mass or more) manufactured by Shin-Etsu Chemical Co., Ltd.
- yttrium oxide powder (Y 2 O 3 , purity 99.9% by mass) are used.
- the above were prepared and weighed so that Tb 2 O 3 : Y 2 O 3 was a molar ratio of 60:40.
- zirconium oxide (ZrO 2 ) powder (purity of 99.9% by mass or more) manufactured by Daiichi Rare Element Chemical Co., Ltd. is used as a total of 100 parts by mass of the rare earth oxide.
- each particle size (average primary particle size) of the terbium oxide powder, yttrium oxide powder and zirconium oxide powder was 0.1 to 1 ⁇ m.
- These raw materials were used as six types of raw materials with varying contents of the sintering aid, and further, ethyl cellulose and an effective amount of polyvinyl alcohol as a dispersant and a binder were mixed in a pot mill to obtain six types of mixtures. Subsequently, granules having a particle size of several tens of ⁇ m were obtained by spray drying.
- a molded body was obtained by a CIP method at a pressure of 200 MPa as a secondary molding.
- the obtained molded body was calcined at 1000 ° C. in an oxygen atmosphere, and then fired in a vacuum furnace at 1650 to 1700 ° C. for 8 hours in a vacuum of 5 ⁇ 10 ⁇ 2 Pa.
- the obtained sintered body was processed by a hot isostatic pressing (HIP) method at 1800 ° C., a pressure of 100 MPa, and 10 hours to obtain six kinds of ceramic samples having a diameter of 6 mm.
- HIP hot isostatic pressing
- terbium oxide powder (Tb 2 O 3 , purity 99.9% by mass or more) manufactured by Shin-Etsu Chemical Co., Ltd.
- yttrium oxide powder (Y 2 O 3 , purity 99.9% by mass) are used as raw materials for rare earth oxides.
- the above were prepared and weighed so that Tb 2 O 3 : Y 2 O 3 was a molar ratio of 60:40.
- This terbium oxide powder and yttrium oxide powder were mixed and dissolved in a 5N aqueous nitric acid solution.
- aqueous ammonia (NH 4 OH) is added dropwise at a constant dropping rate while the aqueous solution is stirred to neutralize it, and further added dropwise to make it alkaline with a pH of 9 to 10 (chemical formula (Tb 0.6 Y 0.4 ) ( OH) 3 ) was precipitated (co-precipitated).
- an aqueous ammonium hydrogen carbonate solution (NH 4 HCO 3 ) was added dropwise thereto and aged for 1 hour. Thereafter, ammonia water was further added to cause complete precipitation, followed by filtration and washing with ultrapure water, followed by drying. The obtained dry powder was put in an alumina crucible and heat dehydrated at 700 ° C.
- Zirconium Oxide (ZrO 2 ) powder (purity: 99.9% by mass or more) manufactured by Daiichi Rare Element Chemical Co., Ltd. is used as a sintering aid for the obtained powder.
- ZrO 2 Zirconium Oxide
- it is made into parts by mass, it is weighed and added so as to have a content of 6 levels in the range of 0.4 to 5.3 parts by mass, and further, effective amounts of ethyl cellulose and polyvinyl alcohol are added as a dispersant and a binder, Six types of mixtures were obtained by mixing with a pot mill. Subsequently, granules having a particle size of several tens of ⁇ m were obtained by spray drying.
- a molded body was obtained by a CIP method at a pressure of 200 MPa as a secondary molding.
- the obtained molded body was calcined at 1000 ° C. in an oxygen atmosphere, and then fired in a vacuum furnace at 1650 to 1700 ° C. for 8 hours in a vacuum of 5 ⁇ 10 ⁇ 2 Pa.
- the obtained sintered body was processed by a hot isostatic pressing (HIP) method at 1800 ° C., a pressure of 100 MPa, and 10 hours to obtain six kinds of ceramic samples having a diameter of 6 mm.
- HIP hot isostatic pressing
- Example 1 and Comparative Examples 1A and 1B are shown in Tables 1 to 3. Each sample of Example 1 has improved optical characteristics as compared with the corresponding compositions of Comparative Examples 1A and 1B.
- Example 2 In Example 1, the sintering assistant was made hafnium oxide (HfO 2 ), and the content thereof was changed to 6 levels. Otherwise, a ceramic sintered body was produced and evaluated in the same manner as in Example 1.
- HfO 2 hafnium oxide
- Comparative Example 2A In Comparative Example 1A, a sintered ceramic was produced and evaluated in the same manner as in Comparative Example 1A except that the sintering aid was hafnium oxide and the content thereof was changed to 6 levels.
- Comparative Example 2B In Comparative Example 1B, the sintered assistant was made into hafnium oxide, and its content was changed to 6 levels. Otherwise, a ceramic sintered body was produced and evaluated in the same manner as in Comparative Example 1B.
- Tables 4 to 6 show the results of Example 2 and Comparative Examples 2A and 2B. Each sample of Example 2 has improved optical characteristics as compared with the corresponding compositions of Comparative Examples 2A and 2B.
- Example 3 In Example 1, rare earth oxide transparent ceramics containing terbium oxide were produced by changing to the raw materials and conditions shown in Tables 7 to 15, and optical characteristics such as insertion loss were measured. Examples 3 and 4 are obtained by changing the molar ratio of terbium oxide and yttrium oxide and the content of zirconium oxide in Example 1. In Examples 5 and 6, the molar ratio of terbium oxide and yttrium oxide and the content of hafnium oxide were changed in Example 2. In Example 7, the molar ratio of terbium oxide and yttrium oxide in Example 1 was changed to 70:30, and the content of the sintering aid was changed to titanium oxide (TiO 2 ).
- Example 8 the combination of terbium oxide and lutetium oxide (Lu 2 O 3 ) in Example 1 was changed to a molar ratio of 80:20, and the zirconium oxide content was changed.
- Example 9 the combination of terbium oxide and scandium oxide (Sc 2 O 3 ) in Example 1 was changed to a molar ratio of 70:30, and the sintering aid was changed to hafnium oxide (HfO 2 ). It is a thing.
- Example 10 is a combination of terbium oxide, yttrium oxide and gadolinium oxide (Gd 2 O 3 ) in Example 1 with a molar ratio of 60:10:30, and a sintering aid is titanium oxide (TiO 2 ).
- Example 11 the molar ratio of terbium oxide and yttrium oxide was changed to 50:50 in Example 1, and the content was changed by further combining the sintering auxiliary agent with zirconium oxide and titanium oxide (TiO 2 ). It is. All the above results are summarized in Tables 7 to 15.
- FIG. 2 shows the results of observation of the crystal structures of the polished surfaces of Example 1-3 and Comparative Example 1A-3 as reflected electron images of an electron microscope.
- Comparative Example 1A-3 (FIG. 2B)
- white spots and ZrO 2 optical defects which are Tb-rich phases
- Example 1-3 FIG. 2A
- the crystal structure of the polished surface of Comparative Example 1B-3 was observed as a backscattered electron image of an electron microscope, white spots and ZrO 2 optical defects, which are Tb-rich phases similar to those in FIG. 2B, were observed. .
- a heterogeneous phase was also observed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
θ=V×H×L (A)
式(A)中、Vはベルデ定数でファラデー回転子の材料で決まる定数であり、Hは磁束密度、Lはファラデー回転子の長さである。光アイソレータとして用いる場合は、θ=45度になるように、Lを決定する。
更に、入射した光と異なる偏光成分が出射光内に生じると、この異なる偏光成分は、偏光子を透過するので、戻り光の遮断が不十分になる。
S=-10log(Imin/Imax) [単位dB]
消光比は、大きいことが重要であり、一般的には30dB以上が求められている。
(1)焼結性に優れた特定の粒度分布を有する出発原料を使用し、
(2)焼結性が優れ、かつセラミックスの結晶構造を立方晶に維持できる焼結助剤を使用し、
(3)最適温度で真空焼結又は酸素を含まない雰囲気で焼結させて、HIP処理を行い、
(4)上記で得られた焼結体を、酸素を含まない雰囲気で熱処理する、
ことで、散乱の原因となる異相析出物又は気孔を低減することで、組成変動が少ない光学的に均一な希土類酸化物を主成分とする光学セラミックスで、挿入損失1.0dB以下のものが得られたことが記載されている。
また、光学材料に光吸収原因となる欠陥があると、その欠陥で吸収された光が熱に変換されるため、この熱レンズが更に大きくなる課題があった。
〔1〕 酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とを主成分とする透明セラミックスの製造方法であって、(a)テルビウムイオン、(b)イットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選ばれる少なくとも1種のその他の希土類イオン、(c)第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオンを含む水溶液において(a)、(b)、(c)成分を共沈させ、その共沈物をろ別、加熱脱水して、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む原料粉末を作製し、この原料粉末を用いて成形体を成形した後、該成形体を焼成し、次いで加圧焼成することを特徴とする透明セラミックスの製造方法。
〔2〕 上記原料粉末は、焼結助剤を希土類酸化物100質量部に対して0.5質量部超5質量部以下含むことを特徴とする〔1〕記載の透明セラミックスの製造方法。
〔3〕 上記(c)成分がチタンイオン、ジルコニウムイオン、ハフニウムイオン、カルシウムイオン及びマグネシウムイオンから選ばれる少なくとも1種のイオンである〔1〕又は〔2〕記載の透明セラミックスの製造方法。
〔4〕 更に、加圧焼成後の成形体を酸素を含まない雰囲気下で1500~2000℃で熱処理することを特徴とする〔1〕~〔3〕のいずれかに記載の透明セラミックスの製造方法。
〔5〕 上記焼成前に、成形体を仮焼することを特徴とする〔1〕~〔4〕のいずれかに記載の透明セラミックスの製造方法。
〔6〕 〔1〕~〔5〕のいずれかに記載の透明セラミックスの製造方法で製造される透明セラミックスであって、酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む透明セラミックス。
〔7〕 上記焼結助剤の含有量が希土類酸化物100質量部に対して0.5質量部超5質量部以下である〔6〕記載の透明セラミックス。
〔8〕 上記焼結助剤がチタン、ジルコニウム、ハフニウム、カルシウム及びマグネシウムから選ばれる少なくとも1種の元素の酸化物である〔6〕又は〔7〕記載の透明セラミックス。
〔9〕 厚さ10mmの試料の厚さ方向において測定面の90%以上の内面における端面の反射損失を含む波長1,064nmの挿入損失が0.97dB以下であることを特徴とする〔6〕~〔8〕のいずれかに記載の透明セラミックス。
〔10〕 〔6〕~〔9〕のいずれかに記載の透明セラミックスを用いて構成される磁気光学デバイス。
〔11〕 〔6〕~〔9〕のいずれかに記載の透明セラミックスをファラデー回転素子として用いる磁気光学デバイス。
〔12〕 〔11〕記載の磁気光学デバイスにおいて、ファラデー回転素子の前後に偏光材料を備える、1,064±40nmの波長域で使用される光アイソレータ用の磁気光学デバイス。
〔13〕 (a)テルビウムイオン、(b)イットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選ばれる少なくとも1種のその他の希土類イオン、(c)第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオンを含む水溶液において(a)、(b)、(c)成分を共沈させ、その共沈物をろ別、加熱脱水して得られる、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む焼結用希土類酸化物粉末。
[透明セラミックスの製造方法]
本発明に係る透明セラミックスの製造方法は、酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とを主成分とする透明セラミックスの製造方法であって、
(1)(a)テルビウムイオン、
(b)イットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選ばれる少なくとも1種のその他の希土類イオン、
(c)第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオン
を含む水溶液において(a)、(b)、(c)成分を共沈させ、その共沈物をろ別、加熱脱水(及び焼成)して、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む原料粉末(焼結用希土類酸化物粉末)を作製する第1工程、
(2)上記原料粉末を成形して成形体を得る第2工程、
(3)上記成形体を仮焼きして仮焼体を得る第3工程、
(4)上記仮焼体を非酸化性雰囲気下で焼成して焼成体を得る第4工程、
(5)上記焼成体を加圧焼成して加圧焼成体を得る第5工程
を有することを特徴とする。
第1工程では、(a)テルビウムイオンと、(b)波長1.064μmにおいて吸収がほとんどないイットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選択される少なくとも1種のその他の希土類イオンと、(c)酸化物となって酸化テルビウム系のセラミックスの結晶構造において立方晶以外の異相の析出を抑制する焼結助剤となる第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオン、例えばチタンイオン、ジルコニウムイオン、ハフニウムイオン、カルシウムイオン、マグネシウムイオンから選ばれる少なくとも1種のイオンとを含む水溶液を用いて、いわゆる共沈法によって(a)~(c)成分を共沈させて、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む原料粉末(焼結用希土類酸化物粉末)を作製する。この作製方法を3成分共沈法と称する。
次に、得られた原料粉末(共沈原料)に、粒径を揃えるため、必要に応じてポリアクリル酸アンモニウム、ポリカルボン酸アンモニウムなどの分散剤、メチルセルロース、ポリビニルアルコールなどのバインダー等の少なくともいずれかを加え、更に溶媒として純水又はエチルアルコールなどを使って、数~10数時間、ボールミルなどの一般的な混合粉砕を行う。
第3工程では、添加した有機成分(分散剤とバインダー)を除去する目的で上記成形体を400~1000℃で仮焼することにより仮焼体を得る。仮焼雰囲気は、一般的には大気中、又は酸化性雰囲気とすればよい。仮焼時間は、仮焼温度にもよるが、一般的には60~180分程度とすればよい。本工程では仮焼体の相対密度を50%以上にすることが望ましい。
第4工程では、上記仮焼体を好ましくは1400~1800℃、より好ましくは1400~1600℃で焼成することにより焼成体を得る。焼成雰囲気は、酸化テルビウムのTb4O7がTb2O3に変化する雰囲気、即ち非酸化性雰囲気であれば特に限定されず、例えば真空(102Pa~10-5Pa)中、還元雰囲気中、不活性ガス雰囲気中等のいずれであってもよい。なお、真空中で焼成を実施する場合は102Pa~10-5Paの減圧条件下とすることができる。焼成時間は、焼成温度にもよるが、一般的には30~480分程度とすればよい。本工程では焼成体の相対密度を90%以上にすることが望ましい。
第5工程では、上記焼成体を好ましくは1400~1800℃、より好ましくは1400~1600℃で加圧焼成することにより加圧焼成体を得る。加圧焼成する方法は、特に限定されず、例えばHP(Hot Press)法、HIP(Hot Isostatic Press)法などのいずれであってもよい。特に、本発明では、圧力が均一に掛かることで歪が入りにくいHIP法を好適に用いることができる。例えば、圧力媒体としてアルゴンガスを用い、圧力を19~196MPaの範囲内で、1時間以上、1400~1800℃にて加圧焼成することにより、透明なセラミックス(加圧透明焼成体)を得ることができる。
本発明では、必要に応じて、更に上記で得られた加圧焼成体を非酸化性雰囲気(酸素を含まない雰囲気)下で1500~2000℃で熱処理してもよい(アニール工程という)。
機械研削であれば、外周面であれば、センタレス研削装置でも、円筒研削装置でもよく、両端面であれば、平面研削装置を用いて、数百μm~数mmを削ってもよい。
研磨であれば、ダイヤスラリー、SiCスラリーなどを用いて粗研磨してから、コロイダルシリカなどの精密研磨を行って、数百μm~数mmを研磨してもよい。
これらの化学エッチング、機械研削又は研磨することで、光学特性に優れた、光学素子を形成することができる。
本発明に係る透明セラミックスは、上述した本発明に係る透明セラミックスの製造方法で製造される透明セラミックスであって、酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含むものである。
(TbxR1-x)2O3 (I)
(式(I)中、xは、0.4≦x<1.0であり、Rはイットリウム、スカンジウム及びランタニド希土類元素(テルビウムを除く)から選ばれる少なくとも1種のその他の希土類元素である。)
また、xは0.4以上0.8以下であることが好ましく、0.45以上0.75以下であることがより好ましい。xが上記範囲内であると高いベルデ定数が得られ、更に透明性に優れるので好ましい。特に、xが0.8以下であると、結晶育成後の冷却中のクラックの発生が抑制され、結晶の白濁が抑制されるので好ましい。
なお、Rms(Root-mean-squre)とは、基準長さにおける断面プロファイルの算術平均値に対する偏差の2乗値の平均に対する平方根として得られる2乗平均平方根粗さである。
消光比=-10log(I/I0)
なお、測定面の90%以上の面内分布はV字ブロックを試料直径の95%まで移動しながら各測定ポイントにおいて測定する。
本発明の透明セラミックスは、磁気光学デバイス用途に好適である。特に、本発明の透明セラミックスは、波長1.06μm域(1,064±40nm)の光アイソレータのファラデー回転子として好適に使用される。
図1において、光アイソレータ100は、ファラデー回転子110を備え、該ファラデー回転子110の前後には、偏光材料である偏光子120及び検光子130が備えられている。また、光アイソレータ100は、偏光子120-ファラデー回転子110-検光子130が光軸112上にこの順で配置され、それらの側面のうちの少なくとも1面に磁石140が載置され、磁石140は筐体150の内部に収納されていることが好ましい。
まず希土類酸化物の原材料として、信越化学工業(株)製の酸化テルビウム粉末(Tb2O3、純度99.9質量%以上)と、酸化イットリウム粉末(Y2O3、純度99.9質量%以上)とを用意し、Tb2O3:Y2O3がモル比で60:40となるように秤量した。更に、焼結助剤の原材料として、第一稀元素化学工業(株)製酸化ジルコニウム(ZrO2)粉末(純度99.9質量%以上)を上記希土類酸化物を合計で100質量部とした場合に0.4~5.2質量部の範囲で6水準の含有量となるように秤量した。これらの3種類の原材料を焼結助剤の含有量を変化させた6種類の原材料としてそれぞれ5N硝酸水溶液に溶解した。
次に、それぞれをこの水溶液を攪拌しながらアンモニア水(NH4OH)を一定滴下速度で滴下して中和し、更に滴下してpH9~10のアルカリ性として水酸化物(化学式(Tb0.6Y0.4)(OH)3)とZr(OH)4)を沈殿(共沈)させた。
次いで、これに炭酸水素アンモニウム水溶液(NH4HCO3)を滴下して1時間熟成した。その後、更にアンモニア水を加え、完全に沈殿させ、ろ過と超純水での洗浄を行って、乾燥した。得られた乾燥粉末をアルミナるつぼに入れて大気中で700℃で3時間の加熱脱水を行って原料粉末を得た。
次に、得られた原料粉末に対して更に分散剤及びバインダーとしてエチルセルロースとポリビニルアルコールを有効量添加した後、これらをポットミルで混合することにより混合物を得、次いでこの混合物をスプレードライすることにより粒径数十μmの顆粒を得た。この顆粒を用いて一次成型として金型成形を行った後、二次成型として200MPaの圧力で冷間静水等方圧(CIP)法により成形体を得た。
得られた成形体を酸素雰囲気中、1000℃で仮焼した後、真空炉で5×10-2Paの真空中、1700~1750℃にて8時間焼成した。
更に、得られた焼結体を1800℃、圧力100MPa、10時間の熱間等方加圧(HIP)法で処理を行って直径6mmのセラミックスの6種類の試料を得た。
こうして得られたそれぞれのセラミックス焼結体を、長さ10mmになるように研削及び研磨処理し、次いでそれぞれのサンプルの光学両端面を光学面精度λ/8(λ=633nm)で最終光学研磨し、更に中心波長が1,064nmとなるように設計された反射防止膜をコートした。
挿入損失は、セラミックスをV字ブロックに載置し、波長1.064μmの20mWのコヒーレント光を、10倍の対物レンズで直径0.3mmに収束させ、セラミックスに対して垂直に入射させる。セラミックスの透過光について、半導体受光器で光強度を測定する。このとき、該セラミックスを挿入しない場合の光強度をI0(mW)として、セラミックスを挿入した場合の光強度をI1(mW)とすると、挿入損失は、次式で表される。
挿入損失=-10log(I1/I0)
全透過率は、日本分光(製)の紫外可視分光光度計V-670を用いて測定した。内壁に高反射率素材を塗布した積分球で光を多重反射させて光を均一にし、試料の濁りで散乱した光なども捕捉した光の強度により測定され、以下の式に基づいて求めた。このときの波長は1,064nmである。
全透過率=I/I0×100
(式中、Iは透過光強度(長さ10mmの試料を透過した光の強度)、I0は入射光強度を示す。)
散乱透過率は、日本分光(製)の紫外可視分光光度計V-670を用いて測定した。上記の積分球を入れて測定するが、このとき、測定光路に当る積分球の部分を開放とすることで、直線透過した光は積分球から抜けていくが、一方、試料の濁りで散乱した光は積分球で捕捉される。その捕捉した光の強度により測定し、以下の式に基づいて求めた。このときの波長は1,064nmである。
散乱透過率=I/I0×100
(式中、Iは散乱光強度(長さ10mmの試料で散乱した光の強度)、I0は入射光強度を示す。)
消光比は、セラミックスをV字ブロックに載置し、波長1.064μmの20mWのコヒーレント光を10倍の対物レンズで直径0.3mmに収束させ、セラミックスに対して、偏光子を通して垂直に入射させる。このときの光は直線偏光になっている。セラミックスの透過光を、前記の偏光子に対して90度回転した偏光子を入れて、半導体受光器で光強度を測定する。このとき、該セラミックスを挿入しない場合の光強度をI0(mW)として、セラミックスを挿入した場合の光強度をI(mW)とすると、消光比は、次式で表される。
消光比=-10log(I/I0)
ベルデ定数Vは、以下の式に基づいて求めた。なお、サンプルに印加される磁界の大きさ(H)は、上記測定系の寸法、残留磁束密度(Br)及び保持力(Hc)からシミュレーションにより算出した値を用いた。
θ=V×H×L
(式中、θはファラデー回転角(min)、Vはベルデ定数、Hは磁界の大きさ(Oe)、Lはファラデー回転子の長さ(この場合、1cm)である。)
波長1,064nmのハイパワーレーザ光を、ビーム径1.6mmの空間光にして出射させ、ビームプロファイラにより、ビームウエスト位置F0(m)を計測する。その後、上記空間光学系に測定試料を配置し、同じく出射光のビームウエスト位置F1(m)を計測する。このときのビームウエスト位置の変化量(ΔF)は次式により表される。
ΔF(m)=F0-F1
なお、ΔFの変化は入力レーザパワーの増大に伴い大きくなるが、ΔF=0.1m以下となるときの最大入射レーザパワー[W]を熱レンズを無視できる値(熱レンズの発生しない入射パワーの最大値)として求めた。
まず希土類酸化物の原材料として、信越化学工業(株)製の酸化テルビウム粉末(Tb2O3、純度99.9質量%以上)と、酸化イットリウム粉末(Y2O3、純度99.9質量%以上)とを用意し、Tb2O3:Y2O3がモル比で60:40となるように秤量した。更に、焼結助剤の原材料として、第一稀元素化学工業(株)製酸化ジルコニウム(ZrO2)粉末(純度99.9質量%以上)を上記希土類酸化物を合計で100質量部とした場合に0.3~5.5質量部の範囲で6水準の含有量となるように秤量した。なお、上記酸化テルビウム粉末、酸化イットリウム粉末、酸化ジルコニウム粉末の各粒径(平均一次粒子径)は、いずれも0.1~1μmであった。
これらの原料を焼結助剤の含有量を変化させた6種類の原材料とし、更に分散剤及びバインダーとしてエチルセルロースとポリビニルアルコールの有効量とをポットミルで混合することにより6種類の混合物を得た。次いで、スプレードライすることによって、粒径数十μmの顆粒を得た。この顆粒を用いて一次成型として金型成形を行った後、二次成型として200MPaの圧力でCIP法により成形体を得た。
得られた成形体を酸素雰囲気中、1000℃で仮焼した後、真空炉で5×10-2Paの真空中、1650~1700℃にて8時間焼成した。
更に、得られた焼結体を1800℃、圧力100MPa、10時間の熱間等方加圧(HIP)法で処理を行って直径6mmのセラミックスの6種類の試料を得た。
こうして得られたそれぞれのセラミックス焼結体を、長さ10mmになるように研削及び研磨処理し、次いでそれぞれのサンプルの光学両端面を光学面精度λ/8(λ=633nm)で最終光学研磨し、更に中心波長が1,064nmとなるように設計された反射防止膜をコートし、実施例1と同様の評価を行った。
まず希土類酸化物の原材料として、信越化学工業(株)製の酸化テルビウム粉末(Tb2O3、純度99.9質量%以上)と、酸化イットリウム粉末(Y2O3、純度99.9質量%以上)とを用意し、Tb2O3:Y2O3がモル比で60:40となるように秤量した。この酸化テルビウム粉末と酸化イットリウム粉末とを混合し、5N硝酸水溶液に溶解した。
次に、この水溶液を攪拌しながらアンモニア水(NH4OH)を一定滴下速度で滴下して中和し、更に滴下してpH9~10のアルカリ性として水酸化物(化学式(Tb0.6Y0.4)(OH)3)を沈殿(共沈)させた。
次いで、これに炭酸水素アンモニウム水溶液(NH4HCO3)を滴下して1時間熟成した。その後、更にアンモニア水を加え、完全に沈殿させ、ろ過と超純水での洗浄を行って、乾燥した。得られた乾燥粉末をアルミナるつぼに入れて大気中で700℃で3時間の加熱脱水を行って粉末を得た。
次に、得られた粉末に対して焼結助剤として第一稀元素化学工業(株)製酸化ジルコニウム(ZrO2)粉末(純度99.9質量%以上)を上記希土類酸化物を合計で100質量部とした場合に0.4~5.3質量部の範囲で6水準の含有量となるように秤量して添加し、更に分散剤及びバインダーとしてエチルセルロースとポリビニルアルコールを有効量添加した後、ポットミルで混合することにより6種類の混合物を得た。次いで、スプレードライすることによって、粒径数十μmの顆粒を得た。この顆粒を用いて一次成型として金型成形を行った後、二次成型として200MPaの圧力でCIP法により成形体を得た。
得られた成形体を酸素雰囲気中、1000℃で仮焼した後、真空炉で5×10-2Paの真空中、1650~1700℃にて8時間焼成した。
更に、得られた焼結体を1800℃、圧力100MPa、10時間の熱間等方加圧(HIP)法で処理を行って直径6mmのセラミックスの6種類の試料を得た。
こうして得られたそれぞれのセラミックス焼結体を、長さ10mmになるように研削及び研磨処理し、次いでそれぞれのサンプルの光学両端面を光学面精度λ/8(λ=633nm)で最終光学研磨し、更に中心波長が1,064nmとなるように設計された反射防止膜をコートし、実施例1と同様の評価を行った。
実施例1の各試料は、比較例1A,1Bの対応する組成のものよりも光学特性が改善されている。
実施例1において、焼結助剤を酸化ハフニウム(HfO2)としてその含有量を6水準に変化させ、それ以外は実施例1と同様にしてセラミックス焼結体を作製して評価した。
比較例1Aにおいて、焼結助剤を酸化ハフニウムとしてその含有量を6水準に変化させ、それ以外は比較例1Aと同様にしてセラミックス焼結体を作製して評価した。
比較例1Bにおいて、焼結助剤を酸化ハフニウムとしてその含有量を6水準に変化させ、それ以外は比較例1Bと同様にしてセラミックス焼結体を作製して評価した。
実施例2の各試料は、比較例2A,2Bの対応する組成のものよりも光学特性が改善されている。
実施例1において、表7~表15に示した原料及び条件に変更して、酸化テルビウムを含む希土類酸化物透明セラミックスを作製し、挿入損失等の光学特性を測定した。
実施例3,4は、実施例1において酸化テルビウムと酸化イットリウムのモル比及び酸化ジルコニウムの含有量を変更したものである。
実施例5,6は、実施例2において酸化テルビウムと酸化イットリウムのモル比及び酸化ハフニウムの含有量を変更したものである。
実施例7は、実施例1において酸化テルビウムと酸化イットリウムのモル比を70:30に変更し、更に焼結助剤を酸化チタン(TiO2)としてその含有量を変更したものである。
実施例8は、実施例1において酸化テルビウムと酸化ルテチウム(Lu2O3)の組み合わせとしてそのモル比を80:20とし、更に酸化ジルコニウムの含有量を変更したものである。
実施例9は、実施例1において酸化テルビウムと酸化スカンジウム(Sc2O3)の組み合わせとしてそのモル比を70:30とし、更に焼結助剤を酸化ハフニウム(HfO2)としてその含有量を変更したものである。
実施例10は、実施例1において酸化テルビウム、酸化イットリウム及び酸化ガドリニウム(Gd2O3)の組み合わせとしてそのモル比を60:10:30とし、焼結助剤を酸化チタン(TiO2)としてその含有量を変更したものである。
実施例11は、実施例1において酸化テルビウムと酸化イットリウムのモル比を50:50に変更し、更に焼結助剤を酸化ジルコニウムと酸化チタン(TiO2)の組み合わせとしてその含有量を変更したものである。
以上の結果をすべて表7~表15にまとめて示す。
比較例1A-3(図2(b))では、図中の楕円で囲んだ部分などに見られるようにTbリッチ相である白斑点やZrO2の光学欠陥が観察された。一方、実施例1-3(図2(a))ではこのような異相や欠陥は認められず均一な組織となっていることが分かる。
また、比較例1B-3の研磨面の結晶組織を電子顕微鏡の反射電子像として観察したところ、図2(b)と同様なTbリッチ相である白斑点やZrO2の光学欠陥が観察された。また、異相も観察された。
110 ファラデー回転子
112 光軸
120 偏光子
130 検光子
140 磁石
150 筐体
Claims (13)
- 酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とを主成分とする透明セラミックスの製造方法であって、(a)テルビウムイオン、(b)イットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選ばれる少なくとも1種のその他の希土類イオン、(c)第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオンを含む水溶液において(a)、(b)、(c)成分を共沈させ、その共沈物をろ別、加熱脱水して、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む原料粉末を作製し、この原料粉末を用いて成形体を成形した後、該成形体を焼成し、次いで加圧焼成することを特徴とする透明セラミックスの製造方法。
- 上記原料粉末は、焼結助剤を希土類酸化物100質量部に対して0.5質量部超5質量部以下含むことを特徴とする請求項1記載の透明セラミックスの製造方法。
- 上記(c)成分がチタンイオン、ジルコニウムイオン、ハフニウムイオン、カルシウムイオン及びマグネシウムイオンから選ばれる少なくとも1種のイオンである請求項1又は2記載の透明セラミックスの製造方法。
- 更に、加圧焼成後の成形体を非酸化性雰囲気下で1500~2000℃で熱処理することを特徴とする請求項1~3のいずれか1項記載の透明セラミックスの製造方法。
- 上記焼成前に、成形体を仮焼することを特徴とする請求項1~4のいずれか1項記載の透明セラミックスの製造方法。
- 請求項1~5のいずれか1項記載の透明セラミックスの製造方法で製造される透明セラミックスであって、酸化テルビウム(化学式:Tb2O3)と、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む透明セラミックス。
- 上記焼結助剤の含有量が希土類酸化物100質量部に対して0.5質量部超5質量部以下である請求項6記載の透明セラミックス。
- 上記焼結助剤がチタン、ジルコニウム、ハフニウム、カルシウム及びマグネシウムから選ばれる少なくとも1種の元素の酸化物である請求項6又は7記載の透明セラミックス。
- 厚さ10mmの試料の厚さ方向において測定面の90%以上の内面における端面の反射損失を含む波長1,064nmの挿入損失が0.97dB以下であることを特徴とする請求項6~8のいずれか1項記載の透明セラミックス。
- 請求項6~9のいずれか1項記載の透明セラミックスを用いて構成される磁気光学デバイス。
- 請求項6~9のいずれか1項記載の透明セラミックスをファラデー回転素子として用いる磁気光学デバイス。
- 請求項11記載の磁気光学デバイスにおいて、ファラデー回転素子の前後に偏光材料を備える、1,064±40nmの波長域で使用される光アイソレータ用の磁気光学デバイス。
- (a)テルビウムイオン、(b)イットリウムイオン、スカンジウムイオン及びランタニド希土類イオン(テルビウムイオンを除く)から選ばれる少なくとも1種のその他の希土類イオン、(c)第2族元素及び第4族元素から選ばれる少なくとも1種の元素のイオンを含む水溶液において(a)、(b)、(c)成分を共沈させ、その共沈物をろ別、加熱脱水して得られる、酸化テルビウムと、イットリウム酸化物、スカンジウム酸化物及びランタニド希土類元素(テルビウムを除く)の酸化物から選ばれる少なくとも1種のその他の希土類酸化物とからなり、モル比率として酸化テルビウムが40モル%以上、その他の希土類酸化物が残部である希土類酸化物と、第2族元素及び第4族元素から選ばれる少なくとも1つの元素の酸化物からなる焼結助剤とを含む焼結用希土類酸化物粉末。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016525156A JP6344468B2 (ja) | 2014-06-04 | 2015-06-01 | 透明セラミックスの製造方法、並びに焼結用希土類酸化物粉末 |
US15/313,885 US10642073B2 (en) | 2014-06-04 | 2015-06-01 | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
CA2950904A CA2950904C (en) | 2014-06-04 | 2015-06-01 | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
EP15803825.7A EP3153483A4 (en) | 2014-06-04 | 2015-06-01 | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
US16/299,512 US11067835B2 (en) | 2014-06-04 | 2019-03-12 | Method for producing transparent ceramic,transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014115995 | 2014-06-04 | ||
JP2014-115995 | 2014-06-04 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/313,885 A-371-Of-International US10642073B2 (en) | 2014-06-04 | 2015-06-01 | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
US16/299,512 Division US11067835B2 (en) | 2014-06-04 | 2019-03-12 | Method for producing transparent ceramic,transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015186656A1 true WO2015186656A1 (ja) | 2015-12-10 |
Family
ID=54766727
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/065756 WO2015186656A1 (ja) | 2014-06-04 | 2015-06-01 | 透明セラミックスの製造方法及び透明セラミックス、磁気光学デバイス並びに焼結用希土類酸化物粉末 |
Country Status (6)
Country | Link |
---|---|
US (2) | US10642073B2 (ja) |
EP (1) | EP3153483A4 (ja) |
JP (1) | JP6344468B2 (ja) |
CA (1) | CA2950904C (ja) |
TW (1) | TWI658027B (ja) |
WO (1) | WO2015186656A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018193848A1 (ja) * | 2017-04-17 | 2018-10-25 | 信越化学工業株式会社 | 常磁性ガーネット型透明セラミックス、磁気光学材料及び磁気光学デバイス |
JP2019104674A (ja) * | 2017-12-12 | 2019-06-27 | 信越化学工業株式会社 | 焼結用ガーネット型複合酸化物粉末の製造方法、及び透明セラミックスの製造方法 |
JP2019523961A (ja) * | 2016-05-13 | 2019-08-29 | コーニング インコーポレイテッド | 量子メモリシステム、及びドープ多結晶セラミック光学素子を有する量子中継器システム、並びにこれを製造する方法 |
EP3536676A1 (en) | 2018-03-09 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Transparent ceramics, manufacturing method thereof, and magneto-optical device |
EP3536675A1 (en) | 2018-03-09 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Transparent complex oxide sintered body, manufacturing method thereof, and magneto-optical device |
KR20190115023A (ko) * | 2017-02-03 | 2019-10-10 | 더 사우스 아프리칸 뉴클리어 에너지 코퍼레이션 리미티드 | 희토류 금속 플루오라이드의 제조 방법 |
JP2019202916A (ja) * | 2018-05-24 | 2019-11-28 | 信越化学工業株式会社 | 焼結用複合酸化物粉末の製造方法及び透明セラミックスの製造方法 |
JP2019207340A (ja) * | 2018-05-30 | 2019-12-05 | 信越化学工業株式会社 | ファラデー回転子用透明セラミックスの製造方法 |
WO2022054595A1 (ja) * | 2020-09-09 | 2022-03-17 | 信越化学工業株式会社 | 常磁性ガーネット型透明セラミックス、磁気光学デバイス及び常磁性ガーネット型透明セラミックスの製造方法 |
US11361822B2 (en) | 2017-03-01 | 2022-06-14 | Coming Incorporated | Quantum memory systems and quantum repeater systems comprising doped polycrystalline ceramic optical devices and methods of manufacturing the same |
US11465941B2 (en) | 2018-09-24 | 2022-10-11 | Corning Incorporated | Rare-earth doped metal oxide ceramic waveguide quantum memories and methods of manufacturing the same |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016143859A1 (ja) * | 2015-03-11 | 2016-09-15 | 信越化学工業株式会社 | 磁気光学材料及びその製造方法、並びに磁気光学デバイス |
CN109354497B (zh) * | 2018-12-12 | 2021-06-22 | 中国工程物理研究院化工材料研究所 | Ho掺杂的透明氧化钪陶瓷及其制备方法 |
CN110256074A (zh) * | 2019-07-16 | 2019-09-20 | 上海应用技术大学 | 一种钇稳定氧化铽粉体、磁光透明陶瓷及其制备方法 |
CN111116199A (zh) * | 2020-01-18 | 2020-05-08 | 湖南工学院 | 一种真空无压烧结制备Gd2Zr2O7透明陶瓷的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63307102A (ja) * | 1987-06-05 | 1988-12-14 | Tama Kagaku Kogyo Kk | 共沈によるセラミックス原料の調整法 |
JPH0826834A (ja) * | 1994-07-19 | 1996-01-30 | Murata Mfg Co Ltd | セラミック原料粉体の製造方法 |
JP2001039716A (ja) * | 1999-07-29 | 2001-02-13 | Tosoh Corp | ジルコニア微粉末の製造法 |
JP2005283635A (ja) * | 2004-03-26 | 2005-10-13 | Hamamatsu Photonics Kk | ファラデー旋光子 |
JP2012206935A (ja) * | 2011-03-16 | 2012-10-25 | Shin-Etsu Chemical Co Ltd | 透明セラミックス及びその製造方法並びに磁気光学デバイス |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5013696A (en) | 1989-09-25 | 1991-05-07 | General Electric Company | Preparation of high uniformity polycrystalline ceramics by presintering, hot isostatic pressing and sintering and the resulting ceramic |
JPH05330913A (ja) | 1992-05-29 | 1993-12-14 | Kurosaki Refract Co Ltd | レーザ用多結晶透明y2o3セラミックス |
US6825144B2 (en) | 2001-07-05 | 2004-11-30 | Konoshima Chemical Co., Ltd. | Translucent rare earth oxide sintered article and method for production thereof |
JP4033451B2 (ja) | 2001-07-05 | 2008-01-16 | 神島化学工業株式会社 | 透光性希土類酸化物焼結体及びその製造方法 |
JP5393271B2 (ja) | 2009-06-09 | 2014-01-22 | 信越化学工業株式会社 | 酸化物及び磁気光学デバイス |
JP5695594B2 (ja) * | 2012-03-27 | 2015-04-08 | 信越化学工業株式会社 | 磁気光学素子用焼結体及び磁気光学素子 |
-
2015
- 2015-06-01 WO PCT/JP2015/065756 patent/WO2015186656A1/ja active Application Filing
- 2015-06-01 US US15/313,885 patent/US10642073B2/en active Active
- 2015-06-01 EP EP15803825.7A patent/EP3153483A4/en active Pending
- 2015-06-01 CA CA2950904A patent/CA2950904C/en active Active
- 2015-06-01 JP JP2016525156A patent/JP6344468B2/ja active Active
- 2015-06-03 TW TW104117948A patent/TWI658027B/zh active
-
2019
- 2019-03-12 US US16/299,512 patent/US11067835B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63307102A (ja) * | 1987-06-05 | 1988-12-14 | Tama Kagaku Kogyo Kk | 共沈によるセラミックス原料の調整法 |
JPH0826834A (ja) * | 1994-07-19 | 1996-01-30 | Murata Mfg Co Ltd | セラミック原料粉体の製造方法 |
JP2001039716A (ja) * | 1999-07-29 | 2001-02-13 | Tosoh Corp | ジルコニア微粉末の製造法 |
JP2005283635A (ja) * | 2004-03-26 | 2005-10-13 | Hamamatsu Photonics Kk | ファラデー旋光子 |
JP2012206935A (ja) * | 2011-03-16 | 2012-10-25 | Shin-Etsu Chemical Co Ltd | 透明セラミックス及びその製造方法並びに磁気光学デバイス |
Non-Patent Citations (1)
Title |
---|
See also references of EP3153483A4 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019523961A (ja) * | 2016-05-13 | 2019-08-29 | コーニング インコーポレイテッド | 量子メモリシステム、及びドープ多結晶セラミック光学素子を有する量子中継器システム、並びにこれを製造する方法 |
KR20190115023A (ko) * | 2017-02-03 | 2019-10-10 | 더 사우스 아프리칸 뉴클리어 에너지 코퍼레이션 리미티드 | 희토류 금속 플루오라이드의 제조 방법 |
KR102444925B1 (ko) | 2017-02-03 | 2022-09-19 | 더 사우스 아프리칸 뉴클리어 에너지 코퍼레이션 에스오씨 리미티드 | 희토류 금속 플루오라이드의 제조 방법 |
US11361822B2 (en) | 2017-03-01 | 2022-06-14 | Coming Incorporated | Quantum memory systems and quantum repeater systems comprising doped polycrystalline ceramic optical devices and methods of manufacturing the same |
US11715521B2 (en) | 2017-03-01 | 2023-08-01 | Corning Incorporated | Quantum memory systems and quantum repeater systems comprising doped polycrystalline ceramic optical devices and methods of manufacturing the same |
WO2018193848A1 (ja) * | 2017-04-17 | 2018-10-25 | 信越化学工業株式会社 | 常磁性ガーネット型透明セラミックス、磁気光学材料及び磁気光学デバイス |
US11472745B2 (en) | 2017-04-17 | 2022-10-18 | Shin-Etsu Chemical Co., Ltd. | Paramagnetic garnet-type transparent ceramic, magneto-optical material, and magneto-optical device |
JP2019104674A (ja) * | 2017-12-12 | 2019-06-27 | 信越化学工業株式会社 | 焼結用ガーネット型複合酸化物粉末の製造方法、及び透明セラミックスの製造方法 |
EP3536675A1 (en) | 2018-03-09 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Transparent complex oxide sintered body, manufacturing method thereof, and magneto-optical device |
US10858294B2 (en) | 2018-03-09 | 2020-12-08 | Shin-Etsu Chemical Co., Ltd. | Transparent ceramics, manufacturing method thereof, and magneto-optical device |
US11208733B2 (en) | 2018-03-09 | 2021-12-28 | Shin-Etsu Chemical Co., Ltd. | Transparent complex oxide sintered body, manufacturing method thereof, and magneto-optical device |
EP3536676A1 (en) | 2018-03-09 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Transparent ceramics, manufacturing method thereof, and magneto-optical device |
CN110526704A (zh) * | 2018-05-24 | 2019-12-03 | 信越化学工业株式会社 | 制备可烧结复合氧化物粉末和制造透明陶瓷 |
JP2019202916A (ja) * | 2018-05-24 | 2019-11-28 | 信越化学工業株式会社 | 焼結用複合酸化物粉末の製造方法及び透明セラミックスの製造方法 |
JP2019207340A (ja) * | 2018-05-30 | 2019-12-05 | 信越化学工業株式会社 | ファラデー回転子用透明セラミックスの製造方法 |
US11465941B2 (en) | 2018-09-24 | 2022-10-11 | Corning Incorporated | Rare-earth doped metal oxide ceramic waveguide quantum memories and methods of manufacturing the same |
US11958780B2 (en) | 2018-09-24 | 2024-04-16 | Corning Incorporated | Rare-earth doped metal oxide ceramic waveguide quantum memories and methods of manufacturing the same |
WO2022054595A1 (ja) * | 2020-09-09 | 2022-03-17 | 信越化学工業株式会社 | 常磁性ガーネット型透明セラミックス、磁気光学デバイス及び常磁性ガーネット型透明セラミックスの製造方法 |
JP7472995B2 (ja) | 2020-09-09 | 2024-04-23 | 信越化学工業株式会社 | 常磁性ガーネット型透明セラミックス、磁気光学デバイス及び常磁性ガーネット型透明セラミックスの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3153483A4 (en) | 2018-01-10 |
US11067835B2 (en) | 2021-07-20 |
JP6344468B2 (ja) | 2018-06-20 |
JPWO2015186656A1 (ja) | 2017-04-20 |
US20170205643A1 (en) | 2017-07-20 |
CA2950904A1 (en) | 2015-12-10 |
US20190212585A1 (en) | 2019-07-11 |
US10642073B2 (en) | 2020-05-05 |
EP3153483A1 (en) | 2017-04-12 |
TW201609605A (zh) | 2016-03-16 |
CA2950904C (en) | 2022-10-18 |
TWI658027B (zh) | 2019-05-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6344468B2 (ja) | 透明セラミックスの製造方法、並びに焼結用希土類酸化物粉末 | |
JP5704097B2 (ja) | 透明セラミックス及びその製造方法並びに磁気光学デバイス | |
JP6848904B2 (ja) | 透明セラミックスの製造方法、透明セラミックス並びに磁気光学デバイス | |
TWI634093B (zh) | 磁光材料以及磁光裝置 | |
KR102262771B1 (ko) | 자기 광학 재료 및 그 제조 방법과 자기 광학 디바이스 | |
JP5692127B2 (ja) | セラミックス磁気光学材料の選定方法 | |
JP6341284B2 (ja) | 透明セラミックスの製造方法 | |
JP6137044B2 (ja) | 磁気光学材料及び磁気光学デバイス | |
JP5575719B2 (ja) | 磁気光学素子用焼結体及び磁気光学デバイス | |
JP5695594B2 (ja) | 磁気光学素子用焼結体及び磁気光学素子 | |
JP7135920B2 (ja) | 透明複合酸化物焼結体の製造方法、透明複合酸化物焼結体並びに磁気光学デバイス | |
JP6187379B2 (ja) | 磁気光学材料及び磁気光学デバイス | |
JP2023129992A (ja) | 透明セラミックス及び磁気光学デバイス | |
JP2023064774A (ja) | 常磁性ガーネット型透明セラミックスの製造方法、並びに常磁性ガーネット型透明セラミックス製造用加圧焼結体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15803825 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016525156 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15313885 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2950904 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015803825 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015803825 Country of ref document: EP |