WO2022054595A1 - Céramique transparente de type grenat paramagnétique, dispositif magnéto-optique et procédé de production de céramique transparente de type grenat paramagnétique - Google Patents

Céramique transparente de type grenat paramagnétique, dispositif magnéto-optique et procédé de production de céramique transparente de type grenat paramagnétique Download PDF

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WO2022054595A1
WO2022054595A1 PCT/JP2021/031348 JP2021031348W WO2022054595A1 WO 2022054595 A1 WO2022054595 A1 WO 2022054595A1 JP 2021031348 W JP2021031348 W JP 2021031348W WO 2022054595 A1 WO2022054595 A1 WO 2022054595A1
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type transparent
garnet
less
sintering
sintered body
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PCT/JP2021/031348
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Japanese (ja)
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卓士 松本
真憲 碇
恵多 田中
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信越化学工業株式会社
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    • 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
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • 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
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
    • C01F17/34—Aluminates, e.g. YAlO3 or Y3-xGdxAl5O12
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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

Definitions

  • the present invention relates to a normal magnetic garnet type transparent ceramic having translucency in the visible and / or near infrared region, and more particularly, a normal magnetic garnet containing terbium suitable for forming a magnetic optical device such as an optical isolator.
  • the present invention relates to a type transparent ceramic, a magnetic optical device using the normal magnetic garnet type transparent ceramic, and a method for manufacturing the normal magnetic garnet type transparent ceramic.
  • the industrial laser processing machine is equipped with an optical isolator for the purpose of preventing the backtracking of light such as reflected light, and inside it, terbium-added glass and terbium gallium garnet (TGG) crystals are mounted as Faraday rotators (for example, Japanese Patent Application Laid-Open No. 2011-21352 (Patent Document 1).
  • Patent Document 4 "High Verdet constant of Ti-doped terbium aluminum garnet (TAG) ceramics" (non-patent).
  • Non-Patent Document 2 “Fabrication and properties of (Tb x Y 1-x ) 3 Al 5 O 12 transparent ceramics by hot isostatic pressing” (Non-Patent Document 2), “ Development of optical grade (Tb x Y 1-x ) 3 Al 5 O 12 ceramics as Faraday rotator material ”(Non-Patent Document 3),“ Effect of (Tb + Y) / Al ratio on Microstructure Evolution and Densification Process of (Tb) 0.6 Y 0.4 ) 3 Al 5 O 12 Transparent Ceramics ”(Non-Patent Document 4)). Since the rare earth aluminum garnet containing Tb exhibits a high thermal conductivity as compared with TGG, it is expected to be a Faraday element having a small thermal lens effect.
  • the thermal lens effect is a phenomenon in which the Faraday element absorbs transmitted light and generates heat, resulting in a change in the refractive index, resulting in a lens shape. If the focal position of the laser processing machine moves due to the thermal lens effect, the beam will be defocused at the processing point and the processing accuracy will decrease, which is not preferable.
  • Scattering by bubbles inside ceramics can be better interpreted by Me theory. For example, it is assumed that there is a bubble having a radius r inside the ceramic for a certain wavelength ⁇ . When r ⁇ ⁇ , it behaves as Rayleigh scattering, and its scattering intensity becomes stronger in proportion to ⁇ -4 . When r >> ⁇ , it behaves as Mie scattering, and its scattering intensity is constant with respect to the wavelength.
  • Non-Patent Document 6 is presintered from YAG ceramics at 1,600 ° C for 3 hours under vacuum and 3 at 1,500 to 1,700 ° C. A method of resintering transparent ceramics that have been HIP-treated for 20 hours at 1,750 ° C., which is higher than the HIP-treated temperature, is shown. Further, in Japanese Patent No.
  • Patent Document 5 a raw pressure powder having an appropriate shape and composition is formed, a presintering step is performed in a temperature range of 1,350 to 1,650 ° C., and HIP is performed.
  • a method for producing a ceramic body in which a treatment step is performed at a temperature of 1,350 to 1,700 ° C. and a resintering step is performed at a temperature exceeding 1,650 ° C. is disclosed, whereby a method for removing pores is disclosed. Is disclosed.
  • the M 2 value is an example of an index of laser beam quality.
  • Japanese Unexamined Patent Publication No. 2011-21352 Japanese Unexamined Patent Publication No. 2002-293693 Japanese Patent No. 4107292 International Publication No. 2017/033618 Japanese Patent No. 2638669
  • the present invention has been made in view of the above circumstances, and is a transparent sintered body of a normal magnetic garnet type oxide containing Tb and Al, which is a normal magnetic garnet type that can obtain transmitted light with low scattering and high laser beam quality. It is an object of the present invention to provide a transparent ceramic, a magnetic optical device using the normal magnetic garnet type transparent ceramic, and a method for manufacturing the normal magnetic garnet type transparent ceramic.
  • the present inventors measure the wavelength dependence of the diffusion transmittance of transparent ceramics, analyze it with an original mathematical formula, and obtain transmitted light with high beam quality by setting the scattering intensity to a certain level or less. I found that. In particular, it is effective for beam quality to reduce the component of the wavelength dependence of the diffusion transmittance that is inversely proportional to the square of the wavelength. Based on this finding, the present inventors have made diligent studies and have come up with the present invention.
  • the present invention provides the following paramagnetic garnet type transparent ceramics, a magnetic optical device, and a method for manufacturing the paramagnetic garnet type transparent ceramics.
  • 1. The following formula (1) (Tb 1-xy Y x Sc y ) 3 (Al 1-z Sc z ) 5 O 12 (1) (In the formula, 0 ⁇ x ⁇ 0.45, 0 ⁇ y ⁇ 0.08, 0 ⁇ z ⁇ 0.2, 0.001 ⁇ y + z ⁇ 0.20.)
  • a sintered body of a rare earth aluminum garnet containing Tb represented by the following formula (2), which has a minimum transmittance T d in the wavelength range of 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for a sample having a length of 20 mm.
  • Paramagnetic garnet type transparent ceramics characterized in that the value of the coefficient b obtained by fitting by the multiplication method is 5.0 ⁇ 105 or less.
  • T Fit a ⁇ -4 + b ⁇ -2 + c (2) (In the formula, a, b, and c are real numbers.) 2.
  • the value of the coefficient c obtained by fitting the diffusion transmittance T d in the wavelength range 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for the sample having a length of 20 mm to the above equation (2) by the least squares method is 1.0 or less.
  • the normal magnetic garnet type transparent ceramics according to 1. 3. 3.
  • a laser beam having a laser intensity of 100 W and a beam quality of M (1 ⁇ m ⁇ 1.2 ) and a wavelength of 1,070 nm is incident on the sample, and the beam quality of the transmitted light is M.
  • the paramagnetic garnet type transparent ceramic according to any one of 1 to 4 containing a sintering aid. 6.
  • a magneto-optical device configured by using the paramagnetic garnet type transparent ceramics according to any one of 1 to 5. 7.
  • the above-mentioned normal magnetic garnet type transparent ceramics is provided as a Faraday rotator, and a polarizing material is provided before and after the optical axis of the Faraday rotator.
  • the sintered body of the rare earth aluminum garnet containing Tb represented by is pressure-sintered, and the pressure-sintered body is further heated to a temperature exceeding the pressure-sintered body to be resintered, and further resintered.
  • a method for producing paramagnetic garnet-type transparent ceramics which comprises performing an oxidative annealing treatment in an oxidizing atmosphere of 1,200 ° C. or higher. 9.
  • the present invention it is possible to provide paramagnetic garnet type transparent ceramics having low scattering and maintaining high transmission beam quality, and to provide materials suitable for forming a magneto-optical device such as an optical isolator.
  • the paramagnetic garnet type transparent ceramic according to the present invention has the following formula (1).
  • Tb rare earth aluminum garnet containing Tb represented by the following equation (2)
  • T d the diffusion transmittance T d in the wavelength range 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for a sample having a length of 20 mm is minimized to 2 in the following formula (2).
  • the site mainly occupied by Tb that is, the parenthesis in the first half of the formula (1) is the A site
  • the site mainly occupied by Al that is, the parentheses in the latter half of the formula (1). Is referred to as a B site.
  • terbium (Tb) is an element having the largest Verdet constant among trivalent rare earth ions, and is used in a fiber laser in the 1,070 nm region (wavelength band 0.9 ⁇ m or more 1). It is the most suitable element suitable for use as a material for optical isolators in this wavelength range because it absorbs very little at .1 ⁇ m or less).
  • Tb (III) ions are easily oxidized to generate Tb (IV) ions.
  • Tb (IV) ions When Tb (IV) ions are generated in the metal oxide, they absorb light in a wide range of wavelengths from the ultraviolet to the near infrared region and reduce the transmittance, so it is desirable to eliminate them as much as possible. It is effective to adopt a crystal structure in which Tb (IV) ions are unstable, that is, a garnet structure, as one strategy that does not generate Tb (IV) ions.
  • Yttrium has an ionic radius about 2% smaller than that of terbium, and when it is combined with aluminum to form a composite oxide, it can form a garnet phase more stably than the perovskite phase, and is therefore preferably used in the present invention. It is an element that can be used.
  • aluminum (Al) is a material having the smallest ionic radius among trivalent ions that can stably exist in an oxide having a garnet structure, and is a Tb-containing paramagnetic garnet type. It is an element that can minimize the lattice constant of an oxide. It is preferable that the lattice constant of the garnet structure can be reduced without changing the Tb content, because the Verdet constant per unit length can be increased. Furthermore, since aluminum is a light metal, its diamagnetism is weaker than that of gallium, and it is expected to have the effect of relatively increasing the magnetic flux density generated inside the Faraday rotator, which also can increase the Verdet constant per unit length. preferable.
  • the Verdet constant of TAG ceramics is improved to 1.25 to 1.5 times that of TGG. Therefore, even if the relative concentration of terbium is reduced by substituting a part of terbium ions with yttrium ions, the Verdet constant per unit length can be kept at the same level as or slightly lower than TGG. It is a suitable constituent element in the invention.
  • a composite oxide containing only Tb, Y, and Al as constituent elements may not have a garnet structure due to a delicate weighing error, and it is difficult to stably produce transparent ceramics that can be used for optical applications. Therefore, in the present invention, scandium (Sc) is added as a constituent element to eliminate the composition deviation due to a delicate weighing error.
  • Sc is a material having an intermediate ionic radius that can be solidly dissolved in both A sites and B sites in an oxide having a garnet structure, and is a compounding ratio of a rare earth element composed of Tb and Y and Al.
  • It is a buffer material that can be solid-dissolved by adjusting the distribution ratio to rare earth sites) and B sites (aluminum sites).
  • B sites aluminum sites.
  • it is an element capable of limiting the abundance ratio of the alumina heterogeneous phase to the garnet matrix to 1 ppm or less and limiting the abundance ratio of the perovskite type heterogeneous phase to the garnet matrix to 1 ppm or less, in order to improve the yield of the product. It is an element that can be added to.
  • the range of x is 0 ⁇ x ⁇ 0.45, preferably 0.05 ⁇ x ⁇ 0.45, more preferably 0.10 ⁇ x ⁇ 0.40, and 0.20 ⁇ x. ⁇ 0.40 is more preferable.
  • the Verdet constant at room temperature (23 ⁇ 15 ° C.) and a wavelength of 1,064 nm is 30 rad / (Tm) or more, and it can be used as a Faraday rotator.
  • the larger x is, the smaller the thermal lens effect tends to be, which is preferable.
  • the larger x is, the smaller the diffusion transmittance tends to be, which is preferable.
  • the Verdet constant at a wavelength of 1,064 nm is less than 30 rad / (Tm), which is not preferable. That is, when the relative concentration of Tb is excessively diluted, the total length of the Faraday rotator required to rotate the laser beam with a wavelength of 1,064 nm (or a wavelength of 1,070 nm) by 45 degrees when a general magnet is used is 30 mm. It is not preferable because it becomes longer than the above and it becomes difficult to manufacture.
  • the range of y is 0 ⁇ y ⁇ 0.08, preferably 0 ⁇ y ⁇ 0.08, more preferably 0.002 ⁇ y ⁇ 0.07, and 0.003 ⁇ y ⁇ 0. .06 is even more preferred.
  • perovskite-type heterogeneous phases can be reduced to levels not detected by X-ray diffraction (XRD) analysis.
  • the abundance of perovskite-type heterogeneous phases typically 1 to 1.5 ⁇ m in diameter and granules that appear to be colored light brown
  • the abundance ratio of the perovskite-type heterogeneous phase to the garnet matrix is 1 ppm or less.
  • the range of z is 0 ⁇ z ⁇ 0.2, preferably 0 ⁇ z ⁇ 0.16, more preferably 0.01 ⁇ z ⁇ 0.15, and 0.03 ⁇ z ⁇ 0. .15 is more preferred.
  • perovskite-type heterogeneous phases are not detected by XRD analysis.
  • the abundance of perovskite-type heterogeneous phases typically 1 to 1.5 ⁇ m in diameter and granules that appear to be colored light brown
  • the abundance ratio of the perovskite-type heterogeneous phase to the garnet matrix is 1 ppm or less.
  • the range of y + z is 0.001 ⁇ y + z ⁇ 0.20. If y + z is in this range, no perovskite-type heterogeneous phase is detected by XRD analysis. Furthermore, the abundance of perovskite-type heterogeneous phases (typically 1 to 1.5 ⁇ m in diameter and granules that appear to be colored light brown) in a field of view of 150 ⁇ m ⁇ 150 ⁇ m is reduced to 1 or less when observed with an optical microscope. preferable. At this time, the abundance ratio of the perovskite-type heterogeneous phase to the garnet matrix is 1 ppm or less.
  • the effect of the present invention can be obtained even if the range of y + z is in the range of 0 ⁇ y + z ⁇ 0.001, it is not preferable because a different phase is likely to occur due to a weighing error of the raw material, and as a result, the yield is lowered.
  • the sintered body further contains a sintering aid.
  • a sintering aid it is preferable to contain SiO 2 as a sintering aid in an amount of more than 0% by mass and 0.1% by mass or less (more than 0 ppm and 1,000 ppm or less). If the content exceeds 0.1% by mass (1,000 ppm), a small amount of light absorption may occur due to crystal defects due to excessive Si, and the manufactured normal magnetic garnet type transparent with a length (optical path length) of 20 mm.
  • the thermal lens effect is generated, so that the value of the beam quality M 2 of the incident light is m, and the beam quality M 2 of the laser light transmitted through the transparent ceramics is M 2.
  • the value is n, n / m is larger than 1.05, which is not preferable.
  • an oxide of magnesium (Mg) or calcium (Ca) can be further added as a sintering aid. Since both Mg and Ca are divalent ions and are elements that can compensate for the deviation of the charge balance inside the garnet structure due to the addition of the tetravalent SiO 2 , they can be suitably added. It is preferable to adjust the addition amount so as to match the SiO 2 addition amount.
  • the normal magnetic garnet type transparent ceramics of the present invention have less light scattering of transmitted light, and are based on the diffusion transmittance Td in the wavelength range of 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for a sample having a length of 20 mm. It is stipulated as follows. That is, the diffusion transmittance T d in the wavelength range of 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for a sample having a length of 20 mm is calculated by the following equation (2).
  • T Fit a ⁇ -4 + b ⁇ -2 + c (2) (In the formula, a, b, and c are real numbers.)
  • the value of the coefficient b (% ⁇ nm 2 ) obtained by fitting to the least squares method is 5.0 ⁇ 105 or less, preferably 3.0 ⁇ 105 or less, and more preferably 1.0 ⁇ . It is 105 or less.
  • the coefficient b is larger than 5.0 ⁇ 105, the Rayleigh Guns Devi scattering loss component of ceramics at a wavelength of 1,064 nm becomes larger than 0.02 dB, and when mounted on a laser machine as a Faraday rotator, the focus is on. It is not suitable because the beam cannot be narrowed down.
  • the value of the coefficient c (%) obtained by fitting the diffusion transmittance Td in the wavelength range 550 nm ⁇ ⁇ ⁇ 1,350 nm measured for the sample having a length of 20 mm to the above formula (2) by the least squares method. Is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less.
  • the coefficient c is larger than 1.0, the Mie scattering loss component of ceramics at a wavelength of 1,064 nm becomes larger than 0.04 dB, and when mounted on a laser processing machine as a Faraday rotator, the beam may not be focused at the focal point. ..
  • the coefficient a is not limited in the present invention because it is a ⁇ -4 ⁇ b ⁇ ⁇ 2 + c. Since the coefficients a, b, and c are numerical values determined by calculation, they may be negative values.
  • the diffused transmittance T d is the transmittance of the diffused light excluding the parallel component among the light rays (all rays) transmitted by shining light on the test piece, and is JIS K7136 (ISO 14782: 1999). It is measured with reference to. Further, in the above equation (2), regarding the diffusion transmittance, Rayleigh scattering (scattering intensity depends on ⁇ -4 ), Rayleigh Guns deby scattering (scattering intensity depends on ⁇ -2 ), and me scattering (scattering intensity depends on wavelength). It is a scattering model in which (depending on) is linearly connected.
  • the average sintered particle size D is preferably 7 ⁇ m or more and 50 ⁇ m or less, more preferably 10 ⁇ m or more and 40 ⁇ m or less, and further preferably 20 ⁇ m or more and 40 ⁇ m or less. If the average sintered particle size is less than 7 ⁇ m, the amount of scattering inside the ceramics will increase, and as a result, when used as a Faraday rotator mounted inside a laser processing machine as a cylindrical shape with a length of 20 mm, this will be used.
  • the average particle size (average sintered particle size) of the sintered particles in the normal magnetic garnet type transparent ceramics (resintered body) is obtained by measuring the particle size of the sintered particles of the target sintered body with a metal microscope.
  • the details are calculated as follows. That is, the transmission mode of the metallurgical microscope is used for the resintered body, and a transmission open Nicol image of the sintered body sample whose both end faces are polished is taken using a 50x objective lens. Specifically, the optically effective region at a predetermined depth of the target sintered body was photographed, a diagonal line was drawn on the photographed image, the total number of sintered particles crossed by the diagonal line was counted, and then the diagonal length was divided by the total number of counts.
  • the value is defined as the average sintered particle size of the sintered particles in the image. Further, after adding up the average particle sizes of each photographed image read by the analysis process, the value divided by the number of photographs is taken as the average sintered particle size of the target sintered body (hereinafter, a method for manufacturing paramagnetic garnet type transparent ceramics). And the same in the examples).
  • the normal magnetic garnet type transparent ceramics of the present invention has a laser intensity of 100 W and a beam quality of M 2 value m (1 ⁇ m ⁇ 1.2) and a wavelength of 1,070 nm when a sample having a length of 20 mm is used.
  • n n
  • n / m is preferably 1.05 or less, more preferably 1.04 or less, still more preferably 1.03.
  • high beam quality M 2 can be obtained when the laser beam is transmitted.
  • the method for producing a paramagnetic garnet-type transparent ceramic according to the present invention is the above-mentioned method for producing the paramagnetic garnet-type transparent ceramic of the present invention, and has the following formula (1).
  • Tb 1-xy Y x Sc y 3 (Al 1-z Sc z ) 5 O 12 (1)
  • the sintered body of the rare earth aluminum garnet represented by Tb is pressure-sintered, and the pressure-sintered body is further heated to a temperature exceeding the pressure-sintered body to be resintered, and further resintered. It is characterized in that the oxidative annealing treatment is performed in an oxidizing atmosphere of 1,200 ° C. or higher.
  • the paramagnetic garnet type transparent ceramics are manufactured by the following procedure.
  • (Sintering raw material powder) First, a raw material powder for sintering corresponding to the above-mentioned garnet-type composite oxide composition of the formula (1) is produced.
  • the method for producing the raw material powder for sintering of the garnet-type composite oxide used in the present invention is not particularly limited, but the metal oxide powder for each component element corresponding to the garnet-type composite oxide is used as a starting material. Each of them may be weighed in a predetermined amount so as to have a composition corresponding to the formula (1) and mixed to obtain a raw material powder for sintering.
  • the starting material at this time is not particularly limited as long as it can be made transparent, but from the viewpoint of suppressing absorption derived from impurities, the purity is preferably 99.9% by mass or more, more preferably 99.99% by mass or more, and 99.99% by mass. % Or more is most preferable.
  • the particle size of the primary particles of the raw material powder is not particularly limited as long as it can be made transparent, but is preferably 50 nm or more and 1,000 nm or less from the viewpoint of easy sintering.
  • the shape of the primary particles is selected from a card house shape, a spherical shape, and a rod shape, and is not particularly limited as long as it can be made transparent.
  • the method for producing the raw material powder for sintering of the garnet-type composite oxide used in the present invention is a coprecipitation method, a pulverization method, a spray pyrolysis method, a sol-gel method, an alkoxide hydrolysis method, a complex polymerization method, or a uniform precipitation method.
  • any other synthetic method may be used.
  • the ceramic raw material of the obtained rare earth composite oxide may be appropriately treated with a wet ball mill, a bead mill, a jet mill, a dry jet mill, a hammer mill or the like in order to obtain a desired particle size.
  • a solid-phase reaction method in which multiple types of oxide particles are mixed and fired to produce uniformity by thermal diffusion of ions, or hydroxides, carbonates, etc. are precipitated from an ion-containing solution in which the oxide particles are dissolved. It is advisable to use a co-precipitation method that produces uniformity by converting it into an oxide by firing to obtain a raw material powder for sintering.
  • the starting material is a metal powder composed of terbium, yttrium, scandium, and aluminum, or the metal powder. Is dissolved in an aqueous solution of nitric acid, sulfuric acid, uric acid or the like, or an oxide powder of the above element can be preferably used.
  • the purity of the raw material is preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more.
  • the starting materials are weighed in a predetermined amount so as to have a composition corresponding to the formula (1), mixed and then calcined to obtain a calcined raw material of a desired metal oxide, which is pulverized to obtain a raw material powder for sintering. May be.
  • the firing temperature at this time is preferably 1,100 ° C. or lower, more preferably 1,050 ° C. or lower, and even more preferably 1,000 ° C. or lower. If the temperature exceeds 1,100 ° C., the raw material powder may be burnt down and may not be sufficiently crushed in the subsequent crushing step.
  • the firing time may be 1 hour or more, and the temperature rising rate at that time is preferably 100 ° C./h or more and 500 ° C./h or less.
  • the atmosphere of firing is preferably an atmosphere or an atmosphere containing oxygen, and a nitrogen atmosphere, an argon atmosphere, a hydrogen atmosphere, or the like is unsuitable.
  • the firing apparatus is exemplified by a vertical muffle furnace, a horizontal tubular furnace, a rotary kiln, etc., and is not particularly limited as long as the target temperature can be reached and oxygen flow can be achieved.
  • the raw material powder for sintering contains a sintering aid.
  • a sintering aid for example, tetraethoxysilane (TEOS) as a sintering aid together with the above starting material is added to the entire raw material powder (garnet-type composite oxide powder ten sintering aid) in terms of SiO 2 in an amount of more than 0 ppm and 1,000 ppm or less (more than 0% by mass). Add 0.1% by mass or less) or add SiO 2 powder to the whole raw material powder (garnet type composite oxide powder 10 sintering aids) more than 0 ppm and 1,000 ppm or less (more than 0% by mass and 0.1% by mass or less).
  • TEOS tetraethoxysilane
  • the sintering aid may be added during the preparation of the raw material powder slurry.
  • Si element may be mixed from the environment such as glassware used in the manufacturing process, and some Si element may volatilize when sintering is performed under reduced pressure, so it is in the final ceramics. It should be noted that when the content of Si contained in the glass is analyzed, it may increase or decrease unintentionally.
  • the grain size of the primary particles of the raw material powder for sintering used (that is, the starting material mixed powder or the composite oxide powder) is nano-sized and the sintering activity is active. It is advisable to select one with an extremely high value. Such choices may be made as appropriate.
  • the crushing method can be selected from either dry or wet, but it is necessary to crush the target ceramic so that it is highly transparent.
  • the firing material is slurried by various pulverization (dispersion) methods such as a ball mill, a bead mill, a homogenizer, a jet mill, and ultrasonic irradiation, and pulverized (dispersed) to primary particles.
  • the dispersion medium of this wet slurry is not particularly limited as long as it is possible to make the finally obtained ceramics highly transparent, and examples thereof include alcohols such as lower alcohols having 1 to 4 carbon atoms and pure water.
  • various organic additives may be added to this wet slurry for the purpose of quality stability and yield improvement in the subsequent ceramics manufacturing process.
  • these are also not particularly limited. That is, various dispersants, binders, lubricants, plasticizers and the like can be suitably used.
  • these organic additives it is preferable to select a high-purity type that does not contain unnecessary metal ions.
  • wet pulverization the dispersion medium of the slurry is finally removed to obtain a raw material powder for sintering.
  • Pre-sintered body a sintered body made of a composite oxide that has been molded into a predetermined shape using the slurry containing the above-mentioned raw material powder for sintering, then degreased, and then pre-sintered to be densified to a relative density of 94% or more.
  • Pre-sintered body Pre-sintered body
  • the sintered body is pressure-sintered, and the pressure-sintered body is heated to a temperature higher than the pressure-sintered body to be resintered. Perform a predetermined oxidative annealing treatment.
  • the slurry as described above is subjected to solid-liquid separation and molded into a predetermined shape.
  • the molding method is roughly classified into dry molding and wet molding, but is not particularly limited as long as a predetermined shape can be stably obtained.
  • dry molding a method of forming granules from a slurry using spray drying, filling the granules in a jig, and then performing press molding is exemplified.
  • the wet molding a casting molding method in which a slurry is poured into a gypsum mold to volatilize a solvent is exemplified.
  • an extrusion molding method, a sheet molding method, a centrifugal casting molding method, and a cold isotropic pressure pressurizing method are exemplified, but all of them are not limited because a predetermined shape can be obtained.
  • Binder may be added to the slurry before molding.
  • the binder can increase the holding power of the molded product and has the effect of making it difficult for cracks and cracks to occur.
  • the type of the binder is not particularly limited, but a binder that is compatible with the solvent and does not leave a residue after heat treatment is preferable, and polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, and polyacrylic acid are exemplified, and two or more of them are exemplified. A polymer obtained by copolymerizing the above may be used.
  • the amount of the binder varies depending on the molding method or the type of the binder, but 0.5% by mass is the minimum required with respect to the raw material powder for sintering, and the upper limit is 8% by mass.
  • the addition of the binder is most preferably during wet pulverization.
  • a normal press molding process can be suitably used. That is, a very general uniaxial pressing process of filling a mold and pressurizing from a certain direction, or cold hydrostatic pressure pressurization (CIP (Cold Isostatic Pressing)) which is hermetically stored in a deformable waterproof container and pressurized with hydrostatic pressure.
  • CIP Cold Isostatic Pressing
  • WIP warm hydrostatic pressure pressurization
  • the applied pressure may be appropriately adjusted while checking the relative density of the obtained molded product, and is not particularly limited. However, for example, if the pressure range is controlled within a pressure range of about 300 MPa or less that can be handled by a commercially available CIP device or WIP device, the manufacturing cost May be suppressed.
  • the molding jig and the molding machine are sufficiently cleaned and dried. It is preferable that the environment in which the molding work is performed is a clean space of class 1000 or less.
  • a normal degreasing step can be preferably used. That is, it is possible to go through a temperature raising and degreasing step using a heating furnace. Further, the type of atmospheric gas at this time is not particularly limited, and air, oxygen, hydrogen and the like can be preferably used.
  • the degreasing temperature is also not particularly limited, but if a raw material mixed with an organic additive is used, it is preferable to raise the temperature to a temperature at which the organic component can be decomposed and eliminated.
  • Pre-sintering As a sintered body before heat sintering, a pre-sintered body preferably densified to a relative density of 94% or more and preferably having an average sintered particle size of 3 ⁇ m or less is produced. At this time, it is necessary to set the conditions of temperature and holding time so that the sintered particle size is within a desired range.
  • a general sintering process can be suitably used. That is, a heating sintering step such as a resistance heating method or an induction heating method can be suitably used.
  • the atmosphere at this time is not particularly limited, and various atmospheres such as air, inert gas, oxygen gas, hydrogen gas, and helium gas can be preferably used, but more preferably sintering under reduced pressure (in vacuum) is used. can.
  • the degree of vacuum of the presintering is preferably less than 1 ⁇ 10 -1 Pa, more preferably less than 1 ⁇ 10 ⁇ 2 Pa, and particularly preferably less than 1 ⁇ 10 -3 Pa.
  • the sintering temperature in the pre-sintering step of the present invention is preferably 1,450 to 1,650 ° C, particularly preferably 1,500 to 1,600 ° C.
  • the sintering temperature is in this range, densification is promoted while suppressing heterophase precipitation and grain growth, which is preferable.
  • the sintering holding time in the pre-sintering step of the present invention is sufficient to be about several hours, it is preferable that the relative density of the pre-sintered body is densified to 94% or more.
  • the relative density of the pre-sintered body becomes higher than 99%, the particle plastic deformation inside the sintered body is less likely to occur in the subsequent pressure sintering (HIP), and the bubbles remaining in the sintered body can be removed. It will be difficult. Therefore, the relative density of the pre-sintered body is preferably 99% or less at the maximum, and more preferably 98% or less.
  • the average sintered grain size of the crystal grains of the pre-sintered product of the present invention is preferably 3 ⁇ m or less, more preferably 2.5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the average sintered particle size of the sintered grains can be adjusted in consideration of the raw material type, atmosphere, sintering temperature, and holding time. If the sintered particle size is larger than 3 ⁇ m, plastic deformation is less likely to occur in the subsequent pressure sintering (HIP), and it may be difficult to remove air bubbles remaining in the presintered body.
  • the average sintered grain size of the crystal grains of the pre-sintered body is determined by observing the sintered grain size of the crystal grains on the surface of the transparent pressure sintered (HIP) body obtained in the next step with an optical microscope. It is possible.
  • the pre-sintered body is preferably pressure-sintered at a pressure of 50 MPa or more and 300 MPa or less and a temperature of 1,000 ° C. or more and 1,780 ° C. or less (HIP treatment is performed).
  • an inert gas such as argon or nitrogen, or Ar—O 2 can be preferably used.
  • the pressure to be pressurized by the pressurized gas medium is preferably 50 to 300 MPa, more preferably 100 to 300 MPa.
  • the applied pressure is 196 MPa or less that can be processed by a commercially available HIP device.
  • the processing temperature (predetermined holding temperature) at that time is preferably set in the range of 1,000 to 1,780 ° C, more preferably 1,100 to 1,700 ° C. If the heat treatment temperature is higher than 1,780 ° C., grain growth occurs during the HIP treatment and it becomes difficult to remove bubbles, which is not preferable.
  • the heat treatment temperature is less than 1,000 ° C., the effect of improving the transparency of the sintered body may be hardly obtained.
  • the holding time of the heat treatment temperature is not particularly limited, but holding it for too long is not preferable because the risk of oxygen deficiency increases. Typically, it is preferably set in the range of 1 to 3 hours.
  • the heater material, heat insulating material, and processing container to be HIP-treated are not particularly limited, but graphite, molybdenum, tungsten, and platinum (Pt) can be preferably used, and yttrium oxide and gadolinium oxide can also be preferably used as the processing container. ..
  • the treatment temperature is 1,500 ° C or higher
  • graphite is preferable as the heater material and heat insulating material.
  • graphite, molybdenum, or tungsten is selected as the treatment container, and a double container is used inside the heat insulating material. It is preferable to select either yttrium oxide or gadrinium oxide and then fill the container with an oxygen-releasing material because the amount of oxygen deficiency generated during the HIP treatment can be suppressed as much as possible.
  • the type of atmospheric gas at this time is not particularly limited, and air, oxygen, hydrogen, etc. can be preferably used, but it is more preferable to treat under reduced pressure (under vacuum of less than 1 ⁇ 10 ⁇ 2 Pa).
  • the resintering temperature is preferably 1,650 ° C. or higher and 1,800 ° C. or lower, and more preferably 1,700 ° C. or higher and 1,800 ° C. or lower. If the temperature is lower than 1,650 ° C., grain growth does not occur, which is not preferable.
  • the average sintered grain size of the resintered crystal grains is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
  • the holding time in the resintering step is not particularly limited, but is preferably 5 hours or more, more preferably 10 hours or more, and particularly preferably 20 hours or more. Generally, the longer the holding time, the more the grain growth of the sintered body progresses.
  • the temperature and holding time of the resintering step may be appropriately adjusted after confirming the average sintered particle size. However, in general, if the sintering temperature is raised too high, unexpected abnormal grain growth will occur, making it difficult to obtain a homogeneous sintered body. Therefore, it is preferable to allow a certain margin for the resintering temperature and adjust the size of the average sintered particle size of the resintered body by extending the holding time.
  • the oxidation annealing treatment (oxygen deficiency recovery treatment) is performed in an oxidizing atmosphere (oxygen-containing atmosphere) such as in the atmosphere.
  • the annealing treatment temperature is 1,200 ° C. or higher, preferably 1,300 ° C. or higher. Further, it is preferably 1,500 ° C. or lower.
  • the holding time in this case is not particularly limited, but it is preferably selected within a time sufficient for recovering the oxygen deficiency and within a time during which the treatment is wastefully performed for a long time and the electricity cost is not consumed. Moreover, you may perform a slight oxidation HIP treatment. By these treatments, even if the resintered body is colored, oxygen deficiency can be recovered, so that the size and quantity of the scattering source (scattering contrast source) can be controlled within the specified range.
  • Paramagnetic garnet-type transparent ceramics with low absorption due to oxygen defects can be used. Of course, the essential coloring (absorption) of the material due to the addition of colored elements such as dopants and impurities for imparting functions cannot be removed.
  • the size and amount of residual bubbles inside the sintered body may increase. Then, the size and amount of air bubbles and microcracks remaining inside the final sintered body cannot be controlled within the specified range, which is not preferable. In this case, if the sintered body is subjected to HIP treatment again and then oxygen atmosphere annealing treatment is performed again, the size and amount of air bubbles and microcracks remaining inside the sintered body are controlled within the specified range. It is preferable because it can be used.
  • both end faces thereof are optically mirror-finished, and then antireflection films are formed on both end faces.
  • the shape of the normal magnetic garnet type transparent ceramics that has undergone the above series of manufacturing steps is cylindrical or prismatic, and both end faces on the axis that are optically used ( It is preferable to finish the optical end face by optical polishing (optical mirror finish).
  • the optical surface accuracy at this time is preferably ⁇ / 2 or less, and particularly preferably ⁇ / 8 or less.
  • an antireflection film AR coat
  • the value of the coefficient b obtained is 5.0 ⁇ 105 or less.
  • a sample having a coefficient c of 1.0 or less is obtained, and a sample having an average sintered particle size D of 7 ⁇ m or more and 50 ⁇ m or less is obtained, and when a sample having a length of 20 mm is used, a laser is used.
  • n When a laser beam having a wavelength of 1,070 nm having an intensity of 100 W and a beam quality M 2 value m (1 ⁇ m ⁇ 1.2) is incident and the beam quality M 2 value of the transmitted light is n, n / m is Those of 1.05 or less can be provided.
  • the paramagnetic garnet type transparent ceramics of the present invention are suitable for use in magneto-optical devices, and are particularly preferably used as Faraday rotators for optical isolators having a wavelength of 0.9 to 1.1 ⁇ m.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical isolator which is an optical device having a Faraday rotator made of the magneto-optical material of the present invention as an optical element.
  • the optical isolator 100 includes a Faraday rotator 110 made of the paramagnetic garnet-type transparent ceramics of the present invention, and before and after the Faraday rotator 110, a polarizing element 120 and an analyzer 130, which are polarizing materials, are provided. Is provided. Further, it is preferable that the optical isolator 100 is arranged in the order of the polarizing element 120, the Faraday rotator 110, and the analyzer 130, and the magnet 140 is placed on at least one of the side surfaces thereof.
  • the optical isolator 100 can be suitably used for an industrial fiber laser apparatus. That is, it is suitable for preventing the reflected light of the laser light emitted from the laser light source from returning to the light source and making the oscillation unstable.
  • Terbium oxide powder, yttrium oxide powder, scandium oxide powder manufactured by Shin-Etsu Chemical Co., Ltd., and aluminum oxide powder manufactured by Daimei Chemical Co., Ltd. were obtained. Further, liquids of tetraethyl orthosilicate (TEOS) manufactured by Kishida Chemical Co., Ltd. and polyethylene glycol 200 manufactured by Kanto Chemical Co., Inc. were obtained.
  • TEOS tetraethyl orthosilicate
  • the purity of the powder raw material was 99.9% by mass or more, and that of the liquid raw material was 99.99% by mass or more.
  • the mixing ratio was adjusted to prepare the following oxide raw materials having a total of four types of crystal structures having the final composition shown in Table 1.
  • each of the obtained four types of powder raw materials was subjected to uniaxial press molding and hydrostatic pressure pressing at a pressure of 198 MPa to obtain a CIP molded product.
  • the obtained molded product was degreased in a muffle furnace at 1,000 ° C. for 2 hours.
  • the degreased molded product was placed in a vacuum furnace and pre-sintered at 1,600 ° C. for 2 hours under a reduced pressure of less than 1.0 ⁇ 10 -3 Pa to obtain a total of 4 types of pre-sintered product.
  • the relative sintering densities of the samples were 94% or more and 99% or less.
  • Each of the obtained presinters was charged into a carbon heater HIP furnace and subjected to pressure sintering (HIP) treatment in Ar at 196 MPa, 1,600 ° C. for 3 hours to obtain a pressure sintered body. ..
  • the appearance of the pressure sintered body was all transparent.
  • some of the four types of pressure sintered bodies were stored without being put into the subsequent resintering step.
  • the remaining four types of pressure sintered bodies were recharged in a vacuum furnace and resintered at 1,700 ° C. for 20 hours under a reduced pressure of less than 1.0 ⁇ 10 -3 Pa.
  • Four kinds of resintered bodies were obtained.
  • the appearance of the resintered body was all transparent.
  • the pressure sintered body (for comparative example) and the resintered body (for example) thus obtained were ground into columns having a diameter of 5 mm, respectively, and subjected to oxidative annealing treatment at 1,300 ° C. in the atmosphere for 24 hours. .. After that, they were polished so that the length was 20 mm and both end faces were mirror surfaces. The following measurements were performed on the samples obtained as described above.
  • the diffusion transmittance Td at a length (optical path length) of 20 mm of each sample was measured with reference to JIS K7136 (ISO 14782: 1999).
  • a spectrophotometer manufactured by JASCO Corporation, V-670 was used for the measurement.
  • the measurement was performed by a double beam method using a halogen lamp as a light source, a photomultiplier tube (wavelength less than 750 nm) and a PdS photoelectric cell (wavelength 750 nm or more) as a detector.
  • the measurement range was from 550 nm to 1,350 nm in 1 nm increments, and the measured values were expressed as percentages.
  • antireflection films designed to have a center wavelength of 1,070 nm were applied to both end faces of the optically polished sample.
  • Beam quality (M 2 ) change amount (n / m) evaluation The beam quality was measured using a collimated CW laser beam having a wavelength of 1,070 nm, an emission power of 100 W, and a diameter of 1.6 mm.
  • the beam quality M 2 value of this laser beam was measured using a Coherent ModeMaster PC M 2 beam propagation analyzer. First, the M 2 value of the original beam (incident light) was measured, and the value at this time was defined as m. Next, each sample having a length of 20 mm was placed in the optical path, and the M 2 value of each transmitted light was measured and set to n.
  • N / m was calculated as the amount of change in beam quality in the present invention, and if it was 1.05 or less, it passed, and if it exceeded 1.05, it was rejected.
  • the incident light and the transmitted light intensity of the sample were attenuated to about 1/1000 using a beam splitter before being introduced into the analyzer.
  • m 1.12.
  • the amount of change in beam quality (n / m) of the paramagnetic garnet type transparent ceramic samples (Examples 1-1 to 1-4) having a coefficient b of 0.6 ⁇ 10 5 to 1.7 ⁇ 105 . ) was 1.05 or less.
  • the beam quality changes (n / m) of the samples (Comparative Examples 1-1 to 1-4) having a coefficient b of 5.8 ⁇ 10 5 to 7.1 ⁇ 105 were all larger than 1.05. rice field. That is, it was confirmed that when the coefficient b is 3.5 ⁇ 105 or less, paramagnetic garnet-type transparent ceramics having high beam quality can be obtained.
  • TEOS tetraethyl orthosilicate
  • polyethylene glycol 200 manufactured by Kanto Chemical Co., Inc.
  • the purity of the powder raw material was 99.9% by mass or more, and that of the liquid raw material was 99.99% by mass or more.
  • the mixing ratio was adjusted to prepare the following oxide raw materials having a total of four types of crystal structures having the final composition shown in Table 2.
  • each of the obtained four types of powder raw materials was subjected to uniaxial press molding and hydrostatic pressure pressing at a pressure of 198 MPa to obtain a CIP molded product.
  • the obtained molded product was degreased in a muffle furnace at 1,000 ° C. for 2 hours.
  • the degreased molded product was placed in a vacuum furnace and pre-sintered at 1,600 ° C. for 2 hours under a reduced pressure of less than 1.0 ⁇ 10 -3 Pa to obtain a total of 4 types of pre-sintered products.
  • the relative sintering densities of the samples were 94% or more.
  • Each of the obtained presinters was charged into a carbon heater HIP furnace and subjected to pressure sintering (HIP) treatment in Ar under the conditions of 196 MPa, 1,600 ° C. and 3 hours.
  • the pressurized sintered body was put into a vacuum furnace again and resintered at 1,700 ° C. for 20 hours under a reduced pressure of less than 1.0 ⁇ 10 -3 Pa to obtain a resintered body.
  • the resintered body thus obtained was ground into a columnar shape having a diameter of 5 mm, and polished so that both end faces became mirror surfaces. Then, the oxidation annealing treatment was performed at 1,300 ° C. in the atmosphere for 24 hours.
  • the average sintered particle size D, the coefficient b by the diffusion transmittance fitting, the coefficient c, and the amount of change in beam quality were measured and determined in the same manner as in Example 1. The above results are summarized in Table 2.
  • the coefficients b of the samples of Examples 2-1 to 2-3 were 0.6 ⁇ 105 or less, and the beam quality change amount (n / m) was 1.05 or less. That is, it was confirmed that the paramagnetic garnet type transparent ceramics having a coefficient b of 5.0 ⁇ 105 or less and high beam quality can be obtained within the range of the composition of the present invention.
  • Example 3 In Example 2-2, the resintering time was set to 2 hours (Comparative Example 3-1), 6 hours (Example 3-1), and 40 hours (Example 3-2), and the other times were set to Example 2
  • a sample of paramagnetic garnet type transparent ceramics was prepared under the same conditions as in -2.
  • the average sintered particle size D, the coefficient b by the diffusion transmittance fitting, the coefficient c, and the amount of change in beam quality were measured and determined in the same manner as in Example 1. The evaluation results are shown in Table 3.
  • the average sintered particle size of the samples of Examples 3-1 and 3-2 is 13 to 38 ⁇ m
  • the coefficient b is 0.6 ⁇ 10 5 to 4.2 ⁇ 105
  • the beam quality is The amount of change (n / m) was all 1.05 or less.
  • the average sintered particle size of the sample of Comparative Example 3-1 was 6.1 ⁇ m
  • the coefficient b was 18 ⁇ 105
  • the beam quality change amount (n / m) was 1.15. ..
  • the coefficient b is 4.2 ⁇ 105 or less
  • the beam quality change amount (n / m) is 1.05 or less, which is a paramagnetic garnet type with high beam quality. It was confirmed that transparent ceramics could be obtained.

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Abstract

La présente invention concerne une céramique transparente de type grenat paramagnétique qui présente une faible diffusion et produit une lumière transmise qui présente une qualité de faisceau laser élevée, ladite céramique étant un corps fritté d'un grenat d'aluminium de terres rares contenant du Tb représenté par la formule (1) : (Tb1-x-yYxScy)3A1-zScz)5O12 (Dans la formule, 0 ≤ x < 0,45, 0 ≤ y< 0,08, 0 ≤ z < 0,2 et 0,001 < y + z < 0,20), et étant caractérisé en ce que la valeur du coefficient b obtenu par ajustement du facteur de transmission diffusé Td dans la plage de longueurs d'onde de 550 nm ≤ λ ≤ 1 350 nm, telle que mesurée à l'aide d'un échantillon présentant une longueur de 20 mm à la formule (2) au moyen d'un procédé des moindres carrés, est inférieure ou égale à 5,0 × 105.　Formule (2) : TFit=aλ-4+bλ-2+c (dans la formule, a, b et c sont des nombres réels.)
PCT/JP2021/031348 2020-09-09 2021-08-26 Céramique transparente de type grenat paramagnétique, dispositif magnéto-optique et procédé de production de céramique transparente de type grenat paramagnétique WO2022054595A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015008553A1 (fr) * 2013-07-19 2015-01-22 信越化学工業株式会社 Matériau magnéto-optique, son procédé de production et dispositif magnéto-optique
WO2015186656A1 (fr) * 2014-06-04 2015-12-10 信越化学工業株式会社 Procédé de production de céramique transparente, céramique transparente, dispositif magnéto-optique et poudre d'oxyde de terres rares pour frittage
JP2019156666A (ja) * 2018-03-09 2019-09-19 信越化学工業株式会社 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
JP2019199387A (ja) * 2018-05-18 2019-11-21 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015008553A1 (fr) * 2013-07-19 2015-01-22 信越化学工業株式会社 Matériau magnéto-optique, son procédé de production et dispositif magnéto-optique
WO2015186656A1 (fr) * 2014-06-04 2015-12-10 信越化学工業株式会社 Procédé de production de céramique transparente, céramique transparente, dispositif magnéto-optique et poudre d'oxyde de terres rares pour frittage
JP2019156666A (ja) * 2018-03-09 2019-09-19 信越化学工業株式会社 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
JP2019199387A (ja) * 2018-05-18 2019-11-21 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

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