WO2016121655A1 - Matériau verre et procédé de fabrication de ce matériau - Google Patents

Matériau verre et procédé de fabrication de ce matériau Download PDF

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Publication number
WO2016121655A1
WO2016121655A1 PCT/JP2016/051902 JP2016051902W WO2016121655A1 WO 2016121655 A1 WO2016121655 A1 WO 2016121655A1 JP 2016051902 W JP2016051902 W JP 2016051902W WO 2016121655 A1 WO2016121655 A1 WO 2016121655A1
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WIPO (PCT)
Prior art keywords
glass
glass material
content
raw material
present
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PCT/JP2016/051902
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English (en)
Japanese (ja)
Inventor
太志 鈴木
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015224404A external-priority patent/JP6694154B2/ja
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to US15/503,012 priority Critical patent/US10227254B2/en
Priority to CN201680007774.4A priority patent/CN107207321A/zh
Publication of WO2016121655A1 publication Critical patent/WO2016121655A1/fr
Priority to US15/704,126 priority patent/US10093574B2/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a glass material suitable for a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, and a magnetic sensor, and a manufacturing method thereof.
  • a glass material containing terbium oxide which is a paramagnetic compound, exhibits a Faraday effect which is one of magneto-optical effects.
  • the Faraday effect is an effect of rotating the polarization plane of linearly polarized light passing through a material placed in a magnetic field. Such effects are used in optical isolators, magnetic field sensors, and the like.
  • the optical rotation (rotation angle of the polarization plane) ⁇ due to the Faraday effect is expressed by the following equation, where H is the strength of the magnetic field and L is the length of the substance through which the polarized light passes.
  • V is a constant depending on the type of substance, and is called Verde's constant.
  • the Verde constant is a positive value for a diamagnetic material and a negative value for a paramagnetic material. The greater the absolute value of the Verde constant, the greater the absolute value of the optical rotation, resulting in a large Faraday effect.
  • an object of the present invention is to provide a glass material that exhibits a Faraday effect greater than that of the conventional art.
  • the glass material of the present invention is characterized by containing 48% or more (but not including 48%) of Tb 2 O 3 in mol%.
  • the glass material of the present invention has a large Verde constant due to containing a large amount of Tb 2 O 3 as described above. As a result, the Faraday effect which is larger than the conventional one is shown.
  • glass materials containing a large amount of Tb 2 O 3 are generally difficult to crow.
  • the content of Tb 2 O 3 is preferably 80% or less in terms of mol%. If the content of Tb 2 O 3 is in the above range, vitrification can be performed relatively easily.
  • the glass material of the present invention further contains, in mol%, SiO 2 0-50%, B 2 O 3 0-50%, Al 2 O 3 0-50%, P 2 O 5 0-50%. Is preferred. Since SiO 2 , B 2 O 3 , Al 2 O 3 , and P 2 O 5 are components constituting a glass skeleton, vitrification can be performed relatively easily by containing these components.
  • the glass material of the present invention can be used as a magneto-optical element.
  • the glass material of the present invention can be used as a Faraday rotation element which is a kind of magneto-optical element. By using it for the above application, the effects of the present invention can be enjoyed.
  • the method for producing a glass material according to the present invention is a method for producing the above glass material, and after the glass material lump is suspended and held, the glass material lump is heated and melted to obtain a molten glass. And a step of cooling the molten glass.
  • a glass material is produced by melting a raw material in a melting container such as a crucible and cooling (melting method).
  • a melting container such as a crucible and cooling (melting method).
  • the glass material of the present invention has a composition containing a large amount of Tb 2 O 3 that does not basically constitute a glass skeleton as described above, and is a material that is difficult to vitrify. There is a problem that crystallization proceeds from the contact interface with the substrate.
  • composition Even if the composition is difficult to vitrify, it can be vitrified by eliminating contact at the interface with the melting vessel.
  • a containerless floating method in which a raw material is melted and cooled in a suspended state is known. When this method is used, since the molten glass hardly comes into contact with the melting vessel, crystallization starting from the interface with the melting vessel can be prevented, and vitrification becomes possible.
  • the glass material of the present invention contains 48% or more (but not 48%) of Tb 2 O 3 in mol%, preferably 49% or more, particularly preferably 50% or more.
  • Tb 2 O 3 is too small, the absolute value of the Verdet constant is reduced, a sufficient Faraday effect is difficult to obtain.
  • the content of Tb 2 O 3 is too large, vitrification tends to be difficult, and therefore it is preferably 80% or less, 75% or less, and particularly preferably 70% or less.
  • the content of trivalent oxide is prescribed
  • the magnetic moment that causes the Verde constant for Tb is greater for Tb 3+ than for Tb 4+ . Therefore, the larger the ratio of Tb 3+ in the glass material, the greater the Faraday effect, which is preferable.
  • the ratio of Tb 3+ in the total Tb is preferably 50% or more, 60% or more, 70% or more, 80% or more, and particularly 90% or more in mol%.
  • the glass material of the present invention can contain various components shown below. In the following description regarding the content of each component, “%” means “mol%” unless otherwise specified.
  • SiO 2 , B 2 O 3 and P 2 O 5 are components that become a glass skeleton and widen the vitrification range. However, since these components do not contribute to the improvement of the Verde constant, if the content is too large, it is difficult to obtain a sufficient Faraday effect. Accordingly, the contents of SiO 2 , B 2 O 3 and P 2 O 5 are preferably 0 to 50%, 1 to 45%, particularly 2 to 40%, respectively.
  • the total amount of SiO 2 and B 2 O 3 is preferably 0 to 52%, 15 to 51%, particularly 20 to 50%.
  • the total amount of B 2 O 3 and P 2 O 5 is preferably 0 to 52%, 15 to 51%, particularly preferably 20 to 50%.
  • the total amount of SiO 2 , B 2 O 3 and P 2 O 5 is preferably 0 to 52%, 15 to 51%, particularly preferably 20 to 50%.
  • Al 2 O 3 is a component that forms a glass skeleton as an intermediate oxide and widens the vitrification range.
  • the content of Al 2 O 3 is preferably 0 to 50%, 0.1 to 40%, 1 to 30%, 1 to 20%, particularly 1 to 10%.
  • La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and Y 2 O 3 have the effect of stabilizing the glass, but if the content is too large, it becomes difficult to vitrify. Therefore, the contents of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 and Y 2 O 3 are each preferably 10% or less, particularly preferably 5% or less.
  • Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 stabilize the glass and contribute to the improvement of the Verde constant.
  • the contents of Dy 2 O 3 , Eu 2 O 3 and Ce 2 O 3 are each preferably 15% or less, particularly preferably 10% or less.
  • the content of the trivalent oxide is specified, but for oxides other than trivalent (for example, CeO 2 etc.), the content when converted to the trivalent oxide The amount is preferably within the above range.
  • the content of these components is preferably 0 to 10%, particularly 0 to 5%.
  • Ga 2 O 3 has the effect of increasing the glass forming ability and expanding the vitrification range. However, when there is too much the content, it will become easy to devitrify. Further, since the Ga 2 O 3 it does not contribute to the improvement of the Verdet constant, when the content is too large, a sufficient Faraday effect difficult to obtain. Therefore, the Ga 2 O 3 content is preferably 0 to 6%, particularly preferably 0 to 5%.
  • Fluorine has the effect of increasing the glass forming ability and expanding the vitrification range. However, if the content is too large, the composition volatilizes during melting and the composition may change, or the stability of the glass may be affected. Therefore, the fluorine content (F 2 conversion) is preferably 0 to 10%, more preferably 0 to 7%, and still more preferably 0 to 5%.
  • Sb 2 O 3 can be added as a reducing agent.
  • the content of Sb 2 O 3 is preferably 0.1% or less in order to avoid coloring or in consideration of environmental load.
  • the glass material of the present invention preferably has a light transmission loss as small as possible particularly when used as a magneto-optical element such as an isolator. Therefore, the light transmittance of the glass material of the present invention is preferably 50% or more, 60%, particularly 70% or more at a wavelength of 633 nm.
  • FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for producing a glass material by a containerless floating method.
  • FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for producing a glass material by a containerless floating method.
  • the manufacturing method of the glass material of this invention is demonstrated, referring FIG.
  • the glass material manufacturing apparatus 1 has a mold 10.
  • the mold 10 also serves as a melting container.
  • the molding die 10 has a molding surface 10a and a plurality of gas ejection holes 10b opened in the molding surface 10a.
  • the gas ejection hole 10b is connected to a gas supply mechanism 11 such as a gas cylinder. Gas is supplied from the gas supply mechanism 11 to the molding surface 10a via the gas ejection hole 10b.
  • the type of gas is not particularly limited, and may be, for example, air or oxygen, or a reducing gas containing nitrogen gas, argon gas, helium gas, carbon monoxide gas, carbon dioxide gas, or hydrogen. Good.
  • the glass raw material lump 12 is first arrange
  • the glass raw material block 12 for example, a raw material powder integrated by press molding or the like, a sintered body obtained by integrating raw material powder by press molding or the like, and a composition equivalent to the target glass composition are used. For example, an aggregate of crystals.
  • the glass raw material block 12 is floated on the molding surface 10a by ejecting gas from the gas ejection holes 10b. That is, the glass raw material block 12 is held in a state where it is not in contact with the molding surface 10a. In this state, the glass material block 12 is irradiated with laser light from the laser light irradiation device 13. Thereby, the glass raw material lump 12 is heated and melted to be vitrified to obtain molten glass. Thereafter, the glass material can be obtained by cooling the molten glass.
  • Table 1 shows examples and comparative examples of the present invention.
  • Each sample was prepared as follows. First, raw materials prepared so as to have the glass composition shown in the table were press-molded, and sintered at 1100 to 1400 ° C. for 12 hours to produce a glass raw material lump.
  • the glass raw material lump was roughly pulverized in a mortar to obtain small pieces of 0.05 to 0.5 g.
  • a glass material (about 1 to 8 mm in diameter) was produced by the containerless floating method using the apparatus according to FIG. A 100 W CO 2 laser oscillator was used as the heat source.
  • nitrogen gas was used as a gas for floating the raw material lump, and was supplied at a flow rate of 1 to 30 L / min.
  • the Verde constant of the obtained glass material was measured using a Kerr effect measuring device (manufactured by JASCO Corporation, product number: K-250). Specifically, the obtained glass material was polished to a thickness of about 1 mm, the Faraday rotation angle at a wavelength of 400 to 850 nm was measured in a magnetic field of 15 kOe, and the Verde constant at wavelengths of 633 nm and 850 nm was calculated. . The wavelength sweep rate was 6 nm / min. The results are shown in Table 1.
  • the glass materials of Examples 1 to 7 exhibited Verde constants of ⁇ 0.69 to ⁇ 1.04 at a wavelength of 633 nm and ⁇ 0.34 to ⁇ 0.52 at a wavelength of 850 nm.
  • the Verde constant of the glass material of Comparative Example 1 was ⁇ 0.37 at a wavelength of 633 nm and ⁇ 0.18 at a wavelength of 850 nm, and the absolute value was small.
  • the glass material of the present invention is suitable as a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, or a magnetic sensor.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une composition de verre qui présente un effet Faraday accru par rapport à la technique antérieure. Cette composition de verre est caractérisée en ce qu'elle comprend, en % en moles, une proportion de Tb2O3 strictement supérieure à 48 %.
PCT/JP2016/051902 2015-01-28 2016-01-22 Matériau verre et procédé de fabrication de ce matériau WO2016121655A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/503,012 US10227254B2 (en) 2015-01-28 2016-01-22 Glass material and method for manufacturing same
CN201680007774.4A CN107207321A (zh) 2015-01-28 2016-01-22 玻璃材料及其制造方法
US15/704,126 US10093574B2 (en) 2015-01-28 2017-09-14 Glass material and method for manufacturing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015013950 2015-01-28
JP2015-013950 2015-01-28
JP2015-224404 2015-11-17
JP2015224404A JP6694154B2 (ja) 2015-01-28 2015-11-17 ガラス材及びその製造方法

Related Child Applications (2)

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US15/503,012 A-371-Of-International US10227254B2 (en) 2015-01-28 2016-01-22 Glass material and method for manufacturing same
US15/704,126 Continuation US10093574B2 (en) 2015-01-28 2017-09-14 Glass material and method for manufacturing same

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WO2016121655A1 true WO2016121655A1 (fr) 2016-08-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017061389A (ja) * 2015-09-24 2017-03-30 日本電気硝子株式会社 ガラス材及びその製造方法
JP2018058728A (ja) * 2016-10-06 2018-04-12 日本電気硝子株式会社 ガラス材及びその製造方法
WO2018079090A1 (fr) * 2016-10-24 2018-05-03 日本電気硝子株式会社 Élément magnéto-optique et procédé de fabrication de cet élément
JP2018080066A (ja) * 2016-11-14 2018-05-24 日本電気硝子株式会社 磁界センサ用ファラデー回転子

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04170338A (ja) * 1990-11-01 1992-06-18 Matsushita Electric Ind Co Ltd 磁性ガラス
JPH08259242A (ja) * 1995-03-24 1996-10-08 Hooya Precision Kk ガラス素材の浮上軟化方法、光学素子の製造方法、および光学素子
JPH10297933A (ja) * 1997-04-25 1998-11-10 Sumita Kogaku Glass:Kk ファラデー回転素子用ガラス
US6482758B1 (en) * 1999-10-14 2002-11-19 Containerless Research, Inc. Single phase rare earth oxide-aluminum oxide glasses
WO2009004710A1 (fr) * 2007-07-02 2009-01-08 Ohara Inc. Composition de verre
WO2014103662A1 (fr) * 2012-12-28 2014-07-03 日本電気硝子株式会社 Procédé pour la fabrication de matériau en verre

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04170338A (ja) * 1990-11-01 1992-06-18 Matsushita Electric Ind Co Ltd 磁性ガラス
JPH08259242A (ja) * 1995-03-24 1996-10-08 Hooya Precision Kk ガラス素材の浮上軟化方法、光学素子の製造方法、および光学素子
JPH10297933A (ja) * 1997-04-25 1998-11-10 Sumita Kogaku Glass:Kk ファラデー回転素子用ガラス
US6482758B1 (en) * 1999-10-14 2002-11-19 Containerless Research, Inc. Single phase rare earth oxide-aluminum oxide glasses
WO2009004710A1 (fr) * 2007-07-02 2009-01-08 Ohara Inc. Composition de verre
WO2014103662A1 (fr) * 2012-12-28 2014-07-03 日本電気硝子株式会社 Procédé pour la fabrication de matériau en verre

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
G. P. SMITH: "Some Light on glass", GLASS TECHNOLOGY, vol. 20, 1979, pages 149 - 157 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017061389A (ja) * 2015-09-24 2017-03-30 日本電気硝子株式会社 ガラス材及びその製造方法
WO2017051685A1 (fr) * 2015-09-24 2017-03-30 日本電気硝子株式会社 Matériau de verre et procédé de fabrication de ce matériau
US10737969B2 (en) 2015-09-24 2020-08-11 Nippon Electric Glass Co., Ltd. Glass material and method for manufacturing same
JP2018058728A (ja) * 2016-10-06 2018-04-12 日本電気硝子株式会社 ガラス材及びその製造方法
WO2018079090A1 (fr) * 2016-10-24 2018-05-03 日本電気硝子株式会社 Élément magnéto-optique et procédé de fabrication de cet élément
JP2018072384A (ja) * 2016-10-24 2018-05-10 日本電気硝子株式会社 磁気光学素子及びその製造方法
US11686958B2 (en) 2016-10-24 2023-06-27 Nippon Electric Glass Co., Ltd. Magneto-optic element and method for producing same
JP2018080066A (ja) * 2016-11-14 2018-05-24 日本電気硝子株式会社 磁界センサ用ファラデー回転子

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