Classifications

• • 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
  • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
• • 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
  • C03C3/253—Silica-free oxide glass compositions containing germanium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/1005—Forming solid beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
  • C03B40/04—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it using gas
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
  • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
  • C03B5/235—Heating the glass
• • 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
• • 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
  • C03C3/127—Silica-free oxide glass compositions containing TiO2 as glass former
• • 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
  • C03C3/16—Silica-free oxide glass compositions containing phosphorus
  • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
• • 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
  • C03C2203/00—Production processes
  • C03C2203/10—Melting processes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/24—Coupling light guides
  • G02B6/26—Optical coupling means
  • G02B6/32—Optical coupling means having lens focusing means positioned between opposed fibre ends
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Definitions

• Titanium-based oxide glass and method for producing the same
• the present invention relates to a titanium-based oxide glass and a method for producing the same, and more particularly to a titanium-based oxide glass having a high refractive index and a method for producing the same.
• a glass material can achieve desired physical properties by appropriately selecting the constituent components constituting the glass material and changing the proportion of each component. For this reason, glass materials are used in various technical fields such as electro-optics!
• compositions that are difficult to vitrify, or powder or flake glass are obtained by the general method of charging the raw material into a ceramic or platinum crucible and melting the raw material in a high-temperature furnace.
• compositions that cannot be made into bulky (balta-like) glass than powders and flakes.
• titanium oxide (TiO 2) is known as a glass material with a high refractive index (for example, “Precision press technology for low-melting lead-free glass lenses as seen in recent patent trends (2)”, Materials Integration Vol. 18, No. 10, (2005), p. 58-66), which is expected to be applied in the optical field.
• TiO 2 titanium oxide
• TiO 3 mixed materials of titanium oxide and lanthanum oxide (La 2 O 3)
• the present invention provides a titanium-based oxide glass that is expected to have a high refractive index.
• the purpose is to provide a strong buttery glass.
• Another object of the present invention is to provide a method for producing Balta-like titanium-based oxide glass.
• the titanium-based oxide glass of the present invention has a bata-like shape, and substantially has the formula (Ml) (M2
• Ti (M3) has a composition represented by O,
• Ml force Ba La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na, and Ca.
• M2 force Mg, Ba, Ca, Sr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na, Sc, Y, Hf, Bi and Ag Is at least one element selected from
• M3 force V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Al, Si, P, Ga, Ge, In, Sn, Sb and Te At least one element, and x, 1, 2 and 2 are
• glass refers to a substance whose glass transition point (Tg) is observed by measurement of DTA or the like.
• Tg glass transition point
• substantially means to allow the presence of impurities up to lmol%, preferably 0.5 mol%, more preferably 0.1 mol%.
• the titanium-based oxide glass of the present invention contains titanium oxide, a high refractive index can be realized. Furthermore, since the titanium-based oxide glass of the present invention has a butter shape and can obtain high visible light transmittance, it can be suitably used as a material for optical components such as lenses.
• a method for producing a titanium-based oxide glass of the present invention is a method for producing the above-described titanium-based oxide glass of the present invention, (a) a step of suspending a raw material adjusted to a predetermined composition in the air and heating and melting the raw material in a suspended state;
• a method of melting a raw material in a suspended state in the air may be referred to as a “floating method”.
• the method for producing a titanium-based oxide glass of the present invention it is generally said that vitrification is difficult because the raw material can be melted without contact with a container such as a crucible and then cooled. Even a composition containing a large amount of titanium oxide can be vitrified. For example, it is difficult to vitrify because it contains crystallized material and materials! / In the case of composition, the contact portion between the container and the glass material during melting may cause crystal precipitation. there were. On the other hand, in the method of the present invention, since the raw material is melted and cooled without being brought into contact with the container, crystal precipitation of titanium oxide can be suppressed. This makes it possible to produce Balta-like titanium-based oxide glass. Furthermore, according to the method of the present invention, the titanium-based oxide glass can be produced easily and in a short time.
• FIG. 1 is a schematic diagram showing an example of a gas floating device used in the method for producing a titanium-based oxide glass of the present invention.
• FIG. 2 is a view showing an example in which the titanium-based oxide glass of the present invention is used as a coupling lens.
• FIG. 3 is a view showing an example in which the titanium-based oxide glass of the present invention is used as SIL.
• FIG. 4 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 5 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 6 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 7 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 8 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 9 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 10 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 11 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 12 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 13 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 14 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 15 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 16 shows a differential thermal analysis (DTA) measurement result of the sample manufactured in Example 1.
• FIG. 17 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 18 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 19 is a measurement result of differential thermal analysis (DTA) of the sample manufactured in Example 1.
• FIG. 20 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 21 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 1.
• FIG. 22 shows the results of differential thermal analysis (DTA) measurement of the sample prepared in Example 1.
• FIG. 23 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 2.
• FIG. 24 is a diagram for explaining a refractive index measurement method.
• FIG. 25 is an optical micrograph of the sample prepared in Example 6.
• FIG. 26 shows the results of differential thermal analysis (DTA) measurement of the sample produced in Example 6.
• FIG. 27A is an X-ray diffraction pattern of a sample prepared in Example 6.
• FIG. 27B is an X-ray diffraction pattern of the sample prepared in Example 6 annealed at 790 ° C. for 1 minute.
• FIG. 27C is an X-ray diffraction pattern of the sample prepared in Example 6 annealed at 900 ° C.
• FIG. 28A is an optical micrograph of a sample produced in Example 10.
• FIG. 28B is an optical micrograph of the sample produced in Example 10.
• FIG. 28C is an optical micrograph of the sample prepared in Example 10.
• the titanium-based oxide glass of the present invention is represented by the formula (Ml) (M2) (Ti (M3)) O.
• Ml is Ba, La, Ce, Pr, Nd, Sm, Eu, G It is one element selected from d, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na and Ca.
• M2 M2, Mg, Ba, Ca, Sr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na, Sc, Y, Hf, Bi, and Ag Is at least one element selected from
• Ml may be, for example, one element selected from Ba, La, Ce, Pr, Nd, Sm and Ca, and Ml is one element selected from La, Ce, Pr, Nd and Sm. It may be an element.
• Ml may be one element selected from Ba, La, Nd and Ca, and may be one element selected from Ba, La and Nd.
• the value of yl indicating the content of the element (M3) substituting Ti can be, for example, 0.1 or less, and is 0.05 or less.
• TiO is the main component of the titanium-based oxide glass of the present invention.
• ZrO reffractive index
• nd 2.2 (see reference)
• the value of yl indicating the content of the element (M3) replacing Ti is preferably 0.05 or more, and more preferably 0.25 or more.
• the value of y2 is 3 The following is preferred.
• the titanium-based oxide glass of the present invention can contain, for example, 57 mol% or more of titanium oxide (TiO 2), and further contains 80 mol% or more when expressed by the oxide content.
• TiO 2 titanium oxide
• the balance in the titanium-based oxide glass of the present invention substantially consists of oxides of elements other than Ti listed above as Ml, M2 and M3.
• the balance is substantially La (La 2 O 3)
• the content of titanium oxide is 80 mol% or more.
• the relationship may be satisfied.
• Ml is Ba
• the element M2 replacing Ba is selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu X, yl, y2 and z are used when at least one element is used
• the relationship may be satisfied.
• Zr has a chemical property similar to that of Ti and is a heavy element. Therefore, Zr is preferably used as an element (M3) replacing Ti.
• the titanium-based oxide glass of the present invention has a visible light range (wavelength range of about 380 nm to 780 nm).
• the refractive index at is preferably 2.0 or more, more preferably 2.1 or more.
• the titanium-based oxide glass of the present invention can be a glass having good transparency to visible light.
• the titanium-based oxide glass of the present invention has a butter shape that is not a conventional powder or the like.
• balta-like glass having a high refractive index with respect to visible light and good transparency with respect to visible light. can be applied.
• balta means to exclude thin films and powders, and has a minimum dimension (minimum value passing through the center of gravity) of lO ⁇ m or more (preferably 50 Hm or more). That is.
• the raw material melt is solidified into a spherical shape by its own surface tension during the cooling process. Therefore, according to the method of the present invention, a spherical titanium-based oxide glass can be obtained, and a spherical glass having a minimum diameter of 0.5 mm or more and further a minimum diameter of 1 mm or more can be obtained. Depending on the application, spherical glass with a minimum diameter of 5 cm or less may be used.
• the titanium-based oxide glass of the present invention can also be used for optical parts such as a spherical lens without performing spherical processing or spherical surface processing.
• FIG. 1 is a schematic view showing an example of an apparatus (floating apparatus) for performing a floating method used in the method for producing a titanium-based oxide glass of the present invention.
• the floating apparatus includes a gas floating furnace 2 for floating the raw material 1 in the air, a fixed base 3 for preventing the movement of the gas floating furnace 2 and supplying the floating gas to the gas floating furnace 2, A flow rate regulator 4 for adjusting the flow rate of gas supplied to the fixed base 3, a carbon dioxide laser device 5 for emitting a laser beam for heating the floating raw material 1, and a laser device 5 A beam splitter 6 that splits the laser beam into two directions, an imaging device (in this case, a CCD camera) 7 and a monitor 8 for monitoring the floating state of the raw material 1, and radiation for measuring the temperature of the raw material 1 A thermometer 11 and a control device 12 for controlling the laser output of the laser device 5 and the like are provided.
• a gas floating furnace 2 for floating the raw material 1 in the air
• a fixed base 3 for preventing the movement of the gas floating furnace 2 and supplying the floating gas to the gas floating furnace 2
• a flow rate regulator 4 for adjusting the flow rate of gas supplied to the fixed base 3
• a carbon dioxide laser device 5 for
• the gas for suspending the raw material 1 is upward (the direction opposite to the direction of gravity). ) Is provided with a gas supply path (not shown) for blowing air, and gas is supplied to the gas supply path via a nozzle (not shown) provided below (bottom of the furnace).
• the gas floating furnace 2 floats the raw material 1 in the air by the pressure of the blown gas.
• the flow rate of the gas to be blown is not particularly limited because it is related to the mass of the raw material, but for example, when a raw material of 0.005 g to 0.05 g is floated, for example, 0.1 l / mii! ⁇ 0.5L / min of gas should be blown.
• the gas floating furnace 2 is fixed to the fixed base 3 by a fixed wire 13.
• the fixed base 3 is provided with a gas supply port 3 a, and the flow rate regulator 4 is connected to the gas supply port 3 a of the fixed base 3 to control the flow rate of the gas supplied to the gas floating furnace 2. Since the floating state of the raw material 1 can be confirmed by the photographing apparatus 7 and the monitor 8, the gas flow rate can be adjusted according to the floating state of the raw material 1.
• the raw material 1 is heated to a predetermined temperature in a floating state, and a laser beam is used for heating at this time.
• the laser beam emitted from the carbon dioxide laser device 5 is divided into two parts with almost equal power by the beam splitter 6, and is irradiated in the vertical direction of the raw material 1 through the reflection mirrors 9 and 10.
• the temperature of the raw material 1 is measured by the radiation thermometer 11 in a non-contact manner.
• the temperature information measured by the radiation thermometer 11 is input to the control device 12.
• the control device 12 is configured to read this temperature information and control the laser output as the heating source of the raw material 1 by a predetermined control program so as to control the temperature of the raw material 1.
• the raw material 1 is set in the gas floating furnace 2, and the raw material 1 is floated by blowing gas into the gas floating furnace 2.
• gas for example, air, Ar, or N can be used as the floating gas.
• the laser output of the carbon dioxide laser device 5 is adjusted by the control device 12, and the raw material 1 is heated by irradiating the laser beam.
• the temperature of the raw material 1 is measured by the radiation thermometer 11, and the raw material 1 is heated to a temperature equal to or higher than the melting point while considering both evaporation and complete melting of the raw material 1.
• the heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the melting point of the raw material 1.
• the heating temperature is preferably in the range of 100 ° C to 500 ° C higher than the melting point of the raw material 1.
• the floating state and melting state of the raw material 1 photographed by the photographing device 7 are observed by the monitor 8, Adjust the gas flow rate and heating temperature to stably float the molten material.
• a predetermined temperature for a predetermined time severed minutes.
• the predetermined temperature for holding the raw material in a molten state is not particularly limited.
• the temperature can be set in a range of 100 ° C. to 500 ° C. higher than the melting point.
• the time for maintaining the molten state is not particularly limited, and can be, for example, 0.5 to 5 minutes.
• the molten raw material is cooled at a predetermined speed by adjusting the output of the laser beam irradiated to the raw material 1 or by cutting off the laser beam.
• Glass can be obtained by solidifying the molten raw material without crystallizing it.
• the cooling rate is, for example, preferably in the range of 500 ° C / sec to 1000 ° C / sec, more preferably in the range of 1000 ° C / sec to 1500 ° C / sec.
• the glass raw material used in the production method of the present invention has a glass composition obtained by the formula (Ml)
• a glass raw material capable of obtaining a composition of a target titanium-based oxide glass (a predetermined composition represented by ⁇ on (Ml) (M2) (Ti (M3)) O xx -yl y)
• a predetermined composition represented by ⁇ on (Ml) (M2) (Ti (M3)) O xx -yl y) a predetermined composition represented by ⁇ on (Ml) (M2) (Ti (M3)) O xx -yl y)
• a target weight ratio For example, lg Ba Er Ti
• the weighed raw material powder is wet-mixed using ethanol (the first wet-mixing) and calcined. Specifically, for example, the dried mixed powder is put in an electric furnace and calcined at, for example, 1000 ° C. for 12 hours to sinter the mixed powder. The mixed powder after calcining is further wet-mixed (second wet mixing), and then formed into a bar shape by press molding. A solid body of a predetermined size is cut out from this molded body and, for example, main baking is performed at 1250 ° C. for 12 hours to obtain a glass raw material. [0034] A glass raw material can be produced as described above. The glass raw material production method described above is merely an example, and the size of the raw material and the temperature and time during calcination and main baking are not limited thereto.
• FIG. 2 is a diagram schematically showing a state in which a spherical titanium-based oxide glass is used as a coupling lens for optical communication.
• the titanium-based oxide glass 21 can be used as a coupling lens that collects the light beam 24 emitted from the semiconductor laser 22 and couples it to a single mode fiber (SMF) 23. Since the spherical aberration of the spherical lens is reduced when the refractive index is increased, a material having a high refractive index such as the titanium-based oxide glass of the present invention is suitable as a ball lens for coupling.
• the titanium-based oxide glass of the present invention it is desirable to use one having a refractive index of 2.0 or more.
• FIG. 3 shows an example of an objective lens in which a gradient index rod lens 31 and a ball lens 32 in which a part of a sphere is cut and processed into a dome shape are combined.
• 33 indicates the luminous flux.
• a lens with a hemispherical shape or a shape exceeding the hemisphere (a shape obtained by cutting a part of the sphere with a plane. More specifically, a shape obtained by cutting a part of the sphere with a plane perpendicular to the center line thereof) It works to increase NA (numerical aperture) by being arranged, and is called SIL.
• NA numbererical aperture
• the larger the refractive index of SIL the more NA can be increased.
• the titanium-based oxide glass of the present invention has a very high refractive index and is suitable for use as SIL.
• a sample of a titanium-based oxide glass represented by (5) was prepared.
• the composition of each sample is as shown in Tables 11 and 12.
• glass of each sample was produced using the glass raw material produced as described above.
• the floating device shown in FIG. 1 was used.
• 2mm square glass material is gas floated
• the raw material was suspended in the gas floating furnace 2 by the gas pressure of the compressed air gas, which was put into the furnace 2 and the flow rate was adjusted by the flow regulator 4.
• the raw material in a floating state was irradiated with a laser beam, and the raw material was heated to a temperature equal to or higher than the melting point to be melted.
• the temperature of the raw material is measured by the radiation thermometer 11, and the molten state of the raw material photographed by the photographing device 7 is confirmed by the monitor 8, and each raw material is considered while taking into consideration both the evaporation and the molten state of the raw material.
• the floating state of the raw material was observed on the monitor 8 and the gas flow rate was adjusted to stably float the molten raw material.
• the molten state was maintained for 2 minutes to remove bubbles in the molten raw material. Thereafter, the laser beam was interrupted, and the molten raw material was rapidly cooled at a cooling rate of 1000 ° C./se C to be solidified. Note that no exothermic peak due to crystal solidification was observed in the cooling curves of all the samples shown in Table 1.
• the sample excluding 9 Nd Ti 2 O contains the element indicated by M2 (x> 0).
• the refractive index of the lath is related to the weight of the element (the size of the atomic number). In general, the heavier the element (the larger the atomic number), the higher the refractive index.
• the element shown by M2 is included, especially the atomic number larger than Ba, and the lanthanoid element is used as the substitution element (M2). As a result, the refractive index is increased.
• the titanium-based oxide glass of this example has yl> 0, and includes a transition metal element having high magnetism and electrical conductivity as a substitution element (M3) of Ti, thereby providing magnetism and electrical conductivity characteristics. This suggests that the glass can be made.
• the diameter and refractive index were measured, and the coloring state was visually observed.
• the sample diameter was measured using a micrometer.
• ⁇ Measurement method of refractive index and sample diameter> the focal position when a spherical glass sample was inserted was measured, and the refractive index was calculated. Specifically, as shown in FIG. 24, the spherical glass 41 to be measured is placed on the glass substrate 42, and the surface opposite to the surface on which the spherical glass 41 is placed with respect to the glass substrate 42 is predetermined. The focal position from the surface of the spherical glass 41 was measured with a microscope. A pattern 43 is formed on the light irradiation side surface of the glass substrate 42, and the focal position was measured by measuring the distance d from the surface of the spherical lens 41 to the image 44 of this pattern.
• Light having a predetermined wavelength was obtained by using an interference filter 45 that transmits the wavelength.
• the refractive indices at wavelengths of 486 nm, 589 nm, and 658 nm were measured.
• 47 indicates white light.
• the optical thickness of the glass substrate 42 at each measurement wavelength was obtained by focusing both surfaces with a microscope and measuring the difference in position.
• the diameter of the spherical glass 41 was obtained by focusing on the surface of the glass substrate 42 in contact with the spherical glass 41 and the spherical glass surface on the opposite side, and measuring the difference in position. From the values of “distance d”, “optical thickness of glass substrate 42”, and “diameter of spherical glass 41” thus obtained, the refractive index of the spherical glass was determined by geometric optical calculation.
• Ml Ba
• M2 La
• the upper limit of the content X of M2 substituting Ba is related to the difference (rr) in the ionic radius between Ba and M2, and as the difference decreases, x becomes smaller. growing.
• the difference in ion radius with Ba is the smallest.
• the maximum value of X of La is 0.5 (Sample 3-7).
• the maximum value of X of Lu, which has the largest difference in ion radius with Ba, was 0.5 (sample 120). Therefore, it was suggested that the upper limit of X for all lanthanide elements can be 0.5.
• Samples of lanthanum titanium oxide glass represented by the following formulas 4; The composition of each sample is shown in Table 4.
• the glass raw material was produced by the same method as in Example 1.
• the same apparatus and method as in Example 1 were used for the glass manufacturing method of each sample.
• the highest refractive index nd 2.375 of the present example at a wavelength of 0.589 ⁇ 111 was obtained.
• the glass raw material was produced in the same manner as in Example 1.
• the same apparatus and method as in Example 1 were used for the glass manufacturing method of each sample.
• the refractive index can be further improved by using Ml as the element Nd heavier than Ba.
• the sample N d Er Yb Ti O contains the complex elements Er and Yb in M2, which is the highest in this example.
• the floating state of the raw material was observed on the monitor 8 and the gas flow rate was adjusted to stably float the molten raw material. After the raw material was completely melted, the molten state was maintained for a predetermined time, and the bubbles in the molten raw material were removed. Thereafter, the laser beam was shut off and the molten raw material was rapidly cooled and solidified.
• FIG. 25 shows an optical micrograph of the obtained lanthanum titanium oxide glass. Real According to the example, a glass having a spherical shape with a diameter of about 2 mm and good transparency to visible light as shown in FIG. 25 was obtained.
• the X-ray diffraction pattern of the sample was (A) the sample prepared by the above method (room temperature), (B) the sample prepared by the above method annealed at 790 ° C for 1 minute, (C) Three types of samples prepared by the above method, annealed at 900 ° C, were measured. The measurement results are shown in FIGS. 27A, 27B, and 27C. As is clear from FIG. 27C, the sample annealed at 900 ° C. shows a diffraction pattern having a sharp peak peculiar to the crystal, and it can be seen that the glass is changed to the crystal. On the other hand, the diffraction pattern of the sample as prepared (see Fig. 27A) is a diffuse curve peculiar to glass, similar to the diffraction pattern (see Fig. 27B) of the sample that was dialed at 790 ° C for 1 minute. No sharp peaks indicating the presence of crystals were observed.
• the refractive index of the sample at two wavelengths (632/8 nm and 1313 nm) was measured at room temperature.
• the measurement results are shown in Table 6.
• the refractive index in this example was measured by a prism coupling method using a refractive index measuring device (Model 2010 Prism Coupler) manufactured by Metricon.
• the measurement accuracy was ⁇ 0.001.
• La O powder and TiO powder are mixed with LaTi Zr 2 O 3 composition (in molar ratio:
• a lanthanum / titanium acid represented by the formula La (M2) (Ti (M3)) O
• Chemical glass samples 9 9 22 were prepared.
• the composition of each sample is as shown in Table 7 and Table 8, and was prepared by the same method as in Example 6. These samples were confirmed by the same method (DTA and X-ray diffraction pattern) as in Example 6. As shown in Tables 7 and 8, it was confirmed that all the samples were glass. The diameter and visual color of each sample are also shown in Table 7 and Table 8. Also, samples 9-23-9-25 having the compositions shown in Table 9 were not vitrified by the same method as in Example 6.
• FIG. 28A, FIG. 28B and FIG. 28C show optical micrographs of the obtained titanium-based oxide glass. As shown in FIG. 28A, FIG. 28B and FIG. 28C, it was confirmed that vitrification was possible even with the composition of this example. Note that the composition shown in FIG. 28A SmTi
• the glass of O was light green and had a diameter of lmm or less.
• Composition shown in Figure 28B CeTi Yes The glass was black and had a diameter of lmm or less.
• the glass of composition PrTi 2 O shown in FIG. 28C was green and had a diameter of 1 mm or less.
• the titanium-based oxide glass and the method for producing the same of the present invention it is possible to obtain a butter-like glass having a high refractive index in the visible light region, which could not be realized conventionally. Furthermore, according to the production method of the present invention, it is possible to produce such a balta-shaped ballast having a high refractive index easily and in a short time. Therefore, the present invention can be suitably used for optical components such as lenses.

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