JP3301036B2 - Glass composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass composition and a method for producing the same, and more particularly to magnetic measurement, magnetic processing, a powder permanent magnet used for magnetic powder, optical measurement, optical processing,
The present invention relates to a technique that is effective when applied to a laser composition used for optical communication or the like or a glass composition exhibiting an optical amplification action.

[0002]

2. Description of the Related Art Conventionally, as an example of a composite magnet in which magnetic fine particles are dispersed in a non-magnetic material, an ESD (Elongated Single) has been used.
Domain) Magnets, magnets in which a magnetic metal is filled in an anodized porous aluminum oxide film, and plastic magnets in which barium ferrite, a rare earth cobalt compound, or the like is mixed in rubber or resin are known. .
These methods use a method of electroplating in a harmful metal salt solution or require repeated operations of high-temperature heat treatment, which complicates the magnet manufacturing process and has large magnetic fluctuations with respect to the operating temperature.

On the other hand, YAG conventional, as an application example using stimulated emission of Cr ⁴⁺ ions were doped with Cr ⁴⁺ ions
(Yttrium aluminum garnet: a material having a garnet-shaped crystal structure) or Y ₂ SiO ₅ and Mg ₂ S
Single crystal lasers such as iO ₄ are known, but these examples all contain Cr ions in the crystal lattice and cannot be processed into optical fibers for optical communication media.

[0004] In addition, most of the Cr ion valence contained in generally produced Cr-doped glass is Cr ³⁺ or Cr ⁶⁺ .

[0005]

However, the composite magnet in which the above-described conventional magnetic fine particles are dispersed in a non-magnetic material can be obtained by using an electroplating technique in a metal salt solution or by performing a high-temperature heat treatment. There is a problem that the magnet manufacturing process is complicated, for example, a repetitive operation is required, and the magnetic fluctuation is large with respect to the use temperature.

Further, in the case where Cr ⁴⁺ ions are contained in the glass, there is a problem that the luminous intensity is extremely low because the content of Cr ⁴⁺ ions in the glass is low.

An object of the present invention is to have a ferromagnetic property applicable to a powdered permanent magnet, a remarkably wide wavelength range exhibiting laser oscillation or optical amplification, and the center wavelength of which is important for an optical communication wavelength range. It is an object of the present invention to provide a technique capable of obtaining optical characteristics usable for a laser or an optical amplifier having a diameter of 1.3 to 1.5 μm with the same glass composition.

The above and other objects and novel features of the present invention will become apparent from the description of the present specification and the accompanying drawings.

The inventor of the present application has studied the luminous action of glass having transition metal ions as active ions, and found that the above-mentioned Cr dopant material was added to glass mainly containing alkaline earth carbonate or its oxide. He, Ne, Ar, K used for the atmosphere during the melting and reheating treatment
r ₂ , H ₂ , CO, CO ₂
It has been found that fine CrO ₂ fine particles are dispersed and contained in glass by controlling the oxidation-reduction equilibrium by a mixed gas with at least one kind of gas selected from chromyl chloride (CrO ₂ Cl ₂ ) gas.

The CrO ₂ fine particle-dispersed glass produced by this production method can obtain strong fluorescence in a wide wavelength band of 1.1 to 1.7 μm. Optical amplification over a wide range is possible. Also,
By applying the ferromagnetic properties of the CrO ₂ fine particles in the glass and pulverizing it into a powder, it is possible to obtain the optimal magnetic powder as a raw material of the present invention. Is possible.

That is, by dispersing nanometer-sized CrO ₂ fine particles in a glass mainly composed of alkaline earth divalent ions, a 1.3 to 1.5 μm band which is important as a practical communication wavelength for optical communication. A glass composition having a combination of fluorescent properties that can be configured for an optical amplifier and ferromagnetic properties that can be applied to a powdered permanent magnet having a wide range of applications can be obtained.

Hereinafter, the present invention will be described in detail.

The basic glass composition of the present invention is selected from the group consisting of beryllium, magnesium, calcium, strontium and barium carbonates or oxides.
The glass composition contains 10 to 75 mol% (mol%) of one or more kinds of compounds, and further contains CrO ₂ fine particles and Cr ⁴⁺ ions.

In the glass composition of the present invention, an alkaline earth oxide composed of at least one of BeO, MgO, CaO, SrO and BaO is contained in a crucible.
and at least one compound selected from the group consisting of chromium metal, chromium oxide, chromium sulfide, chromium chloride, chromium nitrate, chromium hydroxide, and organic chromium compounds. A chromium-doped glass material containing a glass material is blended, and the chromium-doped glass material is mixed with an inert gas, an oxygen gas, a hydrogen gas, a carbon monoxide gas, or an atmosphere of a gas selected from a plurality of carbon dioxide gases. The chromium-doped glass raw material is heated and melted, the molten chromium-doped glass raw material is quenched, and the quenched chromium-doped glass raw material is reheated to a temperature higher than the glass transition temperature and lower than the softening point.

Further, the glass composition formed by the above-mentioned method for producing a glass composition is pulverized into glass powder, an organic resin raw material is mixed with the glass powder, and a pressure and a magnetic field which are orthogonal to each other are applied. Compression molding.

The content of the alkaline earth oxide is 10 mol.
%, The magnetic properties and the emission intensity are significantly reduced. On the other hand, if the content of the alkaline earth oxide is 75 mol% or more, problems such as difficulty in vitrification are caused. The content of Cr ions is 10 to 50,000 ppm by weight, and the optimum addition amount range is 200 to 5000 ppm. If the content of Cr ions is less than this range, the effect of addition is not obtained, while if it exceeds the above range, the effect of addition is reduced.

The characteristics of the basic glass composition of the present invention are as follows.
This is because B ₂ O ₃ , V ₂ O ₅ , and As ₂ O ₅ having glass forming ability are not contained at all. However, in order to stabilize the glass, it contains SiO ₂ , GeO ₂ , and SnO ₂ in an amount of 0 to 50 mol%,
In addition, a few mol% of CeO ₂ , SnO, Sb ₂ O _{3 and the} like are contained as a thermal reducing agent. That is, in mol% display,

[0018]

## EQU1 ## [SiO ₂ + GeO ₂ + SnO ₂ ]: 0 to 50 mol
%, Preferably 5 to 15 mol%. Here, the mol% of the whole components is shown in the symbol [].

Other glass compositions are mainly BeO, M
monovalent, divalent, trivalent glass components that contribute to stabilization of alkaline earth oxides such as gO, CaO, SrO, and BaO;
It consists of tetravalent and pentavalent oxides. The mol% is

[0020]

[Al ₂ O ₃ + Ga ₂ O ₃ + In ₂ O ₃ ]: 0 to 60
mol%, preferably 5 to 25 mol%,

[0021]

## EQU3 ## [ZnO + CdO + PbO]: 0 to 40 mol
%, Preferably 15 to 25 mol%,

[0022]

[Sc ₂ O ₃ + Y ₂ O ₃ + La ₂ O ₃ ]: 0 to 40 mo
l%, preferably 5-20 mol%,

[0023]

[TiO ₂ + ZrO ₂ ]: 0 to 40 mol%, preferably 10 to 20 mol%,

[0024]

[Ta ₂ O ₅ + Nb ₂ O ₅ ]: 0 to 40 mol%, preferably 10 to 20 mol%,

[0025]

[As ₂ O ₃ + Bi ₂ O ₃ ]: 0 to 40 mol%, preferably 10 to 20 mol%,

[0026]

[Equation 8] [Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂
O]: a glass composition represented by 0 to 30 mol%, preferably 5 to 10 mol%. These glass compositions can be roughly classified into the following three from the aspect of the constituent composition.

The first group is composed of Be ²⁺ , Mg ²⁺ ,
This is a glass composition containing a carbonate or oxide of Ca ²⁺ , Sr ²⁺ , and Ba ²⁺ as a main component, into which trivalent ions such as aluminum oxide, gallium oxide, and indium oxide are introduced. The feature of this composition is that charge compensation of Cr ions doped using a large amount of alkaline earth divalent ions such as Ca ²⁺ and Mg ^{2+ as} a main component is performed, and the melting atmosphere at the time of glass melting is changed as necessary. The glass is melted by adjusting the temperature under an oxidizing or reducing atmosphere to produce CrO ₂ fine particles and Cr ³⁺ , Cr ⁴⁺ in the glass melt, and the Cr ions remaining in the glass by the subsequent reheating treatment Is synthesized into CrO ₂ fine particles. In this glass system, Cr ⁴⁺ ions and CrO 2 are controlled by controlling the reheating temperature and the atmosphere gas composition.
_Two fine particles can be mixed at the same time, and as a result, the broadband light emission characteristics shown in FIG. 1 and the ferromagnetic characteristics shown in FIG. 2 are obtained.

The Cr ⁴⁺ ions generated in the melt tend to increase their content in proportion to the increase in the alkaline earth oxide composition ratio in the glass composition. When the composition is 50 mol% or more, the tendency becomes more remarkable. In addition, Cr by alkaline earth divalent ion
^{The 4+} ion generation effect is represented by Be ²⁺ , Mg ²⁺ , Ca ²⁺ , S
r ²⁺ , Ba ²⁺ , and in order to increase the Cr ⁴⁺ ion generation efficiency, Be ²⁺ , M
It is preferable to use a composition such as g ²⁺ and Ca ²⁺ .

In the glass composition, a part of CaO is replaced with another divalent ion (BeO, SrO, BaO), or
The thermal characteristics such as the glass transition temperature and the melting point can be adjusted by the addition of pentavalent and pentavalent ions, and as a result, a stable glass can be formed. Also, by substituting a part of Al ₂ O ₃ with another trivalent ion, it is possible to adjust the same thermal characteristics as the effect of adding the divalent ion. On the other hand, part of CaO is converted to PbO
Can significantly reduce the melting point of the glass, and the substitution of P ₂ O ₅ can expand the vitrification range.

The second group includes Be ²⁺ , Mg ²⁺ , C
This is a glass composition in which trivalent ions such as scandium oxide, yttrium oxide, and lanthanum oxide are introduced into a composition mainly containing carbonate or oxide of a ²⁺ , Sr ²⁺ , and Ba ²⁺ . Also in this glass system, Cr ⁴⁺ ion and CrO
₍₂₎ Fine particles can be generated and the broadband emission characteristics and ferromagnetic characteristics can be provided. This composition provides higher emission intensity than the first glass composition, but this is due to an increase in the concentration of Cr ⁴⁺ ions generated in the glass melt. As this reason, in addition to the alkaline earth oxide ions to Cr ⁴⁺ ion generation, Sc ^3+, Y ³⁺ and La
It seems that ³⁺ is working effectively. In any case, in this glass composition, a large emission characteristic can be obtained by the active ion effect. This glass composition has a melting temperature of 50 to 2 compared to the first group.
Although the temperature rises by 00 ° C., in this glass system, similarly to the first group, stabilization of the glass is achieved by substituting a part of the composition with mono-, di-, tri-, tetra-, and pentavalent ions Thermal properties can be controlled.

The third group is composed of Be ²⁺ , Mg ²⁺ , C
This is a composition comprising carbonates or oxides of a ²⁺ , Sr ²⁺ , and Ba ²⁺ and titanium oxide or zirconium oxide. The compositional feature of this glass is that the glass can be formed without containing aluminum oxide. In this glass system, as in the first group, Cr ⁴⁺ ions and C
rO ₂ fine particles can be generated, and the broadband emission characteristics and ferromagnetic characteristics described above can be provided. In addition, monovalent, divalent, trivalent,
By substituting a part of the composition with tetravalent and pentavalent ions,
Can control glass stabilization and thermal properties.

(Types of Dopant Material) Metallic chromium and chromium oxide (CrO, Cr ₂ O ₃ , CrO ₂ ,
CrO ₃ ), chromium sulfide (Cr ₂ (SO ₄ ) ₃ .nH
₂ O), chromium chloride with _{(CrCl 3 · 6H 2 O)} , chromium nitrate _{(Cr (NO 3) 3 ·} 9H 2 O) and chromium hydroxide _{(Cr (OH) 3 · nH} 2 O). Doped Cr
The ions take a valence state corresponding to various sites in the glass, but when using the glass compositions in Tables 1 and 3 to 4 of the glass composition table, there is a difference in all chromium dopant materials. 1.1-1.7 μm due to Cr ⁴⁺ active ions
It was confirmed that the fluorescent characteristics and the ferromagnetic characteristics in a wide wavelength band over the range of were obtained. Particularly, metallic chromium and chromium oxide _{(CrO, Cr 2 O 3,} CrO 2, CrO 3) glass with the dopant, the fluorescence intensity and the residual magnetic flux density is much higher characteristics.

The glass comprising the above-described glass composition and a Cr dopant material has a Cr ion concentration of 10 ppm.
Above, all show a fluorescence spectrum similar to that of FIG. 1 and, when excited by a YAG laser, have a wavelength of 1.2 to 1.7.
Laser oscillation is confirmed in the wavelength range of μm, and when the Cr ion concentration is 100 ppm or more, ferromagnetic characteristics applicable to powdered permanent magnets are exhibited.

The state of Cr in the glass is inferred from the results of observation with a transmission electron microscope, and the bonding state is C
In addition to the rO ₂ oxide, the existence of a composite oxide of chromium and a trivalent oxide such as Al, Sc, Y, and La can be considered. In addition, pentavalent ions to trivalent ions such as Cr ³⁺ , Cr ⁴⁺ , and Cr ⁵⁺ exist as ions. Among them, CrO ₂ oxide and Cr ⁴⁺ ion are alkaline earth oxides which strongly influence the formation of tetravalent ligand field and oxide compositions such as yttrium and lanthanum as described above, and the atmosphere during glass production. It largely depends on the gas composition.

That is, Be ²⁺ , Mg ²⁺ , C
a ²⁺ , Sr ²⁺ , Ba ²⁺ , containing one or more of carbonates or oxides in an amount of 10 to 75 mol%, and heating temperature and atmosphere gas composition during glass melting and reheating treatment. By strictly controlling it, chromium ions are oxidized or reduced to a tetravalent state, and further oxidized with non-crosslinked oxygen to produce CrO ₂ fine particles. And

The production of the glass of the present invention was carried out by a crucible melting method. On the other hand, CrO
_{(2) As} a method for producing fine particles, the metal chromium and the chromium compound described above are charge-compensated with alkaline earth divalent ions, and the composition is melted by controlling the composition of the melting atmosphere to an oxidizing or reducing atmosphere as necessary. CrO in the melt
₍₂₎ Fine particles and Cr ions such as Cr ³⁺ ions and Cr ⁴⁺ ions coexist.

The atmosphere gas used at the time of melting the glass was as follows:
In order to use the above-mentioned gas species as an oxidizing atmosphere, pure oxygen gas is used in the inert gas in an amount of 0.01 to 0.1% by volume, and when used as a reducing atmosphere, pure oxygen gas is used in the inert gas. And the amount of hydrogen or CO is mixed in the range of 0.1 to 1%.

Next, this is set to a temperature equal to or higher than the glass transition point, and
By performing the reheating treatment in the temperature range below the softening point,
Part of the Cr ions remaining in the glass can be generated as CrO ₂ fine particles, and the Cr ⁴⁺ concentration can be increased.

The CrO ₂ fine particles produced by this reheating treatment have a needle-like shape, and the size is about 50 mm in length.
１００100 nm, width about 5-20 nm. The reheating temperature is 500 to 800 ° C., and the atmosphere gas composition is the same as the above-mentioned atmosphere gas composition. If the production conditions are outside this range, the amount of synthesis from Cr ions to CrO ₂ fine particles will decrease, and the particle size will fluctuate, thereby greatly reducing the optical quality of the glass.

By adding a thermal reducing agent such as SnO or Sb ₂ O ₃ in advance to the glass composition, the amount of CrO ₂ synthesized in the reheating step increases. For the synthesis of CrO _2, it is preferable to use these thermal reducing agents in addition to the above-mentioned production conditions.

FIG. 3 is a schematic view of CrO ₂ fine particle dispersed glass observed by a transmission electron microscope. As shown in FIG. 3, the CrO ₂ fine particles have a length of about 50-100 nm and a width of about 5 nm.
Needles having a size of ２０20 nm are formed and distributed in a random state. Ferromagnetic characteristics shown in FIG. 2 this CrO ₂
Due to the appearance of fine particles, the individual CrO ₂ fine particles are covered with the surrounding glass, so that the CrO ₂ fine particles do not directly coalesce even during pulverization, and the coercive force due to magnetic interaction is sharply increased. It has a feature that can prevent a significant drop.

By pulverizing the glass into a powder, a suitable magnetic powder can be obtained. The powder magnet of the present invention, after crushing this glass into fine powder of about 1 μm or less, compression-molded in a magnetic field so that the applied magnetic field is perpendicular to the applied direction,
A permanent magnet is obtained by solidifying the thermosetting organic resin as a binder.

The powder permanent magnet according to the present invention is different from the conventional magnet in that the powder has no magnetic fluctuation even with a temperature change, is excellent in weather resistance, does not decrease in coercive force even in the compacting process, and is easy to manufacture. It is a permanent magnet composition.

This glass composition can be used alone as a powdered magnet material as well as a laser oscillation material and an optical amplification material. In particular, if this material is processed into a fiber as an optical amplifying material, an optical amplifier having an optical band applicable to the entire 1.3-1.5 μm band which is a practical wavelength of optical communication is realized, and the reliability of the communication system is improved. It is possible to achieve economy.

The glass composition for laser or optical amplification according to the present invention uses a crucible melting method as a glass preparation method, controls the melting temperature in the range of 1450 to 1600 ° C., and sets He, Ne, Ar, and Ar in a melting atmosphere. A mixed gas of an inert gas such as Kr and Xe and at least one of O ₂ , H ₂ , CO and CO ₂ gases is used. Adjust the melting atmosphere to the desired oxidizing and reducing atmosphere and add Cr to the glass melt.
O ₂ oxide fine particles and Cr ions such as Cr ³⁺ , Cr ⁴⁺ and Cr ⁵⁺ are generated. Further, after the molten glass is cooled to room temperature in the atmosphere or the inert gas,
After performing a reheating treatment for 10 hours or more at ~ 800 ° C,
It was gradually cooled to room temperature at a cooling rate of 0.5 to 2 ° C / min. He, Ne, Ar, Kr, X
A mixed gas of an inert gas such as e and at least one of O ₂ , H ₂ , CO and CO ₂ gases is used.

In such a reheating treatment, the Cr ion valence in the glass can be controlled to a desired Cr ion valence depending on the processing conditions.
The synthesis reaction to O ₂ oxide fine particles also proceeds. As a result, the content of the CrO ₂ oxide fine particles in the glass is increased by the reheating treatment.

According to the above-mentioned means, the glass composition according to the present invention exhibits a laser or light amplifying action in a bulk form, but is also applicable to an optical waveguide or an optical fiber in which a region centered on a core is doped with Cr ions. A similar effect was demonstrated. As a manufacturing method, a conventional method can be applied.
For example, as a method for producing an optical fiber, a rod-in-tube method or a method of drawing the glass composition of the present invention into a glass tube containing the present composition containing no quartz glass and Cr and drawing the same can be applied.

According to the method for producing a permanent magnet and a glass composition for laser / light amplification of the present invention, inexpensive alkaline earth carbonates and oxides are used as main glass compositions, and a general crucible melting method is used as a glass production method. Is used, the synthesis of CrO ₂ fine particles and Cr ⁴⁺ ions is realized by an easy method such as control of the heating temperature and the atmosphere gas composition at the time of glass melting and subsequent reheating, which is extremely advantageous in glass production. Has features.

Further, in this manufacturing method, the synthesized Cr
O ₂ oxide and Cr ⁴⁺ ions do not largely depend on the chemical bonding state of the dopant material or the valence thereof, and thus have a feature that a wide variety of dopant agents can be applied. Moreover, after forming the element from the molten glass, or after producing the fiber, the same treatment as the reheating treatment is performed to regenerate CrO ₂ oxide fine particles and Cr ⁴⁺ ions in the element and the fiber. be able to.

[0050]

Embodiments of the present invention will be described below in detail with reference to the drawings.

In all the drawings for describing the embodiments, those having the same functions are denoted by the same reference numerals, and their repeated description will be omitted.

Tables 1 and 3 to 4 show composition tables of the glass composition for optical amplification according to one embodiment of the present invention.

(Embodiment 1) FIG. 1 shows a glass composition according to an embodiment (Embodiment 1) of the present invention.
FIG. 2 is a hysteresis curve measured by a sample vibration type magnetometer of Sample No. 11 shown in Table 1 of the glass composition of one embodiment (Embodiment 1) of the present invention. FIG. 3 shows the CrO used in the powder permanent magnet according to the present invention.
FIG. 2 is a schematic view of a _two- particle dispersed glass observed by a transmission electron microscope. In FIG. 1, the horizontal axis is wavelength (Wavelength) and the vertical axis is fluorescence intensity.

The glass composition for light amplification of one embodiment (embodiment 1) of the present invention was prepared by synthesizing the glass composition (mol%) shown in Table 1 by the following method. First, a carbonate or oxide, which is a glass material, is sufficiently mixed in an agate mortar, and then a predetermined amount is put into a platinum crucible, and a mixed gas of oxygen and He whose oxygen concentration is adjusted to 0.01%. From room temperature to 2 ° C / min to 20 ° C /
After heating at 1000 ° C. for 1 hour and holding at 1000 ° C. for 1 hour to degas moisture and adsorbed oxygen in the glass raw material, 2 ° C.
/ Min to 20 ° C / min at a heating rate of 1400 to 16
Heating was controlled to 00 ° C, and the temperature was maintained at the same temperature for 30 to 90 minutes to perform melt synthesis. Melt-synthesized glass is 600-75
The glass melt was poured out onto a mold preheated to 0 ° C., and was naturally cooled to room temperature.

Next, the atmosphere gas composition was changed to He, Ne, A
inert gas such as r, Kr, Xe, etc. and oxygen concentration of 0.05 to 5
600 to 7 in an electric furnace controlled to a range of 0.1%.
Hold at 50 ° C for 10 hours, then 0.5 ° C / min (min)
It was gradually cooled to room temperature at a rate of 2 ° C./min (min). The slowly cooled glass was cut into a plate of 10 mm × 20 mm × 2 ^t mm, and the cut surface was polished to the number 4000.

In the fluorescence measurement of the glass, the oscillation wavelength was 1.06.
When a wavelength range from 1100 nm to 1700 nm was measured with a spectroscopic optical system using cooled Ge as a detector using a μm YAG laser beam as excitation light, a fluorescence spectrum similar to that in FIG. 1 was obtained. Table 2 shows the results of the fluorescence measurement of this glass system.
Shown in As Table 2 shows, the fluorescence intensity was calcium oxide,
It can be seen that it largely depends on the magnesium oxide composition and the oxygen concentration in the melting atmosphere.

The fiber was manufactured by a rod-in-tube method, using a quartz glass tube or glass of sample No. 8 not doped with Cr as a clad glass, and inserting a glass composition shown in Table 1 as a core glass into a silica-based fiber. Drawing was performed by a drawing apparatus.

Glass Composition The glass composition shown in Table 1
m, cut to a length of 20 mm, polished the end face, center wavelength 1.
It was fixed in a laser resonator with a 4 μm narrow band filter. 200 m of 1.06 μm YAG laser light from one side
When the incident light was w, an output of 100 mw was obtained. At this time, the oscillation wavelength was 1.4 μm and the line width was 0.01 μm or less. As described above, the glass compositions shown in Table 1 are useful as laser or optical amplification matrices. In this glass system, the laser oscillation efficiency is improved by increasing the composition of calcium oxide and magnesium oxide and controlling the oxygen concentration in the melting atmosphere, as in the case of the above-mentioned fluorescence characteristics, and the calcium oxide composition is 50 mol% (mol%) and the magnesium oxide is 3 mol
% Or more, and a mixed gas of oxygen, He, Ne, Ar, Kr, or Xe whose oxygen concentration is adjusted to 0.01 to 0.001% as an atmosphere gas at the time of glass production. As a result, the oscillation efficiency was significantly increased.

The fluorescence and laser characteristics described above vary greatly depending on the glass composition and the atmosphere gas composition.
This is because the content of Cr ⁴⁺ ions as active ions greatly varies depending on the glass composition and the atmosphere gas composition. According to the method for producing a laser and optical amplification composition of the present invention, a CrO ₂ fine particle is obtained by using an alkaline earth material as a main composition in a glass composition and precisely controlling the oxygen concentration in an atmosphere gas. The particle synthesis reaction could be promoted.

The glass of Example 1 having a saturation magnetization of 1.2 emu / g was pulverized using a ball mill or a stamp mill to prepare a glass powder having a pulverized particle size of 1 μm or less. Knead with a thermosetting resin such as epoxy resin or phenol resin, put this mixture in a non-magnetic mold, make the direction of pressure and the direction of applied magnetic field perpendicular, and apply an applied force of 3 tons / cm ² . Compression molding was performed under the conditions of a magnetic field of 15 kilogauss (KG). The compression molded body was heated in air at 120 ° C. for 1 hour to be solidified. This magnet has a density of 4.2 g / cm ³ , and its magnetic characteristics are saturation magnetization (4πIs).
230 Gauss (G), residual magnetic flux density (4πIr) 208
G, the coercive force was 570 Oersted (Oe). It should be noted that increasing the applied pressure at the time of manufacturing the magnet increases the density, so that the saturation magnetization and the residual magnetization increase, and the quality of the magnet improves.

(Embodiment 2) In another embodiment (Embodiment 2) of the present invention, the glass composition (mo
1%) was synthesized in the same manner as in Example 1. This glass system is a glass composition obtained by adding the Y ₂ O ₃ and La ₂ O ₃ compositions to the compositions shown in Table 1. Also in this glass composition, a fluorescence spectrum similar to that of FIG. 1 was obtained. In this glass system, an increase in fluorescence intensity could be achieved by a combination of an increase in the composition of yttrium oxide and lanthanum oxide and an optimum atmosphere gas composition. In particular, in a glass composition having a yttrium oxide composition of 5 mol% or more and a lanthanum oxide composition of 7 mol% or more, the oxygen concentration of the atmosphere gas is 0.01 to 10 mol%.
In the range of 0.001%, the fluorescence intensity increased remarkably. Also in this glass composition, a fiber was formed by the method of Example 1 and laser characteristics and magnetic characteristics having the same oscillation efficiency as in Example 1 were obtained.

The increase in the fluorescence intensity with the increase in the yttrium oxide and lanthanum oxide compositions in the glass compositions in Table 2 is due to the increase in Cr ⁴⁺ ions in the glass.

That is, it shows that the ligand field of Cr ⁴⁺ ions can be controlled by yttrium and lanthanum ions. In this glass system, the composition range for controlling Cr ⁴⁺ ions is greatly expanded, and more effective control can be performed as compared with the first embodiment.

The glass composition of the present invention having a saturation magnetization of 1.5 emu / g was pulverized by using the pulverizer to prepare a glass powder having a pulverized particle size of 1 μm or less, which was mixed with 5 parts by weight of an epoxy resin. %. Next, this mixture is placed in a non-magnetic mold, the pressure direction and the direction of the applied magnetic field are made perpendicular to each other, and the mixture is heated at 120 ° C. for 1 hour under the conditions of a pressure of 3.5 ton / cm ² and an applied magnetic field of 13 KG to perform compression molding. did. This magnet has a density of 4.5 g / cm ³ and a magnetic characteristic of a saturation magnetization (4πI
s) It was 280 G, residual magnetic flux density (4πIr) 247 G, and coercive coercive force 650 Oe. The powder magnet produced in this manner could be cut.

(Embodiment 3) In another embodiment (Embodiment 3) of the present invention, the glass composition (mo
1%) was synthesized in the same manner as in Example 1. The feature of this glass system is that the calcium oxide composition is 30 mol%
And that no aluminum oxide is contained at all. Also in this composition, the fluorescence spectrum shown in FIG. 1 was obtained similarly to the glass compositions in Tables 1 and 2. Also in this glass composition, a fiber was formed by the method of the first embodiment, and a laser characteristic having the same oscillation characteristics and oscillation efficiency as in the first embodiment was obtained. Also,
Also in this glass composition, although the remanence magnetic flux density and the coercive force were slightly reduced as compared with Examples 1 and 2, the magnetic properties were exhibited, and as an application thereof, a powder magnet could be manufactured by the same method as described above.

Table 4 shows the results of fluorescence measurement when the Cr content of the glass composition of Sample No. 10 was changed.

By using the manufacturing method of the above embodiment, all of the above glass compositions can be applied to a powdered permanent magnet,
Further, a laser or an optical amplifier having Cr ⁴⁺ ions as an active center can be configured.

As described above, the invention made by the present inventor is:
Although the present invention has been described in detail with reference to the embodiment, the present invention is not limited to the embodiment, and it is needless to say that various changes can be made without departing from the scope of the invention.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

As described above, according to the present invention, if a laser or an optical amplifier using a glass composition is constituted, practical communication including 1.3 to 1.5 μm which is the most important in optical communication. An unprecedented laser or optical amplifier that can cover the entire wavelength region can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an emission spectrum of a glass composition of Sample No. 18 of one embodiment (Embodiment 1) of the present invention.

FIG. 2 is a hysteresis curve measured by a sample vibration type magnetometer of glass number 11 in the first embodiment.

FIG. 3 shows CrO ₂ used in the powder permanent magnet according to the present invention.
FIG. 3 is a schematic view of the fine particle-dispersed glass observed by a transmission electron microscope.

[Explanation of symbols]

1 ... magnetic powder of the present glass in which CrO ₂ fine particles are dispersed, 2
... acicular CrO ₂ particles, 3 ... the glass, 4 ... size of CrO ₂ particles.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-211979 (JP, A) JP-A-4-219345 (JP, A) JP-A 7-144932 (JP, A) JP-A-6-214 296058 (JP, A) JP-A-5-58674 (JP, A) JP-A-6-92647 (JP, A) JP-A-8-310831 (JP, A) JP-A-8-310830 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 3/062 C03C 4/12 H01F 1/032

Claims (3)

(57) [Claims] 1. One or more compounds selected from the group consisting of beryllium, magnesium, calcium, strontium and barium carbonates or oxides
From about 75 mol% to which CrO ₂ fine particles and Cr ⁴⁺
A glass composition characterized by containing ions. 2. BeO, MgO, CaO, Sr in a crucible
A metal chromium, a chromium oxide, a chromium sulfide, a chromium chloride;
Blending a chromium-doped glass material containing one or more compounds selected from the group consisting of chromium nitrate, chromium hydroxide, and an organic chromium compound and a glass material; 1 from oxygen gas, hydrogen gas, carbon monoxide gas, carbon dioxide gas
A step of heating and melting in an atmosphere of a gas selected from one or a plurality of kinds; a step of rapidly cooling the chromium-doped glass raw material; And producing the glass composition. 3. A step of pulverizing a glass composition formed by the method for producing a glass composition according to claim 2 into glass powder, and mixing an organic resin raw material with the glass powder to form a glass powder. A method for producing a glass composition, comprising a step of applying compression and magnetic fields at right angles to perform compression molding.