JPH0920529A - Glass composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a glass composition, having a remarkably wide wavelength region capable of manifesting laser oscillating or optical amplifying actions and capable of using the central wavelength thereof for laser or optical amplification located at 1.3-1.5μm important to the optical communication wavelength region and realizing permanent magnet characteristics alone. SOLUTION: This glass composition comprises 10-75mol% one or more alkaline carbonates or oxides of Be<2+> , Mg<2+> , Sr<2+> , Ba<2+> , etc., with Ca<2+> as the center and further contains fine particles of CrO2 and Cr<4+> ions. The glass composition is produced by including Cr ions in a glass having the alkaline carbonate or oxides thereof as a main composition and preparing the glass composition with a mixed gas of an inert gas such as He, Ne, Ar, Kr or Xe with at least one gas selected from O2 , H2 , CO and CO2 gases as an atmospheric gas.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass composition and a method for producing the same, and more particularly to magnetic measurement, magnetic processing, powder permanent magnets used for magnetic powder, and optical measurement, optical processing,
The present invention relates to a technique effectively applied to a laser used in optical communication or the like or a glass composition having an optical amplification effect.

[0002]

2. Description of the Related Art Conventionally, as an example of a composite magnet in which magnetic particles are dispersed in a non-magnetic material, an ESD (Elongated Single)
Domain) magnets, magnets in which magnetic metal is filled in anodized porous aluminum oxide film, and plastic magnets in which barium ferrite, rare earth cobalt compound, etc. are mixed with rubber or resin are known. .
These are complicated in the magnet manufacturing process such as using electroplating method in a harmful metal salt solution or requiring repeated operation of high temperature heat treatment, and have a large magnetic variation 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: Material with garnet crystal structure) or Y ₂ SiO ₅ and Mg ₂ S
Single crystal lasers such as iO ₄ are known, but in all of these examples, Cr ions are contained in the crystal lattice, and they cannot be processed into optical fibers for optical communication media.

Most of the Cr-doped glasses that are generally produced contain Cr ion valences of Cr ³⁺ or Cr ⁶⁺ .

[0005]

However, the above-mentioned composite type magnet in which the above-mentioned conventional magnetic fine particles are dispersed in a non-magnetic material is used in a metal salt solution by electroplating or by high temperature heat treatment. There is a problem that the magnet manufacturing process is complicated, such as requiring repeated operations, and the magnetic fluctuation is large with respect to the operating temperature, so that the temperature stability of the magnet characteristics and the weather resistance are not sufficient.

In addition, in the example in which the Cr ⁴⁺ ion is contained in the glass, there is a problem that the emission intensity is extremely small because the content rate of the Cr ⁴⁺ ion in the glass is low.

The object of the present invention is to have a ferromagnetic property applicable to powder permanent magnets and to have a remarkably wide wavelength range exhibiting a laser oscillation or optical amplification action, and its central wavelength is important for the optical communication wavelength range. It is an object of the present invention to provide a technique capable of obtaining optical characteristics that can be used for a laser or an optical amplifier having a wavelength 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 this specification and the accompanying drawings.

[0009]

In order to achieve the above-mentioned object, the present invention was conducted to investigate the light emitting action of glass having a transition metal ion as an active ion. Inert gas such as He, Ne, Ar, Kr, and Xe used in the atmosphere during melting and reheating treatment by adding the above Cr dopant material to the glass having the main composition, and O ₂ , H ₂ , CO, By controlling the redox equilibrium with a mixed gas with at least one gas selected from CO ₂ and chromyl chloride (CrO ₂ Cl ₂ ) gas,
It has been found that fine CrO ₂ fine particles are dispersedly contained in glass.

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. A wide range of optical amplification is possible. Also,
By applying the ferromagnetic property expressed by CrO ₂ fine particles in glass and crushing it into a powder form, an optimum magnetic powder as a raw material of the present invention can be obtained. Is possible.

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

Hereinafter, the present invention will be described in detail.

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

In the glass composition of the present invention, 10 parts of an alkaline earth oxide of at least one of BeO, MgO, CaO, SrO and BaO is contained in the crucible.
1 to more than one compound selected from the group consisting of metal chromium, chromium oxide, chromium sulfide, chromium chloride, chromium nitrate, chromium hydroxide, or organic chromium compound and containing mol% to 72 mol%. A chromium-doped glass raw material containing a glass raw material is blended, and the chromium-doped glass raw material is mixed in an atmosphere of a gas selected from one or more of inert gas, oxygen gas, hydrogen gas, carbon monoxide gas and carbon dioxide gas. It is produced by heating and melting, quenching the molten chromium-doped glass raw material, and reheating the quenched chromium-doped glass raw material to a temperature not lower than the glass transition temperature and not higher than the softening point temperature.

Further, the glass composition formed by the above method for producing a glass composition is crushed into glass powder, and an organic resin raw material is mixed with the glass powder, and a pressure and a magnetic field orthogonal to each other are applied. Compress and mold.

The content of the alkaline earth oxide is 10 mol
If it is less than%, the magnetic properties and the emission intensity are significantly reduced. Further, when the alkaline earth oxide is 75 mol% or more, there is a problem that vitrification formation becomes difficult. The content of Cr ions is 10 to 50,000 ppm on a weight basis, and the optimum addition amount range is 200 to 5,000 ppm. If the content of Cr ions is less than this range, the effect is not obtained, while if it exceeds the range, the effect is reduced.

The characteristics of the basic glass composition of the present invention are as follows:
It 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 0 to 50 mol% of SiO ₂ , GeO ₂ , and SnO ₂ ,
In addition, CeO ₂ , SnO, Sb ₂ O _{3 and the} like are contained as the thermal reducing agent in an amount of several mol%. That is, in mol% display,

[0018]

[Formula 1] [SiO ₂ + GeO ₂ + SnO ₂ ]: 0 to 50 mol
%, Preferably 5 to 15 mol%, is a glass composition. Here, mol% of all components is shown in the symbol [].

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

[0020]

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

[0021]

[Formula 3] [ZnO + CdO + PbO]: 0 to 40 mol
%, Preferably 15-25 mol%,

[0022]

[Formula 4] [Sc ₂ O ₃ + Y ₂ O ₃ + La ₂ O ₃ ]: 0 to 40 mo
l%, preferably 5 to 20 mol%,

[0023]

## EQU5 ## [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]

## EQU7 ## [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 constitutional composition.

The first group is Be ²⁺ , Mg ²⁺ ,
This is a glass composition in which a carbonate or oxide of Ca ²⁺ , Sr ²⁺ , Ba ²⁺ is a main component, and trivalent ions such as aluminum oxide, gallium oxide and indium oxide are introduced into this. This composition is characterized by charge compensation of Cr ions doped with a large amount of alkaline earth divalent ions such as Ca ²⁺ and Mg ²⁺ , which are the main components, and the melting atmosphere at the time of glass melting can be adjusted as necessary. The glass is melted by adjusting it to an oxidizing or reducing atmosphere to produce CrO ₂ fine particles and Cr ³⁺ , Cr ⁴⁺ in the glass melt, and then the reheating treatment is carried out, so that the Cr ions remaining in the glass Is synthesized into CrO ₂ fine particles. In this glass system, Cr ⁴⁺ ions and CrO are controlled by controlling the reheating temperature and the atmosphere gas composition.
It is possible to mix _two fine particles at the same time, and as a result, the broadband emission characteristics shown in FIG. 1 and the ferromagnetic characteristics shown in FIG. 2 are obtained.

The Cr ⁴⁺ ions formed in the melt tend to increase their content concentration in proportion to the increase in the composition ratio of the alkaline earth oxide in the glass composition. When the composition is 50 mol% or more, the tendency becomes more remarkable. Also, Cr due to divalent alkaline earth ions
^The effect of ⁴⁺ ion generation is Be ²⁺ , Mg ²⁺ , Ca ²⁺ , S
In order of r ²⁺ and Ba ²⁺ , in order to increase the production efficiency of Cr ⁴⁺ ions, Be ²⁺ and M having a relatively small ion radius are used.
It is preferable to use compositions 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 3
The thermal characteristics such as glass transition temperature and melting point can be adjusted by adding valent and pentavalent ions, and as a result, stable formation of glass can be achieved. Also, by replacing a part of Al ₂ O ₃ with another trivalent ion, it is possible to adjust the thermal characteristics similar to the effect of adding the divalent ion. On the other hand, part of CaO is PbO
The melting point of glass can be significantly lowered by substituting with, and the vitrification range can be expanded by substituting P ₂ O ₅ .

The second group is Be ²⁺ , Mg ²⁺ , C
A glass composition in which trivalent ions such as scandium oxide, yttrium oxide, and lanthanum oxide are introduced into a composition containing a carbonate or oxide of a ²⁺ , Sr ²⁺ , Ba ²⁺ as a main component. Also in this glass system, Cr ⁴⁺ ions and CrO
₂ Fine particles can be generated, and the broadband emission characteristics and ferromagnetic characteristics can be provided. This composition gives higher emission intensity than the first glass composition, but this is due to the increase in the concentration of Cr ⁴⁺ ions generated in the glass melt. The cause of this is that, in addition to the alkaline earth oxide ion, Sc ³⁺ , Y ³⁺ and La are used for the generation of Cr ⁴⁺ ion.
^This is probably due to the effective action of ³⁺ . In any case, with this glass composition, a large luminescent property can be obtained due to its active ion effect. This glass composition has a melting temperature of 50 to 2 as compared with the first group.
Although the temperature rises by 00 ° C., in this glass system as well, stabilization of the glass can be achieved by substituting a part of the composition with monovalent, divalent, trivalent, tetravalent and pentavalent ions as in the first group. The thermal characteristics can be controlled.

The third group is Be ²⁺ , Mg ²⁺ , C
It is a composition comprising a carbonate or oxide of a ²⁺ , Sr ²⁺ , Ba ²⁺ and titanium oxide or zirconium oxide. The compositional feature of this glass is that it can be formed without aluminum oxide. In this glass system as well as in the first group, Cr ⁴⁺ ions and C
The rO ₂ fine particles can be produced, and the above-mentioned broadband emission characteristics and ferromagnetic characteristics can be provided. In addition, 1, 2, 3,
By substituting a part of the composition with tetravalent and pentavalent ions,
Controls glass stabilization and thermal properties.

(Types of Dopant Materials) As the dopant materials contained in the glass compositions shown in Tables 1 and 3 to 4, metal chromium and chromium oxides (CrO, Cr ₂ O ₃ , CrO ₂ ,
CrO ₃ ), chromium sulfide (Cr ₂ (SO ₄ ) ₃ · nH
₂ O), chromium chloride (CrCl ₃ .6H ₂ O), chromium nitrate (Cr (NO ₃ ) ₃ .9H ₂ O) and chromium hydroxide (Cr (OH) ₃ .nH ₂ O) were used. Doped Cr
Ions take a valence state according to various sites in the glass, but when using the glass compositions of Table 1 and Tables 3 to 4 of the glass composition table, there is a difference in degree in all chromium dopant materials. Of Cr ⁴⁺ active ions of 1.1 to 1.7 μm
It was confirmed that the fluorescence characteristics and the ferromagnetic characteristics were obtained in a wide wavelength band over the range. In particular, glass using metallic chromium and chromium oxides (CrO, Cr ₂ O ₃ , CrO ₂ , CrO ₃ ) as dopants has characteristics that fluorescence intensity and residual magnetic flux density are much higher.

The glass composed of the glass composition and the Cr dopant material described above has a Cr ion concentration of 10 ppm.
If it is above, all will show the fluorescence spectrum similar to FIG. 1, and will be 1.2-1.7 by YAG laser excitation.
Laser oscillation was confirmed in the wavelength range of μm, and when the Cr ion concentration was 100 ppm or more, ferromagnetic properties applicable to the powder permanent magnet were exhibited.

Regarding the state of Cr in the glass, by analogy with the results of observation with a transmission electron microscope, the binding state is C.
In addition to the rO ₂ oxide, the existence of a complex oxide of chromium and a trivalent oxide such as Al, Sc, Y, and La is considered. In addition to these, in the state of ions, there are trivalent to pentavalent ions such as Cr ³⁺ , Cr ⁴⁺ , Cr ⁵⁺ . Among these, CrO ₂ oxide and Cr ⁴⁺ ion strongly influence the formation of the tetravalent ligand field as described above, the alkaline earth oxide, and the oxide composition of yttrium / lanthanum and the atmosphere during glass production. It is highly dependent on the gas composition.

That is, the glass composition has Be ²⁺ , Mg ²⁺ , C
a ²⁺ , Sr ²⁺ , Ba ²⁺ containing one or more carbonates or oxides of 10 to 75 mol%, and the heating temperature and its atmospheric gas composition during glass melting and reheating treatment. By strict control, chromium ions are oxidized or reduced to a tetravalent state, and further, CrO ₂ fine particles are generated by an oxidation reaction with non-bridging oxygen or the like, and a powder permanent magnet or a glass composition for laser / light amplification is produced. I am trying.

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

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

Next, this is higher than the glass transition point, and
By performing reheating treatment in the temperature range below the softening point,
A part of the Cr ions remaining in the glass can be produced 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 their size is about 50 in length.
˜100 nm, width about 5-20 nm. The reheating treatment temperature is 500 to 800 ° C., and the atmosphere gas composition is the same as the above atmosphere gas composition. If the production conditions are out of this range, the amount of Cr ions to be synthesized into CrO ₂ fine particles will decrease, and the particle size will fluctuate, resulting in a significant decrease in the optical quality of the glass.

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

FIG. 3 shows 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 to 100 nm and a width of about 5 nm.
Needle-like particles having a size of ˜20 nm are formed and distributed in a random state. Ferromagnetic characteristics shown in FIG. 2 this CrO ₂
Although caused by the appearance of the fine particles, the individual CrO ₂ fine particles are in a state of being covered with the surrounding glass, and therefore the CrO ₂ fine particles do not directly coalesce even during the pulverization, and the coercive force due to the magnetic interaction is rapidly increased. It has a feature that can prevent the deterioration.

Suitable magnetic powder can be obtained by crushing this glass into powder. The powder magnet of the present invention is obtained by crushing this glass into a fine powder of about 1 μm or less, and then compression-molding in a magnetic field so that the pressing direction and the applied magnetic field are at right angles,
A thermosetting organic resin is used as a binder to solidify to obtain a permanent magnet.

The powdered permanent magnet according to the present invention is different from the above-mentioned conventional magnets in that it does not change magnetically with respect to temperature changes, has excellent weather resistance, and does not lower the coercive force during powder compaction and is easy to manufacture. It is a composition of a permanent magnet.

This glass composition can be used not only as a laser oscillating material and a light amplifying material but also as a powder magnet material by itself. In particular, if this material is processed into a fiber as an optical amplification material, an optical amplifier with an optical band that can be applied to the entire wavelength range of 1.3 to 1.5 μm, which is the practical wavelength of optical communication, is realized, and the reliability of communication system is improved. It is possible to achieve economic efficiency.

In the glass composition for laser or optical amplification according to the present invention, a crucible melting method is used as a glass manufacturing method, the melting temperature is controlled within a range of 1450 to 1600 ° C., and He, Ne, Ar, and A mixed gas of an inert gas such as Kr and Xe and at least one gas selected from O ₂ , H ₂ , CO and CO ₂ gas 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 cooling the molten glass to room temperature in the atmosphere or the inert gas, 500
After reheat treatment at ~ 800 ° C for 10 hours or more,
It was gradually cooled to room temperature at a cooling rate of 0.5 to 2 ° C./min. He, Ne, Ar, Kr, X are used as this atmosphere gas.
A mixed gas of an inert gas such as e and at least one gas selected from O ₂ , H ₂ , CO, and CO ₂ gas is used.

In such a reheat treatment, the Cr ion valence in the glass can be controlled to a desired Cr ion valence depending on the treatment conditions, and the Cr ion of Cr can be controlled.
The synthetic reaction to form O ₂ oxide fine particles also proceeds. As a result, the reheating treatment increases the content concentration of CrO ₂ oxide fine particles in the glass.

According to the above-mentioned means, the glass composition according to the present invention exhibits a laser or optical amplifying action in a bulk form, but also in an optical waveguide or an optical fiber in which a region centering on the core portion is doped with Cr ions. It showed a similar effect. As a manufacturing method thereof, a conventional method can be applied.
For example, as an optical fiber manufacturing method, a rod-in-tube method or a method of putting the glass composition of the present invention in a glass tube of the present composition containing no quartz glass and Cr and drawing it 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-purpose crucible melting method is used as a glass manufacturing method. Since it is possible to synthesize CrO ₂ fine particles and Cr ⁴⁺ ions by an easy method such as controlling the heating temperature and the composition of the atmosphere gas during melting of glass and subsequent reheating, it is extremely advantageous for glass production. It has features.

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

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

In all the drawings for explaining the embodiments, parts having the same functions are designated by the same reference numerals, and the repeated description thereof 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 is a glass composition of one 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 CrO used in the powder permanent magnet according to the present invention.
FIG. 2 is a schematic view of a glass with _two fine particles dispersed therein, observed by a transmission electron microscope. In FIG. 1, the horizontal axis represents the wavelength (Wavelength) and the vertical axis represents the fluorescence intensity (Fluoresence intensity).

The glass composition for optical 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, after thoroughly mixing carbonates or oxides, which are glass raw materials, in an agate mortar, 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%. 2 to 20 ° C / min from room temperature in an atmosphere furnace consisting of
After heating at a temperature rising rate of min and holding at 1000 ° C for 1 hour to deaerate water and adsorbed oxygen in the glass raw material, 2 ° C
/ 16 to 16 at a heating rate of / min to 20 ° C / min
The temperature was controlled to 00 ° C., and the temperature was maintained at the same temperature for 30 to 90 minutes for melt synthesis. Melt-synthesized glass is 600-75
The glass melt was poured onto a mold preheated to 0 ° C. and naturally cooled to room temperature.

Next, the atmosphere gas composition is changed to He, Ne, A.
Inert gas such as r, Kr, Xe and oxygen concentration of 0.05 to
600 to 7 in the electric furnace controlled in the range of 0.1%
Hold at 50 ℃ for 10 hours, then 0.5 ℃ / min (min)
It was gradually cooled to room temperature at a rate of ~ 2 ° C / min (min). The gradually cooled glass was cut into a plate shape of 10 mm × 20 mm × 2 ^t mm, and the cut surface was polished up to the No. 4000 equivalent.

The fluorescence measurement of glass has an oscillation wavelength of 1.06.
When a wavelength range from 1100 to 1700 nm was measured by a spectroscopic optical system using cooling Ge as a detector and using YAG laser light of μm as excitation light, the same fluorescence spectrum as in FIG. 1 was obtained. The results of this glass-based fluorescence measurement are shown in Table 2.
Shown in As shown in Table 2, the fluorescence intensity is calcium oxide,
It can be seen that the composition largely depends on the magnesium oxide composition and the oxygen concentration in the molten atmosphere.

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

Glass composition A glass composition shown in Table 1 was directly added to 2 m.
The center wavelength is 1.
It was fixed in a laser cavity with a 4 μm narrow band filter. 200m of 1.06μm YAG laser light from one side
An output of 100 mw was obtained when w was incident. 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 a matrix for laser or light amplification. 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 molten atmosphere in the same manner as the above-mentioned fluorescence characteristics, and the calcium oxide composition is 50 mol% (mol%) and the magnesium oxide is 3 mol.
% Or more of a glass composition, and using a mixed gas of oxygen and 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. This significantly increased the oscillation efficiency.

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

The glass of Example 1 having a saturation magnetization of 1.2 emu / g was crushed using a ball mill or a stamp mill to prepare glass powder having a crushed 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 and make the pressurizing direction and the applied magnetic field direction at right angles, and apply force 3 tons / cm ² . Compression molding was performed under the condition of a magnetic field of 15 kilogauss (KG). This 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, coercive force was 570 oersted (Oe). It should be noted that since the density is increased by increasing the applied pressure during the manufacture of the magnet, the saturation magnetization and the residual magnetization are increased and the quality of the magnet is improved.

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

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

That is, it is shown 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 remarkably widened, and more effective control is possible as compared with the first embodiment.

The glass composition of the present invention having a saturation magnetization of 1.5 emu / g was crushed using the crusher to prepare a glass powder having a crushed particle size of 1 μm or less. Kneaded with. Next, this mixture is put into a non-magnetic mold, the pressing direction and the applied magnetic field direction are perpendicular to each other, and the mixture is heated at 120 ° C. for 1 hour under the conditions of a pressing force of 3.5 ton / cm ² and an applied magnetic field of 13 KG, and compression molding. did. This magnet has a density of 4.5 g / cm ³ and a magnetic property of saturation magnetization (4πI
s) 280 G, residual magnetic flux density (4πIr) 247 G, and coercive force 650 Oe. The powder magnet manufactured in this manner could be cut.

(Embodiment 3) In another embodiment (Embodiment 3) of the present invention, the glass composition (mo
l%) was synthesized by the same method as in Example 1 above. The characteristic of this glass system is that the calcium oxide composition is 30 mol%
The following is that aluminum oxide is not 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 above. This glass composition was also made into fibers by the method of Example 1, and laser characteristics having the same oscillation characteristics and oscillation efficiency as those of Example 1 were obtained. Also,
Even in this glass composition, the residual magnetic flux density and the coercive force are slightly reduced as compared with Examples 1 and 2, but the magnetic properties are exhibited, and as an application thereof, a powder magnet can be manufactured by the same method as described above.

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

By using the manufacturing method of the above-mentioned embodiment, it is possible to apply to the powder permanent magnet with all the above-mentioned glass compositions,
^Moreover , a laser or optical amplifier having Cr ⁴⁺ ions as the active center can be constructed.

The inventions made by the present inventor are as follows.
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, when a laser or an optical amplifier using a glass composition is formed, practical communication including 1.3 to 1.5 μm, which is the most important in optical communication, is performed. It is possible to obtain an unprecedented breakthrough laser or optical amplifier that can cover the entire wavelength range.

[Brief description of drawings]

FIG. 1 is a diagram showing an emission spectrum of a glass composition of Sample No. 18 according to 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 according to the first embodiment.

FIG. 3 CrO ₂ used in a powder permanent magnet according to the present invention
It is a schematic diagram of a 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
... Sizes of acicular CrO ₂ particles, 3 ... main glass, 4 ... CrO ₂ particles.

Claims (3)

[Claims] 1. One or more compounds selected from the group consisting of carbonates or oxides of beryllium, magnesium, calcium, strontium, barium are used.
To 75 mol% of CrO ₂ fine particles and Cr ⁴⁺
A glass composition containing an ion. 2. BeO, MgO, CaO, Sr in the crucible
10 mol% to 72 mol% of an alkaline earth oxide containing at least one of O and BaO, and metal chromium, chromium oxide, chromium sulfide, chromium chloride,
A step of blending a chromium-doped glass raw material containing one or more compounds selected from the group consisting of chromium nitrate, chromium hydroxide, or an organic chromium compound and a glass raw material; 1 from oxygen gas, hydrogen gas, carbon monoxide gas, and carbon dioxide gas
A step of heating and melting in an atmosphere of a gas selected from one or more kinds, a step of rapidly cooling the chromium-doped glass raw material, and reheating the chromium-doped glass raw material to a temperature not lower than the glass transition temperature and not higher than the softening point temperature. The method for producing a glass composition, comprising: 3. A step of crushing the glass composition formed by the method for producing a glass composition according to claim 2 into glass powder, and a step of mixing the glass powder with an organic resin raw material, and mutually A method for producing a glass composition, comprising a step of applying compression and a magnetic field orthogonal to each other to perform compression molding.