JPH0446033A - Production of chalcogenide glass - Google Patents

Abstract

PURPOSE:To obtain chalcogenide glass having high IR transmissivity, superior weather resistance and mechanical strength by heat-treating chalcogenide glass based on S and/or Se in a quartz glass vessel while feeding a gaseous mixture of inert gas with gaseous halogen into the vessel. CONSTITUTION:Chalcogenide glass based on S and/or Se is put in a quartz glass vessel and heated to the softening point or above while feeding a gaseous mixture of inert gas with gaseous halogen into the vessel. The feed of the gaseous mixture is then stopped and the vessel is evacuated while continuing heating. The inert gas is preferably nitrogen, argon or helium and the gaseous halogen is preferably gaseous chlorine. The pref. volume ratio of the gaseous halogen to the inert gas is 10-100,000ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing chalcogenide glass which has low absorption by S-H, 5e-H, O-H, etc. and has excellent infrared transmission characteristics.

[Conventional Technique #J] Chalcogenide glass is attracting attention as a material for infrared transmitting fibers. Among them, glass fibers containing sulfur (S) or serene (Se) as their main components are useful for low-temperature temperature measurement, gas analysis, and c.

Applications are being developed in various fields such as laser power transmission. The length of fibers used in these fields is from several meters to several tens of meters, and it is desirable that the fiber transmission loss be less than 1 dB/m.

However, in glasses whose main components are s and se, hydrogen or water is S-H, 5e-H.

It is contained as an impurity in the form of 0-H and causes strong absorption in the wavelength range of 2 to 6 μm, so depending on the wavelength, the loss may be 10 dB/I11 or more.

In order to remove such impurities, it is necessary to sufficiently purify the glass raw materials and the glass itself, and various methods have been studied in the past, among which vacuum distillation is said to be effective. However, the vacuum M distillation method can relatively easily remove metal impurities such as iron, nickel, and cobalt among the impurities contained in raw materials or glass;
Hydride such as -H%5e-H and water (◯-H) cannot be sufficiently removed even if the distillation is repeated multiple times.

As a means to efficiently remove hydrides such as S-H, 5e-H and moisture (○-H), 82C12 or 5e2C
] It is known that S or Se can be distilled in a chlorinated gas atmosphere of grade 2 (Japanese Patent Application Laid-Open No. 58-120538).
). However, the liquid S C1 used in this method
or 5e2C[2 is an extremely unstable substance, so
The distillation operation is difficult, and trace amounts of halogen elements remain in the resulting S or Se, so when chalcogenide glass is created using these as raw materials, the weather resistance and mechanical strength of the glass are reduced. there were.

[Problems to be Solved by the Invention] In order to eliminate these drawbacks, the present inventors melted a chalcogenide glass raw material in a mixed gas flow of an inert gas and a halogen gas, and then distilled it while degassing under vacuum. proposed a method for purifying chalcogenide glass raw materials, 'FT Application No. 1983-277330, 1988.
(filed on January 4th). This results in 5−)− in the glass.
Loss due to absorption of foreign substances such as 1,5e-H and 0-H was reduced to 1/10 or less of the conventional value.

However, in the case of this method, it has been found that the quality of the glass fiber obtained will not be constant unless the atmosphere during blending, the cleaning of the glass synthesis container, and the atmosphere during the synthesis process are extremely strictly controlled. For example, when glass is synthesized under conditions where the humidity of the outside air is 80% or more, water is incorporated into the carnigenide glass during the synthesis process, and the transmission loss due to absorption of impurities clearly increases.

The present invention is a chalcogenide glass with high transmittance, especially S-
Non-KAgI such as H, 5e-H, O-H! J! It is an object of the present invention to provide a new method for producing chalcogenide glass that has a low temperature coefficient and excellent weather resistance and mechanical strength.

[Means for Solving the Problems] The above object of the present invention is to store chalcogenide glass containing at least one of smelt or selenium as a main component in a quartz glass container, and to store an inert gas and a halogen gas inside the container. This is accomplished by heating the chalcogenide glass above its softening point while flowing a mixed gas with it, then stopping the mixed gas and evacuating the inside of the glass container while continuing to heat the glass.

That is, in the method for producing chalcogenide glass of the present invention, S- present in chalcogenide glass containing sulfur, selenium, or at least one of them.
By reacting impurities involving hydrogen atoms such as H, 5e-)-1, and ○-H with a halogen gas (indicated by X here) at a temperature higher than the melting point of the glass, HX is generated,
It is characterized in that HX or unreacted X is then removed from the glass under vacuum.

The quartz glass container used for refining is placed in the melting chamber and the first trap! , second trap! It is desirable to separate the

In other words, the raw glass is melted while flowing a mixed gas of inert gas and halogen gas inside the container! The chalcogenide glass melt is transferred from the first trap chamber to the second trap chamber by distillation, and then the flow of the mixed gas into the quartz container is stopped, and while the inside of the quartz glass container is vacuum degassed, the chalcogenide glass melt is transferred from the first trap chamber to the second trap chamber. By distilling and moving to the trap, halides such as Se C[2 and S2''2.3 unreacted halogens remaining in the chalcogenide glass can be removed more effectively.

Chlorine gas is preferred as the halogen gas used in the present invention, but when chlorine gas and a chalcogenide glass melt containing dioxium, selenium, or at least one of them are brought into direct contact, the two react violently within a short period of time. and chlorides of glass constituents, such as AsCl,
Since large amounts of Gec14, 52C12, Se C12, etc. are produced, not only does the composition of the glass change significantly, but even if the glass is subsequently distilled under vacuum, these chlorine compounds or unreacted chlorine cannot be sufficiently removed. There are cases. Therefore, it is usually preferable to use a halogen gas diluted with an inert gas. The inert gas used in the present invention is preferably helium gas, nitrogen gas or argon gas, and the volume ratio of halogen gas to inert gas is Fi
Although it depends on the purity of chalcogenide glass before manufacturing,
10pt) m or more car) 500000I] Dm below, good ma L < ha 1000pl] mu u and 1ooo
The range is preferably ooppm or less. When the volume ratio is lower than the lower limit of the above-mentioned limited range, impurities such as S-H, 5e-H, and O-H in the chalcogenide glass after purification may not be sufficiently removed. In addition, if the volume ratio is higher than the upper limit of the above-mentioned limited range, the composition of the glass may change, or S C1 may be present in the chalcogenide glass raw material after purification.
, Se3C12, etc., or unreacted halogens remain, and when carnigenide glass is produced using these raw materials, the weather resistance and mechanical strength of the glass may decrease.

[Example] Next, the present invention will be explained in detail.

Example 1 FIG. 1 is a sectional view of an anhydrous quartz glass container made of II used in this example. Here, 1 is the melt to melt the chalcogenide glass before purification! ! ! , 2 is a first trap chamber for trapping the glass vapor moving from the melting chamber by distillation, and 3 is a second trap chamber for trapping the glass vapor moving from the first trap drop by vacuum degassing distillation.

First, melt = 1 before refining A S 2 S 3 glass 4
was introduced into the quartz glass container through the gas inlet 5, and the inside of the quartz glass container was sufficiently replaced with argon gas. After that, from the same gas inlet port 4, the purity 9
9.99999% chlorine gas 1000010000p
While introducing p-containing argon gas at a flow rate of 50 cc/win, the melting chamber 1 was heated from room temperature to 7 using a heating beater 7.
The temperature was raised to 00°C in 2 hours. This allows As2S3
However, the last 4 moved completely to the 1st trap to 2. Thereafter, the gas inlet 5 was closed, the entire interior of the quartz glass container was reduced to 10'torr through the gas outlet 6, and the temperature of the first trap chamber was raised from room temperature to °C over 12 hours.

As253 collected in the second trap chamber in this way
A Teflon clad fiber with an outer diameter of 400 μm was made using glass, and its transmission loss was measured.
As shown in the figure, with a wavelength of 41 μm [f7) S-1-if,
: Due to noise peak 2 dB/m, 2.9gm 〇-8
A minimum loss of 0.99 dB/m was achieved at 2.5 em and 3.5 g m.

Example-2 Using quartz glass vessels with the same mouth shape as in Example-1,
” 15Δ52oSe65 glass was purified using the same procedure as in Example-1. However, when distilling from the melt! 1 to the first trap to 2, the temperature of the melting chamber 1 was raised from room temperature to 800 ° C. During distillation from the first trap! 2 to the second trap! 3, the first trap chamber 2 was heated from air temperature to 700° C. in 12 hours using a rotor 8.

Ge15A collected in the second trap to 3 in this way
A Teflon-clad fiber with an outer diameter of 400 um was fabricated using S2oSe65 glass, and its transmission loss was measured. As shown in Figure 3, a peak of 526 B/lll due to 3e-Hl:E around a wavelength of 45 um was obtained. A minimum loss of 02 dB/m was achieved at 3 μm and 6 em.

Comparative Example-1 A Teflon Clarad fiber was prepared using the unpurified AS283 glass used in Example-1 as it was, and the transmission loss was measured, as shown in Figure 4. The peak due to S-H near the wavelength 4.1 μm is 10 dB/ffl, and the lowest loss is 0 at 2.5 μm.
．． There was 5dB/l1lr.

Comparative Example-2 Ge, 5AS2oSe1, used in Example-2 before purification
A Teflon clad fiber of the same size as in Example 2 was prepared using glass as it was, and its transmission loss was measured.
-Hl,: the resulting peak was 72 dB/m and the lowest loss was 0.4 dB/m at 6 μm.

[Effect of the invention] According to the method of the invention, S
Chalcogenide glass with high infrared transmittance, especially without using C1 or Se C12, has a low concentration of impurities such as S-H, 5e-1〇-H, etc., which exhibit strong absorption in the wavelength range of 2 to 6μ tiles, and Chalcogenide glass with excellent weather resistance and mechanical strength can be easily produced.

[Brief explanation of the drawing]

Figure 1 shows the anhydrous silica glass purification vessel used in the present invention, and Figures 2 to 5 show the transmission loss spectra of the fibers obtained in Examples-1 and -2 and Comparative Examples-1 and -2, respectively. It is. . 1: Melting chamber, 2: First trap chamber, 3: To the second trap, 4: Chalcogenide glass before purification, 5: Argon gas and halogen gas inlet, 6: Gas outlet, 7: Melting! Heater 8: First trap! Heating Heater Non-oxide Glass Research and Development Co., Ltd.

Claims (4)

[Claims] (1) Chalcogenide glass containing at least one of sulfur or selenium as a main component is stored in a quartz glass container, and the chalcogenide glass is softened while flowing a mixed gas of an inert gas and a halogen gas into the container. 1. A method for producing chalcogenide glass, which comprises heating the glass container to a temperature above a point, and then, while continuing the heating, stopping a mixed gas and vacuum degassing the inside of the glass container. (2) A quartz glass container is placed in a melting chamber, a first trap chamber,
The chalcogenide glass is separated into a second trap chamber, and the chalcogenide glass is moved from the melting chamber to the first trap chamber by distillation while flowing a mixed gas of inert gas and halogen gas.Then, the mixed gas is stopped and the inside of the quartz glass container is removed. 2. The method for producing chalcogenide glass according to claim 1, wherein the chalcogenide glass is distilled and transferred from the first trap chamber to the second trap chamber while being vacuum degassed. (3) The method for producing chalcogenide glass according to claim 1 or 2, wherein the inert gas is helium, nitrogen, or argon, and the halogen gas is chlorine gas. (4) The method for producing chalcogenide glass according to claim 1, 2, or 2, wherein the volume ratio of the halogen gas to the inert gas is 10 ppm or more and 100,000 ppm or less.