JPS60246242A - Halide glass for infrared transmission - Google Patents

Abstract

PURPOSE:To provide the titled glass having a specific composition containing Cd<+2>, Ba<+2>, Sr<+3>, K<+>, Rb<+> and Pb<+2> as cationic components and Cl<-> as anionic component, free from deliquescence, having high glass transition temperature, and transparent to radiation with a wavelength range extending from visible region to far infrared region. CONSTITUTION:The titled halide glass contains 34-53(mol)% Cd<+2>, 8-40% Ba<+2>, 2-30% Sr<+2>, 0-23% K<+>, 0-23% Rb<+>, and 0-29% Pb<+2> as the glass-constituting cation components, wherein Ba<+2>+Sr<+2>=11-42%, K<+>+Rb<+>=8-26% and Cd<+2>+ Ba<+2>+Sr<+2>+K<+>+Rb<+>Pb<+2>=90-100%, and 86-100% Cl<-> as the anion component, and if necessary, total <=10% cations such as Li<+>, Na<+>, Cs<+>, Ag<+>, Zn<+2>, etc. Salts of the above metals are mixed together at ratios corresponding to the above composition, and the mixture is dried, melted and cooled to obtain the objective halide glass.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a halide glass that is transparent in a wide wavelength range from visible to far infrared.

b. Prior Art Today, the applications of optical fibers, for which research and development are becoming more active, can be roughly divided into two categories: information transmission (communication) media and red-tapered single-wire energy transmission media. Materials for information transmission fibers include quartz glass, which is already in practical use, germanium (GeOg) glass, zirconium fluoride (Zrli'4) thread glass, and other materials that are currently being researched. The light transmission range of 7 Eyebars is from the visible light range to the near-infrared light range (2 to
It was blocked by Izm)f and could not be used as an energy transmitter.

here? Transmits optical energy from mid-infrared to far-infrared of 1 rm or more (if the fiber is made of a transparent material, it can be oscillated from a CO2 laser (wavelength: 10.0cm), CO laser (wavelength: jj7zm), etc.). It has been developed because it can be applied to optical waveguides for medical and industrial processing equipment.

There are three energy transmission fibers reported for VC to date: halide crystal, chalcogenide glass, and metal hollow waveguide.

As a halide crystal, thallium halide (TVBr-
TVI), polycrystalline silver halide (AgCl-AgBr), and single crystalline cesium iodide (C6I). It is said that it is difficult to reduce the loss due to the following reasons, and the process for both sounds is extremely complicated.

On the other hand, it is difficult to reduce the loss of lucogenide glass due to its structural defects, which are the essential characteristics of the 4V4 material. The limit was also 5 to 9 μm.

Further, metal hollow waveguides have disadvantages in that the manufacturing process is complicated, that they cannot be manufactured in a length of several meters or more, and that it is extremely difficult to reduce transmission loss.

It is said that the most promising material for energy transmission fibers is non-7) compound halide glass. That is because chlorine, bromine, and iodine have very large atomic weights, so most of these halide compounds are
3 tt m or more 1. It has the property of being transparent up to the far infrared, and if it is a glass material, the scattering loss seen in crystals is extremely small, there are no structural defects like chalcogenide glass, and it is expected to simplify the manufacturing process. This is to be done.

However, the reality is that no glass has yet been reported that is transparent to the far infrared region of 10 μm or more and is stable enough to be made into fibers. ZnC12) glass has a significant deliquescent property, making it difficult to put it into practical use.
Since the glass transition temperature of r2) type glass is as low as 0°C or less, there is a risk that it may soften or crystallize during power transmission.

Problems to be Solved by the Invention The present invention has been made in order to eliminate the various drawbacks listed below.
The object of the present invention is to obtain a halide glass that is bright across C, does not exhibit deliquescent properties, has a high glass transition wettability 1f, and is easy to manufacture.

Means for Solving the Problems The present invention uses cadmium ions 3q~j3 barium ions za~rt as cationic components constituting glass.

Strontium ion 2~30 Potassium ion 0~. 23 Rubidium Ion 0~23 Lead Ion 0~. 29 However, barium ion + strontium ion//~genokalium ion + rubidium ion - 2J cadmium ion + barium ion 10 strontium ion + potassium ion 10 rubidium ion + lead ion 90 to 100 mol% of each, and constitutes glass This halide glass for transmitting red i-rays is characterized in that the proportion of anion components is 100 mol%.

Here, even if ca, Ba, and sr exist in the glass together with Cl ions and the like, the wavelength is S~/3
1.4Sr is used as the main component of the glass of the present invention because it has no absorption 1 (Y) in the infrared region of /I m and does not cause deliquescent properties in the glass. The tendency towards vitrification can be reversed by coexisting with
It is an essential component of the present invention.

The content of Cd as a cation component for constituting the glass of the present invention is 3M-! 3 mol%, the Ba content is g-uo mol%, the Sr content is 2 to 30 mol%, and the combined Ba and 3r content J1 is 77 to 72 mol%
It is.

Furthermore, the content of each cation component is Cr34IO~SO mol%, Ba/2~31. mol %, Sr q-23 mol 1, where the sum of Ba and Sr is limited to 20-3 g mol %, and is further stabilized by keeping the molar ratio of Ba and Sr from q to 1 to 3 to 2. A glass body can be obtained.

If the content of each component of C(] and Ba5Sr is out of the above-mentioned limited range, the rate of crystallization during the cooling process from the melt increases, making it difficult to obtain a stable glass body.

Furthermore, even if K, Rb, or Pb used as a cation component for the glass forming aid exists in the glass together with halide ions such as Cl ions, it has no absorption in the infrared region of wavelengths 2.5 to 20.11+71. Moreover, it is a component that is preferably included in (9) -m- in the glass since it does not cause deliquescent properties in the glass.

The content of K as the cation A/Hh for constituting the glass of the present invention is 0 to 23 mol%, and the content of Rb is:'; 41
it is 0 to 23 mol%, and the content of K and Rb is
Fi! The total amount is J-26 mol%. In addition, the content of each cation component is KJ~/2 mol%, Rb3~72 mol%.
, where the sum of K and Rb is 10-20 mol% KqJs,
! By maintaining the molar ratio of I and K to Rb at 1:3 to 3:/ (.), a more stable glass body can therefore be obtained (C). ↑t. As for the cation composition for constituting the glass of the present invention), the content of PB is 0 to 29 mol%, preferably 1. ,
, <+; 1- to /1 mol%. K, Rb, Pb
If each of the cationic components falls outside the above-mentioned range, the rate of crystallization during the cooling process of the melt for glass production increases, making it difficult to obtain a stable glass body.

In addition, the glass of the present invention may contain cation components such as Li, Na, Os, Tl, Ag, Znr, r, etc. within a range that does not change its infrared filtration properties and stability against crystallization. can be added to.

(10) The h IJrl iJ ffl□ R'+ is the Li ion O~g, the Na ion 0~10. Cs ion 0~g
, TI ion θ~10. Ag ion 0~g, Zn
The ions are 0-g (unit: mol %), and the total of all these additives is 70 mol % or more. Containing each additive n0 more than each limited range, or combining all additives
If it exceeds 10 mol %, the melt during glass production becomes cloudy and tends to crystallize, resulting in the loss of the properties of the glass of the present invention.

Chloride ions are preferably used as the anion component for constituting the glass of the present invention, but a portion of Br1I
It is possible to substitute other halogen ions such as. Here, the proportion of the main anion component constituting the glass of the present invention is 6 to 700 mol% of C1. Here C1
If the content is less than 6 mol %, the melt becomes cloudy and tends to crystallize. The content of 13r, which can be substituted, is preferably 0 to /q mol%, and the content of 13r is preferably 0 to 10 mol%. Here f3
If the contents of r and ■ exceed the double-limited range, the melt becomes cloudy and tends to crystallize.

Next, the present invention will be explained in more detail by referring to an embodiment.

isub(/20) for halide compounds used as raw materials for glass
Highly pure 1θ anhydrous crystals dried at 2°C in a dryer were used. CdCl21 (-le%, Bacg22
CdCl2-BaCl2-8r prepared with a ratio of 1 mol%, 5rG129% + KClg%, RbClff mol%, and PbCl2 1 mol%.
C12-KCl-RbC1-PbC12'IJJ and gold powder were placed in a quartz test tube with a diameter of 10 mm and a length of t mm, and dried at 200° C. for 1 hour in a chlorine gas atmosphere. After that, reduce the furnace temperature to 320°C [7
The mixed powder was melted and melted for about 4 hours while blowing 10 cc/min of chlorine gas into the melt.

Ta. After that, stop the chlorine and add 10cc of dry nitrogen per minute to about 70℃.
It was blown into the melt for a minute. The resulting melt was preheated to isooC and had a parallel spacing of about 9.1 mm/mm. Inside 1
1) and was slowly cooled at a rate of 1/min/C.

The X-ray diffraction pattern of the obtained quenched body is shown in Figure 7 (al). As is clear from Figure 7 (al), sharp peaks seen in the crystalline case were observed in this quenched body. This material was confirmed to be a glass body.

In addition, differential thermal analysis of this material revealed that it was 21 yen 1.
As shown in , a glass transition point (Tg) was observed around 763°C, and this also confirmed that this material was a glass body. Furthermore, an infrared transmission characteristic diagram of this material measured by the direct transmission method is shown in FIG. From Figure 3, this material has a wavelength of 2. It was found that there was no absorption over the range of S to /Sttm. Taking out Figure 3, 2
Even at a distance of 4 to 15 μm, a decrease of 20 to 2 S% in transmitted light is observed, but this is thought to be due to the irregular size @JVC caused by imperfections in the sample surface, and is not considered to be an essential absorption. do not have.

In addition, even if this material is left in air at temperatures above SO°C, no change in surface quality is observed, and even if it is left in the air at room temperature, the surface will only slightly deform, and no deliquescence will occur. Not observed at all, Uta.

Example 2~// Using exactly the same raw materials as Example//-4 yo) shown in Table 1
C (3C12-BaC12-
The SrC12-KCI-RbC1-PbC12 mixed powder was dried, melted, and cooled in exactly the same manner as in Example/.
A glass material having a thickness as shown in Table 1-4 was obtained. The fact that this material is in a glass state is confirmed by the fact that no scattering characteristic of anisotropic crystals is observed when observed under a polarizing microscope, that sharp peaks characteristic of crystalline materials do not appear in the X-ray diffraction pattern, and that Tg is observed by differential thermal analysis. 1ii1 edict was given in such a way as to be done. Table 1 shows the Tg of each glass measured by differential thermal analysis. When looking at all the infrared tsI3 transient characteristics of each material, the wavelength was 2.3~/Sμ as in Example 1.
No absorption occurred in the m range. As a representative example, the infrared transmission characteristics of the material of Example λ are shown in FIG. In addition, the weather resistance of each of the materials obtained in Examples 2 to 1 is as follows:
The results were similar to J, and no deliquescent properties were observed.

Examples 72-31 Drying at 720°C for 211 minutes or more in the same manner as in Example 1
The mixed powders of Examples/2 to 3/ were prepared using the various raw materials shown in Table 1 in the proportions shown in Table 7, and were dried, melted, and cooled in substantially the same manner as in Example 1. A thick glass material as shown in Table 1 was obtained. Confirmation that the material was glassy was performed in the same manner as in Examples / to //. However, the atmosphere during melting was a chlorine atmosphere in Examples 72 to 7, and a nitrogen atmosphere in Examples /g to 3/. The weather resistance of these materials was not significantly different from that of the materials in Examples/Examples, and no deliquescent properties were observed.

Comparative Examples/~j Each of the mixed powders of Comparative Examples/~j prepared in the proportions shown in Table 1 using the same raw materials as in Example/ was dried, melted, and cooled in the same manner as in Example/. Thickness 0, . A material with an off-white color of less than 2 mm was obtained. These materials were found to be crystalline since sharp diffraction peaks were observed in their X-ray diffraction patterns. As a representative example, the X1 diffraction patterns of Comparative Example/and S are shown in FIGS. 7(b) and (C)K. Further, the infrared transmittance of these materials was below j% (15) in the wavelength range of 2.5 to 25 μm.

f As described in detail of the invention, the infrared transmitting halide glass of the present invention was able to transmit infrared rays with wavelengths up to lj μm. In addition, it was possible to relatively easily produce sheet glass with a thickness of 1 mm or more, and it showed a high glass transition point of 730"C or more. For the above reasons, the halide glass for infrared transmission of the present invention has a wavelength of IO 0. Not only can it be used for power transmission of CO2 laser beams of 0pm and CO2 laser beams of 3., !11m, etc., but it can also be applied to infrared fjl wetness temperature optical waveguides in low-temperature areas.

It is an X-ray diffraction pattern of the material of Comparative Example J. Figure 2 shows Example 1
It is a differential thermal analysis curve diagram of the material. FIG. 3 and FIG. 1 are infrared transmission characteristic diagrams of Example/and λ, respectively.

(/9)

Claims (3)

[Claims] (1) Cadmium ions as cationic components constituting the glass 3'l~S3 Barium ions gtIO Strontium ions 2~30 Potassium ions O~23 Rubidium ions 0~23 Lead ions 0~29 However, barium ions + strontium ions Sum ions l/~q, 2 Potassium ions + Rubidium ions ~26 Cadmium ions + Barium ions + Strontium ions + Potassium ions + Rubidium ions + Lead ions 90~100 (/),. 4 mol %, and the proportion of the anion component constituting the glass is chloride ion gt ~ 100 mol %.
'Id glass for 8 rivers. (2) Cadmium ion qO~SO barium ion A ion /2 to 3t strontium ion 'a-, 25 car. Mui A S~/2 Rubidium I A-> 3~/, 2 Lead ion 2~/l However, barium ion 1 sl [, + Nchiu 13 ion 20~3
g barium ion 1sl', runo, ion 3/2~
q Potassium ion rubidium ion (2) Cadmium ion + barium ion 10 strontium ion + potassium ion 10 rubidium ion + lead ion 90 to 100 mol% each, and the proportion of anion components constituting the glass is chlorine ion gt The halide glass for infrared [H4] according to claim 1, wherein the amount is 100 mol %. (3) As cationic components constituting glass: Lithium ion 0-g Sodium ion 0-10 Cesium ion 0-g Thallium ion θ-10 Silver ion 0-g dI8 Lead IA 0-g However, Lithium ion + Sodium ion The halide glass for transmitting infrared rays according to claim 7 or 2, having a mol% of cesium ions + thallium ions, silver ions, and zinc ions. (tl Infrared rays according to claims 1 to 3, which have bromine ions O~/4' iodine ions 0-10, provided that bromine ions + iodine ions O-1 each mol% as anion components constituting the glass. Halide glass for transmission.