EP0538365A1

EP0538365A1 - Tellurium and selenium halide-based glasses, their preparation and use

Info

Publication number: EP0538365A1
Application number: EP91913252A
Authority: EP
Inventors: Jacques Lucas; Xiang Hua Zhang
Original assignee: Centre National de la Recherche Scientifique CNRS
Current assignee: Centre National de la Recherche Scientifique CNRS
Priority date: 1990-07-12
Filing date: 1991-07-12
Publication date: 1993-04-28
Also published as: FR2664584B1; US5352639A; FR2664584A1; WO1992000926A1

Abstract

Compositions solides vitreuses de formule (I): Tew Sey Xx Zz dans laquelle: X représente au moins un halogène choisi parmi le chlore, le brome et l'iode, Z représente au moins un élément choisi parmi As, Sb et Bi, w, x, y et z représentent les pourcentages molaires respectifs des éléments Te, X, Se et Z, w étant un nombre pouvant varier de 5 à 50, x étant un nombre pouvant varier de 5 à x1, y étant un nombre pouvant varier de 5 à 80, z étant un nombre pouvant varier de 5 à z1, les nombres w, x, y et z étant tels que la somme (w+x+y+z) est égale à 100, les nombres x1 et z1 étant tels que: lorsque X représente majoritairement de l'iode, x1 = 50 et z1 = 60, lorsque X représente majoritairement du brome, x1 = 60 et z1 = 50, et lorsque X représente majoritairement du chlore, x1 = 60 et z1 = 40, étant entendu que le pourcentage molaire de l'élément Bi, lorsqu'il est présent, n'est pas supérieur à 12, et que le pourcentage molaire de l'élément Sb, lorsqu'il est présent, n'est pas supérieur à 20; leur préparation et leur application notamment dans le domaine de la transmission infrarouge.Glassy solid compositions of formula (I): Tew Sey Xx Zz in which: X represents at least one halogen chosen from chlorine, bromine and iodine, Z represents at least one element chosen from As, Sb and Bi, w, x, y and z represent the respective molar percentages of the elements Te, X, Se and Z, w being a number which can vary from 5 to 50, x being a number which can vary from 5 to x1, y being a number which can vary from 5 to 80, z being a number which can vary from 5 to z1, the numbers w, x, y and z being such that the sum (w + x + y + z) is equal to 100, the numbers x1 and z1 being such that : when X mainly represents iodine, x1 = 50 and z1 = 60, when X mainly represents bromine, x1 = 60 and z1 = 50, and when X mainly represents chlorine, x1 = 60 and z1 = 40, being understood that the molar percentage of the element Bi, when present, is not greater than 12, and that the molar percentage of the element Sb, when present, is not greater than 20; their preparation and their application in particular in the field of infrared transmission.

Description

Verre_s_à_ b_as_e_ 'halogénur_es_ de_tellure et de selenium _, their preparation and their application.

The present invention relates to new glasses based on tellurium halide, their preparation and their application in particular in the field of infrared transmission.

In French patent application 2,594,115, glasses based on tellurium halide and selenium or sulfur have been described which have good infrared transmission properties. However, these glasses have relatively low glass transition temperatures which do not allow them to be used at high temperatures. In addition, these glass transition temperatures vary only very slightly when the proportions of sulfur or selenium are varied.

It has now been discovered that it is possible to improve the properties of glasses based on tellurium halide and selenium by adding an additional constituent such as arsenic, antimony or bismuth.

It has been found in particular that it is possible to increase the glass transition temperature by increasing the proportion of this additional constituent, and that it even becomes possible to adjust the glass transition temperature to a predetermined value by adjusting the proportion of said additional constituent. It is thus possible, thanks to the invention, to obtain glasses based on tellurium halide and selenium having glass transition temperatures higher than 130 ° C., and even higher than 150 ° C. , whereas for glasses based on tellurium halide and sulfur or selenium, the glass transition temperature rarely exceeds 80 ° C.

In addition, the glasses of the invention are less brittle than glasses based on tellurium halide and selenium. They also have the advantage of making it possible to obtain solid parts by hot pressing, when the glass is in its plasticity zone, at a temperature a few tens of degrees higher than the glass transition temperature. These glasses can thus be shaped, by moderate pressure, in pyrex glass enclosures. It can be seen that the glasses of the invention, thus shaped, are capable of duplicating the polished surface of the pyrex mold, so that subsequently the polishing of the part obtained is not necessary, which allows to considerably reduce the cost prices. In addition, the glasses of the invention can be deposited in thin layers to obtain anti-reflective deposits or integrated optics. They also allow easy production of double index preforms for the production of optical fibers.

The present invention therefore relates to solid glassy compositions of formula I:

Te Se X Z (I) w y x z where:

X represents at least one halogen chosen from chlorine, bromine 10 ^e and iodine,

Z represents at least one element chosen from As, Sb and Bi, w, x, y and z represent the respective molar percentages of the elements Te, X, Se and Z, w being a number which can vary from 5 to 50, τ_5 x being a number that can vary from 5 to x. , y being a number which can vary from 5 to 80, z being a number which can vary from 5 to z. , the numbers w, x, y and z being such that the sum (w + x + y + z) is equal to 100, 20 the numbers x and z being such that:

- when X mainly represent iodine, x = 50 and

^Z l ^{= 60} '

- when X mainly represents bromine, x = 60 and z. = 50, 25 - and when x mainly represents chlorine, x = 60 and z _χ - "0, it being understood that the molar percentage of Bi, when it is present, is not greater than 12 and that the molar percentage of the element Sb, when it is present, is not greater than 20. _Q The restrictive conditions concerning the maximum antimony and bismuth content are conditions generally making it possible to obtain glasses by simple cooling of the mixture of the constituents in the molten state, without rapid cooling (without quenching).

Among the glassy compositions of the invention, there may be mentioned in particular:

- those for which X represents iodine, bromine or their mixtures; - those for which w is a number which can vary from 10 to 40 and y and a number which can vary from 5 to 65;

- those for which z is a number at least equal to 10. Among the compositions of the invention, some are particularly advantageous in that their thermal analysis does not make it possible to observe any phenomenon linked to crystallization. In other words, these compositions form glasses which are not susceptible to devitrification. Such compositions can be found in particular in the following fields: a) compositions for which w is a number which can vary from

15 to 25, x from 5 to 15, y from 20 to 60 and z from 10 to 50; and in particular for which y can vary from 30 to 50 and / or z from 20 to 40; and in particular for which y can vary from 35 to 45 and / or z can vary from 25 to 35; these compositions being in particular those for which Z mainly represents As (preferably Z represents As), and in particular those for which X represents ma mainly iodine (X preferably represents iodine); b) compositions for which w can vary from 5 to 20, x from 5 to 15, y from 55 to 65 and z from 10 to 25; in particular those for which w can vary from 10 to 20 and / or z can vary from 10 to 20; these compositions being in particular those for which Z mainly represents As (preferably Z represents As), and in particular those for which X represents mainly iodine (X preferably representing iodine) _; c) compositions for which X represents mainly bromine, w is a number which can vary from 15-25, x from 5 to 15, y from 45 to 55 and z from 15 to 25, X being preferably bromine, and in particular for which Z mainly represents As (and preferably As).

The invention also relates to a process for preparing the glass compositions as defined above.

This process is characterized by the fact that in the proportions indicated by formula I as defined above, a source of tellurium is mixed with a source of halogen, a source of selenium, and a source of the element Z, that the said mixture is heated in an inert atmosphere or under vacuum to a temperature sufficient to obtain a complete melting of the starting materials, that the liquid obtained is maintained at said temperature for a time sufficient to homogenize said mixture. liquid, that, if desired, said mixture is shaped, and cooled to obtain a glassy solid.

As sources of the starting elements, one generally uses these elements themselves. Defined compounds containing these elements can also be used as sources. For example, the source of halogen and tellurium can be TeCl, TeBr, etc.

Preferably, the preparation is carried out in a sealed tube, after having evacuated. Pyrex glass tubes can be used, for example. One can also transfer the glass in the softened state into a mold, as indicated above, to obtain by moderate pressing a solid piece of desired shape.

The temperature to which the starting material is heated can be determined in each case by routine experiments. Generally, the mixture of starting materials is heated to a temperature of the order of about 300 to 600 ° C. For cooling, quenching is generally not necessary. It is sufficient to allow the composition to cool to room temperature.

The glass compositions of the invention can also be obtained in the form of thin layers, in particular by sputtering.

They can in particular be fiberized and serve as a waveguide for the light emitted by lasers at CO 2. In addition, their wide transmission band allows them to be used in infrared radiation analysis or thermal imaging devices.

The glasses of the invention p ^'euvent particular be deposited as thin layers on vitreous substrates of varied nature. By sputtering, it is possible to produce guiding structures with index variation which can serve as a flat waveguide for integrated optics, or for coating optics, for example made of germanium, with layers of significantly lower index.

With the glasses of the invention, it is also possible to prepare double index glass preforms by one of the following two methods. According to the first method, a glass rod having a refractive index n is first prepared. , for example having a length of 100mm and a diameter of 6mm. We plunge this bar into a cylindrical crucible having an internal diameter slightly greater than the diameter of the glass rod prepared previously, for example an internal diameter of 10mm. Said crucible contains a glass according to the invention of index n (n being

, - _. less than n), the temperature in the crucible being such that this second glass is liquid and viscous. The whole is allowed to cool and a preform with two indices is obtained which can then be fiberized according to the usual techniques.

_ The second method consists in holding the bar of index n ₁ in the center of a tube having an inside diameter slightly greater than the diameter of the bar, for example 10 mm. Another glass according to the invention is then poured into the tube, with an index n "of less than n. , said second glass being at a temperature sufficient for the second glass to be in a softened state and to be poured into the tube by filling the space around the bar. The whole is then left to cool as before. The following examples illustrate the invention without, however, limiting it.

EXAMPLE 1:

Glass having the composition:

^Te 20 ^Se 60 ^T 10 ^AS 10 The starting materials are the purified elements, which are introduced, in the required proportions, into a silica tube. A vacuum is made in the part of the silica tube located above the mixture of constituents, then the tube is sealed. The tube is then heated at 350 ° C for two hours to obtain good homogenization. The tube is then allowed to cool to room temperature.

The glass obtained has a glass transition temperature, measured by differential thermal analysis, with a heating rate of 10 ° C / min. : Tg - 80 ° C. Similarly, glasses containing iodine having the following composition were prepared:

Similarly, glasses having the following composition were prepared

Similarly, glasses were prepared, containing bromine, having the following composition:

Similarly, glasses were prepared, containing chlorine, having the following composition:

Tg (° C)

90

104

122

To introduce chlorine into the starting mixtures, the required quantity of chlorine is reacted with the mixture Te + Se + As. It is also possible to use at least one chloride of these three elements, in the anhydrous state, in suitable proportion.

Claims

1. Solid vitreous compositions of formula I:

Te Se X Z (I) w y x z where:

X represents at least one halogen chosen from chlorine, bromine and iodine,

Z represents at least one element chosen from As, Sb and Bi, w, x, y and z represent the respective molar percentages of the elements Te, X, Se and Z, w being a number which can vary from 5 to 50, being a number can vary from 5 to x, y being a number that can vary from 5 to 80, z being a number that can vary from 5 to z, the numbers w, x, y and z being such that the sum (w + x + y + z) is equal to 100, the numbers x ₁ and z being such that:

- when X mainly represent iodine, x ₁ = 50 and

1 z. ≈ 60,

- when X represents mainly bromine, x- 1 = 60 and z _χ - 50, - and when X represents mainly chlorine, = 60 and _χ = 40, it being understood that the molar percentage of the element Bi, when is present, is not greater than 12, and that the molar percentage of the element Sb, when present, is not greater than 20.

2. Glassy compositions according to claim 1, characterized in that X represents iodine, bromine or their mixtures.

3. Compositions according to any one of the preceding claims, characterized in that w is a number which can vary from 10 to 40, and y is a number which can vary from 5 to 65.

4. Compositions according to any one of the preceding claims, characterized in that z is a number at least equal to 10.

5. Compositions according to claim 4, characterized in that w is a number which can vary from 15 to 25, x from 5 to 15, y from 20 to 60, and z from 10 to 50.

6. Compositions according to claim 5, characterized in that y can vary from 30 to 50 and / or z from 20 to 40.

7. Compositions according to claim 5, characterized in that y can vary from 35 to 45 and / or z can vary from 25 to 35.

8. Compositions according to claim 4, characterized in that w can vary from 5 to 20, x from 5 to 15, y from 55 to 65 and z from 10 to 25.

9. Compositions according to claim 8, characterized in that w can vary from 10 to 20 and / or z can vary from 10 to 20.

10. Compositions according to claim 4, characterized in that w can vary from 10 to 20, x from 15 to 25, y from 25 to 35 and z from 30 to

40.

11. Compositions according to any one of the preceding claims, characterized in that Z mainly represents As.

12. Compositions according to claim 11, characterized in that Z represents As.

13. Compositions according to any one of the preceding claims, characterized in that X mainly represents iodine.

14. Compositions according to claim 13, characterized in that X represents iodine.

15. Compositions according to claim 4, characterized in that X mainly represents bromine, w is a number which can vary from 15-25, x from 5 to 15, y from 45 to 55 and z from 15 to 25.

16. Compositions according to claim 15, characterized in that X represents bromine.

17. Compositions according to claims 15 or 16, characterized in that Z mainly represents As, and in particular represents As.

18. Compositions according to any one of the preceding claims, characterized in that they are in the form of solid parts, fibers or thin layers.

19. Process for the preparation of vitreous compositions as defined in any one of the preceding claims, characterized in that a source of tellurium is mixed in the proportions indicated by formula I with a source of halogen, a source of selenium, and a source of the element Z, which is heated said mixture in an inert atmosphere or under vacuum at a temperature sufficient to obtain a fusion complete the starting materials, that the liquid obtained is maintained at said temperature for a time sufficient to homogenize the liquid mixture, that, if desired, it is shaped, and that it is cooled to obtain a glassy solid.

20. The method of claim 19, characterized in that the shaping step comprises transfer to a mold to obtain by moderate pressing a solid piece of desired shape.

21. The method of claim 19, characterized in that, to obtain a double index glass preform, a glass rod is prepared which is placed in the center of a cylindrical crucible with an inner diameter greater than the diameter of the rod , said crucible containing, in the liquid and viscous state, a glass of index lower than that of the glass of said bar, and which is allowed to cool all.

22. The method of claim 19, characterized in that, to obtain a double index glass preform, a glass rod is prepared which is placed in the center of a cylindrical crucible with an inner diameter greater than the diameter of the rod , that a second glass of lower index, in the softened state, is poured into the crucible so that it fills the space around the bar, and the whole is allowed to cool.