RO132655A2 - Manufacturing process and borophosphate glass product containing lithium oxide, aluminium oxide and zinc oxide, doped with rare earths and transition and post-transition metals, with magneto-optical properties - Google Patents

Abstract

The invention relates to a borophosphate glass containing lithium oxide, aluminium oxide and zinc oxide, doped with rare earths, transitional and post-transitional metals and to a process for manufacturing the same, the glass being meant to be used for making Faraday rotators or magneto-optical sensors, as well as in other applications requiring materials with magneto-optical properties. According to the invention, the glass comprises network-forming elements, expressed as mole percentage: 5...20% BO, 14...75% PO, glass network modifiers: 2...15% LiO, chemical, thermal and mechanical stabilizers: 2...20% AlO, 2...20% ZnO, together with 3...75% of the following transitional and post-transitional metal oxides that induce magneto-optical properties, supplied as such or in pairs: CoO, FeO, FeO, FeO, VO, ZrO, NbO, MoO, WO, SnO, SbO, PbO, BiO, and rare earths oxides: TbO, DyO, CeO, EuO, PrO, NdO, SmO, GdO, HoO, ErO, TmOand YbO. The process, as claimed by the invention, has the following stages: wet preparation of raw material mixture while stirring continuously up to 120...150°C, after which it is poured, while still fluid, into the melting crucible, premelting of the said mixture at temperatures ranging between 150...900°C and controlled temperature growth up to the melting of the mixture, at temperatures of 950...1300°C, melt refining, homogenization and conditioning, pouring the glass melt into pure spectral graphite moulds preheated up to the annealing temperature, annealing in electric furnace with SiC wire resistors, followed by sample processing for determining their physical and chemical properties by cutting, grinding with Si carbide of 250, 400 and 600 mesh and polishing with cerium oxide suspensions with a grain size of 800 mesh.

Description

BACKGROUND OF THE INVENTION Process for the manufacture and product of boron-phosphate bottles, containing lithium oxide, aluminum oxide and zinc oxide, doped with rare earths and transitional and posttransitional metals, with magneto-optical properties

Technical field: Applied chemistry, bottles, C b. According to WIPO: Applied chemistry, glass

BACKGROUND: Patent “Glass for Faraday rotator element” / US 3971723 A / Jul 27, 1976 refers to a boron-silicate glass, used as an element of a Faraday rotator, consisting mainly of (in molar%): 10-30 Tb2O3, 10-30 AI2O3 and 30-80 S1O2 + B2O3, provided that S1O2 ^ 15 and B2O3 = 10, plus optional components 0-5 Z1O2, 0-1 Sb2O3, 0-1 AS2O3, and 0-2 AIF3. The glass has a constant high Verdet and a reduced light absorption in the visible and infrared wavelength regions.

The patent "Faraday rotation glasses" / US 3935020 A / Jan 27, 1976, refers to boron-silicate bottles for Faraday rotators that have a high constant Greenness and low susceptibility and are obtained by introducing a high quantity of rare earth oxides into a basic borate glass. Bottles can be widely melted under standard conditions. The bottles have the following composition, in gravimetric percentages: 0-12 S1O2, 10-42 B2O3, 0-1 alkaline-earth oxides, 25-57 a rare earth oxide, 8-24 alkaline oxides, 1-7 Z1O2, 0-7 WO3, 0-2 AI2O3 and 0-0.5 tuning agent, where alkaline earth oxide is selected from CaO, BaO, ZnO, and combinations thereof, rare earth oxide is Tb4O7 or the combination of Tb4O7 and La2O3, Tb ₄ O ₇ being present in an amount of 20-45 percent gravimetric, and the alkali metal oxide is selected from the group consisting of Na2O, K2O and combinations thereof.

Patent CN1342617A / Apr 3, 2002 / "Faraday-rotation phosphorate glass with low nonlinear vity refracts" refers to a phosphatic bottle for Faraday rotator with a low non-linear screw refraction and high Tb ³⁺ content containing 17-26% Tb2O3, 70-80% P2O5, 0-6% A1 ₂ O ₃ , 0-6% B2O3, 0-6% SiO ₂ , 0-6% Na ₂ O plus K ₂ O, 0-6% BaO, 0.1- 0.8% Sb ₂ O ₃ , or 0.1-0.8% AS2O3, or 0.1-0.8% Sb ₂ O ₃ plus AS2O3. The advantages are the high Verdet constant, low nonlinear refractivity, high transparency in the visible or near infrared region and fairly good stability.

US Patent No.20020041750 / Apr 11, 2002 / "Rare earth element-doped, Bi-Sb-Al-Si glass and its use in optical amplifiers" shows a glass doped with rare earth elements, from system B12O3 — Sb ₂ O ₃ —AI2O3— S1O2, containing 1-50% molar of B12O3, which is easier to incorporate than fluorine. The glass can be manufactured using the standard melting technique of 2016 01008

12/14/2016 of the mixture of raw materials. The composition of the glass is: 1-60% molar Sb2Cb; -60% molar B12O3; 0-20% molar AI2O3; 20-90% molar S1O2; and 0-4% molar EnCb.

The patent "Preparation method of bismuth-containing paramagnetic Faraday optical rotation giass", CN 102627404 A / Aug 8, 2012 describes the method of preparation of a Faraday glass paramagnetic wheel. The preparation method provides for uniform mixing of Er2O3, B12O3, B2O3, AI2O3, SiO2, Sb ₂ O ₃ and Ζ1Ό2 to obtain the batch, melting at 1200-1400 ° C, for 3 hours, casting the melt in a graphite mold, annealing at 550 ° C for 3 hours and cooling to room temperature to obtain the Faraday rotator. The field of glass formation is extended and the melting temperature reduced. The composition is (molar%) 5-35 Er2O3, 10-38 B12O3, 5-40 B ₂ O ₃ , 15-45 AI2O3, 0-5 S1O2, 0-1 Sb ₂ O ₃ and 0-1 ZrO ₂ .

The patent "Paramagnetic Faraday rotator giass and preparation method thereof" / CN 103708726 A / Apr 9, 2014 presents a bottle for the Faraday paramagnetic rotator of composition: 20-25% molar SiC, 35-42% molar Tb2C> 3, 18-20% molar AI2O3, 16-21% molar B2O3, 1-5% molar P2O5 and its preparation method. The method of preparation comprises the following steps: uniform mixing of tetrapherbium heptaoxide, boric acid, aluminum oxide, ammonium diacid phosphate, tin oxide, and silicon carbide to obtain the mixture of raw materials, and then melting it at high temperature. in the air, and finally, the casting of the glass melt in the stainless steel mold, and careful annealing, so as to obtain the paramagnetic glass for the Faraday rotator. The preparation method has the advantage that by the oxidation-reduction characteristics of the mixture of raw materials, the low valence of the rare earth ion in the glass is ensured, the platinum crucible provides protection against corrosion, and the inclusion of platinum ions in the glass is prevented. The optical quality of the paramagnetic glass for the Faraday rotator is improved and the obtaining technology is improved and simplified. The paramagnetic glass for the Faraday rotator thus prepared, has high content in rare earths, low valence, high Verdet constant, high transmission in the visible field, simple preparation technology and industrially applicable.

Presentation of the technical problem: Silicate bottles with magneto-optical properties melt at high temperatures and have lower magneto-optical properties than those of phosphate bottles. Phosphatic bottles with magneto-optical properties melt at lower temperatures but have low chemical and mechanical resistance.

4.

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Exposure of the invention; The invention relates to a novel product, doped boron-phosphatic glass containing vitreous network formers: 5-20% molar boron oxide - B2O3 and 14-75% molar phosphorous oxide - P2O5, as well as modifiers of vitreous network: oxide de lithium - L12O, in proportion of 2-15% molar, chemical, thermal and mechanical stabilizers: aluminum oxide - AI2O3, 2-20% molar and zinc oxide - ZnO, 2-20% molar, together with oxides that induce the properties magneto-optics, in the percentage of 3-75% molar, of the following oxides, introduced alone or in pairs: of the transition metals: cobalt oxide CoO, iron oxide FeO, Fe2O3, Fe3O4, vanadium oxide V2O3, zirconium oxide, Ζ1Ό2, niobium oxide, Nb2O3, molybdenum oxide, MoO2, tungsten oxide, WO3, of the post-transition metals: tin oxide, Sn2O3, tin oxide, Sb2O3, lead oxide PbO, bismuth oxide, B12O3, ai rare earths: Tb2O3, Dy2C> 3, CeC> 2, EU2O3, PftCb, Nd2C> 3, Sm2C> 3, Gd2C> 3, HO2O3, EnQj, ΤΠΪ2Ο3, Yb2C> 3 and at the self of obtaining this new type of bottles, by the method of wet preparation of the mixture of raw materials, followed by pre-painting, melting, refining, conditioning, pouring, annealing, molding of the obtained glass.

The operations within the process of preparing the wet material mixture used to obtain the boron-phosphate bottles according to the invention are as follows;

□ Gravimetric and volumetric dosing of raw materials;

□ Introduction of raw materials into the mixing vessel in the default order;

□ Cold homogenization of raw materials, in niche, with mechanical homogenizer;

□ Partial drying mixture of raw materials, with the partial elimination of water (in quartz crucibles provided with electric stirrer with flexible shaft, on the electric hob) with continuous mixing, to temperatures of 120-150 ° C;

□ Pour the mixture, when still fluid, into the melting crucible.

The melting step is performed between 150 ° C and 700-900 ° C, with a slow increase in temperature, to eliminate gases from the mixture of raw materials and results from chemical reactions without losing the mixture of raw materials.

The melting stage at temperatures of 950-1300 ° C comprises the following technological operations:

• Melting the mixture of raw materials;

• Tuning the melt;

• Homogenization of the melt;

• Melt conditioning;

• Lower the temperature to the casting temperature.

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The molding of the glass is performed by pouring the glassy glass melt conditioned into pure spectral graphite molds, preheated in the annealing furnace, at the annealing temperature, specific to each glass composition. The molds contain parallelepiped nests with dimensions of 50x50x 10 mm, in which the melt is poured.

The annealing is performed in electric ovens for the dental technique, provided with canthal resistors (SiC wire), and the processing of the samples for the determination of the physical-chemical properties is performed by the cutting with a diamond disc, with a diameter of 100 mm. The samples cut to the required dimensions are subjected to the polishing and polishing operations.

Presentation of the advantages of the invention in relation to the prior art; Boron-phosphatic bottles containing lithium oxide, aluminum oxide and zinc oxide, as well as oxide dopants of transitional, post-transitional and rare earth elements have the advantages of lower melting temperatures and higher magneto-optical properties than glass silicates with magneto-optical properties, and compared to phosphate bottles have the advantages of chemical stability and better mechanical properties, under similar or higher magneto-optical properties. The novelty of the invention consisted in the fact that new glass materials were obtained with magneto-optical uses, combining the properties of phosphatic bottles with the advantages and novelty of the introduction of B2O3 and ZnO. As the applications of phosphatic bottles are diminished due to the reduced chemical stability, by adding trivalent ions, as a substitution of the alkaline ions, the chemical and mechanical resistance has been improved. Stabilization of phosphatic bottles was performed with B2O3 combined with ZnO and / or PbO. Dopants, oxides of transition metals, post-transition and rare earths, provide the high magneto-optical properties of these bottles, which have the advantages of combining these properties with high chemical and mechanical stability.

Boron-phosphatic volume bottles, containing lithium oxide, aluminum oxide and zinc oxide, doped with one or pairs of transition and post-transition metal oxides, or with one or pairs of rare earth oxides, have the following improved characteristics. : i) High homogeneity, throughout the volume of the glass; ii) Lack of defects of inclusions or stones; iii) Small number of gaseous inclusions and their very small size; iv) lack of defects of strips, threads, comes; v) Lack of stresses due to thermal gradients; vi) Optical transmission in visible (function of use and near UV or near IR) high, more than 80% in all the useful field; vii) high chemical, mechanical and thermal resistance; viii) Magneto-optical effect, rotating the plane of polarized light, comparable to the world level.

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Presentation of the figures in the drawings; Fig. 1. Technological flow according to the process proposed in the invention, comprising the main technological operations.

Fig. 2. Pre-melting-melting-tuning-homogenizing-conditioning program according to the invention, comprising the temperatures, duration, mixing regime, for BPM2 glass.

Fig. 3. Recovery program for BPM2 glass doped according to the method proposed in the invention, comprising the temperatures and the durations of the steps of the annealing process of the molded glass plate.

Fig. 4. Optical transmission of one of the boro-phosphatic bottles doped according to the invention, the BPM2 glass bottle.

Fig. 5. Recovery program for BPM6 glass doped according to the method proposed in the invention, comprising the temperatures and the durations of the steps of the annealing process of the molded glass plate.

Detailed presentation of at least one embodiment of the claimed invention; Example 1. The molar and gravimetric oxide composition for example 1 is the one in table 1, for glass BPM2 code, doped with Bi and Pb ions.

Table 1. Molecular and gravimetric oxide composition for boron-phosphatic glass doped BPM2 code

Glass Oxide B2O3 P2O5 It ₂ O Al2O3 ZnO B12O3 PbO Total BPM2 % molar 20 50 10 9 5 3 3 100 BPM2 % gravimetric 11.43 58.27 2.45 7.53 3.34 11.48 5.50 100

The raw materials used are of analytical purity: lithium carbonate, L 2 CO 3, aluminum oxide, AI 2 O 3, ZnO zinc oxide, phosphoric acid, H 3 PO 4, lead oxide, PbO, bismuth oxide, B12O3.

The technological flow for the process for obtaining the doped boron-phosphatic glass according to the invention is that shown in Fig. 1.

The composition of the mixture of raw materials to obtain 100 g of boron-phosphatic glass doped BPM2 code is that of table 2.

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Table 2. Composition of raw materials for 100 g glass, for boro-phosphatic glass doped BPM2 code

Glass Raw material B2O3 H3PO4 L12CO3 Al2O3 ZnO B12O3 PbO BPM2 g 8.57 75.43 5.24 5.65 2.51 8.61 4.12

The raw materials used to introduce the oxides from tables 1 and 2 into the glass melt are:

> Phosphoric acid, H3PO4 p.a., for the introduction of phosphorus oxide;

> Lithium carbonate, L12CO3, p.a., for the introduction of lithium oxide;

> Aluminum oxide, AI2O3, of purity p.a., for introducing aluminum oxide;

> Zinc oxide, ZnO, p.a., for the introduction of zinc oxide;

> Bismuth oxide III, B12O3, p.a., for the introduction of bismuth oxide;

> Lead oxide II, liturgy, PbO, p.a., for the introduction of lead oxide;

For the calculation of the composition of the mixture of raw materials, the percentage of volatilization of phosphorus oxide, 25% and lithium oxide, 15% is taken into account.

The dosing of the raw materials is carried out using the technical balance with an accuracy of ± 1 g, for the main raw materials and of the analytical balance with an accuracy of ± 10 ' ⁵ g for the dopants. Pipettes with a precision of ± 0.1 mL are used for dosing phosphoric acid. The technological operations within the process of preparing the wet material mix, used to obtain BPM2 bottles, are as follows: gravimetric and volumetric dosing of raw materials; introduction of raw materials into the mixing vessel in the default order; cold homogenization of raw materials, in niche, with mechanical homogenizer, for 15 minutes; partial drying of a mixture of raw materials, with the partial elimination of water (in quartz crucibles provided with electric stirrer with flexible shaft, on the electric hob) with continuous mixing, up to 150 ° C; pouring the mixture, when still fluid, into the melting crucible, from alumina.

The important chemical reactions that occur during the preparation of the mixture of raw materials are:

3L12CO3 + 2H3PO4 -> 2L13PO4 + 3H2O + CO ₂ (1)

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AI2O3 + 2H3PO4 -> 2A1 (PO ₄ ) + 3H ₂ O (2)

3ZnO + 2H3PO4 -> Zn ₃ (PO ₄ ) 2 + 3H ₂ O (3)

This process for obtaining the wet mixture of the raw materials for obtaining the BPM2 glass provides the advantages of a good homogenization of the raw materials in the preparation phase of the raw material mixture and also ensures the initiation of phosphates formation from the homogenization phase of the raw materials and metaphosphates from the pre-coating heat treatment phase. This process leads to shorter melting, tuning and conditioning times and helps to achieve high optical and magnetic homogeneity for the phosphatic bottles made.

The preliminary heat treatment, pre-coating - thermal conditioning of the mixture of raw materials is carried out in an electric furnace with silica bars (SiC), the mixture of raw materials being already introduced in the aluminum crucible where the melting takes place. The oven features are: maximum working temperature: 1400 ° C; heating elements: strain bars; dimensions of the enclosure: 400x300x200 mm; Automatic temperature control in the oven. The heat treatment program for the BPM2 glass is presented, together with the melting program, in Fig. 2 and table 3.

The melting takes place in the melting furnace provided with superkanthal heating elements (M0S12), with the following characteristics: maximum working temperature: 1600 ° C; heating elements: superkanthal elements; working enclosure dimensions: 280x150x150 mm; Automatic temperature control in the oven. The melting program of the BPM2 glass is presented, together with the preliminary heat treatment program, in Fig. 2 and table 3.

The melting stage comprises the following technological operations: melting of the mixture of raw materials; melt firing; melt homogenization; melt conditioning; lowering the temperature to the casting temperature.

Table 3. Pre-painting - melting - mechanical homogenization program for BPM2 glass

Time [H] Temperature [° C] Stirring speed [rot / min] 0 20 0.5 70 1 120

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1.5 170 2 two hundred 2.25 two hundred 2.5 220 2.75 240 3 260 3.25 260 3.5 280 3.75 295 4 310 4.25 310 4.5 310 4.75 310 5 310 5.25 330 5.5 350 5.75 375 6 400 6.5 450 7 525 7.5 600 8 700 9 1000 10 1250 10.5 1250 two hundred 11 1250 two hundred 12 1250 two hundred 12.5 1200 150 13 1200 150 13.5 1200 -

For the homogenization of the glass melt, a mechanically operated stirrer, equipped with a stirring body of sintered alumina of high purity, over 99% is used. The homogenization programs are established according to the viscosity of the melt, in this example the rotational speeds are 200 and 150 rot / min.

BPM2 glass molding is performed by molding the glass melt conditioned in pure spectral graphite molds, preheated in the annealing oven, at annealing temperature, specific to each glass composition, in this example, for BPM2 glass, being 500 ° C. The molds contain parallelepiped nests with dimensions of 50x50x10 mm, in which

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The annealing operation aims to eliminate the stresses due to the thermal gradients arising during the molding and cooling processes of the molded glass. The annealing is performed in an electric furnace provided with kanthal resistors (SiC wire), with the following characteristics: maximum working temperature: 1300 ° C; heating elements: Kanthal wire resistors; enclosure dimensions: 300x250x150 mm; Automatic temperature control in the oven.

The annealing program for BPM2 glass, according to the data on the characteristic temperatures and its coefficient of thermal expansion, is shown in Fig. 3.

The processing of the samples for the determination of the physico-chemical properties is executed by the cutting with diamond disk, with diameter 100 mm, to the dimensions imposed by the methods of physical-chemical analysis and of the possible subsequent uses.

The samples cut to the required dimensions are subjected to the polishing and polishing operations. They are executed on sanding machines, on metal discs covered with felt, using as silicon carbide suspensions of three finer granulations, 250, 400 and 600 mesh and finally with the suspensions of Cerium oxide of at least 800 mesh granulation, used as polishing agents.

The optical transmission for the BPM2 glass is shown in Figure 4.

Example 2.

The procedure is similar to the one in Example 1, with the following differences:

The composition of the boro-phosphatic glass in example 2, doped with dysprosium oxide, Dy ₂ O3 and terbium oxide, Tb ₂ O3 is the one presented in table 4.

Table 4. Molecular and gravimetric oxide composition for BPM6 doped boro-phosphatic glass

Glass Oxide B2O3 p ₂ or ₅ It ₂ O Al2O3 ZnO Dy ₂ O ₃ Tb ₂ O ₃ Total BPM6 % molar 20 50 10 9 5 3 3 100 BPM6 % gravimetric 11.29 57.57 2.42 7.44 3.30 9.08 8.90 100

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The starting materials for the introduction of the dysprosium and terbium oxides are dysprosium oxide, Dy ₂ O3 and terbium oxide, Tb ₂ O3 of analytical purity. The coating programs are carried out with an intermediate level at 300 ° C. The melting temperature is increased by 50 ° C to 1300 ° C. The speed of the refractory agitator is higher, of 250 and 200 rpm respectively and it is positioned closer to the bottom of the crucible. For BPM6 glass, the mixing - mixing homogenization program is the one presented in table 5.

Table 5. Pre-melting - melting - mechanical homogenization program for BPM6 glass

Time [H] Temperature [° C] Speed [R / min] agitation 0 20 0.5 70 1 120 1.5 170 2 220 2.25 240 2.5 260 2.75 280 3 300 3.25 300 3.5 300 3.75 300 4 300 4.25 320 4.5 340 4.75 360 5 380 5.25 400 5.5 425 5.75 450 6 475 6.5 550 7 700 7.5 850 8 1000 9 1300 9.5 1300 240 10 1300 240 11 1300 240

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11.5 1200 two hundred 12 1200 two hundred

The annealing program for the BPM6 glass is similar to the one for the BPM2 glass from example 1, but the annealing temperature is 480 ° C.

Example 3.

The procedure is similar to the one in Example 1, with the following differences:

The composition of the boron-phosphatic glass in example 3, doped with lead oxide PbO and bismuth oxide, B12O3 is the one presented in table 6.

Table 6. Molecular and gravimetric oxide composition for boron-phosphatic glass doped BPM8 code

Glass Oxide B2O3 P2O5 It ₂ O Al2O3 ZnO B12O3 PbO Total BPM8 % molar 5 14 2 2 2 15 60 100 BPM8 % gravimetric 100

Pre-coating programs are performed at lower speeds and intermediate levels for temperatures of 175 ° C and 275 ° C. The melting temperature is lowered by 250 ° C to 1000 ° C. The speed of the refractory shaker is 175 and 125 rpm and it is positioned higher than the bottom of the crucible. For BPM8 glass, the melting - conditioning - homogenization program is the one presented in table 7.

Table 7. Pre-melting - melting - mechanical homogenization program for BPM8 glass

Time [H] Temperature [ "C] Stirring speed [rot / mind 0 20 0.5 70 1 120 1.5 175 2 175 2.25 175 2.5 175 2.75 two hundred 3 220 3.25 240 3.5 260

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3.75 275 4 275 4.25 275 4.5 275 4.75 275 5 275 5.25 300 5.5 325 5.75 350 6 375 6.5 425 7 500 7.5 600 8 700 9 1000 10 1000 175 10.5 1000 175 11 1000 175 12 975 125 12.5 950 125 13 950 125 13.5 950 125 14 950 -

The annealing schedule for the BPM8 glass is similar to the one in Example 1, but the annealing temperature is 400 ° C.

Indication of how the invention is likely to be applied industrially. The invention can be applied industrially to obtain Faraday rotary bottles or high quality magneto-optical sensors, as well as to any applications that require materials with magneto-optical properties, the product according to the invention being obtained with a low energy consumption and mechanical, thermal and thermal resistance. improved chemistry compared to classic phosphate bottles.

Claims (5)

1. Product doped boro-phosphatic glass containing vitreous network formers: 5-20% molar boron oxide - B2O3 and 14-75% molar phosphorus oxide - P2O5, as well as vitreous network modifiers: lithium oxide - L12O, in 2-15% molar ratio, chemical, thermal and mechanical stabilizers: aluminum oxide - AI2O3, 2-20% molar and zinc oxide - ZnO, 2- 20% molar, together with oxides that induce magneto-optical properties, in percent of 3- 75% molar, of the following oxides, introduced alone or in pairs: of the transition metals: cobalt oxide CoO, iron oxide FeO, Fe2O3, Fe3O4, vanadium oxide V2O3, zirconium oxide, Z1O2, niobium oxide, Nb2O3 , molybdenum oxide, MoO2, tungsten oxide, WO3, of post-transition metals: tin oxide, Sn2O3, tin oxide, Sb ₂ O ₃ , lead oxide PbO, bismuth oxide, B12O3, rare earths: Tb2O3 , Dy2O3, CeO2, EU2O3, ΡΓ2Ο3, Nd2O3, Sm2O3, Gd2O3, HO2O3, EnCb, ΤΠΙ2Ο3, Yb2O3. The process for obtaining the product according to claim 1, which comprises the wet preparation of the mixture of raw materials, followed by pre-coating, melting, refining, conditioning, pouring, annealing, molding of the obtained glass. The process according to claim 2, wherein the operations of the process of preparing the wet material mixture used to obtain the borophosphatic bottles according to the invention are the following: gravimetric and volumetric dosing of the raw materials; Introduction of raw materials into the mixing vessel in the default order; Cold homogenization of raw materials, in niche, with mechanical homogenizer; Partial drying mixture of raw materials, with partial removal of water (in quartz crucibles provided with electric stirrer with flexible shaft, on the electric hob) with continuous mixing, up to temperatures of 120-150 ° C; Pour the mixture, when still fluid, into the melting crucible. 4. The process according to claim 3, wherein the pre-coating step is performed between 150 ° C and 700-900 ° C, with slow temperature controlled growth, and the melting stage, at temperatures of 950-1300 ° C, comprises the following technological operations: melting the mixture of raw materials; melting of the melt; melt homogenization; melt conditioning; lowering the temperature to the casting temperature. to 2016 01008 12/14/2016 5. The process according to claim 4, wherein the molding of the glass is carried out by molding the vitreous melt conditioned in pure spectral graphite molds, preheated in the annealing furnace, at annealing temperature, and annealing is performed in electric ovens for dental technique, provided with kanthal resistant (SiC wire), and the processing of samples for the determination of physical-chemical properties is performed by cutting with diamond disc, followed by polishing and polishing, with silicon carbide of 250, 400 and 600 mesh and finally with the suspensions of Cerium oxide of at least 800 mesh granulation, used as polishing agents.