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    • 专利摘要:
    Method of obtaining flexible glass. Thanks to the diffusion of pure cyclohexaazufre, which is a stable material in the absence of light and impurities and whose absorption peaks are in resonance with the glass, it is achieved that the mechanical properties of the glass are improved by stabilization of the product and filling of its pores to finally obtain a flexible glass. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2665816A1
    申请号:ES201631381
    申请日:2016-10-27
    公开日:2018-04-27
    发明作者:Fidel FRANCO GONZÁLEZ
    申请人:Universitat Politecnica de Catalunya UPC；
    IPC主号:
    专利说明:

    DESCRIPTION FLEXIBLE GLASS OBTAINING METHOD
    image 1
    TECHNICAL SECTOR 5
    The present invention is situated in the field of the art corresponding to:
     Thermal insulation. Thermal comfort
     Building. Heating of buildings. Windows. Glass enclosures
     Materials. Transparency of materials: refractive indices.
     Pure silica glasses, soda glass, phosphate glasses, 10 borosilicate glasses. Vehicle glasses.
     Infrared, ultraviolet radiation.
     Resistance to earthquakes
    BACKGROUND OF THE INVENTION 15
    Obtaining flexible glass is of great interest from a technological point of view, both in the transport sector and in the construction of houses or other sectors. Indeed, there are a large number of transparent and flexible plastics, but all of them have the problem of low resistance to heat or combustibility and premature aging due to environmental ultraviolet radiation. For this reason, soda glass or the like continue to maintain their presence in the market: they are cheap and age very slowly, they can be easily molded and the starting materials are very abundant. However, classic glasses have a low mechanical resistance to vibrations and when they break into large pieces they are dangerous for users. For example, in the event of earthquakes, large pieces of glass become a source of serious traumatic injuries to building occupants. Another example is found in vehicle glass that is replaced by safety glass.
    These effects are intended to be avoided by using tempered glass. A kind of safety glass, processed by heat or chemical treatments to increase its resistance compared to normal glass. The stresses generated cause the glass, when broken, to crumble into small granular pieces instead of splintering into jagged fragments. Granular chunks are less likely to
    cause injury.
    As an alternative to the previous types of glass, a flexible type of glass is proposed, capable of withstanding bending deformations without breaking.
    EXPLANATION OF THE INVENTION
    1.-The invention proposes a method of making and obtaining a flexible glass, capable of undergoing deformations without breaking by bending and which maintains the maximum of the advantages of the initial glass in terms of transparency and thermal insulation.
    2.-The invention consists of
    2.1.- Selection of materials
    2.1.1.-Select the type of glass that allows the diffusion of sulfur and retains it inside. When the sulfur diffuses, the mechanical properties of the glass are altered with loss of brittleness and the acquisition of a pseudo-plastic behavior.
    2.1.3.-The success of the process is based on the resonance between both materials, that is, on matching the absorption peaks in the different frequency ranges of the selected glass and the allotropic form of the chosen sulfur. Specifically for soda glass, the absorption peaks of soda glass and cyclohexa sulfur in the infrared range for the values 465 cm-1 and 3436 cm-1 are matched.
    2.1.2.-Since pure sulfur has a great variety of allotropic forms, the quality of the product obtained will improve as the allotropic forms of density closer to the density of glass take advantage of the sulfur (or sulfur). The best-density allotropic form is sulfur S6 or cyclohexaulfur (cyclohexasulfide).
    2.1.3.-The effectiveness of the process is associated with the stability of the cyclohexaulfur, that is, its properties are maintained and it is not altered by external agents. Indeed, its stability depends fundamentally on it not being subjected to sunlight and having very few impurities.
    2.2.-The process of diffusion of cyclohexasulfide S6 in the glass will be done in a state of melting or simple softening, depending on its properties. The S6 sulfur to be diffused will be in a liquid state since its melting point is much lower than glass. Furthermore, the process must be carried out without the presence of sunlight and under conditions that avoid contamination.
    2.3.- The result obtained is optimal when the absorption peaks of the new glass gain in intensity by incorporating appreciable amounts of cyclohexasulfide into the glass that correct the mechanical properties of the glass to make it flexible. 35
    PHYSICAL FOUNDATIONS OF THE INVENTION
    Glass is a brittle material, that is, it lacks a plastic area when it is subjected to tensile stress.
    A material subjected to bending supports tensile and compressive stresses and in the case of a brittle material, breakage would occur mainly as a result of tensile stresses. Therefore, the expression improving the flexibility of the glass means that said material gains in resistance to bending since it is capable of deforming when a bending moment is applied.
    Fragile materials such as glass stand out for having a large number of pores inside and when subjected to tensile stresses, the pores behave like 10 cracks that expand along the material in the direction in which the crack is "more sharp ”. This is the explanation given by Griffith's Theory to the mechanical behavior of brittle materials.
    The pores of the glass are usually visible to the naked eye when the material is of low quality but it is reduced in size when its quality improves. If the pores of a brittle material are filled with some kind of stable product related to its components, its flexural strength improves markedly. For example, concrete filled with a polymer retained inside its setting pores has a behavior similar to aluminum: it is not too hard but at the same time loses brittleness. twenty
    Extrapolating this conclusion to the glass we see that there is the possibility of improving its resistance to bending thanks to a product that is stable, diffuses inside without decomposing and at the same time makes it easier for the same glass components to fill the pores by reinforcing its internal bonds. . The material chosen to achieve these results is cyclohexaulfur (cyclohexasulfur). 25
    DEVELOPMENT OF THE INVENTION
    1.-Sulfur diffusion experiments in glass.
    1.1.-The experiments described in the bibliography for the introduction of sulfur in glass refer mainly to the addition of metal sulfates such as ferrous sulfate. Sulfates contaminate the glass and when they incorporate the metal, they tend to change its color. For example, the iron in ferrous sulfate gives it a reddish color, but the diffused sulfur in its interior is in excessively small amounts and with a very low or completely negligible proportion of cyclohexaulfur.
    1.2.-When normal sulfur is added to the glass without attending to the conditions set forth in the stated method, a large part of it is lost and, furthermore, it degrades, presenting a quasi-null impact on the final properties of the material.
    2.-Characteristics of cyclohexazufur or rhombohedral sulfur S6. Experimental data.
    In figures 1, 2 and 3 we observe that the allotropic form of sulfur S6 stands out for the following properties (Elemental sulfur, Author: Beat Meyer, Chemistry Department, University of Washington….) (Laura Crapanzano. Polymorhism of sulfur. 40
    Structural and Dynamical Aspects. Physics. Université Joseph-Fourier-Grenoble I, 2006. English. HAL ID: tel-00204149. https://tel.archives-ouvertes.fr/tel-0020149. Submitted 14-Jan-2008
    Physical properties It melts at temperatures between 50 and 60 ºC and is the densest of all the allotropic forms of sulfur (2.26gr / cm3). 5
    Cyclohexaulfur has its strongest absorption peaks in the infrared range for values of approximately 471 cm-1 and 262 cm-1. That is to say, of all the allotropic forms of sulfur, it is the material that has the highest density, a lowest melting point and also the absorption peaks of lower intensity have a lower value than the others (Figure 5a). In the ultraviolet range the absorption peak corresponds to values of 230 nm (Figure 4).
    2.2.-Preparation method of cyclohexaulfur. Experimental data.
    2.2.1.-Reaction of sodium thiosulfate with hydrochloric acid: The oldest method of synthesis in isolated form is by reaction of sodium thiosulfate with hydrochloric acid, however the product obtained is not pure because it has been found that 15 also contains the allotropic form S8 (cyclooctasulfur), however other ways to obtain cyclohexaulfur can be found in the literature.
    2.2.-It is obtained by the following reaction in ether.
    S2Cl + H2S4 S6 + 2HCl or by adding concentrated HCl to a solution of Na2S2O3 at 10 ° C. It decomposes 20 fairly quickly and is chemically much more reactive than S8 because the ring is more stressed.2.2.3.-Stability: Reactions are deeply affected by impurities and light. That is, cyclohexaulfur stands out for its high instability if it has 25 impurities or is affected by light. Both impurities and light alter its structure and convert it to the allotropic form S8. Experimental data. The existence of air-stable crystals of cyclohexaulfur (
    Air-Stable Cyclohexasulfur as Cocrystal
    Sugimoto, K. / Uemachi, H. / Maekawa, M. et al. Zeitschriftenaufsätze | 2013) 30
    2.2.4.- Existence of other isomers. Experimental data. In the bibliography there are theoretical works related to the existence of isomers with higher absorption peaks in the infrared range, however we have not found experimental data related to these isomers. (Nobel isomers of hexasulfur: 35 prediction of a stable prism isomer and implications for the thermal reactivity of elemental sufur. (Ming Wah Wong, Yana Steudel and Ralph Steudel. Journal of Chemical Physics, Volume 121, number 12, September 22, 2014).
    3.-Chemical properties: Cyclohexa sulfur diffuses into pure quartz 40 and soda glass. To check this possibility we compare the absorption peaks of glass and sulfur compounds.
    4.-Comparison of the properties of soda glass and cyclohexaulfur.
    4.1.-Experimental data. Density comparison at room temperature: The density of the glass varies between 2.49 and 2.2 (Figure 7) compared to the value of 2.26 gr / cm3 for cyclohexaulfur. Therefore, the densities of both are very similar.
    4.2.-Comparison of absorption peaks in the UV range. Experimental data: the peak of cyclohexa sulfur has a value of 220-230 nm (figure 4). Footnote reading of figure 5: Absorption spectrum in the ultraviolet range of cyclohexasulfide (left) and cycloheptasulfide in methanol and in methylcyclohexane.
    4.3.-Experimental data. Soda glass ceases to be transparent for wavelengths below 300 nm (figure 5c). Foot reading of figure 5c: Soda glass absorption spectrum in different bands. The 1045 cm-1 band has disappeared in the soda glass (figure 5c)
    4.4.-Comparison of absorption peaks in the IR range. Experimental data. For cyclohexa sulfur, the most important peak is found at values of 471 cm-1 (peak of greater intensity) and the lowest value at the lower peak, approximately 262 cm-1. Figure 5a. fifteen
    For soda glass the absorption peak is approximately 465 cm-1, however pure silica (quartz) also has another typical absorption peak located at 1045 cm-1 (Figures 5b). Figure caption 5b: Spectrum in the infrared band of pure silica glass with typical absorption peaks at approximately 1045 cm-1 and 465 cm-1. twenty
    Conclusion: the values of the absorption peaks of glass and cyclohexaulfur coincide closely in the infrared range.
    EFFECTS OF THE DIFFUSION OF SULFUR IN THE GLASS
    The starting point is that silicon controls the transport mechanisms involved in crystal growth and in the viscous flow of silica glasses. 25
    1.-Experimental data.
    (Diffusion processes in vitreous silica revisited Marcio Luis Ferreira Nascimento & Edgar Dutra Zanotto Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, August 2007, 48 (4), 201–217) 30
    Abstract of the cited work: We have analyzed the data from the scientific literature on the crystal growth rate, viscosity and diffusivity of silicon and oxygen between the glass transition temperature and the melting point of four classes of commercial silica glass glasses. and thin films. The self-diffusion coefficients and 35 the viscosity in these glass networks are extremely dependent on the level of impurities and much more than in multicomponent glasses, depolymerized of silicate glasses ... The explanation for this fact is that either the unbonded oxygens diffuse a lot more rapidly or perhaps silicon and oxygen with ligands diffuse from each other separately. There are no signs of decoupling 40 between the diffusivity of the silicon and the viscous flow ... Therefore, it is concluded that it is the silicon that controls the transport mechanism included in the growth of the crystal and the viscous flow within the glasses.
    2.-Application of this conclusion
    Both the sulfur diffusion process and its effects on the properties of the glass depend on the existence of a coupling between cyclohexa sulfur and the glass. Thus, the diffused cyclohexaulfur plays the role of stabilizer. Indeed, the oxygen diffusion process is catalyzed by the cyclohexaulfur 5 diffused in the glass and thanks to the glass-cyclohexaulfur resonance the coupling between silicon and oxygen is reinforced. The end result is that pores of any size tend to disappear within the glass and its final mechanical behavior is more typical of a ductile material.
    BRIEF DESCRIPTION OF THE DRAWINGS 10
    To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, a set of drawings is attached as an integral part of this description in which, with an illustrative and non-limiting nature, the following has been represented :
    Figure 1.-Properties of some allotropic forms of sulfur. fifteen
    Figure 2.- Absorption peaks in the infrared range of cyclohexaulfur.
    Figure 3.- Hexagonal structure of cyclohexaulfur.
    Figure 4.- Absorption peaks in the ultraviolet range of cyclohexa sulfur
    Figure 5a.-Absorption peaks in the infrared range of cyclohexaulfur.
    Figure 5b.-Absorption peaks of silica glass in the infrared range. twenty
    Figure 5c.- Absorption peaks of soda glass in different frequency bands (infrared and visible).
    Figure 6.- List of some properties of soda glass.
    25
    权利要求:
    Claims (4)
    [1]

    1.-Method of obtaining flexible glass "characterized in that" it comprises the following stages
    Stage1.Selection of glass capable of diffusing and retaining sulfur inside.
    Stage2. Prepare cyclohexa sulfur (cyclohexasulfide) as it is the allotrope of sulfur that meets the conditions of maximum density, density values closer to the density of glass and stability under working conditions.
    Stage 3.Diffuse the selected cyclohexaulfur in the glass in the melting or softening state and in conditions of absence of sunlight and contamination.
    [2]
    2. Method for obtaining flexible glass according to claim 1 "characterized in that" the absorption peaks of the silica glass and cyclohexa sulfur are matched in the infrared range for the values 465 and 1045 cm-1 approximately.
    [3]
    3. Method for obtaining flexible glass according to claim 1 "characterized in that" the absorption peaks of soda glass and cyclohexa sulfur are determined in the infrared range for the values 465 cm-1 and 3436 cm-1.
    [4]
    4. Method for obtaining flexible glass according to claim 1 "characterized in that" the selected glass is preferably soda glass.
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    引用文献:
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    US4908339A|1987-06-01|1990-03-13|Blount David H|Flexible glass|
    US20160002103A1|2013-03-15|2016-01-07|Schott Glass Technologies Co. Ltd.|Chemically Toughened Flexible Ultrathin Glass|
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