JP5832266B2 - Method for producing glass, especially glass ceramic - Google Patents

Description

  The present invention relates to a method for producing Sn-containing glass.

  In principle, the production of glasses widely used in the industry is generally known with regard to their composition and their intended use. In the past several decades, particular attention has been given to producing glass ceramics, and thus the materials that connect between glass and ceramic. In addition to producing and shaping the glass melt, in the case of glass ceramics, at least partial crystallization is achieved by controlled nucleation in the glass melt using a suitable heat treatment.

Here, special nucleating agents are used, including in particular noble metals and oxides and phosphates. For lithium aluminosilicate glass ceramic (LAS-GC), titanium dioxide (TiO ₂ ) and zirconium dioxide (ZrO ₂ ) are actually preferably used as nucleating agents. When manufacturing LAS-GC, technical raw materials are preferably used for economic reasons, apart from making it inevitable contamination of LAS-GC with ferric oxide (Fe ₂ O ₃ ). Is done. A typical Fe ₂ O ₃ content is at least 150 ppm, often above 200 ppm. During their Fe ₂ O ₃ content, inevitable interactions between ferric oxide and titanium dioxide added for nucleation occur in LAS-GC. The result is a clearly visible brown stain. Therefore, if it is desired to control brown stains (and associated raw material costs) with the same Fe content, the Ti content of the glass must be reduced completely or partially. An equimolar amount of SnO ₂ is ideally suited to replace TiO ₂ as a nucleating agent because SnO ₂ is observed as a stain without causing any interaction with iron, This is because it also acts as a nucleating agent.

Thus, a glass melt with stannic oxide (SnO ₂ ) added as a nucleating agent results in a glass or glass ceramic with very little intrinsic color. Therefore, the SnO ₂ system is particularly important when using a glass ceramic when high transparency is required. Furthermore, SnO ₂ is also used as a fining agent in the production of glass, ie to expel bubbles from the finished molten glass.

In this case, concentrations starting with 0.1 mol% are usually used for SnO ₂ as fining agent. When using SnO ₂ as a nucleating agent, its concentration is generally higher than to ensure only the fining operation, at least 0.5 mol% and above 0.7 mol%. For tin (Sn) -containing glasses, if the concentration exceeds the range of 0.2 mol%, difficulties may arise in the formation of an excessively high devitrification upper limit (UDL), especially in contact with Pt materials.

Since tin can be dissolved in the glass as tin oxide (SnO) and stannic oxide (SnO ₂ ) in two different redox states at the same time, the crystallization tendency of the tin (Sn) containing glass is Besides the content and temperature, it depends on the redox state of the glass.

The critical temperature range is due to the contact temperature between the glass and the molding material and is usually adjusted to maintain the glass viscosity range required for the molding process (glass temperature = _VA ). The condition for maintaining the molding process window obtained therefrom is that the temperature difference between the higher devitrification temperature and the glass temperature is less than zero: UDL- _VA <0.

Methods for producing glass in a production system comprising platinum or molybdenum are known from US Pat. No. 5,785,726 and from WO 98/018731. There, the hydrogen partial pressure is adjusted outside the production vessel or inside the production vessel with respect to the hydrogen partial pressure in the glass. In this case, the number of bubbles on the surface can be adjusted or reduced, respectively. This is achieved by pre-setting a high hydrogen partial pressure outside the container so that the hydrogen does not flow out through the walls of the platinum production container. Thus, oxygen enrichment in the interface region between glass and platinum is avoided. By avoiding oxygen enrichment at the interface, bubble formation is suppressed as much as possible. Such adjustment of the hydrogen vapor partial pressure can be made to such an extent that it completely or partially replaces the usual protective effect of fining agents, in particular arsenic oxide (As ₂ O ₃ ). However, this gas treatment has not been fully studied with regard to avoiding crystallization.

US5785726 WO98 / 018731

  The object of the present invention is therefore to enable a molding process for glass production, in particular of lithium aluminosilicate glass ceramics, ensuring an acceptable viscosity for glass melts with a high tin content. It is.

  This problem is solved by the contents of claim 1.

Accordingly, a method for producing glass or glass ceramic, in particular tin-containing glass, and / or tin-containing lithium aluminosilicate glass ceramic (LAS-GC), the step of producing a glass melt, shaping the glass melt A method is provided that includes a step, a cooling step, a stress relieving step, and a post-treatment step (including ceramming). The method requires and / or is required for an object that contains, guides, or is introduced into the glass at the glass interface to produce reducing conditions for the forming process. In the medium, the dominant oxygen partial pressure (p _O2 ) is locally adjusted to avoid the dissolution of tin-containing components from the glass.

  Therefore, according to the present invention, the redox state can be adjusted in the glass melt.

According to the present invention, by setting the reducing condition in advance, the higher devitrification temperature can be selectively adjusted, particularly reduced. Glass or LAS glass ceramic that is not sufficiently melted can be produced. According to the present invention, the critical temperature difference (UDL- _VA ) between the higher devitrification temperature and glass temperature is not only material specific based on composition but also process specific based on redox conditions. Is regarded as.

  According to the present invention, the solubility of tin is adjusted by providing reducing conditions so that the dissolution of tin agglomerates or tin-containing components from the glass, especially the dissolution of stannic oxide or metallic tin, Compared to normal conditions, it is reduced and especially avoided or suppressed as much as possible.

  The invention advantageously enables the shaping of lithium aluminosilicate glass ceramics using platinum parts, in particular the drawing and rotation, while avoiding undesired crystallization phenomena in the glass and glass ceramic.

  According to the invention, the local oxygen partial pressure is at least in the vicinity of the device, for example in the platinum contact area, or in the withdrawal nozzle in contact with the glass and / or glass ceramic, or in their pre-product that is also present in molten form. In the case of glass and / or glass-ceramic manufacturing processes and subsequent processing, it should be understood as the dominant oxygen partial pressure.

According to one embodiment of the present invention, the oxygen partial pressure is adjusted to reduce the accumulation of stannic oxide (SnO ₂ ) and / or tin (Sn) agglomerates. The oxygen partial pressure may preferably be adjusted so that liquid metallic tin (Sn) agglomerates are reduced. In this case, process parameters, preferably oxygen partial pressure as a function of temperature, can also be adjusted to avoid liquid tin dissolution at the glass surface.

In a preferred embodiment of the method according to the invention, the oxygen partial pressure (p _O2 ) is adjusted to avoid the formation of a liquid platinum-tin alloy.

  With the method according to the invention, if the nucleation and / or crystallization stage is carried out after the forming stage, a glass ceramic having a high tin content is advantageously obtained, in particular with a reduced titanium content, And it can also manufacture by having the iron content resulting from manufacture.

In an embodiment of the method according to the invention, the local oxygen partial pressure (p _O2 ) at the contact point between the glass and the noble metal is determined by the tin added to the glass or glass melt due to the increase in solubility caused thereby ( To the extent that each precipitation of Sn) is avoided using chemical processes.

  Preferably, this is achieved according to the invention by presetting the reducing conditions by setting a low local oxygen partial pressure.

  According to an embodiment of the present invention, the gas treatment of the noble metal wall (for example, made of platinum) is performed using a water-containing or hydrogen-containing gas. Further development of this embodiment proposes gas treatment with pure water vapor in particular. However, it is also conceivable to chemically adjust the reducing conditions by supplying humidified nitrogen or humidified air.

  The proposed gas treatment is based on the platinum permeability for hydrogen which has a reducing effect on Sn-containing glass. Since platinum is preferably used as a material used for manufacturing, melting, and feeding systems, the process according to the present invention is therefore a common facility in industrial production, without high technical reconfiguration. Enables the use of.

  According to the invention, the chemical means are implemented by providing a suitable, refractory, preferably porous material system, for example for gas treatment of LAS glass ceramics. According to the present invention, gas processing is facilitated by a continuous gas supply.

  In a further embodiment of the present invention, as an electrochemical method for adjusting the oxygen partial pressure at the contact point between the glass and the precious metal manufacturing system, melting system or supply system, or vessel, the cathode protection current is used. Is applied.

  In this case, furthermore, within the scope of the present invention, a suitable counter electrode is used, respectively, for the protective current or their application, said counter electrode comprising a roller or arranged in a stirred tank In addition, a voltage source and a current measuring device are prepared.

  According to the present invention, monitoring the change achieved by applying a reduced oxygen partial pressure, or monitoring the corresponding electrochemical override, is preferably done with a platinum component without grounding. Must be provided by electrochemical potential measurements.

  In a further embodiment of the method according to the invention, the oxygen partial pressure is adjusted, at least locally, as a function of temperature, so as to increase with increasing temperature above the threshold temperature and above the threshold pressure. However, ensuring a range of tin solubility in the glass, the temperature is variable in the range of at least 400 degrees at a constant oxygen partial pressure.

  The method may be carried out so as to avoid the dissolution of stannic oxide or the fluidization of tin by maintaining the solubility range of tin by presetting the oxygen partial pressure and / or temperature. .

For the method according to the invention, the glass and / or glass ceramic may have an iron content of at least 0.015 weight percent, preferably 0.01 weight percent ferric oxide (Fe ₂ O ₃ ). Further, the glass and / or glass ceramic may have less than 1.0 weight percent, preferably less than 0.05 weight percent titanium dioxide (TiO ₂ ). A preferred embodiment of the method according to the invention produces a glass and / or glass ceramic having at least 0.01 weight percent ferric oxide (Fe ₂ O ₃ ) and less than 0.05 weight percent titanium dioxide (TiO ₂ ). Is done.

  The process according to the invention for the production of glass or glass ceramic provides a suitable process window with respect to pressure and temperature, depending on the material composition. The process window of the molding according to the invention allows a tin content of 1 mol% and higher.

  In the following, the invention will be described in more detail using exemplary embodiments and with reference to the accompanying drawings. In this case, the exemplary embodiments described should be understood as not limiting the inventive concept.

FIG. 1 is a graph plotting the solubility of tin against temperature. FIG. 2 shows the calculated tin solubility of the lithium aluminosilicate glass-ceramic system according to the invention. FIG. 3 is a phase diagram of a LAS melt with stannic oxide. FIG. 4 shows the molar solubility of tin as a function of local oxygen partial pressure. FIG. 5 shows the molar solubility of tin as a function of local electrochemical potential. FIG. 6 illustrates the molar solubility of various tin species as a function of gas treatment status. FIG. 7 shows a quasi-binary phase diagram Pt-Sn-O. FIG. 8 shows the temperature dependence of the oxygen partial pressure for the LAS system with SnO ₂ . FIG. 9 is a view corresponding to FIG. 6 for the LAS system manufactured by the float process.

FIG. 1 shows a description of the molar solubility of various tin species in lithium aluminosilicate glass ceramic (LAS), which is important for understanding the present invention. There, the molar solubility of the total content of tin (total Sn), the molar solubility of tin oxide (SnO), and the molar solubility of stannic oxide (SnO ₂ ) are in the range of 1100 to 1600 ° C. Shown as a function. The reduced state of tin has different solubility characteristics in LAS glass, corresponding to SnO and SnO ₂ . While the divalent form is non-limitingly soluble in the range of less than 10 mol%, the tetravalent form of tin, which is a form corresponding to the compound SnO ₂ , is several ppm (parts per million) From 1 to 1 mol% maximum. Under normal molding conditions prevailing in the production of glass ceramics, the solubility of SnO ₂ is, according to the invention, less than 0.5 mol% for high melting glass.

Thus, the overall solubility of tin depends on the oxygen partial pressure p _O2 dominating in the reduced state or glass, respectively. The oxygen partial pressure in the glass depends on the temperature T. However, the solubility measurements shown may be influenced externally by contact between glass and, for example, platinum (Pt) walls. When the platinum wall comes into contact, water dissolved in the glass is decomposed, so that the reduction state locally changes to the oxidized species. In the case of a measurement corresponding to the solubility value, this suggests that the measurement should be carried out in a platinum container with walls that are not too thin. Crystallization that takes place on the wall can lead to high dissolution temperatures, which can distort solubility values.

In the case of the measurements shown, the reduction state was defined by a pure oxygen rinsing process. Since contact with the platinum wall was additionally avoided, the correct molar solubility of tin can be measured at temperatures above T = 1300 ° C., and the solubility can be expressed for the LAS glass system using the following formula:
X _Sn [mol%] = 0.216 + 1.143 · 10 ⁶ · exp (-24773 / T [° C.])
This functional relationship corresponds to the “total Sn” graph shown in FIG. 1, and extrapolation was performed below 1200 ° C. Using the following reaction equation:
SnO ₂ = SnO + 1 / 2O ₂
The concentration depending on the temperature of the bivalent and tetravalent species can be measured. The divalent species Sn is
SnO = Sn ⁰ + 1 / 2O ₂
And can be reduced to pure metal tin.

  Neutral tin is not soluble in the glass and results in the deposition of a metallic phase that deposits on the surface as SN droplets or in the glass in colloidal form. Thus, when used properly, reducing conditions will lead to higher SnO content and thereby higher total tin solubility.

FIG. 2 shows the content of the two above mentioned tin species as well as the total content of tin during the cooling process, taking into account the resulting oxygen partial pressure p _O2 (T), as a function of the temperature within the range of FIG. Will be described. In contrast to FIG. 1, the actual dominant oxygen partial pressure p _O2 was taken into account here. The oxygen partial pressure p _{O2 in} the glass of the melt clarified at a high temperature continuously decreases as the temperature decreases. Therefore, taking this temperature dependence into account results in the solubility characteristics shown in FIG. Since the reduction in oxygen partial pressure compared to the constant pressure on which the data of FIG. 1 is based corresponds to reducing conditions, a relatively higher solubility is achieved. The solubility of Sn is associated with more reducing conditions, ie with a lower oxygen partial pressure (0.06 bar to 1 bar at 1350 ° C.) compared to the prevailing pressure during the measurement according to FIG. To rise.

Assuming that the melting temperature and the oxygen partial pressure are independent thermostoichiometry, an undissolved region of the glass melt phase diagram can be obtained for a certain total concentration of tin, as shown in FIG. This can be achieved with 0.7 mol% SnO ₂ . At low temperature and high pressure, glass and SnO ₂ are formed, whereas at high temperature and low oxygen partial pressure, dissolution of Sn in liquid form occurs. The range of pressure and temperature between the two solid and liquid dissolution ranges defines the range of LAS glass with 0.7 mol% tin that is homogeneous and non-dissolving. Excess tin dissolution as a metal liquid phase is noticeable in the case of the float process, which is an important forming process for the production of glass or glass ceramic. In so doing, the glass melt is solidified during movement from the hot zone to the cold zone in the tin bath.

As shown in FIG. 4, slightly reducing conditions lead to an increase in tin solubility at a constant temperature. An Sn partial solubility of 2 mol% may be achieved at an oxygen partial pressure p _O2 of 0.001 bar, which is dominant at the platinum contact. According to the present invention, this reduction in oxygen partial pressure that leads to increased solubility can be adjusted using chemical and / or electrochemical methods within the scope of the present invention.

However, it should be noted that according to the present invention tin in the form of SnO ₂ acts as a nucleating agent, whereas the divalent species SnO always only forms part of the residual glass phase. There must be. Therefore, when adjusting the higher devitrification temperature, it must be taken into account that the overall deviation between the SnO ₂ and SnO portions in the entire glass volume is not beneficial. The object according to the invention is therefore in particular the local adjustment of the reducing conditions exclusively, for example in the Pt wall of the production system, melting system or supply system or vessel.

  The description of tin concentration as a function of oxygen partial pressure according to FIG. 4 can be translated into a description of tin concentration as shown in FIG. 5 and using the Nernst equation at potential E. In that case, all contact possibilities between glass and platinum are protected by protective current conditions and by applying a corresponding potential in a suitably selected anode, for example a roller, or in a stirred vessel. It must be taken into account that local polarization occurs. However, if the molding apparatus is a complex geometry, the desired protective effect can only be adjusted very limitedly because their protective current is a limited effect.

Therefore, chemical pressure regulation is more important within the scope of the present invention. For this purpose, according to the invention, the platinum / glass contact is gassed with hydrogen from the back, whereby a local reduction of the contact is achieved. Obviously, the value of the oxygen partial pressure p _O2 must be expressed as a value specific to the process of the ratio H ₂ / H ₂ O illustrated in FIG. In this case, the thermochemical relationship Log (pH ₂ O + pH ₂ ) = log K + 1/2 · log (pO ₂ ) [unit of p is bar]
(Wherein, log K = −2.971 + 12000 / T [unit of T is K])
Is taken into account.

  In an alternative embodiment of the invention, the gas treatment is carried out with humidified nitrogen or with pure water vapor, for example similar to the application of droplets. In this embodiment of the invention, this effect of undesirable side reactions is advantageously reduced since only very weak reducing conditions dominate.

The higher devitrification temperature (UDL) during the electrochemical reduction proposed within the scope of the invention, as well as during the chemical reduction, is disturbing on the inner wall of the platinum container or on the inner wall of the platinum wall Water decomposition reactions must be taken into account. Due to normal water decomposition, an increase in oxygen partial pressure p _O2 may be observed here. However, this is not sufficient for the formation of oxygen bubbles, because the glass already has a temperature that is too low.

If As ₂ O ₃ is used as a fining agent in LAS glass ceramic and its concentration of 0.3% is not negligible considering more than 0.7 mol% SnO ₂ , arsenic is mostly as As ₂ O ₃ Exists and reacts with the tin species during the cooling process. Thus, the reduction of SnO ₂ occurs and the dissolution temperature is advantageously reduced. Overall, however, the use of arsenic, and thus the use of antimony, should be avoided with the process according to the invention, since here the water observed in platinum in the As-free melt. This is because the decomposition effect and the devitrification upper limit (UDL) can be lowered.

The interaction between platinum and tin must be further taken into account by the method according to the invention or using the equipment provided to carry out this method. In this case, a solid solution of tin platinum having a face-centered cubic structure (fcc) and its two liquid alloys must be considered. The stability of the fcc phase depends on the temperature as well as the total content of tin. This is determined by the redox state or the dominant p _O2 , respectively.

When oxygen is included in the platinum-tin (Pt-Sn) phase diagram, a quasi-binary phase diagram Pt-Sn-O for a constant oxygen partial pressure is obtained as shown in FIG. Among them, the solid phase of platinum-tin in the fcc structure is limited by liquefaction (alloying and melting) and SnO ₂ dissolution (cooling and internal oxidation). When considering the specific solubility of SnO ₂ and O _{2 in} the LAS glass melt, it is shown at 1300 ° C. (this temperature is the working point according to the invention) at the draw nozzle used in glass production. The phase diagram shown in FIG. 8 with the processed process window can be derived. This can be achieved without excessive risk of alloy formation by moderately reducing gas treatment or by applying a direct current that causes the same chemical action. If the formation of Pt ₃ Sn is taken into account, as shown in FIG. 8, the process window is correspondingly reduced accordingly, as also shown in FIG.

In the float process used for large scale glass or glass ceramic production, the glass is exposed to strong reducing conditions at the surface. Even at pressures p _O2 <10 ^-16 bar, dissolved SnO ₂ is converted to SnO, and the latter is not completely transformed into metallic tin. The tin is then released at the lower and upper sides of the glass ribbon. In accordance with the present invention, in order to avoid precipitation of liquid tin on the glass surface, it must be matched to a p _O2 and narrow process window, as exemplarily shown in FIG. In that regard, in the temperature range of 700-950 ° C., the present invention is the dominant process window in the float bath, limited by higher temperatures and liquid tin precipitation and lower by SnO ₂ . A process window limited on the pressure side is proposed. In the diagram of FIG. 9, a working window using a gate valve (or twill) is shown simultaneously.

  When practicing the present invention, it must generally be considered that the same tin content must be retained in the glass. Furthermore, the local process temperatures should be fixed to each other and have as little fluctuation as possible. Abrupt cooling results, for example, in the spontaneous release of the reducing agent Sn dissolved in the glass in platinum. This can cause intense gas production. The possibility of embrittlement of the face centered cubic (fcc) Pt phase is also facilitated by periodic and steep changes.

Claims (18)

A method for producing a tin-containing glass comprising the following steps:
Producing a glass melt,
The step of shaping the glass melt,
Cooling and relieving stress,
And, in the manufacturing method including the step of post-processing, to produce reducing conditions on construction process of the glass melt at the interface of the glass melt, containing a glass melt, lead to glass melt, or In the body introduced into the glass melt and / or in the required medium, the dominant oxygen partial pressure (p _O2 ) is locally adjusted so that the tin-containing component from the glass melt A manufacturing method, characterized by reducing dissolution. Local oxygen partial pressure at the contact between the glass melt and the noble metal (p _O2 The method according to claim 1, characterized in that is reduced using a chemical process to the extent that the dissolution of tin-containing components is reduced due to the increase in solubility caused thereby. Adjust the oxygen partial pressure (p _O2), characterized in that reducing the exsolution of stannic oxide (SnO _2), The method according to claim 1 or 2. Adjust the oxygen partial pressure (p _O2), and wherein the reducing coagulum tin (Sn), the method according to any one of claims 1 to 3. The method according to claim 4 , characterized in that the oxygen partial pressure (p _O2 ) is adjusted to reduce liquid metallic tin (Sn) agglomerates. Method according to claim 4 , characterized in that the partial pressure of oxygen (p _O2 ) is adjusted to avoid the formation of a liquid platinum-tin alloy. A nucleation and / or crystallization step is performed between the step of shaping the glass melt and the step of cooling and stress relaxation, according to any one of claims 1 to 6 The method described. Local oxygen partial pressure (p _O2), characterized in that the chemically adjusted A method according to any one of claims 1 to 7. The adjustment of oxygen partial pressure (p _O2), the metal mold to be used during the construction process, characterized in that it accomplished by backside gas treatment with hydrogen (H _2), of the claims 1 to 8 The method according to any one of the above. 10. A method according to any one of claims 1 to 9 , characterized in that the local oxygen partial pressure ( _pO2 ) is adjusted by supplying humidified nitrogen. Local oxygen partial pressure (p _O2), and adjusting by supplying steam, a method according to any one of claims 1 to 10. Local oxygen partial pressure (p _O2), characterized in that the electrochemically adjusting method according to any one of claims 1 to 11. 13. The method according to claim 12 , characterized in that the local oxygen partial pressure (p _O2 ) is adjusted by applying a voltage. 14. A method according to claim 12 or 13 , characterized in that a protective current is applied at the platinum contacts used during manufacture. Adjusting the oxygen partial pressure at least locally as a function of temperature, the oxygen partial pressure, which rises with increasing temperature above and above the critical temperature, is the 15. Method according to any one of claims 1 to 14 , characterized in that the temperature is variable within a range of at least 400 degrees with a constant oxygen partial pressure, ensuring a solubility range. . By preliminarily setting the oxygen partial pressure and / or temperature, by maintaining the solubility range of tin, characterized in that the fluidization of exsolution or tin stannic oxide is avoided, in claim 15 The method described. Glass, and having at least 0.01 percent by weight of ferric oxide (Fe ₂ O _3), The method according to any one of claims 1 to 16. Glass, and having a 0.05 weight percent less titanium dioxide (TiO _2), The method according to any one of claims 1 to 17.

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