EP2493827A1 - Phase-separated soda-lime-silica glass - Google Patents

Phase-separated soda-lime-silica glass

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Publication number
EP2493827A1
EP2493827A1 EP10768950A EP10768950A EP2493827A1 EP 2493827 A1 EP2493827 A1 EP 2493827A1 EP 10768950 A EP10768950 A EP 10768950A EP 10768950 A EP10768950 A EP 10768950A EP 2493827 A1 EP2493827 A1 EP 2493827A1
Authority
EP
European Patent Office
Prior art keywords
glass
inclusions
glass according
crystalline particles
soda
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10768950A
Other languages
German (de)
French (fr)
Inventor
Michel Bogaerts
Stéphane GODET
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Glass Europe SA
Universite Libre de Bruxelles ULB
Original Assignee
AGC Glass Europe SA
Universite Libre de Bruxelles ULB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AGC Glass Europe SA, Universite Libre de Bruxelles ULB filed Critical AGC Glass Europe SA
Priority to EP10768950A priority Critical patent/EP2493827A1/en
Publication of EP2493827A1 publication Critical patent/EP2493827A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/005—Compositions for glass with special properties for opaline glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the field of the invention is that of vitreous materials in the silico-soda-lime system. More specifically, the invention relates to a soda-lime glass which has a good mechanical strength, in particular a good resistance to the propagation of claws, and which allows improved quenching.
  • the glass according to the invention has these properties coupled with a pleasant aesthetic appearance.
  • Glass in its broadest definition, is an amorphous material, free from crystalline and isotropic order.
  • a phenomenon of crystallization called devitrification, can occur.
  • crystallization occurs accidentally or uncontrollably, it causes the formation of relatively coarse crystals of very different sizes and distributed heterogeneously in the vitreous matrix, often in the form of needles on the surface.
  • the presence of such crystals leads to an optical defect (decrease in transparency) and / or mechanical (decrease in resistance to mechanical stresses) of the resulting glass.
  • liquid / liquid phase separation, or demixing which corresponds to the growth of amorphous phases of different compositions.
  • immiscibility in many silicates in the molten state one can observe two liquid phases of different compositions, one speaks then of immiscibility.
  • the phase diagrams of many molten liquids show immiscibility domains or stable miscibility gaps above the liquidus: this is particularly the case for alkaline earth silicates, in the case of compositions rich in silica. In other cases, this immiscibility is observed below the liquidus (metastable immiscibility), for example in alkali silicates.
  • a homogeneous glass, heated to a temperature at which the demixing occurs, will therefore separate into two glasses of different compositions. They exist two types of demixing generating interfaces between the amorphous phases which have different morphologies. These two types of interfaces are illustrated in Figure 1: (a) either the separation is effected by a germination / growth mechanism and, in this case, the separation generates isolated inclusions, called “droplets", which are dispersed in a vitreous matrix, (b) either the separation is carried out by spinodal decomposition (spontaneous separation) and, in this case, it morphologically results in the appearance of inclusions, often called “vermiculites", generating an interlaced structure with a more diffuse border between the two amorphous phases.
  • composition of silico-soda-lime glass has been optimized to limit these parasitic phenomena of devitrification and phase separation and thus obtain a totally amorphous, vitreous material.
  • a silico-soda-lime glass which is not conducive to heat, shows a strong expansion at the place where it is heated.
  • the expanded glass exerts a thrust on the surrounding parts which causes a rupture of the glass object, it is the "thermal break".
  • the thickness of the protective layer is limited and any macroscopic claw exposes an unprotected glass to the external environment or leads to the creation of a crack initiation in a weakened zone of the glass.
  • the deposition of such a layer only improves the claw resistance of the glass and does not change its coefficient of thermal expansion.
  • glasses having an amorphous glassy phase and a crystalline phase are well known in the art. These glasses result from the controlled uniform devitrification of a glass.
  • the transformation into semi-crystalline ceramic, also called vitrocrystalline or commonly glass-ceramic material is obtained from a glass by a controlled heat treatment which makes it possible to produce a high density of small crystals dispersed homogeneously in the volume of the material. Unlike uncontrolled devitrification, this homogeneous crystal distribution improves the mechanical properties of the product.
  • Some ceramics have high resistance to claw and rupture and no expansion at high temperatures, making them virtually invulnerable to thermal shocks. By controlling the proportion and nature of the different crystals, the TEC of the glass ceramic can be adjusted and very low values are often achieved.
  • the glass-ceramic is, for example, used for the manufacture of cooking plates or chimney walls.
  • compositions are based, e.g., on systems Li 2 O-SiO 2 (silicate) or Li 2 O-Al 2 O 3 -S1O 2 (aluminosilicates). They also often have one or more nucleating agents such as TiO 2 , ZrO 2 or P 2 O 5 .
  • nucleating agents such as TiO 2 , ZrO 2 or P 2 O 5 .
  • the state of the art does not propose any glass-ceramic in the Na 2 O-CaO-SiO 2 silico-soda-lime system.
  • vitrocrystalline materials Although many known vitrocrystalline materials have properties of mechanical and thermal resistance far superior to amorphous soda-lime-calcium glass, they are still much more expensive to produce and therefore non-transposable to current applications for reasons economic. Due to its ease of production and the low cost of raw materials, silica-soda-lime glass still holds a prominent place in the glass industry and in particular for the construction, automotive and automotive markets. the decoration.
  • opalins glasses comprising a vitreous phase and a crystalline phase are also well known in the art and are obtained by introducing an opacifier, conventionally fluorides, into a silicate, an aluminosilicate or a borosilicate, by a intentional or controlled crystallization of crystals (in the case of the addition of fluorides, the crystals are typically CaF 2 or NaF).
  • the opal glasses very present in the everyday life, are opaque and diffuse the light. They are therefore mainly used in decoration and in the manufacture of consumer products such as table services or lighting fixtures.
  • Classic opal glasses, marketed under the brand name Arcopal® are milky white and are fluorosilicates.
  • the object of the invention is in particular to overcome the drawbacks of the prior art by solving the technical problem, namely to obtain a soda-lime glass, that is to say belonging to the Na 2 O-CaO-SiO system. 2 , with increased mechanical properties, in particular good resistance to the propagation of claws, and which also allows improved quenching.
  • Another object of the invention is to provide a soda-lime-silica glass having, in addition to the desired mechanical strength and the fact that it allows an improved quenching, the desired aesthetic character depending on the application to which it is applied. intended.
  • the invention proposes in this context to provide a silico-soda-lime glass which is transparent or alternatively, having a pleasing milky opaque appearance, comparable to that of opal glasses.
  • an object of the invention is to provide a solution to the disadvantages of the prior art that is simple, economical and with a low environmental impact. 4. Presentation of the invention
  • the invention relates to a glass having as main components SiO 2 , Na 2 O and CaO and which comprises two amorphous phases of different compositions, one of the two phases being in the form of inclusions dispersed in the volume. from the other phase.
  • said inclusions comprise crystalline particles.
  • the glass according to the invention makes it possible to solve the disadvantages of the materials of the prior art and to solve the technical problem raised.
  • the inventors have indeed demonstrated that it was possible, by generating a demixing phenomenon coupled to crystallization at the amorphous / amorphous interface and / or in the volume of the inclusions created by the demixing to obtain a glass in the silico-soda-lime system with increased mechanical properties, in particular good resistance to the propagation of claws, and which has an acceptable appearance or aesthetically pleasing.
  • a silico-soda-lime glass having a demixing coupled to a crystallization made it possible to reach higher CET values than a correspondingly totally amorphous glass.
  • the silico-soda-lime glass demixed according to the invention thus has an increased mechanical strength, in particular a good resistance to the propagation of claws, and it also allows improved quenching. This glass is, moreover, economically and aesthetically acceptable for common applications in the building or automobile.
  • the invention also relates to a sheet consisting of glass as described above and an article comprising at least one such sheet.
  • FIG. 1 represents a photograph obtained by electron microscopy of demixed glasses of the state of the art.
  • Figure 2 shows the position of the crystalline particles according to the invention.
  • the glass according to the invention is a silico-soda-lime glass, that is to say which belongs to the Na 2 O-CaO-SiO 2 system.
  • the glass of the invention therefore has SiO 2 main components, Na 2 O and CaO.
  • the glass of the invention comprises, as a percentage by total weight, 60 to 85% of SiO 2 , 1 to 25% of Na 2 O and 1 to 25% of CaO. Additionally, it may comprise other components in minor amounts such as K 2 O, MgO, Al 2 O 3 , BaO, various dyes or residues from redox modifying additives (NaNO 3 , Na 2 SO 4 , coke , ).
  • these components if present in the glass of the invention, will not exceed a total of 15% by weight of the glass.
  • the glass is free of the fluorine element.
  • a silico-soda-lime glass therefore has a low environmental impact, particularly compared to opal lenses whose opacifier is conventionally based on one of these components.
  • the term "free" means in the present invention that the glass only has the fluorine element in the trace state.
  • the glass comprises the fluorine element only in content of less than 500 ppm by weight.
  • the glass is also free of the lithium element. Since lithium oxide is more expensive than oxides such as Na 2 O and CaO, such a soda-lime type glass is therefore of undeniable economic interest, in particular compared with the glass-ceramic materials known from the state of the art. which include, most often, lithium oxide. Exempt of the lithium element means that the glass of the invention comprises this element only in trace. Preferably, the glass comprises the lithium element only in content of less than 500 ppm by weight.
  • the glass may comprise lithium in amounts of up to about 3% by weight, expressed in the form of the oxide.
  • the presence of lithium in these amounts makes it possible to reduce the viscosity of the glass in the molten state and thus to promote crystallization.
  • the glass of the invention is free of the lead element. Exempt from the lead element means that the glass of the invention comprises this element only in the trace state.
  • the glass of the invention is free of the boron element. Free from the boron element means that the glass of the invention comprises this element only in the trace state.
  • the glass according to the invention comprises two amorphous phases of different compositions, one of the two phases being in the form of inclusions distributed in the volume of the other phase, called the matrix phase.
  • the silico-soda-lime glass of the invention comprises two glassy phases of different compositions.
  • the glass of the invention comprises a vitreous phase in the form of inclusions which is enriched in SiO 2 and dispersed in the other matrix vitreous phase which is enriched in network modifying elements, such as sodium and calcium.
  • the inclusions are in the form of droplets or in the form of vermiculites.
  • the inclusions comprise crystalline particles.
  • the glass of the invention may comprise crystalline particles in the form of an assembly of several particles or in isolated form.
  • the crystalline particles have a size of between 5 nm and 500 ⁇ .
  • the crystalline particles in order to obtain a glass which is transparent, the crystalline particles have a size of between 5 nm and 500 nm.
  • the crystalline particles in order to obtain a glass having an opaque milky appearance, comparable to that of opal glasses, the crystalline particles have a size of between 500 nm and 500 ⁇ m.
  • the crystalline particles are:
  • crystalline particle on the surface of an inclusion is meant a particle that has crystallized at the amorphous / amorphous interface.
  • the presence of crystalline particles on the surface of the inclusions makes it possible to further increase the mechanical properties, in particular the resistance to the propagation of cracks in the glass.
  • the presence of crystalline particles on the surface of the inclusions also makes it possible to limit the excessive crystallization in the volume of the inclusions and thus to prevent the volume growth of said inclusions.
  • crystalline particles when crystalline particles are on the surface of the inclusions, they may consist of compounds which can crystallize from the overall composition of the glass such as diopside (CaMgSi 2 0 6 ), devitrite or wollastonite (CaSiO 3 ). Similarly, they may consist of compounds added in a small amount in the overall composition of the glass such as BaO, TiO 2 , ZrO 2 , Nb 2 O 5 , etc.
  • crystalline particles when crystalline particles are in the volume of the inclusions, they consist essentially of SiO 2 .
  • Impurities such as components from the glass composition and essentially in the matrix phase, may be present in minute amounts. If such impurities are present in the crystalline particles, they are preferably present in a quantity less than 5% by weight in total. More preferably, they are in an amount of less than 2% by weight in total.
  • the crystalline particles of SiO 2 can be in the form of a single polymorph of this component.
  • the crystalline particles of SiO 2 can be in the form of several polymorphs of SiO 2 .
  • the glass according to the invention may also comprise both particles in the form of a single polymorph of SiO 2 and particles in the form of several polymorphs of SiO 2 .
  • Examples of polymorph of SiO 2 are quartz (a or ⁇ ), cristobalite ( ⁇ or ⁇ ) or tridymite ( ⁇ or ⁇ ).
  • the crystalline particles of SiO 2 are essentially in the form of cristobalite.
  • the glass according to the invention has an increased mechanical strength, in particular a good resistance to the propagation of claws, in comparison with a correspondingly totally amorphous glass.
  • the mechanical strength of a material is often expressed in terms of hardness and toughness.
  • Hardness characterizes the ability of a material to be scratched or scratched (expressed in MPa or GPa).
  • Toughness is the ability of a material to resist the propagation of an existing crack.
  • the fragility (B or "brittleness") can complement these parameters and corresponds to the ratio between hardness (H) and toughness (Kc), H / Kc (expressed in ⁇ "05 ) .
  • the hardness and fragility are measured by Vickers indentation.
  • the glass according to the invention has a brittleness less than 6.5 ⁇ 0 5 . By way of comparison, this value is of the order of 7 ⁇ 0 5 for a totally amorphous silico-soda-lime glass, with no particular treatment.
  • the glass has a higher CET than a corresponding totally amorphous glass.
  • the heating or partial cooling of a material can, if it has a low thermal conductivity, lead to stresses that can cause thermal breakages as is the case for the totally amorphous silico-soda-lime glass.
  • This coefficient of thermal expansion or TEC corresponds to the elongation per unit length for a variation of 1 ° C (expressed in ° C
  • the glass according to the invention has a CTE, as measured for a temperature change from 25 to 300 ° C, which is higher than 100.10 "7 / ° C.
  • the TEC for the same temperature range a completely amorphous silico-soda-lime glass, without any particular treatment, is of the order of 90.10 ° C.
  • the glass of the invention allows for improved quenching.
  • glass which allows an improved quenching, is meant a glass which, in order to obtain a compression stress on the surface equivalent to that of a corresponding totally amorphous glass, requires quenching at a lower temperature and / or for a shorter time. . Therefore, this advantage allows an energy gain which results in an additional positive effect of the invention from an environmental and economic point of view.
  • glass which allows improved quenching a glass which has, with equivalent heat treatment, a compression stress on the surface greater than that of a correspondingly totally amorphous glass.
  • glass is also meant for improved quenching, a glass which allows the quenching of "thin" sheets made of this glass.
  • the silico-soda-lime glass according to the invention can be obtained by any process capable of generating a demixing phenomenon coupled with crystallization at the amorphous / amorphous interface and / or in the volume of the inclusions created by the demixing.
  • the glass according to the invention can be obtained by two routes: (i) controlled thermal treatment of glass in the molten state (ceramization), or (ii) controlled annealing of a glass of the same overall composition but previously solidified in the fully amorphous state.
  • ceramization In both cases, a heat treatment called ceramization is performed.
  • the ceramization generally comprises, in a known manner, the following steps, which may be repeated several times: a) raising the temperature to the temperature T (ceramification plateau) which is situated beyond the nucleation interval;
  • the glass according to the invention can be used to manufacture articles of different shapes and sizes. It can, for example, be used to make vials, globes for lighting and decorative objects.
  • the glass of the invention can be used to make a sheet of said glass.
  • it can, for example, be used for a worktop in a kitchen or a laboratory, for tables and shelves or as a floor covering (pavement, walkway).
  • the glass can also be used to manufacture solar panels or automotive glazings.
  • An example of an article according to the invention comprising more than one sheet of said glass is a wall wall which is "laminated" to improve the safety aspect, that is to say which comprises two sheets assembled by one or more plastic interlayer films.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

The invention relates to glass having the following main components: SiO2, Na2O and CaO, which comprises two amorphous phases having different compositions, whereby one of said two phases is in the form of inclusions dispersed in the volume of the other phase and comprises crystalline particles. Such glass has good mechanical strength, in particular good resistance to scratches, and allows improved tempering. In addition, the glass has a pleasing aesthetic appearance.

Description

Verre silico-sodo-calcique démixé  Silico-soda-lime glass demixed
1. Domaine de l'invention 1. Field of the invention
Le domaine de l'invention est celui des matériaux vitreux dans le système silico-sodo-calcique. Plus précisément, l'invention concerne un verre silico- sodo-calcique qui présente une bonne résistance mécanique, en particulier une bonne résistance à la propagation des griffes, et qui permet une trempe améliorée. Le verre selon l'invention présente ces propriétés couplées à un aspect esthétique plaisant. The field of the invention is that of vitreous materials in the silico-soda-lime system. More specifically, the invention relates to a soda-lime glass which has a good mechanical strength, in particular a good resistance to the propagation of claws, and which allows improved quenching. The glass according to the invention has these properties coupled with a pleasant aesthetic appearance.
2. Description de l'art antérieur 2. Description of the prior art
Le verre, dans sa définition la plus large, est un matériau amorphe, exempt d'ordre cristallin et isotrope. Lors de la fabrication d'un tel type de matériau amorphe comportant des constituants d'un composé cristallisable, un phénomène de cristallisation, appelé dévitrification, peut se produire. Lorsqu'une cristallisation se produit de façon accidentelle ou non contrôlée, elle entraîne la formation de cristaux relativement grossiers, de tailles très diverses et distribués de façon hétérogène dans la matrice vitreuse, souvent sous forme d'aiguilles en surface. La présence de tels cristaux conduit à un défaut optique (diminution de la transparence) et/ou mécanique (diminution de la résistance aux sollicitations mécaniques) du verre résultant. Glass, in its broadest definition, is an amorphous material, free from crystalline and isotropic order. During the manufacture of such a type of amorphous material comprising constituents of a crystallizable compound, a phenomenon of crystallization, called devitrification, can occur. When crystallization occurs accidentally or uncontrollably, it causes the formation of relatively coarse crystals of very different sizes and distributed heterogeneously in the vitreous matrix, often in the form of needles on the surface. The presence of such crystals leads to an optical defect (decrease in transparency) and / or mechanical (decrease in resistance to mechanical stresses) of the resulting glass.
De plus, un autre phénomène indésirable peut également survenir lors de la fabrication d'un verre. Il s'agit de la séparation de phase liquide/liquide, ou démixtion, qui correspond à la croissance de phases amorphes de compositions différentes. Il est bien connu que, dans de nombreux silicates à l'état fondu, on peut observer deux phases liquides de compositions différentes, on parle alors d' immiscibilité. Les diagrammes de phase de nombreux liquides fondus montrent des domaines d'immiscibilité ou lacunes de miscibilité stables au dessus du liquidus: c'est le cas notamment des silicates alcalino-terreux, dans le cas des compositions riches en silice. Dans d'autres cas, cette immiscibilité est observée en dessous du liquidus (immiscibilité métastable) , par exemple dans les silicates alcalins. Un verre homogène, chauffé à une température à laquelle la démixtion se produit, va donc se séparer en deux verres de compositions différentes. Ils existent deux types de démixtion engendrant des interfaces entre les phases amorphes qui ont des morphologies différentes. Ces deux types d'interfaces sont illustrées à la Figure 1 : (a) soit la séparation s'effectue par un mécanisme de germination/croissance et, dans ce cas, la séparation génère des inclusions isolées, appelées « gouttelettes » et qui sont dispersées dans une matrice vitreuse, (b) soit la séparation s'effectue par décomposition spinodale (séparation spontanée) et, dans ce cas, elle se traduit morphologiquement par l'apparition d' inclusions, souvent qualifiées de « vermiculites », générant une structure entrelacée avec une frontière plus diffuse entre les deux phases amorphes. La séparation de phase lorsqu'elle se produit de manière accidentelle dans un verre modifie la texture de ce verre et entraîne des hétérogénéités optiques et mécaniques indésirables. Le phénomène de démixtion dans le cas particulier d'un verre appartenant au système Na2O-CaO-SiO2 a été investiguée par Burnett et co. {Physics and Chemistry of Glasses, Vol.11 No.5 October 1970). In addition, another undesirable phenomenon can also occur during the manufacture of a glass. This is the liquid / liquid phase separation, or demixing, which corresponds to the growth of amorphous phases of different compositions. It is well known that in many silicates in the molten state one can observe two liquid phases of different compositions, one speaks then of immiscibility. The phase diagrams of many molten liquids show immiscibility domains or stable miscibility gaps above the liquidus: this is particularly the case for alkaline earth silicates, in the case of compositions rich in silica. In other cases, this immiscibility is observed below the liquidus (metastable immiscibility), for example in alkali silicates. A homogeneous glass, heated to a temperature at which the demixing occurs, will therefore separate into two glasses of different compositions. They exist two types of demixing generating interfaces between the amorphous phases which have different morphologies. These two types of interfaces are illustrated in Figure 1: (a) either the separation is effected by a germination / growth mechanism and, in this case, the separation generates isolated inclusions, called "droplets", which are dispersed in a vitreous matrix, (b) either the separation is carried out by spinodal decomposition (spontaneous separation) and, in this case, it morphologically results in the appearance of inclusions, often called "vermiculites", generating an interlaced structure with a more diffuse border between the two amorphous phases. Phase separation when it occurs accidentally in a glass changes the texture of this glass and causes undesirable optical and mechanical heterogeneities. The demixing phenomenon in the particular case of a glass belonging to the Na 2 O-CaO-SiO 2 system has been investigated by Burnett et al. {Physics and Chemistry of Glasses, Vol.11 No.5 October 1970).
Durant des décennies, la composition du verre silico-sodo-calcique a d'ailleurs été optimisée afin de limiter ces phénomènes parasites de dévitrification et de séparation de phases et ainsi obtenir un matériau totalement amorphe, vitreux. For decades, the composition of silico-soda-lime glass has been optimized to limit these parasitic phenomena of devitrification and phase separation and thus obtain a totally amorphous, vitreous material.
Néanmoins , malgré la propriété de transparence d' un verre inorganique, l'absence d'interfaces microstructurales mènent à une fragilité du matériau. Cette fragilité mécanique intrinsèque se traduit par des résistances faibles aux chocs mécaniques. En particulier, l'aspect esthétique du verre se trouve souvent fortement détérioré par la formation de griffes ou de rayures lors son utilisation et/ou de son transport. De plus, même si un verre est dur, il est fragile et peu tenace, c'est- à-dire qu'il n'est pas résistant à la propagation de griffes ou fissures suite à l'absence de discontinuités et de frontières de grains. Nevertheless, despite the transparency property of an inorganic glass, the absence of microstructural interfaces leads to a fragility of the material. This intrinsic mechanical weakness results in low resistance to mechanical shocks. In particular, the aesthetic appearance of glass is often found strongly damaged by the formation of claws or scratches during use and / or transport. In addition, even if a glass is hard, it is fragile and not very tenacious, that is to say that it is not resistant to the propagation of claws or cracks due to the absence of discontinuities and boundaries of grains.
Egalement, un verre silico-sodo-calcique, qui est peu conducteur de la chaleur, enregistre une forte dilatation à l'endroit où il est chauffé. Le verre dilaté exerce une poussée sur les parties environnantes ce qui entraîne une rupture de l'objet en verre, c'est la « casse thermique ». Also, a silico-soda-lime glass, which is not conducive to heat, shows a strong expansion at the place where it is heated. The expanded glass exerts a thrust on the surrounding parts which causes a rupture of the glass object, it is the "thermal break".
De nos jours, la « trempe » thermique du verre, très utilisée dans l'industrie du verre silico-sodo-calcique, permet l'amélioration de la résistance mécanique et thermique. Nowadays, the thermal "tempering" of glass, widely used in the silico-soda-lime glass industry, allows the improvement of the mechanical and thermal resistance.
Malheureusement, ce traitement thermique, une fois effectué, ne permet pas la découpe ultérieure du produit s'il est sous forme de feuille, par exemple. Dans ce cas, il est important que l'usinage et la mise aux cotes définitives se fassent avant la trempe. Ce dernier point représente un inconvénient majeur pour les produits verriers nécessitant une résistance mécanique accrue, comme les carrelages ou les plans de travail, et qui demandent souvent une découpe pour le placement. De plus, la trempe d'un verre silico-sodo-calcique est délicate voire impossible pour le verre dit « mince », c'est-à-dire un verre sous forme de feuille d'une épaisseur environ inférieure à 2,5 mm. En effet, la contrainte en compression à la surface de l'ordre de 100 MPa induite par la trempe est impossible pour de telles feuilles de verres. Cette limitation provient de la valeur du coefficient d'expansion thermique ou CET du verre silico-sodo-calcique, de l'ordre de 90.10"7/°C II est effectivement bien connu, dans le monde des matériaux vitreux, que la trempe est facilitée lorsque le CET augmente. Une valeur plus élevée de CET pour le verre silico-sodo-calcique permettrait ainsi une trempe améliorée et donnerait, par exemple, accès des verres minces trempés. Une voie connue afin d'améliorer la résistance mécanique d'un verre, et en particulier sa résistance à la propagation des griffes, est l'application d'une couche superficielle déposée sur le verre. Cette technique vise à bénéficier de la résistance mécanique spécifique de ladite couche vis-à-vis d'une sollicitation mécanique extérieure. Néanmoins, l'épaisseur de la couche protectrice est limitée et toute griffe macroscopique expose un verre non protégé au milieu extérieur ou mène à la création d'une amorce de fissure dans une zone du verre fragilisée. De plus, le dépôt d'une telle couche améliore uniquement la résistance à la griffe du verre et ne modifie en rien son coefficient d'expansion thermique. Unfortunately, this heat treatment, once performed, does not allow the subsequent cutting of the product if it is in sheet form, for example. In this case, it is important that machining and finalizing are done before quenching. This last point represents a major disadvantage for glass products requiring increased mechanical strength, such as tiles or worktops, which often require cutting for placement. In addition, the quenching of a silico-soda-lime glass is difficult if not impossible for the so-called "thin" glass, that is to say a glass in the form of a sheet having a thickness of less than 2.5 mm. . Indeed, the compressive stress on the surface of the order of 100 MPa induced by quenching is impossible for such glass sheets. This limitation comes from the value of the coefficient of thermal expansion or CET of the silico-soda-lime glass, of the order of 90 × 10 -7 / ° C. It is indeed well known, in the world of vitreous materials, that quenching is When the TEC increases, a higher value of CET for soda-lime-silica glass would allow improved tempering and, for example, give access to tempered thin glasses. A known way to improve the mechanical strength of a glass, and in particular its resistance to the propagation of claws, is the application of a surface layer deposited on the glass. This technique aims to benefit from the specific mechanical strength of said layer vis-à-vis an external mechanical stress. Nevertheless, the thickness of the protective layer is limited and any macroscopic claw exposes an unprotected glass to the external environment or leads to the creation of a crack initiation in a weakened zone of the glass. In addition, the deposition of such a layer only improves the claw resistance of the glass and does not change its coefficient of thermal expansion.
Dans le domaine des matériaux vitreux, des verres comportant une phase vitreuse amorphe et une phase cristalline sont bien connus de la technique. Ces verres résultent de la dévitrification homogène contrôlée d'un verre. La transformation en céramique semi-cristalline, encore appelée matériau vitrocristallin ou communément vitrocéramique, s'obtient à partir d'un verre par un traitement thermique contrôlé qui permet de produire une grande densité de petits cristaux dispersés de façon homogène dans le volume du matériau. Contrairement à la dévitrification non contrôlée, cette distribution homogène des cristaux permet d'améliorer les propriétés mécaniques du produit. Certaines vitrocéramiques possèdent en effet une grande résistance à la griffe et à la rupture ainsi qu'une absence de dilatation à haute température, ce qui les rend pratiquement invulnérables aux chocs thermiques. En contrôlant, la proportion et la nature des différents cristaux, le CET de la vitrocéramique peut être ajusté et des valeurs très faibles sont souvent atteintes. In the field of vitreous materials, glasses having an amorphous glassy phase and a crystalline phase are well known in the art. These glasses result from the controlled uniform devitrification of a glass. The transformation into semi-crystalline ceramic, also called vitrocrystalline or commonly glass-ceramic material, is obtained from a glass by a controlled heat treatment which makes it possible to produce a high density of small crystals dispersed homogeneously in the volume of the material. Unlike uncontrolled devitrification, this homogeneous crystal distribution improves the mechanical properties of the product. Some ceramics have high resistance to claw and rupture and no expansion at high temperatures, making them virtually invulnerable to thermal shocks. By controlling the proportion and nature of the different crystals, the TEC of the glass ceramic can be adjusted and very low values are often achieved.
Sur base de ces propriétés, de nombreuses applications se sont développées pour de tels types de verre. La vitrocéramique est, par exemple, utilisée pour la fabrication de taques de cuisson ou de parois de cheminées. Based on these properties, many applications have developed for such types of glass. The glass-ceramic is, for example, used for the manufacture of cooking plates or chimney walls.
Depuis des décennies et la percée des vitrocéramiques sur le marché dans le milieu des années cinquante, plusieurs compagnies ont développé des vitrocéramiques basées sur la cristallisation partielle d'un verre. Des compositions connues sont basées, par exemple, sur les systèmes Li2O-SiO2 (silicates) ou Li2O- AI2O3-S1O2 (aluminosilicates). Elles présentent en outre souvent un ou plusieurs agents nucléants tels que TiO2, ZrO2 ou P2O5. Par contre, l'état de la technique ne propose aucune vitrocéramique dans le système silico-sodo-calcique Na2O-CaO- SiO2. Il est d'ailleurs soutenu dans la littérature scientifique, et en particulier dans l'article de Strnad et co. publié dans Physics and Chemistry of Glasses (Vol.14 No.2 April 1973), qu'il est impossible de produire une cristallisation homogène dans le volume d'un verre appartenant à ce système et que seule une cristallisation hétérogène, non contrôlée, peut être obtenue dans ce cas. For decades and the breakthrough of glass-ceramics on the market in the mid-fifties, several companies have developed vitroceramics based on the partial crystallization of a glass. Known compositions are based, e.g., on systems Li 2 O-SiO 2 (silicate) or Li 2 O-Al 2 O 3 -S1O 2 (aluminosilicates). They also often have one or more nucleating agents such as TiO 2 , ZrO 2 or P 2 O 5 . On the other hand, the state of the art does not propose any glass-ceramic in the Na 2 O-CaO-SiO 2 silico-soda-lime system. He is also supported in the scientific literature, and in particular in the article by Strnad et al. published in Physics and Chemistry of Glasses (Vol.14 No.2 April 1973), that it is impossible to produce a homogeneous crystallization in the volume of a glass belonging to this system and that only heterogeneous, uncontrolled crystallization can be obtained in this case.
Si beaucoup de matériaux vitrocristallins connus ont des propriétés de résistance mécanique et thermique de loin supérieures au verre silico-sodo-calcique amorphe, ils n'en demeurent pas moins beaucoup plus onéreux à produire et dès lors non transposables à des applications courantes pour des raisons économiques. Grâce à sa facilité de production et au faible prix de revient des matières premières, le verre silico-sodo-calcique garde en effet une place prépondérante dans l'industrie du verre et en particulier pour les marchés du bâtiment, de l'automobile et de la décoration. Although many known vitrocrystalline materials have properties of mechanical and thermal resistance far superior to amorphous soda-lime-calcium glass, they are still much more expensive to produce and therefore non-transposable to current applications for reasons economic. Due to its ease of production and the low cost of raw materials, silica-soda-lime glass still holds a prominent place in the glass industry and in particular for the construction, automotive and automotive markets. the decoration.
Il existe dès lors un intérêt économique évident à produire un verre silico-sodo-calcique aux propriétés mécaniques accrues, en particulier une bonne résistance à la propagation des griffes, et qui permet une trempe améliorée. There is therefore an obvious economic interest in producing a silico-soda-lime glass with increased mechanical properties, in particular good resistance to the propagation of claws, and which allows improved quenching.
D'autre part, des verres dits « opalins » comportant une phase vitreuse et une phase cristallines sont également bien connus de la technique et sont obtenus en introduisant un opacifiant, classiquement des fluorures, dans un silicate, un aluminosilicate ou un borosilicate, par une cristallisation intentionnelle ou contrôlée de cristaux (dans le cas de l'ajout de fluorures, les cristaux sont classiquement CaF2 ou NaF). Les verres opalins, très présents dans la vie courante, sont opaques et diffusent la lumière. Ils sont donc principalement utilisés dans des applications de décoration et dans la fabrication de produits de consommation tels que des services de table ou des luminaires. Des verres opalins classiques, commercialisés sous la marque Arcopal®, sont blancs laiteux et sont des fluorosilicates. Néanmoins, l'introduction d'opacifiants classiques tels que des fluorures dans des compositions de verre présente deux inconvénients majeurs: (i) un impact négatif indéniable sur l'environnement et (ii) un phénomène de corrosion des matériaux réfractaires des fours de fusion qui est accentué. On the other hand, so-called "opalins" glasses comprising a vitreous phase and a crystalline phase are also well known in the art and are obtained by introducing an opacifier, conventionally fluorides, into a silicate, an aluminosilicate or a borosilicate, by a intentional or controlled crystallization of crystals (in the case of the addition of fluorides, the crystals are typically CaF 2 or NaF). The opal glasses, very present in the everyday life, are opaque and diffuse the light. They are therefore mainly used in decoration and in the manufacture of consumer products such as table services or lighting fixtures. Classic opal glasses, marketed under the brand name Arcopal®, are milky white and are fluorosilicates. Nevertheless, the introduction of conventional opacifiers such as fluorides in glass compositions has two major disadvantages: (i) an undeniable negative impact on the environment and (ii) a corrosion phenomenon of the refractory materials of the melting furnaces which is accented.
Il y a dès lors également un intérêt à obtenir un verre silico-sodo- calcique présentant un aspect esthétique plaisant, comparables à celui des verres opalins mais qui est exempt de fluor. There is therefore also an interest in obtaining a silico-soda-lime glass having a pleasant aesthetic appearance, comparable to that of opal glasses but which is free of fluorine.
3. Objectifs de l'invention 3. Objectives of the invention
L'invention a notamment pour objectif de pallier aux inconvénients de l'art antérieur en résolvant le problème technique, à savoir obtenir un verre silico- sodo-calcique, c'est-à-dire appartenant au système Na2O-CaO-SiO2, aux propriétés mécaniques accrues, en particulier une bonne résistance à la propagation des griffes, et qui permet également une trempe améliorée. The object of the invention is in particular to overcome the drawbacks of the prior art by solving the technical problem, namely to obtain a soda-lime glass, that is to say belonging to the Na 2 O-CaO-SiO system. 2 , with increased mechanical properties, in particular good resistance to the propagation of claws, and which also allows improved quenching.
Un autre objectif de l'invention est de fournir un verre silico-sodo- calcique possédant, en plus de la résistance mécanique recherchée et du fait qu'il permette une trempe améliorée, le caractère esthétique désiré en fonction de l'application auquel il se destine. L'invention se propose dans ce contexte de fournir un verre silico-sodo-calcique qui soit transparent ou alternativement, ayant une apparence opaque laiteuse plaisante, comparable à celle des verres opalins. Another object of the invention is to provide a soda-lime-silica glass having, in addition to the desired mechanical strength and the fact that it allows an improved quenching, the desired aesthetic character depending on the application to which it is applied. intended. The invention proposes in this context to provide a silico-soda-lime glass which is transparent or alternatively, having a pleasing milky opaque appearance, comparable to that of opal glasses.
Finalement, un objectif de l'invention est de fournir une solution aux désavantages de l'art antérieur qui soit simple, économique et avec un faible impact environnemental. 4. Exposé de l'invention Finally, an object of the invention is to provide a solution to the disadvantages of the prior art that is simple, economical and with a low environmental impact. 4. Presentation of the invention
Conformément à un mode de réalisation particulier, l'invention concerne un verre ayant pour composants principaux SiO2, Na2O et CaO et qui comprend deux phases amorphes de compositions différentes, une des deux phases étant sous forme d'inclusions dispersées dans le volume de l'autre phase. According to a particular embodiment, the invention relates to a glass having as main components SiO 2 , Na 2 O and CaO and which comprises two amorphous phases of different compositions, one of the two phases being in the form of inclusions dispersed in the volume. from the other phase.
Selon l'invention, lesdites inclusions comprennent des particules cristallines. According to the invention, said inclusions comprise crystalline particles.
Ainsi, le verre selon l'invention permet de solutionner les inconvénients des matériaux de l'art antérieur et de résoudre le problème technique posé. Les inventeurs ont en effet mis en évidence qu'il était possible, en générant un phénomène de démixtion couplé à une cristallisation à l'interface amorphe/amorphe et/ou dans le volume des inclusions créées par la démixtion d'obtenir un verre dans le système silico-sodo-calcique aux propriétés mécaniques accrues, en particulier une bonne résistance à la propagation des griffes, et qui possède une apparence acceptable voire plaisante esthétiquement. Ce résultat est surprenant dans la mesure où la transparence et l'homogénéité nécessaires dans les applications communes du verre silico-sodo-calcique (architecture, automobile, etc.) a toujours entraîné l'homme du métier à envisager uniquement des matériaux amorphes et l'a toujours poussé à optimiser la composition du verre ainsi que son procédé de fabrication afin d'éviter ou du moins limiter les phénomènes parasites de dévitrification et de séparation de phase. Thus, the glass according to the invention makes it possible to solve the disadvantages of the materials of the prior art and to solve the technical problem raised. The inventors have indeed demonstrated that it was possible, by generating a demixing phenomenon coupled to crystallization at the amorphous / amorphous interface and / or in the volume of the inclusions created by the demixing to obtain a glass in the silico-soda-lime system with increased mechanical properties, in particular good resistance to the propagation of claws, and which has an acceptable appearance or aesthetically pleasing. This result is surprising insofar as the transparency and homogeneity required in the common applications of silico-soda-lime glass (architecture, automotive, etc.) has always led the skilled person to consider only amorphous materials and the has always pushed to optimize the composition of the glass as well as its manufacturing process in order to avoid or at least limit parasitic phenomena of devitrification and phase separation.
De plus, les inventeurs ont mis en évidence, de façon très surprenante, qu'un verre silico-sodo-calcique présentant une démixtion couplée à une cristallisation permettait d'atteindre des valeurs de CET plus élevées qu'un verre totalement amorphe correspondant. Le verre silico-sodo-calcique démixé selon l'invention possède ainsi une résistance mécanique accrue, en particulier une bonne résistance à la propagation des griffes, et il permet également une trempe améliorée. Ce verre est, de plus, économiquement et esthétiquement acceptable pour des applications courantes dans le bâtiment ou l'automobile. In addition, the inventors have demonstrated, very surprisingly, that a silico-soda-lime glass having a demixing coupled to a crystallization made it possible to reach higher CET values than a correspondingly totally amorphous glass. The silico-soda-lime glass demixed according to the invention thus has an increased mechanical strength, in particular a good resistance to the propagation of claws, and it also allows improved quenching. This glass is, moreover, economically and aesthetically acceptable for common applications in the building or automobile.
L'invention concerne également une feuille constituée du verre tel que décrit précédemment ainsi qu'un article comprenant au moins une telle feuille. The invention also relates to a sheet consisting of glass as described above and an article comprising at least one such sheet.
La présente invention sera décrite plus en détails et de manière non- restrictive. The present invention will be described in more detail and in a non-restrictive manner.
La figure 1 représente un cliché obtenu par microscopie électronique de verres démixés de l'état de la technique. FIG. 1 represents a photograph obtained by electron microscopy of demixed glasses of the state of the art.
La figure 2 représente la position des particules cristallines conformément à l'invention. Figure 2 shows the position of the crystalline particles according to the invention.
5. Description d'un mode de réalisation de l'invention 5. Description of an embodiment of the invention
Le verre selon l'invention est un verre silico-sodo-calcique, c'est-à-dire qui appartient au système Na2O-CaO-SiO2. Le verre de l'invention a dès lors pour composants principaux SiO2, Na2O et CaO. En particulier, le verre de l'invention comprend, en pourcentage en poids total, 60 à 85 % de SiO2, 1 à 25 % de Na2O et 1 à 25 % de CaO. Additionnellement, il peut comprendre d'autres composants en quantités mineures tels que K2O, MgO, Al2O3, BaO, des colorants divers ou des résidus provenant d'additifs modifiant le redox (NaNO3, Na2SO4, coke, ... ). De préférence, ces composants, s'ils sont présents dans le verre de l'invention, ne dépasseront pas au total 15 % en poids du verre. Selon un mode de réalisation particulier de l'invention, le verre est exempt de l'élément fluor. Un tel verre silico-sodo-calcique possède dès lors un faible impact environnemental, en particulier comparé à des verres opalins dont l'opacifiant est classiquement à base d'un de ces composants. Le terme « exempt » signifie dans la présente invention que le verre ne comporte l'élément fluor qu'à l'état de trace. De préférence, le verre ne comporte l'élément fluor qu'en teneur inférieure à 500 ppm en poids. The glass according to the invention is a silico-soda-lime glass, that is to say which belongs to the Na 2 O-CaO-SiO 2 system. The glass of the invention therefore has SiO 2 main components, Na 2 O and CaO. In particular, the glass of the invention comprises, as a percentage by total weight, 60 to 85% of SiO 2 , 1 to 25% of Na 2 O and 1 to 25% of CaO. Additionally, it may comprise other components in minor amounts such as K 2 O, MgO, Al 2 O 3 , BaO, various dyes or residues from redox modifying additives (NaNO 3 , Na 2 SO 4 , coke , ...). Preferably, these components, if present in the glass of the invention, will not exceed a total of 15% by weight of the glass. According to a particular embodiment of the invention, the glass is free of the fluorine element. Such a silico-soda-lime glass therefore has a low environmental impact, particularly compared to opal lenses whose opacifier is conventionally based on one of these components. The term "free" means in the present invention that the glass only has the fluorine element in the trace state. Preferably, the glass comprises the fluorine element only in content of less than 500 ppm by weight.
Selon un mode de réalisation particulier de l'invention, le verre est également exempt de l'élément lithium. L'oxyde de lithium étant plus onéreux que des oxydes comme Na2O et CaO, un tel verre de type silico-sodo-calcique représente dès lors un intérêt économique indéniable, en particulier comparé aux matériaux vitrocéramiques connus de l'état de la technique qui comprennent, le plus souvent, de l'oxyde de lithium. Exempt de l'élément lithium signifie que le verre de l'invention ne comporte cet élément qu'à l'état de trace. De préférence, le verre ne comporte l'élément lithium qu'en teneur inférieure à 500 ppm en poids. According to a particular embodiment of the invention, the glass is also free of the lithium element. Since lithium oxide is more expensive than oxides such as Na 2 O and CaO, such a soda-lime type glass is therefore of undeniable economic interest, in particular compared with the glass-ceramic materials known from the state of the art. which include, most often, lithium oxide. Exempt of the lithium element means that the glass of the invention comprises this element only in trace. Preferably, the glass comprises the lithium element only in content of less than 500 ppm by weight.
Alternativement, selon un autre mode de réalisation particulier de l'invention, le verre peut comprendre du lithium dans des quantités pouvant aller jusqu'à environ 3% en poids, exprimé sous forme de l'oxyde. La présence de lithium dans ces quantités permet de diminuer la viscosité du verre à l'état fondu et de favoriser ainsi la cristallisation. Alternatively, according to another particular embodiment of the invention, the glass may comprise lithium in amounts of up to about 3% by weight, expressed in the form of the oxide. The presence of lithium in these amounts makes it possible to reduce the viscosity of the glass in the molten state and thus to promote crystallization.
Selon un autre mode de réalisation préféré, le verre de l'invention est exempt de l'élément plomb. Exempt de l'élément plomb signifie que le verre de l'invention ne comporte cet élément qu'à l'état de trace. According to another preferred embodiment, the glass of the invention is free of the lead element. Exempt from the lead element means that the glass of the invention comprises this element only in the trace state.
Selon un autre mode de réalisation préféré, le verre de l'invention est exempt de l'élément bore. Exempt de l'élément bore signifie que le verre de l'invention ne comporte cet élément qu'à l'état de trace. Le verre selon l'invention comporte deux phases amorphes de compositions différentes, une des deux phases étant sous forme d'inclusions réparties dans le volume de l'autre phase, appelée phase matricielle. According to another preferred embodiment, the glass of the invention is free of the boron element. Free from the boron element means that the glass of the invention comprises this element only in the trace state. The glass according to the invention comprises two amorphous phases of different compositions, one of the two phases being in the form of inclusions distributed in the volume of the other phase, called the matrix phase.
Selon l'invention, le verre silico-sodo-calcique de l'invention comporte deux phases vitreuses de compositions différentes. En particulier, le verre de l'invention comporte une phase vitreuse sous forme d'inclusions qui est enrichie en SiO2 et dispersée dans l'autre phase vitreuse matricielle qui est enrichie en éléments modificateurs de réseau, tels que le sodium et le calcium. According to the invention, the silico-soda-lime glass of the invention comprises two glassy phases of different compositions. In particular, the glass of the invention comprises a vitreous phase in the form of inclusions which is enriched in SiO 2 and dispersed in the other matrix vitreous phase which is enriched in network modifying elements, such as sodium and calcium.
Conformément à un mode de réalisation particulier de l'invention, les inclusions sont sous forme de gouttelettes ou sous forme de vermiculites. According to a particular embodiment of the invention, the inclusions are in the form of droplets or in the form of vermiculites.
Selon l'invention, les inclusions comprennent des particules cristallines. According to the invention, the inclusions comprise crystalline particles.
Le verre de l'invention peut comprendre des particules cristallines sous forme d'un assemblage de plusieurs particules ou sous forme isolée. The glass of the invention may comprise crystalline particles in the form of an assembly of several particles or in isolated form.
Conformément à un mode de réalisation particulier, les particules cristallines ont une taille comprise entre 5 nm à 500 μιτι. De préférence, afin d'obtenir un verre qui soit transparent, les particules cristallines ont une taille comprise entre 5 nm à 500 nm. De préférence, afin d'obtenir un verre ayant une apparence opaque laiteuse, comparable à celle des verres opalins, les particules cristallines ont une taille comprise entre 500 nm à 500 μιτι. According to a particular embodiment, the crystalline particles have a size of between 5 nm and 500 μιτι. Preferably, in order to obtain a glass which is transparent, the crystalline particles have a size of between 5 nm and 500 nm. Preferably, in order to obtain a glass having an opaque milky appearance, comparable to that of opal glasses, the crystalline particles have a size of between 500 nm and 500 μm.
Selon l'invention, les particules cristallines se trouvent : According to the invention, the crystalline particles are:
(i) à la surface des inclusions, ou  (i) on the surface of the inclusions, or
(ii) dans le volume des inclusions, ou  (ii) in the volume of inclusions, or
(iii) à la fois à la surface et dans le volume des inclusions. Par particule cristalline à la surface d'une inclusion, on entend une particule qui a cristallisé à l'interface amorphe/amorphe. (iii) both on the surface and in the volume of the inclusions. By crystalline particle on the surface of an inclusion is meant a particle that has crystallized at the amorphous / amorphous interface.
La position des particules cristallines est illustrée à la Figure 2 dans le cas d'une démixtion de type gouttelette: The position of the crystalline particles is illustrated in FIG. 2 in the case of a droplet type demixing:
(i) à la surface des inclusions (position 1), ou  (i) on the surface of inclusions (position 1), or
(ii) dans le volume des inclusions (position 2), ou  (ii) in the volume of inclusions (position 2), or
(iii) à la fois à la surface et dans le volume des inclusions (position 1 et 2).  (iii) both on the surface and in the volume of the inclusions (positions 1 and 2).
Avantageusement, la présence des particules cristallines à la surface des inclusions permet d'accroître davantage les propriétés mécaniques, en particulier la résistance à la propagation des fissures du verre. La présence des particules cristallines à la surface des inclusions permet également de limiter la cristallisation trop importante dans le volume des inclusions et ainsi éviter la croissance en volume desdites inclusions. Advantageously, the presence of crystalline particles on the surface of the inclusions makes it possible to further increase the mechanical properties, in particular the resistance to the propagation of cracks in the glass. The presence of crystalline particles on the surface of the inclusions also makes it possible to limit the excessive crystallization in the volume of the inclusions and thus to prevent the volume growth of said inclusions.
Selon un autre mode de réalisation particulier de l'invention, lorsque des particules cristallines se trouvent à la surface des inclusions, elles peuvent être constituées de composés qui peuvent cristalliser au départ de la composition globale du verre tels que le diopside (CaMgSi206), la dévitrite ou la wollastonite (CaSi03). De même, elles peuvent être constituées de composés ajoutés en faible quantité dans la composition globale du verre tels que BaO, TiO2, ZrO2, Nb2O5, ... According to another particular embodiment of the invention, when crystalline particles are on the surface of the inclusions, they may consist of compounds which can crystallize from the overall composition of the glass such as diopside (CaMgSi 2 0 6 ), devitrite or wollastonite (CaSiO 3 ). Similarly, they may consist of compounds added in a small amount in the overall composition of the glass such as BaO, TiO 2 , ZrO 2 , Nb 2 O 5 , etc.
Selon encore un autre mode de réalisation particulier de l'invention, lorsque des particules cristallines se trouvent dans le volume des inclusions, elles sont constituées essentiellement de SiO2. Des impuretés, telles que des composants provenant de la composition du verre et se retrouvant essentiellement dans la phase matricielle, peuvent y être présentes en quantité minimes. Si de telles impuretés sont présentes dans les particules cristallines, elles y sont de préférence en une quantité inférieure à 5 % en poids au total. De manière plus préférée, elles y sont en une quantité inférieure à 2 % en poids au total. According to yet another particular embodiment of the invention, when crystalline particles are in the volume of the inclusions, they consist essentially of SiO 2 . Impurities, such as components from the glass composition and essentially in the matrix phase, may be present in minute amounts. If such impurities are present in the crystalline particles, they are preferably present in a quantity less than 5% by weight in total. More preferably, they are in an amount of less than 2% by weight in total.
Selon ce mode de réalisation particulier, les particules cristallines de SiO2 peuvent être sous forme d' un seul polymorphe de ce composant. Alternativement, les particules cristallines de SiO2 peuvent être sous forme de plusieurs polymorphes de SiO2. Le verre selon l'invention peut également comprendre à la fois des particules sous forme d'un seul polymorphe de SiO2 et des particules sous forme de plusieurs polymorphes de SiO2. According to this particular embodiment, the crystalline particles of SiO 2 can be in the form of a single polymorph of this component. Alternatively, the crystalline particles of SiO 2 can be in the form of several polymorphs of SiO 2 . The glass according to the invention may also comprise both particles in the form of a single polymorph of SiO 2 and particles in the form of several polymorphs of SiO 2 .
Des exemples de polymorphe de SiO2 sont le quartz (a ou β), la cristobalite (a ou β) ou la tridymite (a ou β). Examples of polymorph of SiO 2 are quartz (a or β), cristobalite (α or β) or tridymite (α or β).
Selon un mode de réalisation particulier de l'invention, les particules cristallines de SiO2 sont essentiellement sous forme de cristobalite. According to a particular embodiment of the invention, the crystalline particles of SiO 2 are essentially in the form of cristobalite.
Le verre selon l'invention possède une résistance mécanique accrue, en particulier une bonne résistance à la propagation des griffes, en comparaison avec un verre totalement amorphe correspondant. The glass according to the invention has an increased mechanical strength, in particular a good resistance to the propagation of claws, in comparison with a correspondingly totally amorphous glass.
La résistance mécanique d'un matériau est souvent exprimée en termes de dureté et de ténacité. La dureté caractérise l'aptitude d'un matériau à être griffé ou rayé (exprimé en MPa ou GPa). La ténacité est la capacité d'un matériau à résister à la propagation d'une fissure existante. La fragilité (B ou « brittleness ») peut venir compléter ces paramètres et correspond au rapport entre dureté (H) et ténacité (Kc), H/Kc (exprimée en μιτι"05). Dans la présente invention, la dureté et la fragilité sont mesurées par indentation Vickers. De préférence, le verre selon l'invention possède une fragilité inférieure à 6,5 μηΥ0 5. A titre comparatif, cette valeur est de l'ordre de 7 μηϊ0 5 pour un verre silico-sodo-calcique totalement amorphe, sans traitement particulier. The mechanical strength of a material is often expressed in terms of hardness and toughness. Hardness characterizes the ability of a material to be scratched or scratched (expressed in MPa or GPa). Toughness is the ability of a material to resist the propagation of an existing crack. The fragility (B or "brittleness") can complement these parameters and corresponds to the ratio between hardness (H) and toughness (Kc), H / Kc (expressed in μιτι "05 ) .In the present invention, the hardness and fragility are measured by Vickers indentation. Preferably, the glass according to the invention has a brittleness less than 6.5 μηΥ 0 5 . By way of comparison, this value is of the order of 7 μηϊ 0 5 for a totally amorphous silico-soda-lime glass, with no particular treatment.
De plus, le verre présente un CET plus élevé qu'un verre totalement amorphe correspondant. In addition, the glass has a higher CET than a corresponding totally amorphous glass.
Le réchauffement ou le refroidissement partiel d'un matériau peut, s'il possède une faible conductivité thermique, entraîner des contraintes pouvant provoquer des casses thermiques comme c'est le cas pour le verre silico-sodo- calcique totalement amorphe. The heating or partial cooling of a material can, if it has a low thermal conductivity, lead to stresses that can cause thermal breakages as is the case for the totally amorphous silico-soda-lime glass.
L'importance de ce phénomène de dilatation ou contraction d'un matériau respectivement lors du réchauffement ou du refroidissement partiel est classiquement défini par le coefficient d'expansion thermique linéaire. Ce coefficient d'expansion thermique ou CET correspond à l'allongement par unité de longueur pour une variation de 1°C (exprimé en °C The importance of this phenomenon of expansion or contraction of a material respectively during heating or partial cooling is conventionally defined by the coefficient of linear thermal expansion. This coefficient of thermal expansion or TEC corresponds to the elongation per unit length for a variation of 1 ° C (expressed in ° C
De préférence, le verre selon l'invention présente un CET, mesuré pour une variation de température allant de 25 à 300°C, qui est supérieur 100.10"7/°C. A titre comparatif, le CET, pour le même domaine de températures d'un verre silico- sodo-calcique totalement amorphe, sans traitement particulier, est de l'ordre de 90.10 °C Preferably, the glass according to the invention has a CTE, as measured for a temperature change from 25 to 300 ° C, which is higher than 100.10 "7 / ° C. For comparison, the TEC, for the same temperature range a completely amorphous silico-soda-lime glass, without any particular treatment, is of the order of 90.10 ° C.
Du fait de cette valeur de CET plus élevée, le verre de l'invention permet une trempe améliorée. On entend par verre qui permet une trempe améliorée, un verre qui nécessite, pour obtenir une contrainte en compression à la surface équivalente à celle d'un verre totalement amorphe correspondant, une trempe à une température plus faible et/ou pendant un temps plus court. Dès lors, cet avantage permet un gain d'énergie ce qui entraîne un effet positif supplémentaire de l'invention d'un point de vue environnemental et économique. De même, on entend également par verre qui permet une trempe améliorée, un verre qui présente, à traitement thermique équivalent, une contrainte en compression à la surface supérieure à celle d'un verre totalement amorphe correspondant. Finalement, on entend également par verre qui permet une trempe améliorée, un verre qui permet la trempe de feuilles « minces » faites de ce verre. Because of this higher CET value, the glass of the invention allows for improved quenching. By glass, which allows an improved quenching, is meant a glass which, in order to obtain a compression stress on the surface equivalent to that of a corresponding totally amorphous glass, requires quenching at a lower temperature and / or for a shorter time. . Therefore, this advantage allows an energy gain which results in an additional positive effect of the invention from an environmental and economic point of view. Similarly, we mean also by glass which allows improved quenching, a glass which has, with equivalent heat treatment, a compression stress on the surface greater than that of a correspondingly totally amorphous glass. Finally, glass is also meant for improved quenching, a glass which allows the quenching of "thin" sheets made of this glass.
Le verre silico-sodo-calcique selon l'invention peut être obtenu par tout procédé capable de générer un phénomène de démixtion couplé à une cristallisation à l'interface amorphe/amorphe et/ou dans le volume des inclusions créées par la démixtion. The silico-soda-lime glass according to the invention can be obtained by any process capable of generating a demixing phenomenon coupled with crystallization at the amorphous / amorphous interface and / or in the volume of the inclusions created by the demixing.
En particulier, le verre selon l'invention peut être obtenu par deux voies : (i) un traitement thermique contrôlé du verre à l'état fondu (céramisation), ou (ii) une recuisson contrôlée d'un verre de même composition globale mais solidifié au préalable à l'état totalement amorphe. In particular, the glass according to the invention can be obtained by two routes: (i) controlled thermal treatment of glass in the molten state (ceramization), or (ii) controlled annealing of a glass of the same overall composition but previously solidified in the fully amorphous state.
Dans les deux cas, un traitement thermique appelé céramisation est opéré. La céramisation comprend généralement, de manière connue, les étapes suivantes, qui peuvent être répétées plusieurs fois : a) élévation de la température jusqu'à la température T (palier de céramisation) qui est située au-delà de l'intervalle de nucléation ; In both cases, a heat treatment called ceramization is performed. The ceramization generally comprises, in a known manner, the following steps, which may be repeated several times: a) raising the temperature to the temperature T (ceramification plateau) which is situated beyond the nucleation interval;
b) maintien de la température T pendant un temps t ;  b) maintaining the temperature T for a time t;
c) refroidissement rapide jusqu'à la température ambiante.  c) rapid cooling to room temperature.
Le verre selon l'invention peut être utilisé pour fabriquer des articles de formes et de tailles différentes. Il peut, par exemple, être utilisé pour fabriquer des flacons, des globes pour luminaires et des objets de décoration. The glass according to the invention can be used to manufacture articles of different shapes and sizes. It can, for example, be used to make vials, globes for lighting and decorative objects.
En particulier, le verre de l'invention peut être utilisé pour fabriquer une feuille dudit verre. Conformément à ce mode de réalisation, et du fait de sa résistance accrue à la propagation des griffes, il peut, par exemple, être utilisé pour un plan de travail dans une cuisine ou un laboratoire, pour des tables et étagères ou en tant que revêtement de sol (dallage, passerelle). Toujours conformément à ce mode de réalisation, et du fait que le verre permet également une trempe améliorée, il peut également être utilisé pour fabriquer des panneaux solaires ou des vitrages automobiles. In particular, the glass of the invention can be used to make a sheet of said glass. According to this embodiment, and because of its increased resistance to the propagation of claws, it can, for example, be used for a worktop in a kitchen or a laboratory, for tables and shelves or as a floor covering (pavement, walkway). Still in accordance with this embodiment, and because the glass also allows for improved quenching, it can also be used to manufacture solar panels or automotive glazings.
Un exemple d'article conforme à l'invention comportant plus d'une feuille dudit verre est une paroi murale qui est « feuilletée » pour améliorer l'aspect sécurité, c'est-à-dire qui comprend deux feuilles assemblées par un ou plusieurs films d'intercalaire plastique. An example of an article according to the invention comprising more than one sheet of said glass is a wall wall which is "laminated" to improve the safety aspect, that is to say which comprises two sheets assembled by one or more plastic interlayer films.

Claims

REVENDICATIONS
1. Verre ayant pour composants principaux SiO2, Na2O et CaO, qui comprend deux phases amorphes de compositions différentes, une des deux phases étant sous forme d'inclusions dispersées dans le volume de l'autre phase, caractérisé en ce que lesdites inclusions comprennent des particules cristallines. 1. Glass having as main components SiO 2 , Na 2 O and CaO, which comprises two amorphous phases of different compositions, one of the two phases being in the form of inclusions dispersed in the volume of the other phase, characterized in that said inclusions include crystalline particles.
2. Verre selon la revendication précédente, caractérisé en ce qu'il comprend, en pourcentage en poids total, 60 à 85 % de SiO2, 1 à 25 % de Na2O et 1 à 25 % de CaO. 2. Glass according to the preceding claim, characterized in that it comprises, as a percentage by total weight, 60 to 85% of SiO 2 , 1 to 25% of Na 2 O and 1 to 25% of CaO.
3. Verre selon l'une des revendications précédentes, caractérisé en ce que les inclusions sont sous forme de gouttelettes ou de vermiculites.  3. Glass according to one of the preceding claims, characterized in that the inclusions are in the form of droplets or vermiculites.
4. Verre selon l'une des revendications précédentes, caractérisé en ce que les particules cristallines sont à la surface des inclusions et/ou dans le volume des inclusions.  4. Glass according to one of the preceding claims, characterized in that the crystalline particles are on the surface of the inclusions and / or in the volume of the inclusions.
5. Verre selon la revendication précédente, caractérisé en ce que les particules cristallines dans le volume des inclusions sont constituées essentiellement de SiO2. 5. Glass according to the preceding claim, characterized in that the crystalline particles in the volume of the inclusions consist essentially of SiO 2 .
6. Verre selon la revendication précédente, caractérisé en ce que les particules cristallines sont sous forme d'un ou plusieurs polymorphes de SiO2. 6. Glass according to the preceding claim, characterized in that the crystalline particles are in the form of one or more polymorphs of SiO 2 .
7. Verre selon l'une des revendications 1 à 6, caractérisé en ce que les particules cristallines ont une taille comprise entre 5 nm à 500 μιτι.  7. Glass according to one of claims 1 to 6, characterized in that the crystalline particles have a size between 5 nm to 500 μιτι.
8. Verre selon la revendication précédente, caractérisé en ce que les particules cristallines ont une taille comprise entre 5 nm à 500 nm.  8. Glass according to the preceding claim, characterized in that the crystalline particles have a size between 5 nm to 500 nm.
9. Verre selon la revendication 7, caractérisé en ce que les particules cristallines ont une taille comprise entre 500 nm à 500 μιτι.  9. Glass according to claim 7, characterized in that the crystalline particles have a size between 500 nm to 500 μιτι.
10. Verre selon l'une des revendications précédentes, caractérisé en ce qu'il possède une fragilité, mesurée par indentation Vickers, inférieure à 6,5 μιτι"05. 10. Glass according to one of the preceding claims, characterized in that it has a brittleness, measured by Vickers indentation, less than 6.5 μιτι "05 .
11. Verre selon l'une des revendications précédentes, caractérisé en ce qu'il possède un CET, mesuré pour une variation de température allant de 25 à 300°C, qui est supérieur 100.10 °Ο 11. Glass according to one of the preceding claims, characterized in that it has a CET, measured for a temperature variation ranging from 25 to 300 ° C, which is greater than 100.10 ° Ο
12. Verre selon l'une des revendications précédentes, caractérisé en ce qu'il est exempt de l'élément fluor. 12. Glass according to one of the preceding claims, characterized in that it is free of the fluorine element.
13. Verre selon l'une des revendications précédentes, caractérisé en ce qu'il est exempt de l'élément plomb.  13. Glass according to one of the preceding claims, characterized in that it is free of the lead element.
14. Feuille caractérisée en ce qu'elle est constituée du verre de l'un des revendications 1 à 14.  14. Sheet characterized in that it consists of the glass of one of claims 1 to 14.
15. Article caractérisé en ce qu'il comporte au moins une feuille selon la revendication précédente.  15. Article characterized in that it comprises at least one sheet according to the preceding claim.
EP10768950A 2009-10-26 2010-10-26 Phase-separated soda-lime-silica glass Withdrawn EP2493827A1 (en)

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EP09174013A EP2314551A1 (en) 2009-10-26 2009-10-26 Phase separated soda-lime glass
EP10768950A EP2493827A1 (en) 2009-10-26 2010-10-26 Phase-separated soda-lime-silica glass
PCT/EP2010/066117 WO2011051257A1 (en) 2009-10-26 2010-10-26 Phase-separated soda-lime-silica glass

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EA021638B1 (en) 2015-07-30
EP2314551A1 (en) 2011-04-27
US20120196735A1 (en) 2012-08-02
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WO2011051257A1 (en) 2011-05-05
BR112012009850A2 (en) 2019-09-24

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