EP4237383A1

EP4237383A1 - Reinforced glass-ceramic article

Info

Publication number: EP4237383A1
Application number: EP21811412.2A
Authority: EP
Inventors: Thibault GUEDON; Micheline PLICHARD; Xavier Brajer; Nicolas Roux
Original assignee: Eurokera SNC
Current assignee: Eurokera SNC
Priority date: 2020-10-30
Filing date: 2021-10-28
Publication date: 2023-09-06
Also published as: DE202021004022U1; WO2022090670A1; KR20230096069A; CN116472255A; JP2023547489A; FR3115779A1

Abstract

The present invention relates to a glass-ceramic article comprising at least one substrate, such as a plate, made of glass-ceramic, said substrate being coated on its lower face, in at least one zone, with at least one fibrous structure comprising a resin. The glass-ceramic article thus exhibits markedly improved impact resistance.

Description

Title of the invention: REINFORCED VITRO-CERAMIC ARTICLE

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the field of glass-ceramics. More specifically, it relates to an article, or product, made of glass-ceramic, in particular a glass-ceramic plate intended to be used as a surface for furniture and/or as a cooking surface.

By glass-ceramic or glass-ceramic article is meant an article based on a substrate (such as a plate) of non-porous glass-ceramic material, said substrate possibly being provided with accessories or additional, decorative or functional elements. , required for its end use, the article possibly designating both the substrate alone and that provided with additional equipment (for example a cooking plate provided with its control panel, its heating elements, etc.).

TECHNOLOGICAL BACKGROUND OF THE INVENTION

A glass-ceramic is originally a glass, called precursor glass or mother glass or green-glass, whose specific chemical composition makes it possible to cause controlled crystallization through suitable heat treatments, called ceramization. This specific partially crystallized structure gives glass-ceramics unique properties.

There are currently different types of glass-ceramic hobs, each variant being the result of extensive studies and numerous tests, given that it is very delicate to make modifications to these hobs and/or to their production process without risking an adverse effect on the desired properties.

Vitroceramic hobs must also have sufficient mechanical strength as required in their field of use. In particular, in order to be able to be used as a hob in the field of household appliances or as a surface for furniture, a glass-ceramic hob must have good resistance to pressure, to shocks (support and falling of utensils, etc.), etc. .

Traditionally, ceramic hobs are used as cooking plates, or they can also be associated with heating elements in other applications, for example to form fireplace inserts. Recently, their use has been extended to other areas of daily life: glass-ceramic hobs can thus be used as furniture surfaces, in particular to form worktops, central islands, consoles, etc. the surface they occupy in these new applications being greater than in the past.

Document FR 2868065 A1, in the name of the Applicant, describes glass-ceramic plates whose mechanical strength is reinforced by the addition of a paint applied by screen printing and polymerized at 250° C. in air. This layer is deposited on the entire underside. The present invention aims to obtain greater mechanical strengths.

Currently, to increase the impact resistance of glass-ceramic hobs, it is also possible:

- either to increase their thickness;

- either to carry out a strict control of the manufacturing process: to limit friction/scratches on the underside, or a reinforced quality control of defects at the exit of the oven.

The inventors have demonstrated that it is possible to improve the impact resistance of glass-ceramic plates by applying to their lower surface a fibrous structure comprising a resin, in particular a structure such as those generally called in English “prepreg”.

SUMMARY OF THE INVENTION

The subject of the present invention is a glass-ceramic article, comprising at least one substrate, such as a glass-ceramic plate, said substrate being coated, on its lower face, in at least one zone, with a fibrous structure comprising fibers and a resin matrix, in particular polymeric.

In particular, the article according to the invention is a cooking device further comprising one or more heating elements.

In particular, said fibrous structure comprises fibers chosen from among glass fibers, carbon fibers, aramid fibers, quartz fibers, Kevlar fibers and their mixture.

Preferably, the fibers are glass fibers or carbon fibers, and even more preferably glass fibers.

Advantageously, said fibrous structure has a density of fibers comprised between 50 and 1000 g/m ² , preferably comprised between 100 and 800 g/m ² and even more preferably between 150 and 600 g/m ² .

In particular, said resin is chosen from thermosetting resins, preferably from epoxy, phenolic or polyimide resins.

The fibrous structure can comprise one or more layers of a woven, unidirectional or multiaxial structure, preferably of a woven structure.

In particular, said structure is deposited on at least 40% of the surface of the substrate, preferably over at least 50% and even more preferably at least 60% of the surface of the substrate. Savings are provided in the fibrous structure, at the location of the heating zones, possibly of the control strip, and of the edges of the substrate.

In particular, said fibrous structure has a coefficient of expansion greater than the coefficient of expansion of the glass-ceramic plate.

According to particular embodiments, the substrate also comprises, on certain parts of its surface, an enamel coating, advantageously deposited on the upper face of the substrate.

The present invention also relates to a method for manufacturing a glass-ceramic article comprising at least one substrate, such as a glass-ceramic plate, on which is applied a fibrous structure comprising fibers and a resin matrix, then said substrate, thus coated, is subjected to heat treatment under pressure (in an autoclave) or under vacuum.

The heat treatment is generally carried out at a temperature of between 100 and 200°C, preferably between 120 and 150°C, at a pressure of between 100 and 400 mbar, preferably between 150 and 350 mbar and for a period of between 30 min and 3h, preferably between 40 min and 2h, and more preferably between 50 min and 1h30.

The glass-ceramic article according to the invention is in particular a plate, or a device or appliance, for cooking or any movable article integrating (or comprising, or formed from) at least one substrate made of glass-ceramic (material) (the substrate being the most commonly in the form of a plate, coming to be integrated or to be mounted in the piece of furniture and/or combined with other elements to form the piece of furniture), said substrate possibly being able to present zones of a display nature (in combination for example with light emitting sources) or decorated areas or be combined with heating elements. In its most common application, the article according to the invention is intended to serve as a hob, this hob generally being intended to be integrated into a hob or cooker also comprising heating elements, for example radiant or halogen or induction heating elements.

When the article according to the invention is a cooking plate comprising heating zones and a control strip, before applying the fibrous structure, the latter is pre-cut to the size of the substrate and savings are cut in the structure. at the level of the heating zones and possibly at the level of the control panel.

The thickness of the glass-ceramic substrate is generally at least 2 mm, in particular at least 2.5 mm, and is advantageously less than 15 mm, in particular is of the order of 3 to 15 mm, in particular of the order of 3 to 8 mm or around 3 to 6 mm. The substrate is preferably a flat or quasi-flat plate (in particular with a deflection less than 0.1% of the diagonal of the plate, and preferably of the order of zero).

The substrate may be based on any glass-ceramic, this substrate advantageously having a coefficient of thermal expansion (or in English “Coefficient of Thermal Expansion”, CTE) of zero or almost zero, in particular less (in absolute value) than 30.10′ ⁷ K′ ¹ between 20 and 700°C, in particular less than 15×10′ ⁷ K′ ¹ , or even less than 5×10′ ⁷ K′ ¹ between 20 and 700°C.

The invention is particularly advantageous for substrates with a dark appearance, these substrates being weakly transmissive and not very scattering, and being in particular based on any glass-ceramic having, intrinsically, a light transmission TL of less than 40%, in particular less than 5%, in particular from 0.2 to 2% for glass-ceramics up to 6 mm thick, and an optical transmission (determined in a known manner by making the ratio between the transmitted intensity and the incident intensity at a wavelength data) between 0.5 and 3% for a wavelength of 625 nm in the visible range.

By "intrinsically" is meant that the substrate possesses such transmission by itself, without the presence of any coating. The optical measurements are made according to the EN 410 standard. In particular, the light transmission TL is measured according to the EN 410 standard using the D65 illuminant, and is the total transmission (in particular integrated in the visible range and weighted by the curve sensitivity of the human eye), taking into account both direct transmission and any diffuse transmission, the measurement being made, for example, using a spectrophotometer equipped with an integrating sphere (in particular with the spectrophotometer marketed by the company Perkin Elmer under the reference Lambda 950).

According to one embodiment, the substrate is a substrate with a black or brown appearance, making it possible, in combination with light sources placed underneath, to display light zones or decorations, while masking any underlying elements. It may in particular be based on a black glass-ceramic comprising crystals of 0-quartz structure within a residual vitreous phase, the absolute value of its coefficient of expansion being advantageously less than or equal to 15.10′ ⁷ K′ ¹ , or even at 5.10′ ⁷ K′ ¹ , such as the glass-ceramic plates marketed under the name Kerablack+ by the company Eurokera. It may be in particular a glass-ceramic of composition as described in patent application EP0437228 or US5070045 or FR2657079, or a glass-ceramic refined with tin having a rate of arsenic oxides preferably less than 0.1%. , as described for example in patent application WO 2012/156444, or even a glass-ceramic refined with sulphide(s) as described in patent application WO2008053110, etc.

According to one embodiment, the substrate may have an acid-etched top surface. According to another embodiment, the substrate is a substrate with an opaque and/or low-transmissive appearance, while being diffusing and sufficiently clear (the clarity being given by the luminosity L*), the glass material being in particular colored or dyed in the mass (this coloration including white and all colors with a luminosity L* greater than 10, darker colors such as black or dark brown being excluded), as specified below.

La vitrocéramique utilisée peut être notamment de composition telle que décrite dans les demandes de brevets publiées sous les numéros suivants : EP1300372, US6706653, WO9906334, W02007113242, EP1840093, US2007213192, US7476633, JP2009531261 , WO2012156444, W02012001300, DE202012011811 , cette vitrocéramique étant en particulier une lithium aluminosilicate glass-ceramic and also advantageously comprising colorants.

For example, a glass-ceramic comprising the following constituents and/or obtained by ceramization from a glass of the following composition is advantageously used, within the limits below, expressed in percentages by weight: SiO2: 52-75%; Al2O3: 18 - 27%; Li2O: 2.5 - 5.5%; K2O: 0 - 3%; Na ₂ O: 0 - 3%; ZnO: 0 - 4%; MgO: 0 - 5%; CaO: 0 - 2.5%; BaO: 0 - 3.5%; SrO: 0 - 2%; TiO2: 0 - 5.5%; ZrC>2: 0 - 3%; P2O5: 0 - 8%, B2O3: 0 - 5%, and preferably, within the limits below expressed in percentages by weight: SiO2: 55 - 70%; Al2O3: 18 - 24%; Li2O: 2.5 - 4.5%; K ₂ O: 0 - 2.0%; Na ₂ O: 0 - 2.0%; ZnO: 1.5-4%; MgO: 0.20 - 5%; CaO: 0 - 1%; BaO: 0 - 3%; SrO: 0 - 1.4%; TiO2: 1.8-5%; ZrC>2: 0 - 2.5%, P2O5: 0 - 8%, B2O3: 0 - 5%, this composition also comprising, where appropriate, additional dyes.

The substrate according to the invention can, if necessary, be coated with other coatings or layers with a functional effect (anti-overflow layer, opacifying layer, etc.) and/or decorative, in particular localized, such as usual patterns based on enamels (for example on the upper side to form simple patterns or logos) or a layer of opacifying paint on the underside of the substrate, etc. In particular, the substrate may be coated with at least one layer of enamel and/or paint, in particular of the luster type, localized or nom

The article according to the invention may further comprise, associated or combined with the substrate, one or more light sources and/or one or more heating elements (or heating elements, such as one or more radiating or halogen elements and/or one or more atmospheric gas burners and/or one or more induction heating means), generally placed on the underside of the substrate. The article according to the invention has in particular good thermal resistance compatible with the use of various types of heaters. The product according to the invention in particular does not undergo thermal degradation at temperatures above 400° C. which can be reached in particular in applications such as use as cooking plates.

Where appropriate, the method also includes a cutting operation (generally before ceramization), for example by water jet, mechanical tracing with a wheel, etc. followed by a shaping operation (grinding, bevelling, etc.). BRIEF DESCRIPTION OF FIGURES

[Fig. 1] illustrates the resistance results of examples 1a, 1b and 1c compared to Ref 1; [Fig. 2] illustrates the strength results of Examples 3a, 3b and 3c versus Ref 3; [Fig. 3] illustrates the results of Comparative Example 4 against Ref 4;

DETAILED DESCRIPTION

Ball drop test:

A test has been developed to identify the impact resistance of ceramic hobs. It consists of placing a sample of glass-ceramic substrate on a wooden frame and dropping a 500g steel ball at heights of 5 to 195 cm, incremented in steps of 5 cm until the sample breaks.

The results table includes:

- the height of the sample having broken at the lowest ball drop height;

- the height of the sample having broken at the highest drop height; and

- the average height for all the samples.

Samples that resisted the impact at 195 cm are considered to have broken at 195 cm. This gives a slight underestimate of the average fall height.

Example 1

Fig 1

Reference 1: 10 white vitroceramic plates of the Kerawhite® type, 300×300 mm ² and 6 mm thick, underwent the ball drop test.

Example 1a): 5 samples of white glass-ceramic of the Kerawhite® type, 300×300 mm ² and 6 mm thick, were covered on their underside with three plies of a pre-impregnated fabric of the TenCat Laminate 7781 type. Each ply comprises glass fibers with a density of 300g/m ² , impregnated with an epoxy resin.

The samples then underwent autoclave treatment.

Example 1 b): 8 samples of white glass-ceramic of the Kerawhite® type of 300×300 mm ² and 6 mm thick were covered on their lower face with a fold of a pre-impregnated fabric of the CBX401 type from the Sicomin company. The fabric comprises carbon fibers at a density of 400g/m ² impregnated with an Epoxy resin (IMP503Z). The samples then underwent a heat treatment for 1 hour 30 minutes at 130° C. at atmospheric pressure.

Example 1C) (comparative): 5 samples of white glass-ceramic of the Kerawhite® type, 300×300 mm ² and 6 mm thick, were covered on their underside with an epoxy resin of the Loctite EA9497 type not reinforced with fibres. The polymerization of the resin is done in the open air, without heat treatment.

Example 2

Reference 2: The same white vitroceramic plates of the Kerawhite® type 300×300 mm ² and 6 mm thick as in Example 1 are used. In this example, they are placed on a flat support in laminated wood 28 mm thick.

Example 2: A sample was covered on its underside with three plies of a preimpregnated fabric of the TenCat Laminate 7781 type. Each ply comprises glass fibers impregnated with an Epoxy resin at a density of 300 g/m ² .

The sample then underwent a heat treatment for 1 hour, under vacuum, at 120°C. During the test, the sample is also placed on a flat support in laminated wood 28mm thick.

Example 3

Fig 2

Reference 3: Black glass-ceramic plates 6 mm thick, of the Kerablack+® type are used. In this example they have dimensions of 900×600 mm ² .

Example 3 a: A sample was covered on its underside with two plies of a pre-impregnated fabric of the GG204T Twill type. Each ply comprises carbon fibers with a density of 220g/m ² , impregnated with an Epoxy resin.

The sample then underwent a treatment for one hour, under vacuum, at 120°C.

Example 3 b (comp): A sample was covered on its underside with two plies of a pre-impregnated fabric of the GG204T Twill type. Each ply comprises carbon fibers with a density of 220g/m ² , impregnated with an Epoxy resin.

The sample then underwent a one-hour treatment at 120°C. Example 3c: Another sample was covered on its underside with a ply of a fiberglass fabric (300 g/m2) impregnated with an epoxy resin. The sample then underwent a heat treatment for one hour at 130° C. and at 250 mbar.

Example 4

Fig.3

Reference 4: Black glass-ceramic plates 6 mm thick, of the same Kerablack+® type as in Example 3 are used. In this example, they have dimensions of 300×300 mm ² .

Example 4 (comparative): five samples were covered on their underside with Epoxy glue and then with a fabric of EV200 type glass fibers (not impregnated beforehand). The fabric is glued manually without heat treatment. The polymerization of the resin is done in the open air.

Results

fig. 1 represents the case heights (means, minimum and maximum) of example 1.

fig. 2 represents the case heights (means, minimum and maximum) of example 3.

fig. 3 represents the case heights (means, minimum and maximum) of example 4

The table below shows the break height values of each of the embodiments obtained during the ball drop test. A star “*” indicates that the plate withstood this ball drop height without damage. [Table 1]

Splinter retention

Examples 1a, 1b, 2, 3a, 3c and 4 have made it possible to show retention of glass-ceramic splinters during breakage. The examples of references never made it possible to retain the splinters during the breakage of the substrate. Example 1 c (with resin not reinforced with fibers) does not allow the retention of splinters either.

Break height

Examples 1a, 1b, 2 and 3a and 3c show a significant improvement in the resistance to the fall of a 500 g ball compared to their respective references. Example 4 (non-impregnated fabric ^ bonded without heat treatment) does not show a significant improvement in impact resistance.

The articles according to the invention can in particular be used with advantage to produce a new range of hobs for cookers or hobs or a new range of work tables, consoles, splashbacks, central islands, etc.

Claims

[Claim 1] Glass-ceramic article, comprising at least one substrate, such as a glass-ceramic plate, said substrate being coated, on its underside, in at least one zone, with a fibrous structure comprising fibers and a resin matrix .

[Claim 2] Glass-ceramic article according to Claim 1, characterized in that the said structure comprises fibers chosen from among glass fibers, carbon fibers, aramid fibers, quartz fibers, Kevlar fibers, and their mixed.

[Claim 3] Glass-ceramic article according to any one of Claims 1 and 2, characterized in that the said structure has a fiber density of between 50 and 1000 g/m ² , preferably between 100 and 800 g/m ² and more preferably between 150 and 600 g/m ² .

[Claim 4] Glass-ceramic article according to any one of the preceding claims, characterized in that the said resin is chosen from thermosetting resins.

[Claim 5] Glass-ceramic article according to any one of the preceding claims, characterized in that the said resin is chosen from epoxy, phenolic or polyimide resins.

[Claim 6] Glass-ceramic article according to any one of the preceding claims, characterized in that the fibrous structure comprises one or more layers of a woven, unidirectional or multiaxial structure.

[Claim 7] Glass-ceramic article according to any one of the preceding claims, characterized in that the said structure is deposited on at least 40% of the surface of the substrate, preferably on at least 50% and even more preferably on at least 60% of the surface of the substrate.

[Claim 8] Glass-ceramic article according to any one of the preceding claims, characterized in that the said fibrous structure has a coefficient of expansion greater than the coefficient of expansion of the glass-ceramic plate.

[Claim 9] Glass-ceramic article according to any one of the preceding claims, characterized in that the substrate also comprises, on certain parts of its surface, an enamel coating.

[Claim 10] Glass-ceramic article according to the preceding claim, characterized in that the enamel coating is placed on the upper face of the substrate.

[Claim 11] A method of manufacturing a glass-ceramic article comprising at least one substrate, such as a glass-ceramic plate, on which applies a fibrous structure comprising fibers and a resin matrix, then said substrate, thus coated, is subjected to heat treatment under pressure (in an autoclave) or under vacuum.

[Claim 12] Process according to Claim 11, characterized in that the heat treatment is carried out at a temperature of between 100 and 200°C, preferably between 120 and 150°C.

[Claim 13] Process according to either of Claims 11 and 12, characterized in that the heat treatment is carried out at a pressure of between 100 and 400 mbar, preferably between 150 and 350 mbar.

[Claim 14] Process according to any one of Claims 11 to 13, characterized in that the heat treatment is carried out for a period of between 30 min and 3 h, preferably between 40 min and 2 h, and more preferably between 50 min and 1h30.

[Claim 15] Process according to any one of Claims 11 to 14, in which the article is a cooking plate comprising heating zones and a control strip, the process being characterized in that before applying the fibrous structure, this is pre-cut to the size of the substrate and savings are cut in the structure at the level of the heating zones and possibly at the level of the control panel.