EP2007574A1 - Fireproof glazing - Google Patents

Fireproof glazing

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Publication number
EP2007574A1
EP2007574A1 EP07728237A EP07728237A EP2007574A1 EP 2007574 A1 EP2007574 A1 EP 2007574A1 EP 07728237 A EP07728237 A EP 07728237A EP 07728237 A EP07728237 A EP 07728237A EP 2007574 A1 EP2007574 A1 EP 2007574A1
Authority
EP
European Patent Office
Prior art keywords
layer
intumescent
silica
glazing according
intumescent layer
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Withdrawn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
EP07728237A
Other languages
German (de)
French (fr)
Inventor
Olivier Aldenhoff
Bertrand Dury
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
Original Assignee
AGC Glass Europe SA
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 filed Critical AGC Glass Europe SA
Priority to EP07728237A priority Critical patent/EP2007574A1/en
Publication of EP2007574A1 publication Critical patent/EP2007574A1/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Withdrawn legal-status Critical Current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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/069—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of intumescent material
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials

Definitions

  • the present invention relates to fire-resistant glazing comprising at least one layer of a hydrated alkali silicate whose exposure to fire causes the formation of an opaque foam which opposes the transmission of radiation and maintains the glass sheets to which the layer or layers of alkali silicate are associated.
  • the invention relates more particularly to the glazings in question, the intumescent layer of which is prepared by drying an alkaline silicate solution.
  • the invention is more particularly directed to glazings in which the intumescent layer consists of mainly sodium silicates.
  • the products in which the layer or layers of silicates are formed by drying are traditionally obtained from commercial solutions of silicates, solutions to which are added various additives which improve the properties and / or the conditions of use.
  • the layers are produced by spreading the solution on a support and by proceeding to a more or less prolonged drying. During drying the layer solidifies.
  • the silicate layer thus formed is then included in a laminated assembly during one or more calendering and steaming operations.
  • the industrial solutions of alkali silicates are chosen as the basic raw material of these intumescent layers because of their low cost. In return these solutions whose composition is set so that they remain fluid (their viscosity is of the order of 100 mPax) have a relatively high water content.
  • the commercially available solutions of sodium silicates according to their molar ratio SiO 2 / Na 2 O have the following water content by weight:
  • intumescent layers depend on many factors and in particular their water content but also the molar ratio SiO 2 / Na 2 O.
  • the molar ratio is related to the more or less "refractory" nature of the intumescent layer. The higher it is, the more refractory is the product.
  • This character is quantified in particular by the value of the creep temperature of the intumescent layer. This temperature designated “Td” is that for which the material is deformed under a given pressure. This temperature depends on the stability of the glazing in the fire test. To keep the glass sheets or pieces of the sheets after they have broken under thermal stress, it is important to have a Td as high as possible.
  • the molar ratio of the commercialized solutions does not normally exceed 4.
  • One reason for this situation is that these solutions to remain stable contain all the more water as the molar ratio is higher.
  • the cost of transporting and storing these solutions does not increase the moisture content beyond what is currently practiced.
  • the inventors have proposed to provide glazing comprising an intumescent layer of sodium silicate having a molar ratio SiO 2 / Na 2 O higher than in the usual products prepared from commercial solutions of silicates.
  • the intumescent layers are prepared from solutions of industrial sodium silicates to which appropriate amounts of colloidal silica are added to reach a molar ratio of greater than 4 and which can be up to 7.
  • the molar ratio is advantageously between 4 and 6, and preferably between 4.5 and 5.6.
  • the intumescent layers whose molar ratio is as indicated above also have substantially improved creep characteristics. If all things being equal the molar ratio of the solutions traditionally used is approximately 3.3 for a temperature creep of the order of 428 ° C, creep of the temperatures of the layers according to the invention are greater than 470 0 C and preferably above 480 0 C, and particularly preferably above 490 ° C.
  • the temperature values "Td" are determined as follows. Glazing formed of two glasses on either side of the fireproof layer to be characterized is manufactured. A 50mm square sample is cut from the side and a central hole is drilled.
  • the sample is pre-expanded at 230 ° C. for 30 minutes and then cooled to room temperature.
  • the measurement of Td is carried out in a furnace-dome (marketed under the name
  • TONININDUSTRIE model 57075 with temperature control, charging device, measuring thermocouples and differential measuring device.
  • the sample is positioned in abutment against the lower probe, which thus characterizes the lower face of the sample.
  • the second probe passes through the sample through the central hole and thus characterizes the upper face of the sample.
  • a load of 2.5kg is applied to the sample.
  • Td The temperature Td is that for which the sample begins to flow, which results in a crushing of the layer.
  • the fireproof properties of the intumescent layers also depend significantly on their water content.
  • the water contents recommended according to the invention which result from a compromise between these conflicting requirements are advantageously from 20 to 45% by weight of the layer, and preferably from 22 to 35%.
  • the silicate prepared layers according to the invention are subjected to drying in order to reduce the water contents to the values indicated above. This drying is longer as the initial content of the composition is higher. For this reason it is preferable when adding the colloidal silica suspension to make sure to introduce as little water as possible. It is advantageous to choose suspensions containing at least 30% by weight of silica and preferably at least 40% of silica and the silica content of these suspensions may be up to 50% or more.
  • the intumescent layers according to the invention also advantageously comprise various additives.
  • Plastics of the layers according to the invention are advantageously present in them at levels which do not exceed 25% by weight, and preferably 20% by weight. These contents are advantageously greater than or equal to 5% by weight and preferably greater than 6%.
  • the combined water and polyol contents preferably do not exceed 50% by weight of the intumescent layer, and particularly preferably do not exceed 45% by weight.
  • aqueous silica suspensions contain some polyols introduced to facilitate dispersion and improve the stability of these dispersions.
  • the use of these suspensions is a way of introducing at least some of these polyols into the compositions of the intumescent layers.
  • TEOS tetraethylorthosilicate
  • MTEOS trimethoxy-methylsilane
  • the amine compounds preferably do not exceed 2% by weight of the layer.
  • Other amino compounds such as TMAH (tetramethyl amine hydroxide) or a salt thereof can improve aging behavior (haze).
  • surfactants are frequently introduced into the initial compositions.
  • compositions to form the intumescent layers can be carried out according to the traditional techniques.
  • the composition is poured onto a glass sheet and then dried for a long time in an enclosure with a stream of air whose temperature and moisture content are controlled.
  • the duration of the drying depends in particular on the initial water content, hence the importance as far as possible of limiting it by using the compounds which make it possible to obtain the lowest water content compatible with the stability of the water. the composition.
  • the water content is necessarily relatively high.
  • the initial water content is not less than 55% and generally not less than 60%.
  • the duration of the drying is also a function of the thickness of the composition treated, and consequently of the thickness of the intumescent layer produced.
  • the thicknesses of the layers produced advantageously remain at most equal to 3 mm and are most often between 1 and 2 mm.
  • the drying described above is performed statically.
  • the sheets coated with the composition are treated batchwise in a chamber until the chosen drying is obtained. It is also known to carry out this drying in a "continuous" manner. In these techniques, the composition to be dried is deposited in the form of a film on a support conveyor, which progresses continuously in a tunnel-type drying oven.
  • the time allowed for drying under these conditions is necessarily shorter than that of drying in enclosures, and, given that the drying time increases faster than the thickness of the layer, for a determined final water content, the layers obtained under these conditions can have only a limited thickness compared with those obtained in static drying.
  • the formed layer can be separated from the support, the superposition of several layers can compensate for the small thickness of each.
  • the support may also consist of a flexible film which is integrated in the final laminate.
  • Films of this type are especially polyolefin films (polyethylene, polypropylene) and polyethylene terephthalate (PTFE) films.
  • the determination of the creep temperature Td shows a value of 464 ° C.
  • a higher molar ratio composition is prepared.
  • silicate solution is added 145 g of colloidal silica suspension comprising 30% by weight of silica (product sold under the name Ludox HS 30), 60 g of glycerin and 3 g of TMAH.
  • the molar ratio of the mixture SiO 2 ZNa 2 O is 4.6.
  • the mixture is homogenized by intense stirring and then dried to a water content of 28% by weight.
  • a laminated assembly comprising two glass sheets 3 mm thick on either side of the intumescent layer is constituted.
  • the creep temperature of the intumescent layer of the glazing is measured at 523 ° C.
  • Example 2 A composition is prepared as in Example 1 from the same industrial silicate solution of 3.85 molar ratio. This time, 191 g of silica suspension containing 50% by weight of silica (marketed under the name of Ludox TM 50) is added.
  • the molar ratio is 5.5 and the water content of the intumescent layer is 30%.
  • the creep temperature in the same structure with two glass sheets 3 mm thick each is 537 ° C.
  • the mixture is prepared as in the previous example. To this time, 60 g of silica suspension containing 30% by weight of silica are added to 1000 g of silicate solution.
  • the molar ratio is 7. After drying, the water content is 33% by weight of the layer. The creep temperature is then 548 ° C.
  • assemblies made from the intumescent layers prepared according to the methods of the invention are not limited to the combination comprising an intumescent layer between two sheets of glass.
  • Various assemblies with several intumescent layers associated with several glass sheets increase the fire resistance properties.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention concerns fireproof glazings. The inventive glazings comprise at least one layer of an intumescent material based on hydrated sodium silicate, wherein the intumescent layer is obtained at least partly from a colloidal silica suspension, the intumescent layer having a SiO<SUB>2</SUB>/Na<SUB>2</SUB>O mole ratio greater than 4. The inventive glazings provide an improved resistance to high temperatures.

Description

Vitrage anti-feu Fire-resistant glazing
La présente invention concerne les vitrages anti-feu comprenant au moins une couche d'un silicate alcalin hydraté dont l'exposition au feu engendre la formation d'une mousse opaque qui s'oppose à la transmission des radiations et maintient les feuilles de verre auxquelles la ou les couches de silicate alcalin sont associées. L'invention concerne plus particulièrement les vitrages en question dont la couche intumescente est préparée par séchage d'une solution de silicates alcalins.The present invention relates to fire-resistant glazing comprising at least one layer of a hydrated alkali silicate whose exposure to fire causes the formation of an opaque foam which opposes the transmission of radiation and maintains the glass sheets to which the layer or layers of alkali silicate are associated. The invention relates more particularly to the glazings in question, the intumescent layer of which is prepared by drying an alkaline silicate solution.
L'invention vise encore plus particulièrement les vitrages dont la couche intumescente est constituée de silicates principalement de sodium.The invention is more particularly directed to glazings in which the intumescent layer consists of mainly sodium silicates.
Les produits dans lesquels la ou les couches de silicates sont formées par séchage, sont obtenus traditionnellement à partir de solutions commerciales de silicates, solutions auxquelles sont ajoutés des additifs divers qui en améliorent les propriétés et/ou les conditions de mise en oeuvre. Les couches sont produites en répandant la solution sur un support et en procédant à un séchage plus ou moins prolongé. Au cours du séchage la couche se solidifie.The products in which the layer or layers of silicates are formed by drying are traditionally obtained from commercial solutions of silicates, solutions to which are added various additives which improve the properties and / or the conditions of use. The layers are produced by spreading the solution on a support and by proceeding to a more or less prolonged drying. During drying the layer solidifies.
La couche de silicate ainsi formée, éventuellement directement sur une feuille de verre, est ensuite incluse dans un ensemble feuilleté au cours d'une ou plusieurs opérations de calandrage et d'étuvage.The silicate layer thus formed, optionally directly on a glass sheet, is then included in a laminated assembly during one or more calendering and steaming operations.
Les solutions industrielles de silicates alcalins sont choisies comme matière première de base traditionnelle de ces couches intumescentes en raison de leur faible coût. En contrepartie ces solutions dont la composition est réglée de telle sorte qu'elles restent fluides (leur viscosité est de l'ordre de lOOmPaxs) présentent une teneur en eau relativement élevée. A titre indicatif les solutions disponibles dans le commerce de silicates de sodium en fonction de leur rapport molaire SiO2/Na2O présentent les teneurs en eau pondérales suivantes :The industrial solutions of alkali silicates are chosen as the basic raw material of these intumescent layers because of their low cost. In return these solutions whose composition is set so that they remain fluid (their viscosity is of the order of 100 mPax) have a relatively high water content. As an indication, the commercially available solutions of sodium silicates according to their molar ratio SiO 2 / Na 2 O have the following water content by weight:
On note qu'en pratique, les solutions de silicates industrielles ne sont pas disponibles à des rapports molaires supérieurs à environ 4.It is noted that in practice, industrial silicate solutions are not available at molar ratios greater than about 4.
Les propriétés des couches intumescentes dépendent de nombreux facteurs et en particulier de leur teneur en eau mais aussi du rapport molaire SiO2/Na2O. Le rapport molaire est lié au caractère plus ou moins "réfractaire" de la couche intumescente. Plus il est élevé, plus réfractaire est le produit. Ce caractère est quantifié notamment par la valeur de la température de fluage de la couche intumescente. Cette température désignée "Td" est celle pour laquelle le matériau se déforme sous une pression donnée. De cette température dépend la stabilité du vitrage dans l'épreuve au feu. Pour maintenir les feuilles de verre ou les morceaux des feuilles après que celles-ci se soient brisées sous les contraintes thermiques, il est important d'avoir une Td aussi élevée que possible.The properties of intumescent layers depend on many factors and in particular their water content but also the molar ratio SiO 2 / Na 2 O. The molar ratio is related to the more or less "refractory" nature of the intumescent layer. The higher it is, the more refractory is the product. This character is quantified in particular by the value of the creep temperature of the intumescent layer. This temperature designated "Td" is that for which the material is deformed under a given pressure. This temperature depends on the stability of the glazing in the fire test. To keep the glass sheets or pieces of the sheets after they have broken under thermal stress, it is important to have a Td as high as possible.
L'accroissement de la température de fluage n'est pas sans contrepartie. L'augmentation du rapport molaire tend à réduire la plasticité de la couche intumescente. Suivant le type d'utilisation considéré pour le vitrage, cette plasticité peut être requise en particulier lorsque le vitrage doit résister à ce qui est dénommé "choc mou".The increase in creep temperature is not without compensation. Increasing the molar ratio tends to reduce the plasticity of the intumescent layer. Depending on the type of use considered for the glazing, this plasticity may be required especially when the glazing must withstand what is called "soft impact".
Néanmoins pour d'autres applications l'intérêt de l'accroissement de la résistance au fluage prévaut sur les caractéristiques de plasticité. Pour d'autres applications encore, par des structures de vitrages appropriées, il est possible de combiner l'avantage de la résistance au fluage accrue et le maintien de plasticité globale du vitrage, par exemple par l'association dans un même vitrage de couches de compositions différentes les unes présentant une bonne plasticité, les autres un caractère réfractaire accentué.Nevertheless for other applications the interest of the increase of the creep resistance prevails over the characteristics of plasticity. For still other applications, by appropriate glazing structures, it is It is possible to combine the advantage of the increased creep resistance and the maintenance of overall plasticity of the glazing, for example by the combination in the same glazing of layers of different compositions, one having a good plasticity, the others an accentuated refractory character.
Comme indiqué ci-dessus, le rapport molaire des solutions commercialisées ne dépasse pas normalement 4. Une raison de cette situation tient au fait que ces solutions pour rester stables renferment d'autant plus d'eau que le rapport molaire est plus élevé. Le coût de transport et de stockage de ces solutions ne permet pas d'accroître la teneur en eau au-delà de ce qui est pratiqué à l'heure actuelle.As indicated above, the molar ratio of the commercialized solutions does not normally exceed 4. One reason for this situation is that these solutions to remain stable contain all the more water as the molar ratio is higher. The cost of transporting and storing these solutions does not increase the moisture content beyond what is currently practiced.
Les inventeurs se sont proposés de fournir des vitrages comportant une couche intumescente de silicate de sodium présentant un rapport molaire SiO2/Na2O plus élevé que dans les produits usuels préparés à partir des solutions commerciales de silicates.The inventors have proposed to provide glazing comprising an intumescent layer of sodium silicate having a molar ratio SiO 2 / Na 2 O higher than in the usual products prepared from commercial solutions of silicates.
Selon l'invention les couches intumescentes sont préparées à partir de solutions de silicates de sodium industrielles auxquelles sont ajoutées des quantités appropriées de silice colloïdale pour atteindre un rapport molaire supérieur à 4 et qui peut s'élever jusqu'à 7. Selon l'invention le rapport molaire est avantageusement compris entre 4 et 6, et de préférence compris entre 4,5 et 5,6.According to the invention, the intumescent layers are prepared from solutions of industrial sodium silicates to which appropriate amounts of colloidal silica are added to reach a molar ratio of greater than 4 and which can be up to 7. According to the invention the molar ratio is advantageously between 4 and 6, and preferably between 4.5 and 5.6.
Dans la préparation des compositions soumises au séchage, l'introduction de silice pulvérulente qui aurait pour avantage de ne pas ajouter d'eau, à l'expérience n'apparaît pas réalisable de façon pratique. La dispersion homogène de la silice dans ces solutions de silicates est extrêmement difficile, même sous une agitation intense prolongée. Pour cette raison les inventeurs choisissent d'utiliser de préférence les suspensions aqueuses de silice colloïdale les plus concentrées disponibles dans le commerce.In the preparation of the compositions subjected to drying, the introduction of pulverulent silica which would have the advantage of not adding water, the experiment does not appear practically feasible. The homogeneous dispersion of the silica in these silicate solutions is extremely difficult, even under prolonged intense agitation. For this reason the inventors choose to use preferably the most concentrated aqueous colloidal silica suspensions available commercially.
S'il est possible de préparer entièrement des compositions de silicate de sodium en faisant réagir une suspension de silice avec une solution de soude ou même avec des pastilles de soude, pour des raisons de coût il est préférable selon l'invention dans la préparation de la composition de silicate soumise à séchage, de conserver une part significative de solution de silicate industrielle. Par ailleurs si l'apport de silice sous forme de suspension colloïdale est plus coûteux que celui des silicates industriels, la teneur en eau liée à ces suspensions peut conduire à un séchage moins important. Il s'agit en conséquence de choisir le meilleur compromis. Dans tous les cas l'apport de silice sous forme de suspension aqueuse colloïdale n'est pas inférieur à 10% de la silice totale et peut s'élever à 80% de celle-ci. De préférence la part de silice colloïdale n'est pas supérieure à 60% de la silice totale.If it is possible to fully prepare sodium silicate compositions by reacting a silica suspension with a solution For reasons of cost, it is preferable, according to the invention in the preparation of the silicate composition subjected to drying, to retain a significant proportion of industrial silicate solution. Moreover, if the supply of silica in the form of colloidal suspension is more expensive than that of industrial silicates, the water content related to these suspensions may lead to less drying. It is therefore a question of choosing the best compromise. In all cases the supply of silica in the form of colloidal aqueous suspension is not less than 10% of the total silica and may amount to 80% thereof. Preferably, the portion of colloidal silica is not greater than 60% of the total silica.
Les couches intumescentes dont le rapport molaire est tel qu'indiqué ci-dessus présentent en outre des caractéristiques de fluage sensiblement améliorées. Si toutes choses égales par ailleurs le rapport molaire des solutions traditionnellement utilisées s'établit à environ 3,3 pour une température de fluage de l'ordre de 428°C, les températures de fluages des couches selon l'invention sont supérieures à 4700C et de préférence supérieures à 4800C, et de façon particulièrement préférée supérieures à 490°C.The intumescent layers whose molar ratio is as indicated above also have substantially improved creep characteristics. If all things being equal the molar ratio of the solutions traditionally used is approximately 3.3 for a temperature creep of the order of 428 ° C, creep of the temperatures of the layers according to the invention are greater than 470 0 C and preferably above 480 0 C, and particularly preferably above 490 ° C.
Les valeurs de température "Td" sont déterminées de la façon suivante. Un vitrage formé de deux verres de part et d'autre de la couche anti-feu à caractériser est fabriqué. On y découpe un échantillon carré de 50mm de côté et on y perce un trou central deThe temperature values "Td" are determined as follows. Glazing formed of two glasses on either side of the fireproof layer to be characterized is manufactured. A 50mm square sample is cut from the side and a central hole is drilled.
15mm de diamètre. L'échantillon est pré-expansé à 2300C pendant 30 minutes puis refroidi à température ambiante. La mesure de Td s'effectue dans un four-dôme (commercialisé sous le nom15mm in diameter. The sample is pre-expanded at 230 ° C. for 30 minutes and then cooled to room temperature. The measurement of Td is carried out in a furnace-dome (marketed under the name
TONININDUSTRIE, modèle 5705) avec régulation de température, dispositif de mise en charge, thermocouples de mesure et dispositif de mesure différentielle. A l'aide de cales en alumine, l'échantillon est positionné en butée, contre le palpeur inférieur, qui caractérise ainsi la face inférieure de l'échantillon. Le second palpeur traverse l'échantillon par le trou central et caractérise ainsi la face supérieure de l'échantillon. Une charge de 2.5kg est appliquée sur l'échantillon. Par mesure différentielle des deux palpeurs, on détermine la dilatation/compression de l'échantillon lorsque la température augmente de 5°C/minute. La température Td est celle pour laquelle l'échantillon commence à fluer, ce qui se traduit par un écrasement de la couche. En dehors du rapport molaire les qualités anti-feu des couches intumescentes dépendent aussi significativement de leur teneur en eau. Mais celle-ci intervient aussi sur la qualité optique des vitrages obtenus. Globalement si l'accroissement de la teneur en eau peut améliorer les performances à l'épreuve du feu, les couches intumescentes contenant une forte teneur en eau ont tendance à être moins stables au vieillissement. Il est difficile de garantir que ces produits restent parfaitement transparents. Il se forme souvent un voile qui va en s'accentuant au fil du temps.TONININDUSTRIE, model 5705) with temperature control, charging device, measuring thermocouples and differential measuring device. Using alumina shims, the sample is positioned in abutment against the lower probe, which thus characterizes the lower face of the sample. The second probe passes through the sample through the central hole and thus characterizes the upper face of the sample. A load of 2.5kg is applied to the sample. By differential measurement of the two probes, the expansion / compression of the sample is determined when the temperature increases by 5 ° C./minute. The temperature Td is that for which the sample begins to flow, which results in a crushing of the layer. Apart from the molar ratio, the fireproof properties of the intumescent layers also depend significantly on their water content. But it also affects the optical quality of glazing obtained. Overall, if increasing water content can improve fire performance, intumescent layers with high water content tend to be less stable to aging. It is difficult to guarantee that these products remain perfectly transparent. It often forms a veil that becomes more pronounced over time.
Les teneurs en eau préconisées selon l'invention qui résultent d'un compromis entre ces exigences contradictoires sont avantageusement de 20 à 45% en poids de la couche, et de préférence de 22 à 35%.The water contents recommended according to the invention which result from a compromise between these conflicting requirements are advantageously from 20 to 45% by weight of the layer, and preferably from 22 to 35%.
Les couches préparées à base de silicates selon l'invention font l'objet d'un séchage pour ramener les teneurs en eau aux valeurs indiquées ci- dessus. Ce séchage est d'autant plus long que la teneur initiale de la composition est plus élevée. Pour cette raison il est préférable lors de l'ajout de la suspension de silice colloïdale de faire en sorte d'introduire le moins d'eau possible. On choisit avantageusement des suspensions contenant au moins 30% en poids de silice et de préférence au moins 40% de silice et la teneur en silice de ces suspensions peut s'élever à 50% ou plus.The silicate prepared layers according to the invention are subjected to drying in order to reduce the water contents to the values indicated above. This drying is longer as the initial content of the composition is higher. For this reason it is preferable when adding the colloidal silica suspension to make sure to introduce as little water as possible. It is advantageous to choose suspensions containing at least 30% by weight of silica and preferably at least 40% of silica and the silica content of these suspensions may be up to 50% or more.
Les couches intumescentes selon l'invention comportent encore avantageusement divers additifs.The intumescent layers according to the invention also advantageously comprise various additives.
Traditionnellement, l'adjonction d'un polyol, notamment de glycérine, dans la composition est utilisée pour améliorer les caractéristiques mécaniques des couches intumescentes. En contrepartie, la présence de polyol ou de manière générale de composés organiques doit être précisément ajustée pour ne pas altérer le comportement au feu.Traditionally, the addition of a polyol, especially glycerin, in the composition is used to improve the mechanical characteristics of the intumescent layers. In return, the presence of polyol or in general of organic compounds must be precisely adjusted not to alter the fire behavior.
Les polyols utilisés notamment pour l'amélioration des qualitésPolyols used especially for the improvement of qualities
"plastiques" des couches selon l'invention, sont avantageusement présents dans celles-ci à des teneurs qui n'excèdent pas 25% en poids, et de préférence 20% en poids. Ces teneurs sont avantageusement supérieures ou égales à 5% en poids et, de préférence, supérieures à 6%."Plastics" of the layers according to the invention are advantageously present in them at levels which do not exceed 25% by weight, and preferably 20% by weight. These contents are advantageously greater than or equal to 5% by weight and preferably greater than 6%.
Les teneurs combinées eau et polyols de préférence ne dépassent pas 50% en poids de la couche intumescente, et de manière particulièrement préférée ne dépassent pas 45% en poids.The combined water and polyol contents preferably do not exceed 50% by weight of the intumescent layer, and particularly preferably do not exceed 45% by weight.
Les suspensions aqueuses de silice disponibles dans le commerce, contiennent pour certaines des polyols, introduits pour faciliter la dispersion et améliorer la stabilité de ces dispersions. L'utilisation de ces suspensions est une manière d'introduction au moins partielle de ces polyols dans les compositions des couches intumescentes.Commercially available aqueous silica suspensions contain some polyols introduced to facilitate dispersion and improve the stability of these dispersions. The use of these suspensions is a way of introducing at least some of these polyols into the compositions of the intumescent layers.
D'autres additifs traditionnels avantageusement utilisés dans les couches intumescentes selon l'invention sont constitués par les composés de type TEOS (tétraéthyl-orthosilicate) ou MTEOS (trimethoxy-méthyl-silane). Ces composés sont introduits dans les couches notamment pour en améliorer les propriétés mécaniques. Leur introduction conduit à des teneurs qui ne dépassent pas 3% en poids de la couche.Other traditional additives advantageously used in the intumescent layers according to the invention consist of compounds of TEOS (tetraethylorthosilicate) or MTEOS (trimethoxy-methylsilane) type. These compounds are introduced into the layers in particular to improve the mechanical properties. Their introduction leads to contents that do not exceed 3% by weight of the layer.
Il est encore connu d'introduire des composés aminés, et notamment l'urée, qui améliorent la formation de mousses homogènes lors de l'expansion sous l'effet de la chaleur. Selon l'invention les composés aminés de préférence n'excèdent pas 2% en poids de la couche. D'autres composés aminés tels que le TMAH (tétraméthyl aminé hydroxyde) ou un sel de celui-ci peuvent améliorer le comportement au vieillissement (haze).It is still known to introduce amino compounds, and especially urea, which improve the formation of homogeneous foams during expansion under the effect of heat. According to the invention, the amine compounds preferably do not exceed 2% by weight of the layer. Other amino compounds such as TMAH (tetramethyl amine hydroxide) or a salt thereof can improve aging behavior (haze).
Par ailleurs pour faciliter le contact de la couche intumescente avec le substrat sur lequel elle est déposée pour effectuer le séchage, des agents tensioactifs sont fréquemment introduits dans les compositions initiales.Moreover to facilitate the contact of the intumescent layer with the substrate on which it is deposited to effect drying, surfactants are frequently introduced into the initial compositions.
Le séchage des compositions pour former les couches intumescentes peut être effectué suivant les techniques traditionnelles. Dans la forme la plus usuelle, la composition est versée sur une feuille de verre puis longuement séchée dans une enceinte parcourue par un courant d'air dont la température et le taux d'humidité sont contrôlés.The drying of the compositions to form the intumescent layers can be carried out according to the traditional techniques. In the most usual form, the composition is poured onto a glass sheet and then dried for a long time in an enclosure with a stream of air whose temperature and moisture content are controlled.
La durée du séchage est fonction notamment de la teneur initiale en eau, d'où l'importance dans la mesure du possible de limiter celle-ci en employant les composés qui permettent d'obtenir la plus faible teneur en eau compatible avec la stabilité de la composition. En pratique aux rapports molaires considérés la teneur en eau est nécessairement relativement élevée. Dans les compositions soumises au séchage, aux rapports molaires considérés la teneur en eau initiale n'est pas inférieure à 55% et généralement pas inférieure à 60%.The duration of the drying depends in particular on the initial water content, hence the importance as far as possible of limiting it by using the compounds which make it possible to obtain the lowest water content compatible with the stability of the water. the composition. In practice, at the molar ratios considered, the water content is necessarily relatively high. In the compositions subjected to drying, at molar ratios considered the initial water content is not less than 55% and generally not less than 60%.
La durée du séchage croissant comme le carré de la teneur en eau, le choix de compositions initiales est particulièrement important pour que le temps nécessaire pour le séchage, et donc son coût ne deviennent pas prohibitifs.The increasing drying time as the square of the water content, the choice of initial compositions is particularly important so that the time required for drying, and therefore its cost do not become prohibitive.
La durée du séchage est aussi fonction de l'épaisseur de composition traitée, et par suite de l'épaisseur de la couche intumescente produite. Pour limiter le processus de séchage, en pratique les épaisseurs des couches produites restent avantageusement au plus égales à 3mm et se situent le plus souvent entre 1 et 2mm.The duration of the drying is also a function of the thickness of the composition treated, and consequently of the thickness of the intumescent layer produced. To limit the drying process, in practice the thicknesses of the layers produced advantageously remain at most equal to 3 mm and are most often between 1 and 2 mm.
Pour éviter la formation de couches dont le séchage est trop long, il est aussi traditionnel éventuellement de superposer plusieurs couches préalablement séchées. Le cas échéant les couches superposées peuvent avoir été séparées du support sur lequel elles ont été séchées. Le séchage décrit précédemment est effectué de façon statique. Les feuilles revêtues de la composition sont traitées par lots dans une enceinte jusqu'à obtenir le séchage choisi. Il est connu aussi de procéder à ce séchage de façon "continue". Dans ces techniques la composition à sécher est déposée sous forme d'un film sur un convoyeur support, lequel progresse de façon continue dans un four de séchage de type tunnel.To avoid the formation of layers whose drying is too long, it is also traditional to superimpose several previously dried layers. If necessary, the superimposed layers may have been separated from the support on which they have been dried. The drying described above is performed statically. The sheets coated with the composition are treated batchwise in a chamber until the chosen drying is obtained. It is also known to carry out this drying in a "continuous" manner. In these techniques, the composition to be dried is deposited in the form of a film on a support conveyor, which progresses continuously in a tunnel-type drying oven.
Le temps alloué au séchage dans ces conditions est nécessairement plus court que celui du séchage dans des enceintes, et, compte tenu de ce que le temps de séchage croît plus vite que l'épaisseur de la couche, pour une teneur en eau finale déterminée, les couches obtenues dans ces conditions ne peuvent avoir qu'une épaisseur limitée par rapport à celles obtenues en séchage statique. La couche formée pouvant être séparée du support, la superposition de plusieurs couches permet de compenser la faible épaisseur de chacune d'elles.The time allowed for drying under these conditions is necessarily shorter than that of drying in enclosures, and, given that the drying time increases faster than the thickness of the layer, for a determined final water content, the layers obtained under these conditions can have only a limited thickness compared with those obtained in static drying. The formed layer can be separated from the support, the superposition of several layers can compensate for the small thickness of each.
Dans ces techniques de séchage en continu, le support peut aussi être constitué d'un film souple qui est intégré dans le feuilleté final. Des films de ce type sont notamment des films de polyoléfines (polyéthylène, polypropylène) et des films de polytéréphtalate d'éthylène glycol (PTFE).In these continuous drying techniques, the support may also consist of a flexible film which is integrated in the final laminate. Films of this type are especially polyolefin films (polyethylene, polypropylene) and polyethylene terephthalate (PTFE) films.
Les exemples suivants illustrent l'invention de façon détaillée.The following examples illustrate the invention in detail.
Exemple comparatif 1.Comparative Example 1
Une composition à base de silicate de sodium industrielle de rapport molaire apparent SiO2/Na2O égal à 3,35, de 65% en poids d'eau, comprend en outre 6% en poids de glycérine et 0,25% en poids de TMAH.An industrial sodium silicate composition having an apparent SiO 2 / Na 2 O molar ratio equal to 3.35, of 65% by weight of water, further comprises 6% by weight of glycerine and 0.25% by weight. of TMAH.
Cette solution est coulée sur une feuille de verre "float" de 3mm d'épaisseur bordée par un cordon d'étanchéité maintenant la solution. Après séchage jusqu'à une teneur en eau de 24% en poids de la couche, on forme un feuilleté avec une deuxième feuille de verre de 3mm d'épaisseur. La température de fluage Td mesurée est de 428°C. Exemple comparatif 2.This solution is poured onto a 3mm thick float glass sheet surrounded by a sealing bead holding the solution. After drying to a water content of 24% by weight of the layer, a laminate is formed with a second glass sheet 3 mm thick. The measured creep temperature Td is 428 ° C. Comparative Example 2
Une composition à base de silicate de sodium industrielle de rapport molaire apparent SiO2/Na2O égal à 3,85, de 70% en poids d'eau, comprend en outre 5% en poids de glycérine et 0,50% en poids de TMAH.An industrial sodium silicate composition having an apparent SiO 2 / Na 2 O molar ratio equal to 3.85, of 70% by weight of water, also comprises 5% by weight of glycerol and 0.50% by weight. of TMAH.
Cette composition est séchée jusqu'à une teneur en eau analogue à celle de l'exemple comparatif 1. Elle entre ensuite de la même façon dans un assemblage feuilleté dont chaque feuille de verre est de 3mm d'épaisseur.This composition is dried to a water content similar to that of Comparative Example 1. It then enters the same way into a laminated assembly of which each glass sheet is 3 mm thick.
La détermination de la température de fluage Td montre une valeur de 464°C.The determination of the creep temperature Td shows a value of 464 ° C.
Exemple 1.Example 1
Partant d'une solution de silicate de sodium de rapport molaire 3,85 dont la teneur pondérale en eau est de 70% on prépare une composition à rapport molaire plus élevé. Pour cela à 1000g de solution de silicate on ajoute 145g de suspension de silice colloïdale comprenant 30% en poids de silice (produit commercialisé sous le nom de Ludox HS 30), 60 g de glycérine et 3g de TMAH. Le rapport molaire du mélange SiO2ZNa2O est de 4,6.Starting from a solution of sodium silicate of 3.85 molar ratio with a water content of 70% by weight, a higher molar ratio composition is prepared. For this, 1000 g of silicate solution is added 145 g of colloidal silica suspension comprising 30% by weight of silica (product sold under the name Ludox HS 30), 60 g of glycerin and 3 g of TMAH. The molar ratio of the mixture SiO 2 ZNa 2 O is 4.6.
Le mélange est homogénéisé par agitation intense, puis séché jusqu'à une teneur en eau de 28% en poids. On constitue comme précédemment un assemblage feuilleté comprenant deux feuilles de verre de 3mm d'épaisseur de part et d'autre de la couche intumescente.The mixture is homogenized by intense stirring and then dried to a water content of 28% by weight. As before, a laminated assembly comprising two glass sheets 3 mm thick on either side of the intumescent layer is constituted.
La température de fluage de la couche intumescente du vitrage est mesurée à 523°C.The creep temperature of the intumescent layer of the glazing is measured at 523 ° C.
L'accroissement du rapport molaire dans les conditions de l'invention se traduit par une augmentation significative de la température de fluage de la couche intumescente.Increasing the molar ratio under the conditions of the invention results in a significant increase in the creep temperature of the intumescent layer.
Exemple 2. Une composition est préparée comme à l'exemple 1 à partir de la même solution de silicate industrielle de rapport molaire 3,85. On ajoute cette fois 191g de suspension de silice à 50% en poids de silice (commercialisée sous le nom de Ludox TM 50).Example 2 A composition is prepared as in Example 1 from the same industrial silicate solution of 3.85 molar ratio. This time, 191 g of silica suspension containing 50% by weight of silica (marketed under the name of Ludox TM 50) is added.
Le rapport molaire est de 5,5 et la teneur en eau de la couche intumescente est de 30%.The molar ratio is 5.5 and the water content of the intumescent layer is 30%.
La température de fluage dans la même structure à deux feuilles de verre de 3mm d'épaisseur chacune est de 537°C.The creep temperature in the same structure with two glass sheets 3 mm thick each is 537 ° C.
Exemple 3.Example 3
Le mélange est préparé comme à l'exemple précédent. A 1000g de solution de silicate on ajoute cette fois 608g de suspension de silice à 30% en poids de silice.The mixture is prepared as in the previous example. To this time, 60 g of silica suspension containing 30% by weight of silica are added to 1000 g of silicate solution.
Le rapport molaire s'établit à 7. Après séchage la teneur en eau est de 33% en poids de la couche. La température de fluage est alors de 548°C.The molar ratio is 7. After drying, the water content is 33% by weight of the layer. The creep temperature is then 548 ° C.
Les exemples précédents montrent l'importance de la composition de la couche intumescente et particulièrement du rapport molaire SiO2/Na2O sur le caractère "réfractaire" des vitrages.The preceding examples show the importance of the composition of the intumescent layer and particularly of the SiO 2 / Na 2 O molar ratio on the "refractory" character of the glazings.
Bien entendu les assemblages réalisés à partir des couches intumescentes préparées selon les modalités de l'invention ne se limitent pas à la combinaison comportant une couche intumescente entre deux feuilles de verre. Des assemblages variés comportant plusieurs couches intumescentes associées à plusieurs feuilles de verre permettent d'accroître les propriétés de résistance au feu. Of course, the assemblies made from the intumescent layers prepared according to the methods of the invention are not limited to the combination comprising an intumescent layer between two sheets of glass. Various assemblies with several intumescent layers associated with several glass sheets increase the fire resistance properties.

Claims

REVENDICATIONS
1. Vitrage anti-feu comprenant au moins une couche d'un matériau intumescent à base de silicate de sodium hydraté, dans lequel la couche intumescente est obtenue par séchage d'une solution préparée au moins en partie à partir d'une suspension de silice colloïdale, la couche intumescente présentant un rapport molaire SiO2/Na2O supérieur à 4.An anti-fire glazing comprising at least one layer of an intumescent material based on hydrated sodium silicate, wherein the intumescent layer is obtained by drying a solution prepared at least in part from a silica suspension colloidal layer, the intumescent layer having an SiO 2 / Na 2 O molar ratio greater than 4.
2. Vitrage selon la revendication 1 dans lequel le rapport molaire2. Glazing according to claim 1 wherein the molar ratio
SiO2/Na2O de la couche intumescente est au plus égal à 7.SiO 2 / Na 2 O of the intumescent layer is at most equal to 7.
3. Vitrage selon la revendication 1 dans lequel le rapport molaire3. Glazing according to claim 1 wherein the molar ratio
SiO2/Na2O de la couche intumescente est compris entre 4 et 6.SiO 2 / Na 2 O of the intumescent layer is between 4 and 6.
4. Vitrage selon l'une des revendications précédentes dans lequel la silice introduite sous forme de suspension aqueuse de silice colloïdale représente au moins 10% de toute la silice de la couche.4. Glazing according to one of the preceding claims wherein the silica introduced as an aqueous suspension of colloidal silica is at least 10% of all the silica of the layer.
5. Vitrage selon la revendication 4 dans laquelle la part de silice introduite sous forme colloïdale à la totalité de la silice présente dans la couche intumescente n'est pas supérieure à 80%.5. Glazing according to claim 4 wherein the silica portion introduced in colloidal form to the entire silica present in the intumescent layer is not greater than 80%.
6. Vitrage selon l'une des revendications précédentes dans lequel la couche intumescente présente une température de fluage Td supérieure à 4700C.6. Glazing according to one of the preceding claims wherein the intumescent layer has a creep temperature Td greater than 470 0 C.
7. Vitrage selon l'une des revendications précédentes dans lequel la couche intumescente présente une température de fluage Td supérieure à 4800C.7. Glazing according to one of the preceding claims wherein the intumescent layer has a creep temperature Td greater than 480 0 C.
8. Vitrage selon l'une des revendications précédentes dans lequel la teneur en eau de la couche intumescente est comprise entre 20 et 45% en poids et de préférence de 22 et 35%.8. Glazing according to one of the preceding claims wherein the water content of the intumescent layer is between 20 and 45% by weight and preferably 22 and 35%.
9. Vitrage selon l'une des revendications précédentes dans lequel la couche intumescente comprend en plus un ou plusieurs polyols en quantité au plus égale à 25% et de préférence au plus égale à 20% en poids.9. Glazing according to one of the preceding claims wherein the intumescent layer further comprises one or more polyols in an amount of at most 25% and preferably at most equal to 20% by weight.
10. Vitrage selon la revendication 9 dans lequel la couche intumescente comprend une teneur en polyols qui n'est pas inférieure à 5% en poids.10. Glazing according to claim 9 wherein the intumescent layer comprises a polyol content of not less than 5% by weight.
11. Vitrage selon l'une des revendications précédentes dans lequel une part du sodium présent dans la couche est introduite sous forme d'hydroxyde de sodium en solution concentrée ou sous forme de pastilles. 11. Glazing according to one of the preceding claims wherein a part of the sodium present in the layer is introduced in the form of sodium hydroxide in concentrated solution or in the form of pellets.
EP07728237A 2006-04-19 2007-04-18 Fireproof glazing Withdrawn EP2007574A1 (en)

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PCT/EP2007/053775 WO2007118887A1 (en) 2006-04-19 2007-04-18 Fireproof glazing
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EP2072247A1 (en) * 2007-12-17 2009-06-24 AGC Flat Glass Europe SA Fireproof glazing
CH704939B1 (en) * 2008-03-10 2012-11-15 Akzo Nobel Chemicals Int Bv Translucent heat protection element with aluminate or boratmodifiziertem silica.
CH702479A1 (en) * 2009-12-21 2011-06-30 Vetrotech Saint Gobain Int Ag Protection element and method for producing.
CH703342A8 (en) 2010-06-29 2012-04-30 Vetrotech Saint Gobain Int Ag FIRE PROTECTION COMPOSITE GLASS.
WO2012003593A1 (en) * 2010-07-05 2012-01-12 Gevartis Ag Heat shielding means in the form of a film
BE1019472A3 (en) * 2010-09-03 2012-07-03 Agc Glass Europe GLAZING ANT-FIRE.
BE1019901A3 (en) * 2011-04-06 2013-02-05 Agc Glass Europe FIRE RESISTANT GLAZING.

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US3492137A (en) * 1968-09-20 1970-01-27 Du Pont Siliceous compositions
GB1604388A (en) * 1977-08-03 1981-12-09 Bfg Glassgroup Fire screening panels
GB2155852B (en) * 1984-03-15 1987-11-25 Glaverbel Transparent fire screening panels and their manufacture
DE60232073D1 (en) * 2001-06-12 2009-06-04 Doors & More S R L METHOD AND DEVICE FOR PRODUCING HEAT-RESISTANT AND TRANSPARENT COMPOSITE PANES
ITTN20020003A1 (en) * 2002-01-31 2003-07-31 Doors & More INTUMESCENT GASKET
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