FR2710051A1 - Fire-resistant glass, process for manufacturing such glass and fire-resistant glazing made from such glass. - Google Patents

Abstract

High-temperature resistant fire-resistant pane, in building glass quality, made of a pre-stressed coated sodium-calcium glass, this pane, as a transparent part of a fire-resistant pane, withstands a fire resistance test according to DIN 4102 or BS 476 for at least 30 minutes, the window having a layer of TiO2 or ZrO2 which is completely covered by a layer of SiO2.

Description

"Fire resistant glass, process for manufacturing such a glass and

  fire-resistant glazing made from a

such window ".

  The present invention relates to a glass resistant to fire and to high temperatures, of glass quality for building, in a pre-stressed calco-sodium glass, coated, this glass being capable of withstanding, as a transparent part of a glazing fire, to a fire test according to DIN 4102 or BS

476 for at least 30 minutes.

  The invention also relates to a method for manufacturing such a window and to a window

  firewall made from such a blade.

  For fire-resistant glazing, for example of fire resistance class G according to DIN 4102 part 13 or BS 476, there are various glasses and

window structures.

  Initially, around 1970, we used reinforced glass or glass bricks to make fire-resistant glazing. Reinforced glass is used, either in the form of cast glass, or in the form of reinforced glass, after smoothing and polishing. In the middle of the thickness of the glass is incorporated, in the casting, a mesh welded by points, which ensures the coherence of the broken glass after the action of fire and

  This prevents the passage of smoke and flame.

  The disadvantage of this reinforced glass consists in the fact that it does not have the properties of safety glass and can only be used in a limited way in

areas accessible to the public.

  Fire-resistant glazing made of glass bricks is masonry work and cannot be fitted in doors, light partitions and windows. They can only be installed under the

  form of light-permeable walls.

  In the mid-1970s, firewalls made of borosilicate glass appeared. Their advantage over fire-resistant glass in reinforced glass was that they did not require annoying reinforcing mesh. The softening point and the higher tenacity of the glass allowed fire resistance classes up to minutes. The disadvantage was that the panes were drawn glass and therefore did not have the quality of glass. In addition, using conventional prestressing systems, they could not be prestressed to give fine fragments; therefore, they did not have glass properties of

  safety, for example according to DIN 1249, part 12.

  In the 1980s, sodium-calcium glass with safety glass properties appeared for fire-resistant glazing. The panes presented the quality of glass. Compared to borosilicate glass panes, they had drawbacks such as a lower softening point and reduced toughness. This is why it could only be used in a limited way in special chassis systems for the

fire resistance class G 30.

  At the end of the 80s, beginning of the 90s, panes coated on one side were used for fire-resistant glazing so as to reflect infrared rays. For technological reasons, only one side could be coated to reflect the infrared. This had a fatal impact on fire resistance. If the coated side of the glass was facing fire, the glass could withstand the action of fire for more than 60 minutes, while if the uncoated side of the glass was facing fire, the glass would break within a few minutes of exposure to fire. In this case, the coating layer acts as a heat trap for the radiation from the burning room, that is to say that the glass heats up much more quickly and there is a thermal overload leading to a breakage of the window. This type of fire-resistant glazing is absolutely unsuitable in practice because mounting upside down is always possible on site. Furthermore, according to DIN 4102 part 13, fire tests, for example for partitions,

  must be carried out from both sides.

  Recently, it has been proposed to use composite panes for fire-resistant glazing of fire resistance class G 30. Composite panes are of complicated structure. They consist of at least two glass slides and up to two different intermediate layers, one of which is an organic layer, for example a PVB sheet, to provide the composite glass with the properties of a safety glass. . In the usual executions in practice, they cannot be used for fire resistance classes

greater than G 30.

  Already in the mid-1970s, transparent glass of ceramic glass was officially tested as fire-resistant glazing for a fire duration of 180 minutes. The disadvantage of vitreous ceramic panes consists in the low technical solidity, insofar as they cannot be thermally prestressed; they can only be used, in the event of a fire, in chassis without bending or with very low bending. Frames involving greater bending can cause the windows to break and thereby lead to failure

premature firebreak glazing.

  Document DE-B-24 13 552 discloses fire-resistant glass panes which have a thermal resistance so high that they can withstand, as elements of space delimitation, a fire test according to DIN 4102 (1970) without breaking during the heating phase, these panes having a compression tension in the marginal zone and being constituted by panes of which the product of thermal expansion (") by the modulus of elasticity

  (E) is between 1 and 5dN x cm x C 1.

  Document DE-B-24 13 552 relates to panes which, as elements of space delimitation, resist a fire test according to DIN 4102 (1970 edition), sheet 2, paragraph 5.2.4 or sheet 3, paragraph 4.3.2 for at least 30 minutes without breaking during heating, and which moreover do not require metal reinforcements. Unlike glass bricks, the thicknesses of the panes do not differ or differ only slightly from the thicknesses of the usual panes

in building glazing.

  Patent CH 605,435 relates to a fire-resistant and high-temperature resistant glass which, as space-delimiting glazing, withstands a fire test according to DIN 4102 (1970) for at least 90 minutes without breaking or lose its space-delimiting effect, this pane having a compression tension in the marginal zone, being composed of glasses of which the product of thermal expansion (0) by the modulus of elasticity (E) is included

-2 -1

  between 1 and 5dN x cm x C, a closed crystalline surface layer formed during heating according to

DIN 4102.

  The CH patent requires the use of glass panes of special composition and therefore relatively expensive; the establishment of a compression tension only in the marginal zone of the glass

  is also only achievable by expensive means.

  Document W0 93/07099 describes a fire-resistant pane which undergoes a heat treatment with a view to increasing the resistance and which has at least on one of its surfaces a thin layer of a composition which is stable and remains connected to the surface up to temperatures of 900 C, so that the coated glass is not destroyed up to temperatures of 900 C, the edges of the glass being softened in order to eliminate defects before the heat treatment . The glass according to document W0 93/07099 only has a surface coating which is preferably applied to the glass by relatively expensive methods such as spraying, plasma coating or chemical phase deposition.

steam (CVD).

  Patent application DE-A-42 06 614 by the applicant describes a glass structure for multiple fire-resistant glazing, composed of at least two spaced apart glass blades, at least one of which is prestressed, at least one blade prestressing being provided

  unilaterally of a layer reflecting the infrared

  red arranged on the side facing another blade.

  The object of the present invention is to provide a window which, compared to a standard window, has a higher duration of fire resistance, has the properties of safety glass of the single-strip type, for example according to DIN 4102, part 12 or BS 6206, and has the quality of ice cream. This window must also resist fire from both sides

in fire-resistant glazing.

  The invention further aims to improve

  clearly fire-resistant glazing based on calcium glass

pre-stressed float sodium.

  This result is obtained, according to the present invention, by the fact that the glass pane has a layer of TiO2 or ZrO2 itself completely covered with a layer of SiO2. It is essential for the invention that a glass of sodium-calcium glass having the quality of ice cream is covered with thin layers of TiO2 or ZrO2 and SiO2 and is then prestressed. In an appropriate frame system, the coated glass supports

  the temperature increase according to the time curve-

  unit temperature (ETK) according to DIN 4102.

  The layers are applied to the

  two sides by immersion and are then baked.

  The thickness of the TiO2 or ZrO2 layers can be between 20 and 600 nm. Preferably, however, layer thicknesses of TiO2 or ZrO2 of between 60 and 130 nm are used. The TiO2 or ZrO2 layers are combined with an SiO2 overlay.

2 2

  SiO2 which is between 80 and 100 nm thick,

  preferably 90 nm thick, has an anti-

  reflections on the coated glass and significantly improves

the optical appearance of the windows.

  The immersion process as used according to the present invention is described in

  detail in the utility model DE 74 29 287.

  The TiO2 or ZrO2 layers react with the sodium-calcium glass in the event of fire. They modify the physical characteristics of the glass and

stiffen the windows.

  The layer of TiO2 or ZrO2 reacts, in the event of fire, with partial mixing effect, with the surface of the sodium-calcium glass, with diffusion of the ions of at least one of the sodium, calcium or magnesium elements of the glass in the layer of TiO2 or ZrO2 and ions of

  titanium or zirconium in the glass.

  The stiffening of the windows increases the fire resistance capacity which can, depending on the

  window format, reach times> 60 min.

  We know from experience that the slightest doping of the TiO2 or ZrO2 layer alters the stiffening effect on sodium-calcium glass. This is why the layer of TiO2 or ZrO2 contains less than 0.2% in

weight of impurities.

  The panes coated on both sides with TiO2 or ZrO2 and SiO2 can be of perfectly symmetrical structure. The layer of TiO2 or ZrO2 reacts in the event of fire with the sodium-calcium glass by stiffening the glass. The reaction mechanism has not yet found an exact explanation but it is assumed that diffusion phenomena take place, possibly also leading in combination with the SiO2 layer, to the stiffening of the glass. The stiffening effect of the layers allows a rebate or lower support height than with uncoated sodium-calcium glass, because the layers have an effect of increasing the duration of fire resistance. By the stiffening effect of the layers, the frame constructions for fire-resistant glazing can be produced in a simpler manner and therefore less costly and safer. In addition, larger formats

windows can be produced.

  The soda-lime glass panes currently on the market for fire-resistant glazing require, for example, a rebate or support height of 8 to 12 mm, while the pane produced according to the invention requires only rebate taken at 10 mm. The fire resistance times thus obtained during fire tests are generally, for example for glazing G 30, clearly above

minutes.

  The process according to the invention for manufacturing fire-resistant glass panes is carried out so that the layers are applied on both sides, in particular by immersion, as described for example in utility model DE 74 29 287. The layers applied by immersion are then baked between 360 and 480 C, preferably at 400 C and the coated glasses are prestressed, with establishment of a prestress between 60 and 160 N / mm2, in

particularly between 80 and 120 N / mm2.

  The coated sodium-calcium glass is thus prestressed according to DIN 1249 part 12. The panes thus manufactured for fire-resistant glazing have the properties of safety glasses of the monolame type and

  their surface is of ice quality.

  The invention will be described below in more detail with the aid of the drawing and an exemplary embodiment. A float glass slide supplied for example in the format of 3.75 x 3.21 m by the manufacturer is

  immersed in a bowl according to the utility model DE-

  74 29 287. The cuvette contains an alcoholic solution of chloroethyl titanate with 30 to 50 g / l of TiO2. The slide is removed at a speed of 5 to 10 mm / s from the solution. The solution of liquid adhering to the slide is cooked in an oven at 400 C. The titanium contained in the solution forms, during cooking, a thin layer of TiO2 at 120 nm thick. Then, the SiO2 layer is applied to the TiO2 layer. The cuvette then contains an alcoholic solution of silicate ester containing -22 g / l of SiO2. The slide is removed from the solution at a speed of 4 to 9 mm / s. The liquid solution adhering to the TiO2-coated slide is also baked at 400 C. This creates a layer of SiO2 of a

thickness from 85 to 95 nm.

  A 1 m X 2 m glass is cut from the large blade, it is planted on the edges (DIN 1249) and it is thermally prestressed in a conventional installation. The prestressing is produced according to a known process pertaining to the state of the art, in general by heating the panes in an oven to temperatures above the transformation temperature (Tg), and by subsequent blowing of air.

cold on the windows.

  The attached drawing (Figure 1) illustrates

an example of glazing.

  The glazing consists of a window 2 of 6 mm X 1 m X 2 m, coated on both sides with a layer of TiO2 of approximately 115 nm thick and a layer of Sio2 of approximately 90 nm thick, this window being thermally prestressed to around 100 N / mm2. The glazing is fixed by wedging elements (clamping) 6 and rebate joints 7 and 8 in a steel frame 5 assembled by welding or screwing from

  rectangular tubular steel profiles 3 and 4.

  The glazing described is subjected to a fire resistance test according to DIN 4102 or BS 476. The glazing does not slip out of the frame until after a period of exposure to fire greater than 60 min and thus gives off an opening, so that it no longer assumes its function of

delimitation of space.

  The same fire resistance test, carried out with a window coated on both sides with a layer of ZrO2 with a thickness of 60 to 80 nm, itself completely covered with a layer of SiO2 with a thickness of approximately 90 nm, allowed to note a

  duration of fire resistance of more than 50 min.

  Glazing as described, but with a 6 mm X 1 m X 2 m glass, made of uncoated sodium-calcium glass, tested according to DIN 4102, does not reveal

  a fire resistance duration of 32 min.

Claims (11)

  1. Glass resistant to fire and to high temperatures, of glass quality for building, made of a pre-stressed, coated sodium-calcium glass, this glass being capable of withstanding, as a transparent part of fire-resistant glazing, a test fire resistance according to DIN 4102 or BS 476 for at least 30 minutes, characterized in that the glass has a layer of TiO2 which is in turn   completely covered with a layer of SiO2.   2. Glass resistant to fire and to high temperatures, of glass quality for building, in a pre-stressed calco-sodium glass, coated, this glass being capable of withstanding, as a transparent part of a fire-resistant glazing, a test fire resistance according to DIN 4102 or BS 476 for at least 30 minutes, characterized in that the glass has a layer of ZrO2 which is in turn   completely covered with a layer of SiO2.   3. Fire-resistant glass according to claim 1 or 2, characterized in that the layer of TiO2 or ZrO2 has thicknesses from 20 to   600 nm, in particular from 60 to 130 nm.   4. Fire-resistant glass according to claim 1 or 2, characterized in that the SiO2 layer has thicknesses of 80 to 100 nm, in particular of 90 nm. 5. Firewall glass according to one   any of claims 1 to 3, characterized by   the TiO2 or ZrO2 layer contains less 0.2% by weight of impurities. 6. Firewall glass according to one   any of claims 1 to 5, characterized by   causes the layer of TiO2 or ZrO2 to react in the event of fire with the sodium-calcium glass, with stiffening of the glass. 7. A method of manufacturing fire resistant glass according to any one of   Claims 1 to 6, characterized in that   apply the layers in particular on both sides,   in particular by immersion, on calcium-sodium glass.   8. Method according to claim 7, characterized in that it bakes between 360 and 480 C, in particular at 400 C, the layers applied by immersion. 9. Method according to claim 7 or 8, characterized in that prestressed thermally coated glasses.   10. Method according to claim 9, characterized in that a compression preload of between 60 and   160 N / mm2, in particular between 80 and 120 N / mm2.   11. Fire-resistant glazing composed of a frame with a rebate formed by glazing beads, in which at least one fire-resistant glass resistant to high temperatures according to any one of   Claims 1 to 6, produced by the following process   any one of claims 7 to 10 is mounted   with seals by clamping means arranged in the edge area.