FR2560820A1 - STRATIFIED COMPOSITES AND PROCESS FOR THE PRODUCTION THEREOF - Google Patents

Abstract

THESE LAMINATE COMPOSITES USED AS PARTITIONS, WALLS, DECORATIVE SURFACES, ETC. COMPRISING AT LEAST ONE LAYER OF AT LEAST ONE TYPE OF LAYER FORMING MATERIAL, AT LEAST ONE SIDE OF THAT LAYER OF LAYER FORMING MATERIAL BEING COVERED WITH WATER-RESISTANT PHOSPHATE BOND MATERIAL OBTAINED BY THE REACTION OF A COMPOSITION COMPRISING A METAL OXIDE, CALCIUM SILICATE AND PHOSPHORIC ACID AS CURVED COVERING LAYERS OR TO BIND OTHER LAYERS OF LAYER FORMING MATERIAL.

Description

LAMINATE COMPOSITES AND PROCESS FOR THE PRODUCTION THEREOF

STRATIFIED SITES.

  The present invention relates to structural composites

  and, more specifically, laminate composites

  sand as partitions, walls, decorative surfaces, and the like. The structure of the materials constituting the leaves

  laminates has been the subject of in-depth studies in the

  trie. In particular, efforts have been made to develop

  light, of satisfactory appearance, robust and durable and

  which are flame retardant or fire resistant. We have

  interested in these last qualities. Interior surfaces of buildings, airplanes, automobiles, and

  analogous, often consist of organic matter.

  When these materials are exposed to heat or fire, toxic fumes emerge and, in many cases, lead to asphyxiation or severe lung injury in persons exposed to these fumes. As a result, the industry has spent a great deal of time and effort trying to develop products with all of the above qualities, but without releasing fumes.

  toxic when exposed to fire.

  In the prior art, there are a number of documents that deal with ways of making fire-resistant products. For example, U.S. Patent No. 2,744,589 discloses wallboard elements that include an insulated panel whose core is doubly insulated. It states that the insulation materials are made of rock wool

  and by gypsum sheets. Similarly, the US patent

  United States of America No. 3,466,222 discloses a combination of materials which in themselves would not be suitable for use as flame retardants but which in combination are capable of providing laminate materials indicated as

being fire resistant.

  More recently, the patent of the United States of America

  No. 4,375,516 describes phosphor-based ceramic materials.

  phate, rigid and water resistant and processes for their preparation. Expanded or non-foamed materials may be produced by methods disclosed in this patent, and products which have been obtained are suitable for use as wall panels, ceiling panels, and the like. In addition, these products are flame retardant because they can be manufactured in the form of

  compositions wholly or mainly inorganic.

  Nevertheless, the products obtained in the manner indicated in this document are not entirely satisfactory for all

  uses because they are rigid in nature. More precise

  rather than bending under duress, these panels

tend to break.

  Therefore, it is an object of the present invention to provide inorganic panels which

  are flexible in nature, yet resilient and durable.

  Another object of the present invention is to provide fireproof panels which are intumescent when exposed to heat or fire and which give off

  little or no smoke and flue gas.

  Another object of the present invention is to provide inorganic laminates which are flexible, although they are made using materials described in the art as being usable to provide

rigid products. -

  Cec benefits as well as others of this

  invention will emerge from the detailed description which will

  follow the following preferred embodiments.

  The present invention relates to laminated materials which are made using layers of reinforcing and / or non-reinforcing materials, in combination with layers of a composition, known in the art to provide phosphate resistant ceramic materials. 'water. According to a preferred embodiment, these products are fire-resistant and intumescent when exposed to heat or direct flames, and produce little or no smoke. Nevertheless, these products are

  resistant, durable and have a decorative and pleasant appearance.

  According to one embodiment, the present invention relates to a bonded composite structure comprising at least one layer of at least one type of layer forming material, each of said layers of layer forming material being bonded to adjacent layers of formation material layers, by a strong bonding material

  with phosphate-based water obtained by reaction of a

  composition comprising a metal oxide, calcium silicate

and phosphoric acid.

  According to a second embodiment, the present

  The invention relates to a fire-resistant bonded composite, comprising

  a plurality of layers of at least one type of layer-forming material, and a plurality of layers of a phosphate-based water-resistant bonding material obtained by reacting a composition comprising a metal oxide. calcium silicate and phosphoric acid, each of said layers of layer forming material being bonded to adjacent layers of layer forming material by said bonding material, said bonded composite having intumescent properties when

  is exposed to flames and / or heat.

  According to a third embodiment, the present invention relates to a method for forming a bonded composite structure, said method comprising the steps of preparing a layered composition consisting of at least one layer of a phosphate-based bonding composition comprising a metal oxide, calcium silicate and phosphoric acid, said composition for providing a phosphate-based water-resistant binding material, and at least one layer of at least one type of layers, said composite being made of such

  contiguous layers of said

  TIOR. layers are in contact with interlaced layers

  of said binding composition, and hardening said composition.

  optional layer by subjecting it to

heat and / or pressure.

  The unique characteristics of the products obtainable according to the present invention can be

  attributed to the particularly important role of the use

  cation of a phosphate-based binding composition

  putting in to provide a water-resistant ceramic material

  phosphate-based. These subjects are currently considered

  in the art to provide

  expanded and unexpanded phosphate ceramic filler.

  It has been surprisingly found, however, that when these compounds

  are applied as relatively thin bonding layers, they can be used to

  very flexible laminate structures. As examples of

  to obtain this result, we will mention those

  described in United States Patent No. 4,375,516.

  This patent indicates that compositions comprising calcium silicate, phosphoric acid and a metal oxide selected from the group consisting of aluminum oxide, magnesium oxide, calcium and zinc oxide, as well as their hydrates, to obtain phosphate-resistant materials that are water-resistant; It has now been discovered that other metal oxides can also provide phosphate-resistant water-resistant materials. The present invention accordingly relates, on all compositions comprising a metal oxide, calcium silicate and phosphoric acid, provided that these compositions react by providing a

material resistant to water.

  These compositions are preferably applied as relatively thin layers, about 25-500 microns (1-20 mils) thick, on the surface of a layer forming material which may be a non-reinforcing or non-reinforcing material. The compositions appended to

  normal consistency, or in the form of mechanically formed foams.

  When it is desired to obtain very thin coatings, or laminates of lower weights, the latter technique is preferred, since the foam can be applied with a thickness of the order of 25 microns (μm), the thickness

  then decreasing as the foam collapses.

  Another alternative is to apply the bonding composition discontinuously to portions of the layer forming material. Therefore, the term "layer" of binding material should be understood to encompass applications in which this material is

  uniformly but also non-uniformly

  uniform. After application of the binding composition, the applied material can be allowed to harden or covered with a second layer of the same material or a

  forming different layers, then let it harden.

  Curing can be carried out under ambient temperature and pressure conditions; however, when more dense products are desired, curing can be carried out under pressure. In addition, it can also be heated during curing to speed up the process

hardening.

  Various materials can be used to

  provide laminates, as described below.

  By way of example, it is possible to use as layers, alone or in combination, kraft paper, napkin paper, gauze, woven glass mats.

  and nonwovens, woven and non-woven synthetic

  woven fabrics such as polyester, nylon, and the like, chopped fibers of various materials, mineral wool,

  wire cloth and other well known materials.

  In addition, non-reinforcing materials may also be used.

  such as cement-based materials and the like, although in most cases they lead to

products of a rigid nature.

  As particularly effective reinforcing

  Suitable for use in combination with the phosphate binding materials described herein are materials which are described herein. ------ ----- in U.S. Patent No. 4,239,519 and

  the patents attached to it, the content of which is incorporated

  Referring to the present patent application. These documents, when considered collectively, describe a class of materials herein referred to as "synthetic mica" materials. These are essentially asbestos-free papers or sheets obtained from silicate gels by cation exchange reactions. It is known that materials of this type are relatively unaffected by the temperatures

  high, although they have satisfactory flexibility.

  Layered structures comprising layers of phosphate-based binding materials and

  synthetic mica, had remarkable characteristics

  quables. By way of example, when these composites have been exposed to a direct flame, it has not only been shown

  that they were fire-resistant and produced

  little smoke, but also that they had intumescent properties. Specifically, it has been observed that the exposure of a surface of the structure to a direct flame causes an apparent internal delamination of the structure, leading to the production of air spaces. These air spaces have been shown to have insulating properties, and there have been dramatic thermal differentials between the two sides of the structure thus tested. For example, although one side - a relatively thin structure with a thickness of

  1.5 mm (0.06 inch) was exposed to a temperature

  about 1121 C (2050 F) for one minute, internal swelling and side temperature

  opposite of the structure was less than 316 C (6000 F).

  This phenomenon is not limited to laminates

  using synthetic mica materials. For example, kraft paper laminates also exhibit intumescent properties, and significant temperature differentials were observed when these laminates were tested as described above. The causes of delamination are not clearly understood, but it is thought that this is associated with at least

  partially to the water contained inside the structure.

  In addition to intumescent laminates, it is possible to

  produce thermally conductive laminates

  incorporating a wire mesh as one of the layers.

  Laminates of this type are particularly effective in driving heat away from the point of application; these materials can be useful as sealing materials

  heat conductors, and like products of this type.

  The thickness of the laminates produced in accordance

  The present invention may vary to a large extent.

  According to the needs of the specialist, the thickness of the structure can range from very small (eg 0.76 mm (O, C3 inch) to very large thickness (eg 1.27 cm (0.5 inch) or more) Layered structures having only a single layer of a reinforcing material and a layer of

  phosphate, or containing up to 37 layers of

  and 36 layers of phosphate bonding material.

  However, this illustrative number should not be considered as a limit to the number of layers that can be incorporated into a laminate. In addition, it is not necessary to restrict the reinforcing materials used in the preparation of a laminate structure to a single

  type, combinations of reinforcing

gladly be used.

  The following nonlimiting examples are given

  Illustrative drawing of the present invention.

EXAMPLES

Example 1

  A phosphate-based binder material is prepared from the following ingredients: Weight Components (grams) Al2 O.3H20 15.0 MgO 8, 0 Talc 16.0

H PO at 75%

(P205 to 53.0%) 105.0

H3B03 4.0

3 3 CaSiO3 100.0

H20 18.0

  A phosphate bonding material is prepared by preparing a reaction solution consisting of phosphoric acid, aluminum oxide and water. After obtaining a clear solution, and this being still hot, boric acid is added and the mixture is stirred until it becomes clear again. The reaction solution is cooled to 4 ° C. and a mixture of

dry constituents.

  Five layers of two layers of Reichhold Modiglass 2.5X-SM scrim, 7.6 cm x 30.5 cm (3 inches x 12 inches), are applied rapidly to 76.2 micron layers (3 mils) of the above composition. The five layers were immediately stacked and pressed over each other for 25 seconds under a pressure of 3833 kPa (556 psi) in a 120 C (2500 F) heated press. The resulting sheet is strong and resistant to

water, while being flexible.

  The MOR index of the laminate, essentially measured according to ASTM D1037, is 14479 kPa (2100 pounds per square inch); a MOE index of 428 'MPa (621 kip / sq cm) is found by calculation and the NBS fire resistance index, measured essentially according to ASTM E-66279, is O for a smoldering fire and 2 for the flames.

Example 2

  The process described in Example 1 is repeated, with the excision that one of the faces of the press is provided with an embossing plate. The resulting sample took the details

very fine of the embossing plate.

Example 3

  A layer of 25 microns (1 mil) of a

  phosphate binding material having the formula

  As in Example 1, on each of ten separate sheets of kraft paper having the dimensions 30.5 cm x 30.5 cm x 0.3 mm (12 inches x 12 inches x 0.012 inches). The ten sheets were immediately stacked on top of one another and pressed for one minute under 3861 kPa (560 psi) at 93 C (200 F). The resulting sample is resistant and

  flexible, although it is not flexible in the form of

  1. The MOR number measured in the manner described in Example 1 is 31026.

kPa (4500 pounds per square inch).

  The linked composite structure is broken down into

  10 x 10.1 cm (4 x 4 inches) and two random pieces are selected for testing. Each piece is placed horizontally on an annular support and orn features a thermocouple at a location on the bottom surface where the point of the blue propane flame must be

  applied. A second thermocouple is placed on the upper surface

  laminate directly above the first thermo-

  couple. When the flame is applied, the temperature changes provided by the two thermocouples as a function of time are recorded. The thickness of the sample 3A increases by 2.1 mm (0.15 inches) to 5 mm (0.199 inches) when heated for 7 minutes. At the end of this period, the thermocouple of the surface exposed to the flame measures a temperature of 1033 C (1853 F) while the temperature measured on the upper side is 328 C (622.5 F). Sample 3B was heated for 6 minutes and its thickness was increased from 2.1 mm (0.085 inch) to 4.16 mm (0.166 inch), the temperatures read from the flame side and from the side. superior

  being respectively 1007 C (1844 F) and 378 C (713 F).

Example 4

  A phosphor-based binding material is prepared

  phate as described in Example 1, except that it consists of 50% by weight of NO 17 silica granules

  colors provided by the Ottawa Silica Company. This preparation is obtained

  Nue-er mixing the granules with dry constituents and then preparing the phosphate bonding material. The charged binder material is applied as a 76.2 micron (3 mils) layer to a Johns-Manville fiberglass sheet and, at the same time, applications of 76.2 microns (3 mils) are also applied. mils) on three separate three-ply sheets of the Modiglass scrim described in Example 1. The three layers of Modiglass are stacked on top of each other and the Johns-Manville fiberglass sheet is placed on the top of the pile,

  the binding material loaded granules face up.

  The stacked materials are then pressed at a pressure of 3.833 kPa (556 psi) at 104 C (220 F) for two minutes to give a flexible sheet having

good scratch hardness.

Example 5

  The procedure described in Example 4 is repeated except that one face of the press is provided with an embossing plate. The fineness of the product details

  obtained due to the embossing plate is satisfactory.

Example 6

  A phosphate bonding material comprising the following constituents is prepared: Weight Constituents (grams)

A1203. 3H20 18.0

MgO 8.0 Talc 16.0

HPO4 at 75%

(P205 to 53.0%) 108.0

H3BO3 4.0

CaSiO3 100.0

H 0 18.0

  The reaction solution is prepared by mixing phosphoric acid, water and aluminum oxide trihydrate and stirring until

  a clear solution. Boric acid is added to the hot solution obtained

  held and shaken. After this solution has become clear,

  cool the reaction solution to about 2-4 C (35-39 F).

  148 grams of the cold liquid is added with vigorous stirring, the 124 grams of dry constituents already mixed, which gives a uniform material. The resulting mixture is stirred until it becomes homogeneous, then

  place it in an ice bath to preserve the

  liquid tance; that is, to delay the interaction of the constituents. The pot time of this material can be varied from about 30 seconds to about 7 minutes, depending on the possibility of regulating the temperature of the material.

  the exothermic reaction, in the ice bath.

  A synthetic mica sheet is prepared from the following constituents substantially from the same

  in the patent application under examination

previously. -

  Weight Constituent (grams) Magnesium Fluorhectorite 100.0 Bleached Redwood Cellulose 10.0 Fiber Glass 0.37 cm (1/8 inch) 5.0 Weight Constituents (grams) "Polymin p" as flocculation agent 0.075

  "Hydrate 777" as a flocculation agent 0.037-

  Water --- Bleached redwood cellulose is dispersed in water using a water disintegrator and refined in a Jordan Refiner to a consistency of 500 (Canadian Refining Index). The refined paste is transferred to a large open vessel and is slurried with the glass fibers. After introducing the required amount of water into the vessel to obtain a consistency of 1.3% solids, magnesium fluorhectorite floc is added and the mixture is stirred until homogeneous. Polymin P and Hydrate 777 are then added and the composition is immediately poured onto the forming wire of a paper machine. After removal of most of the water, the mat was vacuumed in a series of vacuum presses. The residual water is then removed by passing the synthetic mica mat over a heated drum. Brush is applied to a thin coating of the

  phosphate binding material (I) above with a thick

  approximately 254 microns (10 mils) on the surface of the synthetic mica sheet (S). A sheet of microlite glass (G), designated SH20 / 1 supplied by Glaswerk Schuller GmbH, is immediately placed in the bonding material and saturated, and a second sheet is placed on the glass layer. synthetic mica. The assembled materials are placed in a press between the glass surfaces and pressurized at 1724 kPa (250 psi) for 5 minutes at 77 ° C (170 ° F). Once the pressing is complete, the pressed composite is conditioned at 77 C (170 F) for several more minutes for

  eliminate the water, giving a strong and flexible product.

  It should be noted that because of the porous nature of the glass sheet, it is not necessary to apply the

  bonding material on both sides of the glass sheet.

  This is able to pass through (saturate) the glass layer under pressure so that the two contiguous layers of synthetic mica can be bonded to the glass by a single application of the bonding material. In this example and the following examples, the saturation is indicated by (GI) or (IG). Therefore, in this example, strata are

arranged in the order S (IG) S.

Example 7

  The procedure of Example 6 is repeated except that glass sheets constitute the outer layers and

  that the composite material has the structure (GI) S (IG).

  The glass sheets are bonded with the phosphate bonding material to the single inner layer of the synthetic mica sheet by placing the composite in a press having shallow pattern embossing plates. These plates give the surface of the laminate a texture

fine in a desired pattern.

Example 8

  The procedure of Example 7 is repeated except that the composite material is placed between an expanded silicone rubber calender and male or female molds bearing a pattern. This allows to provide

  molded products with deep embossed images.

Example 9

  A series of laminates is prepared, practically

  as described in Example 6, each sample

  holding synthetic mica, phosphate bonding material and, optionally, a glass sheet. As in Example 6, the phosphate binder saturates the glass sheet in such a way that, when internally incorporated into a laminate structure, the binder serves to bond adjoining layers of synthetic mica, even if the binder only applied to one side of the glass sheet,

  or on contiguous synthetic mica sheets.

  The modulus of rupture (MOR) values were determined according to ASTM D-1037, while the modulus of elasticity (MOE) values were calculated by conventional mathematical methods from the MOR values. The structures of each of the laminates are indicated from top to bottom. Unless otherwise indicated, the bonding material is applied in 203 micron (8 mil) layers

  of thickness, and a SH-20/1 glass sheet is used.

  Sample Structure MOR in kPa MOE in MPa (psi) (ksi)!

9A SISISIS 9983 (1448) 1130 (164)

  9B S (IG) S (IG) S (IG) S 10810 (1568) 1205 (175)

  9C * S (IG) S (IG) S (IG) S 11596 (1682) 1454 (211)

  9D (GI) S (IG) S (IG) S (IG) S (IG) 26779 (3449) 3371 (576)

  * = I applied as a 305 micron (i2 mils) layer.

  The results for these samples show that there is a pronounced increase in strength when the laminate is brought into contact with the glass sheet. Sample Structure MOR in kPa MOE in MPa (psi) (ksi)

  9E (GI) SISISIS (IG) 22159 (3214) 4054 (588)

  9F ** (GI) SISISIS (IG) 26930 (3906) 3916 (568)

  9G (GI) SISIS (IG) 22387 (3247) L205 (610)

  9H (GI) SIS (IG) 24131.3500) 4012 (582)

  ** = SH 50/1 glass sheet used in place of

SH 20/1 glass sheet.

  These results, compared to the values obtained for the 9D sample, suggest that laminating with nonwoven sheets contributes substantially more to the strength of the laminate than

internal glass.

  Sample Structure MOR in kPa MOE in MPa (psi) (ksi)

9I SISIS 11810 (1713) 2226 '323)

  9J S (IG) S (IG) S 16000 (2320) 2654 (385)

  9K IS (IG) S (IG) SI 16237 (2355) 3247 (471)

  These data are provided for comparison

Example 10

  This example illustrates the results obtained when heating various samples with a blowtorch at

  propane, as described in Example 3. The results are

  states are shown below for laminates containing

  various constituents and having various structures. The heating causes important modifications of the laminates and these

  changes are all the more important as the number of layers is large. For example, when applying heat to a sheet

  synthetic mica, only a slight increase in

  tation. However, when using one or more layers of synthetic and phosphate-bonded mica (with or without glass reinforcement), blistering increases. This has the effect, with the thickest samples, as indicated below, of providing

  satisfactory insulation effects. The table shows the increase

  the thickness of each sample

by heating.

  The samples consist of layers of SH 20/1 glass sheets and / or synthetic mica bonded to each other by a phosphate bonding material as described in Example 9. The laminates obtained are not embossed. They are referred to as samples A at 10H and the column "structure" lists the sequence of

strata from top to bottom.

  Thickness variation in mm (inch): Sample Final Initial Structure Increase

  At S 0.686 (0.027) 0.965 (0.038) 0.279 (0.011)

  IOB ISI 0.864 (0.034) 3.175 (0.129 2,311 (0.01) IOC (GI) S (IG) 0.940 (0.037) 3.302 (0.130 2.362 (0.093)

  D ISISI 1.397 (0.055) 3.800 (0.15G) 2.413 (0.095)

  E (GI) S (GI) S (IG) 1.600 (0.063) 4.394 (0.173 2.794 (0.110)

  1OF ISISISI 1,854 (0,073) 4,927 (0,1943,073 (0,121)

  lOG (GI) S (GI) SIS (IG) 2.159 (0.085) 5.334 (0.210 3.175 (0.125)

  H (GI) S (GI) S (GI) S 2.134 (0.084) 6.350 (0.25CO 4.246 (0.166)

  The temperature differentials, measured at the indicated time intervals, are as follows. The measurements were made by subtracting the temperature measured by

  the upper thermocouple (Ts) than that provided by the thermo-

  torque on the flame side (Tf) to obtain the differential (D).

w w -or-t in o o where l

  TEMPERATURE IN C (O F) AT INDICATED TIMES (SECONDS)

* Sample Position 15 30 60 120 180

  A Tf 1183 (2163) 1193 (2180) 1202 (2196) - -

  Ts 547 (1017) 587 (1090) 597 (1107) - -

  D 636 (1146) 606 (1090) 605 (1089) - -

  B Tf 1201 (2195) 1217 (2222) 1226 (2239) - -

  Ts 457 (855) 555 (1032) 551 (1024) - -

  D 744 (1340) 662 (1190) 675 (1215) -

  C Tf 1246 (2275) 1276 (2329) 1268 (2314) 1255 (2291) 1262 (2304) Ts 234 (454) 573 (1064) 573 (1064) 579 (1074) 575 (1068)

  D 1012 (1821) 703 (1254) 695 (1254) 676 (1217) 687 (1236)

  D Tf 1017 (1862) 1092 (1997) 1102 (2016) 1114 (2038) 1126 (2059) Ts 84 (183) 173 (344) 423 (794) 463 (866) 465 (869).

  D 933 (1679) 919 (1653) 679 (1222) 651 (1172) 661 (1190)

  E Tf 1036 (1897) 1116 (2042) 1117 (2043) 1133 (2072) 1137 (2079) Ts 71 (160) 114 (237) 289 (552) 391 (736) 402 (756)

  D 965 (1737) 1002 (1805) 828 (1491) 742 (1336) 735 (1.323)

ru

  TEMPERATURE IN OC (OF) AUY INSTANTS INDICATED (S1CONDI; S)

  Example, 1 loótiPo. ", It iri 1 ... W '' F Tf 1127 (2060) 1152 (2106) 1183 (2162) 1200 (2192) 1190 (2175) Ts 82 (179) 93 (199) 185 (365) ) 379 (714) 385 (726)

  D 1045 (1881) 1059 (1907) 998 (1797) 821 (1478) 805 (1449)

  G Tf 1194 (2182) 1215 (2219) 1213 (2216) 1234 (2253) 1239 (2262) Ts 76 (169) 83 (182) 138 (281) 348 (658) 364 (687)

  D 1118 (2013) 1132 (2037) 1075 (1935) 886 (1595) 875 (1575)

  ## STR1 ##

  D 1051 (1893) 1029 (1852) 1029 (1852) 869 (1565) 857 (1504)

  These results show that heating causes swelling of the laminates,

  thus leading to intumescent properties.

r> C> O

25608-20

Example 11

  The procedure described in Example 6 is repeated using synthetic mica, Schuller / 1 glass scrim, Burlington glass woven fabric NO 1653 Lenoweave (16x8) (denoted by the abbreviation "B") and / or galvanized wire mesh (W) having 2.1 threads on 2.6 threads per

  square centimeter (14 threads on 17 threads per square inch).

  The following samples are prepared: Sample Structure 11ASis

11B ISI

li11C S (IG) S

11D (GI) S (IG)

11E S (IB) S

  11Fi S (IW) S The tensile strength and the flexibility of the products obtained are tested. Tensile strengths are determined primarily according to ASTM F-152 using sizes of Type 1 specimens on a device

  tensile strength test at a trans-

  verses of 2.54 cm / min (1 inch / min) and a scroll speed of 2.54 cm / min (1 inch / min); however, the samples were not preconditioned. The samples were cut in a 1/27-cm (1/2 inch) dumbbell except for sample 11F which was cut as a 2.54 cm (1 inch) dumbbell. . The following results are obtained:

RESUTLTATS

  Kg samples at break kPa (psi) pounds at break

  11A 11.2 (24.7) - [0.7j1.5 7096 (1030) - f730] t (106-

  11B 5.2 (11.6) - [1.1] 2.4)] 5357 (777) - [944] L (2821

  13.6 (30.0) - [1.7J3.7)] 8825 (1280) - [1654] j240)

  11D 11.1 (24.5) - [0.8] [1.8]] 8242 (1210) - [1241] 180Y

  11E 20.4 (45.1) - [1.0] F2.3)] 12962: 1880) -t12411 [2180u

  11F 66.1 (146) - [5.0] 11) 40196 (5830) - [1172170]]

  The values reported in the table are averages of three measurements, with the numbers in brackets representing the difference between the highest value

  and the lowest recorded for each set.

  Flexibility is determined according to ASTM Standard F-147, commonly referred to as a "mandrel bend test". Samples 11A-11D do not pass the test using a 2.54 cm (1 inch) mandrel; sample 11F is satisfactory when using a 2.54 cm (1 inch) mandrel; and Sample 11E behaves positively when a 2.22 cm (7/8 inch) mandrel is used, none of the samples were preconditioned.

Example 12

  This example is intended to illustrate the thermal conductivity results obtainable by incorporating a wire mesh into a laminate. Laminate C, having the structure (GI) S (WI) S, was prepared from

  the classic way, except that we have incorporated thermo-

  couples in the structure by laying them on the surface

  upper side of the upper synthetic mica sheet.

  They were then cured on site by applying the upper layers (GI). The thermocouples were located at measured distances from the point of application of the flame, either in the direction of the wires (DF) or diagonally across the wire (oblique), as follows: Thermocouple Position Distance in cm ( inch TC 1 Point of application of flame TC 2 oblique 5.08 (2) TC 3 oblique 10.16 (4) TC 4 oblique 12.7 (5) TC 5 oblique 15.24 (6)

TC 6 DF 10.16 (4)

  Laminate C was prepared using a galvanized iron wire as described in Example 11, while laminate B was prepared to contain a comparable copper wire. Laminate A, which does not contain wire is prepared as a control. The following temperatures are recorded: ## EQU1 ## ) EL (9LL) Lú (L6) eE (96) E (L6) EE (96) 9E (66) LE (56) 5d Ol

  (9L) 29 (9YL) 69 (9LL) L) (98) 0E (Z6) E (06) ZE (68) LE (56) 5u (96) 9E

  (8L) 9'5c (08) 9 (18G'LZ (6L '9z (L8) Z L2 (8) Z1LZ (6L) g'9 (L8)' LZ (L8) Z LZ 0 JS to V Sd VD to V

9 O1 S D 7 DI

  (LLL) 79 (OLL) E9 (ZOL) 6E (L92) L11 (LZe) 9LL (00) E6 (LL9L) WOL (LL9L) 9MOL (198L) 90LOL (80L) O (90L) Z (00I) 8E () L (61E) 0L (19L) 9L (6L6L) SOL (998L) LOL (O6L) 690L Ol (96) 9E (L1) 8E (66) Luce (OLE) 66 (L6L) 88 (99L) gL (LL6I) 9 > OL (2681) E0t (686L) L80L E (6L) The 9Z (08) The 9z (8) Z'LZ (8L) 9 9 (08) L9 (L) 9 (0) 8) L9Z (08) ) 9 0 3._S V 3 Sd V 3 Sd V úE3 D __ Z (L) 'L 3L9 (YES) .........

  .....................................; ....__....... .. DTD: ......._.__ Sdma..DTD: (gos) Do N3 S33H & SIO3HNS S3HfiuVHSid3 ..

  These results indicate that a laminated fabric facilitates the dissipation of heat from its point of application, and that the copper wire dissipates heat in a more controlled manner.

  effective than galvanized wire. In addition, the comparison

  its results concerning samples TC 5 and TC 6 shows that heat is more efficiently conducted in the

  direction of the threads only in an oblique direction.

EXAMPLE 13

  This example illustrates the preparation of a sample which is not hardened under heat and pressure. A coating of 152 microns (6 mils) of the bonding composition described in Example 1 (about g) was applied to a 30.5 cm x 30.5 cm (12 inch x 12 inch) piece of scrim of 2 , 5X-SM Modiglass, and a second piece of scrim is placed on the liner. The laminated material is briefly compressed to penetrate the

  binding composition in the respective layers of non-

  woven and allowed to cure the composite under the conditions

  ambient. Curing takes place in about 5 minutes.

EXAMPLE 14

  This example illustrates the application of an expanded bonding composition on a layer of scrim. The binding composition is prepared as described in Example 1 and mixed for about 25 seconds. To the subject

  (268 g), 10.1 g (3.8%) of surfactant are added.

  Millifoam active ingredient supplied by the Onyx Chemical Co., and the foam is produced by mechanically mixing by means of a

  air agitator for 40 seconds. We apply a coat-

  76.2 microns (3 mils) on both surfaces of a 30.5 cm x 30.5 cm (12 in. x 12 in.) piece of non-woven Modiglass 7.5X-SM, the total amount applied. being about 82 g. The coated nonwoven is pressed for 25 hours.

  seconds at 82 C (180 F), which gives a hardened sheet.

  It is understood that the embodiments described above are in no way limiting and may give rise to any desirable modifications, without leaving

for this purpose of the scope of the invention.

Claims (15)

  1. Linked laminated composite structure, in particular   fire-resistant bond, characterized in that it comprises at least one layer of at least one type of layer-forming material, at least one side of said layer of layer-forming material being covered with water-resistant phosphate binding, obtained by the reaction of a composition comprising a metal oxide, calcium silicate and phosphoric acid, as hardened cover layers or to bind other layers of layer formation material. 2. bonded composite structure according to claim 1, characterized in that the metal oxide is selected from the group consisting of aluminum oxide, magnesium oxide, calcium oxide and zinc oxide , so than their hydrates.   3. bonded composite structure according to claim 2, characterized in that the bonding composition comprises aluminum oxide trihydrate.   4. Linked composite structure according to one of the   1 to 3, characterized in that the composition   binding is a substantially uniform layer.   5. Linked composite structure according to one of the   1 to 3, characterized in that the composition   binding is a discontinuous layer.   6. Linked composite structure according to one of the   cations 1 to 5, characterized in that the bound composite   is constituted by a layer of synthetic mica.   7. Linked composite structure according to one of the   cations 1 to 6, characterized in that the bonded composite is constituted by a woven, non-woven or chopped glass layer.   8. Linked composite structure according to one of the   cations 1 to 7, characterized in that the bonded composite is constituted by a woven, nonwoven synthetic layer or chopped.   9. A linked composite structure according to one of the   cations 1 to 8, characterized in that the bound composite   consists of a layer of kraft paper.   10. The linked composite structure according to one of claims 1 to 9, characterized in that the bound composite   is constituted by a wire mesh.   11. Process for forming a bound composite structure   as defined in one of claims 1 to 10, characterized   characterized in that it comprises the steps of applying to at least one side of at least one layer of at least one type of layer-forming material, a layer of a phosphate-based bonding composition comprising a metal oxide, calcium silicate, and phosphoric acid, said composition being capable of providing a water-resistant phosphate binding material as a cover layer or to bond other layers   layer formation material and to harden this structure.   stratified layer, possibly by subjecting it to heat and / or pressure.   12. Process according to claim 11, characterized in that the binding composition is applied with a   thickness from about 0.025 mm to about 0.5 mm.   13. Method according to one of claims 11 and 12,   characterized in that the binding composition is   applied as a mechanically produced foam.   14. Method according to one of claims 11 to 13,   characterized in that the bonding composition is applied in the form of a layer of material substantially keep on going.   15. Method according to one of claims 11 to 13,   characterized in that the binding composition is   applied as a discontinuous layer.