CA1229294A - Laminated composites - Google Patents

Laminated composites

Info

Publication number
CA1229294A
CA1229294A CA000470781A CA470781A CA1229294A CA 1229294 A CA1229294 A CA 1229294A CA 000470781 A CA000470781 A CA 000470781A CA 470781 A CA470781 A CA 470781A CA 1229294 A CA1229294 A CA 1229294A
Authority
CA
Canada
Prior art keywords
hereof
set forth
layer
layer material
composite
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.)
Expired
Application number
CA000470781A
Other languages
French (fr)
Inventor
Jeffery L. Barrall
Ronald J. Leib
Debra L. Morris
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.)
Armstrong World Industries Inc
Original Assignee
Armstrong World Industries Inc
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 Armstrong World Industries Inc filed Critical Armstrong World Industries Inc
Application granted granted Critical
Publication of CA1229294A publication Critical patent/CA1229294A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B32B7/14Interconnection of layers using interposed adhesives or interposed materials with bonding properties applied in spaced arrangements, e.g. in stripes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C04B28/342Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more reactive oxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5076Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
    • C04B41/5092Phosphate cements
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04BGENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92Protection against other undesired influences or dangers
    • E04B1/94Protection against other undesired influences or dangers against fire
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/102Oxide or hydroxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/27Water resistance, i.e. waterproof or water-repellent materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/28Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electromagnetism (AREA)
  • Civil Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

LAMINATED COMPOSITES

Abstract The present invention relates to laminated materials which are constructed using layers of reinforcing and/or non-reinforcing materials in combination with layers of a composition which is known in the art to provide water-resistant phosphate ceramic materials. In a preferred embodiment, the products are fire-resistant and intumescent when exposed to heat or direct flame, and they produce little or no smoke.
Nevertheless, these products are tough, durable and suitable to provide a decorative and pleasing appearance.

Description

A

-- 1 -- LFM--7336 & 7341 .

LAMINATED COMPOSITES

The present invention relates to laminated composites and more particularly to laminated composites which are useful as partitions, walls, decorative surfaces, and the like.
Hack no of t he Invention The construction of laminated sheet materials has received extensive study by industry. In paretic-ular, materials have bee sought which are light in weight have good appearance, are rugged and durable and are fireproof or fire-resistant. The latter I-attributes in particular, have received special attention. Interior surfaces in buildings, aircraft, automobiles, and the like, are often made of organic materials When such materials are exposed to heat or fire, toxic fumes are given off and, in many instances, these fumes lead to asphyxiation or result in severe lung damage to those persons who are exposed to the fumes Accordingly, industry has spent a substantial amount of time and effort in attempting to develop products which will have all of the aforementioned attributes, yet which will give off no toxic fumes when subjected to f ire.
The Prior Art A number of references are found in the prior art which deal with ways in which fire-resistant products can be produced. For example, Us So Patent No.

go 3,~i3~,
- 2 - LO 7336 & 73-~1 2,744,589 discloses wall panel units which comprise an insulated panel whereby the core is doubly insulated.
The insulating materials are indicated to be rock-wool materials and gypsum sheet. Similarly, US S. Patent No.
3,466,222 discloses a combination of materials which by themselves would be unsuitable for use as fire retardants;
however, in combination, they are capable of forming laminated materials which are stated to be fire-resistant.
Recently, U. So Patent No. 4l375,516 disclosed rigid, water-resistant phosphate ceramic materials and processes for preparing them. Both foamed and unframed materials can be produced according to procedures set forth in this patent, and the products which have been produced are remarkably suitable for use as wall boards, ceiling boards, and the like. Further, these products are fire-resistant because they can be produced as totally or primarily inorganic compositions.
Nevertheless, the products produced as indicated in the reference are not entirely satisfactory for all uses because they are rigid in nature. That is, rather than bending under stress, the boards tend to break.
Accordingly, one objective of the present invention is to provide inorganic boards which can be flexible in nature, ye which are strong and durable.
I Another objective of the present invention is to provide fire-resistant boards which are in tumescent when subjected to heat or fire, and which produce little or no smoke and fumes.
Another objective of the present invention is to provide inorganic laminates which are flexible even though they are constructed using materials that are disclosed in the art as being suitable Jo provide rigid products.
These and other advantages of the present invention will become apparent from the detailed description of preferred embodiments which follow.
Summary of the Invention The present invention relates to laminated ~22~
- 3 LF~I-7336 & 7341 materials which are constructed using layers of reinforcing and/or non-reinforcing materials in combination with layers of a composition which is known in the art to provide water-resistant phosphate ceramic materials. In a preferred embodiment, the products are fire-resistant and in tumescent when exposed to heat or direct flame, and they produce little or no smoke.
Nevertheless, these products are Tao durable and suitable to provide a decorative and pleasing lo appearance.
Detailed Description of the Preferred Embodiment In one embodiment, the present invention relates to a bonded composite structure comprising at least one layer of at least one type of layer material, each said layer of layer material being bonded to contiguous layers of layer material by a water-resistant phosphate bonding material obtained from the reaction of a composition comprising a metal oxide, calcium silicate and phosphoric acid.
In a second embodiment, the present invention relates to a fire-resistant bonded composite comprising a plurality of layers of at least one type of layer material, and a plurality of layer of a water-resistant phosphate bonding material obtained from the reaction of a composition comprising a metal oxide, calcium silicate and phosphoric acid, each said layer of layer material being bonded to contiguous layers of layer material by said bonding material, said bonded composite being capable of exhibiting in tumescent properties when exposed to flame and/or heat.
In a third embodiment, the present invention relates to a process for forming a bonded composite structure, said process comprising the steps of preparing a layered composition comprising at least one layer of a phosphate bonding composition comprising a metal oxide, calcium silicate and phosphoric acid said composition being suitable to provide a water-resistant phosphate bonding material, and at least one layer of at least I
- Lo 7336 h 73~1 one type of layer material, said composite being arranged such that contiguous layers of said layer material are in contact with intervening layers of said bonding composition, and curing said layered compost-lion, optionally by subjecting it to heat and/orpress~reO
The unique characteristics of the products which may be produced according to the present invention are attributable in significant part to the use of a phosphate bonding composition which is suitable to provide a water-resistant phosphate ceramic material.
Such materials are presently taught in the art to be suitable to provide rigid foamed and unframed phosphate ceramic products. Surprisingly, however, it has been discovered that when such compositions are applied as relatively thin bonding layers, they are useful to provide laminated structures which are highly flexible.
Examples of compositions which are suitable to achieve this result include those disclosed in Us So Patent No.
4,375,516. That patent disclosed that compositions comprising calcium silicate, phosphoric acid and a metal oxide selected from the group consisting of aluminum oxide, magnesium oxide calcium oxide and zinc oxide, and the hydrates thereof, could be reacted to provide water-resistant phosphate materials, however, it has now been discovered that other metal oxides can also provide water-resis~ant phosphate materials. Accordingly, the present invention contemplates all compositions comprising a metal oxide, calcium silicate and phosphoric acid, provided that these compositions react to provide a water-resistant material.
These compositions are coated, preferably in relatively thin layers on the order of c_ 1-20 miss thick, onto the surface of a layer material which may be a reinforcing or a non-reinforcing material. The compositions may be applied at normal consistency, or they may be applied as mechanically frothed foams Herr very thin coatings are desired or where lighter-
5 - Lo 7336 7341 weight laminates are desired, the latter technique is preferred because the foam may be applied at a thickness of cay 1 mill after which the thickness is reduced to a thinner dimension as the foam collapses. As yet another alternative, the bonding composition may be applied in a discontinuous manner to portions of the layer materiel.
Accordingly, the term "layer" of bonding material is intended to encompass applications in which this material is deposited in a uniform and also a non-uniform manner.
After applying the bonding composition, the coated material may then be allowed to cure, or it may be covered with a second layer of the same or a different layer material and then allowed to cure.
Curing may be achieved under ambient conditions:
however, where more dens products are desired, curing may be effecter under pressure. In addition, heat may also be applied during curing to accelerate the curing process.
A variety of materials may be used to provide laminates as disclosed herein For example, raft paper, paper towel, cheese cloth, woven and non-woven class mats, woven and non-woven synthetic materials such as polyester, nylon, and the like chopped fibers of various materials, mineral wool, wire mesh and other well-known materials may be used alone or in combination as layer materials. In addition, non-reinforcing materials such as Simmons materials and the like may also be used although, in most instances, these will I lead to products which are rigid in character.
Particularly effective reinforcing materials for use in combination with the phosphate bonding materials disclosed herein are materials which are disclosed in cop ending Canadian application Serial No.
476,051, and also in U. S. Patent No. 4,239,519 and patents related thereto. These references, when considered collectively, disclose a class of I 6 - LF~1-7336 & 7341 material which is referred to herein as synthetic mica"
materials. In essence, they are non-asbestos papers or sheets which are derived from silicate gels by cation exchange reactions Materials of this type are known to be relatively unaffected by high temperatures, yet they tend to have good flexibility.
Laminated structures comprising layers of the phosphate bonding materials and synthetic mica sheets have shown remarkable characteristics. For example, lo whey such composites were exposed to direct flame, they have not only been shown to be fire-resistant and relatively smoke-free, but they have also demonstrated in tumescent properties. That is, the exposure of one surface of the structure to direct flame has been lo observed to cause an apparent internal delamination of the structure, resulting in the production of air spaces. Such air spaces haze been shown to be insulative in nature, and dramatic heat differentials have been noted between two sides of a structure tested in this manner, For example, although one side of a relatively thin structure on the order of 0~06 in. in thickness was exposed to direct flame at a temperature of about 2050F for l minute internal swelling occurred and the temperature on the opposite side of the structure was less than 600F.
This phenomenon is not restricted to laminates constructed using synthetic mica materials. For example, laminates comprising raft paper also exhibit in tumescent properties, and large temperature different trials have been noted for these laminates when tested as described above The reason why delamination occurs is not clearly understood, although it is believed to be associated at least in part with water contained within the structure.
In addition to in tumescent laminates, heat conducting laminates can also be produced by including wire screen as one of the Lowry. Laminates of this type have been quite effective in conducting heat away Jo I
Ye 7 - LF~7336 & 7341 .
from the point of application; thus, these materials can be useful as heat-conducting gaskets, and the like.
The thickness of the laminates produced according to the present invention can be highly variable At the desire of the artisan, structure thickness may be varied from very thin (e.g., 0.03 in to very thick (e.g., 0.5 in. or more). Laminated structures have been produced comprising as few as one layer of one reinforcing material and one layer of phosphate bonding material, or as many as 37 layers of reinforcing layers and 36 layers of phosphate bonding material. This illustration, however, is not intended to limit the number of layers which could be included in a laminate. Furthermore, therm is no necessity to restrict the reinforcing materials used in making the laminated structure to a single type, and combinations of reinforcing materials may be used to advantage.
The advantages ox the present invention will become more apparent by reference to the following examples which are intended by way of illustration, and no itationO
EXAMPLES
Example 1 A phosphate bonding material was prepared from the following ingredients Weight Components (grams) AYE 15.0 Moo 8.0 30 Talc 16.0 75% H3P04 ~53~0% Pros) 105.0 H3BO3 4.0 Couch 100.0 35 HO 18.0 .

A phosphate bonding material was produced by preparing a reaction solution comprising the phosphoric acid, the LO
- 8 - LF~-7336 & isle aluminum oxide, and the water After clear solution was obtained, and while the solution was still hot, the boric acid was added and the mixture was stirred until it again became clear. The reaction solution was cooled to 4~C. and a mixture of the dry components was added.
Each of five two-ply layers of Reich hold Modiglass ~.5X-SM scrip measuring 3 in. x 12 in. was rapidly provided with Molly draw downs of the above formula. the five layers were immediately stacked and pressed together for 25 second under 556 psi pressure in a press heated to 250 F. The resulting sheet was strong and water resistant, yet flexible.
The MOW of the laminate, measured essentially according to ASTM D-1037, was 2,100 psi; the IRE value was calculated to be 621 ski; and the NBS fire rating was 0 for smoldering and 2 for flaming, measured essentially according to ASTM E-662-79.
Example 2 The process as set forth in Example 1 was repeated, except that the press was equipped on one face with an embossing plate The resulting sample picked up the very fine details of the embossing plate.
Example 3 A Emil draw down of a phosphate bonding material having the formula set forth in Example 1 was made onto each of ten separate sheets of raft paper having dimensions of 12 in. x 12 in x 00012 in. The ten sheets were immediately stacked together and pressed for 1 minute under 560 psi pressure in a press heated at 200~ Fox The resulting sample was strong and flexible, although it was not as flexible as the glass reinforced structure set forth it Example 1. Its MOW value, measured as described in Example 1, was 4~500 Sue The bonded composite structure was cut into 4 in. x 4 in. pieces and two of the pieces were selected at random for testing. Each piece was placed horizontally on a ring stand and a thermocouple was placed at a location on the bottom surface where the I
- 9 - Lo 7336 7341 point of the blue propane flame was to be applied. A
second thermocouple was placed on the top surface of the laminate directly above the first thermocouple. When the flame was applied, the temperatures at both 5 thermocouples were recorded with time. Sample PA
increased in thickness from 0.085 in. to 0.199 in. when heated for 7 minutes. At the end of that time period, the thermocouple on the flame side of the face measured a temperature of 1893~F whereas the temperature on the top side was measured to be 622. 5F~ Sample 3B was heated for 6 minutes and showed an increase in thickness from 0.085 in. to 0.166 in., and temperature readings of 1844F and 713~F on the flame side and top side, respectively, were recorded Example 4 A phosphate bonding material as set forth in Example 1 was prepared, except that it comprised 50% by weight of colored No. 17 silica granules from Ottawa Silica Company. This was achieved by mixing the granules with the dry components and then preparing the phosphate bonding material. The filled bonding material was drawn down in a Molly layer onto one sheet of Johns-Manville glass paper and, at the same time, Molly draw downs were also prepared on three separate 3-ply sheets of the Modiglass scrip described in Example 1.
The three Modiglass layers were stacked on top of one another and the Johns-Manville lass paper was placed on the top of the stack with the ~ranule-filled bonding material facing up The stacked material was then pressed under 556 psi pressure at ~20 Y. for two minutes to give a flexible sheet with good scratch resistance.
Example 5 The procedure as set forth in Example 4 was repeated except what the press was equipped on one face with an embossing plate. The resulting product exhibited fine detail from the embossing plate.

-I - 10 - LF~I 7336 7341 Example 6 A phosphate bonding material was prepared comprising the following components:
Weight 5 Components (grams) .

AYE 18.0 Moo 8.0 Talc 16.0 75% H3PO4 (53.0% Pus 108.0 Couch 100,0 HO 18.0 The reaction solution was prepared by mixing the phosphoric acid, the water, and the aluminum trihydrate and stirring until a clear solution was obtained. The boric acid was added to the resulting warm solution and stirred After this solution had become clear, the reaction solution was chilled to about 35 39 I.
To the 148 grams of cold liquid was added, with vigorous stirring, the 124 grams of dry components which had been mixed to provide a uniform material. The resulting mixture was stirred until it had become homogeneous, and it juicy then placed in an ice bath to prolong the liquid consistency; it to delay the interaction of the components. The pot life of this material could be varied from about 30 seconds to about 7 minutes, depending on the capability of controlling the exothermic reaction temperature in the ice bath.
A synthetic mica sheet was prepared from the following components essentially as described in the aforementioned cop ending application Weight Component (grams 35 Magnesium fl~lorhectorite 100.0 Bleached redwood cellulose 1/8" DE glass fibers 5.0 LF;1-7336 & 73~1 I
weight Component (grams Palomino P flocculating agent 0.075 Hydra id 777 flocculating agent 0.037 5 Water Jo The bleached redwood cellulose was dispersed in water by means of a hydropulper and was refined in a Jordan Refiner until a consistency of 500 Canadian Freeness) was obtained. The refined pulp was transferred to a large, open-head tank and was slurries with the glass fibers. After charging the required amount of water into the tank to get a consistency of 1.3% solids, the magnesium fluorhectorite floe was added and the mixture was stirred until it was homogeneous. The Palomino P and Hydra id 777 were then added and the composition was immediately flowed onto the forming screen of a Fourdrinier machine. After removing most of the water, the mat was subjected to vacuum it a series of vacuum presses. Residual water was then removed by passing the synthetic mica mat over a heated drum.
A thin coating of the above phosphate bonding material (It was brushed at an approximate thickness of 10 miss onto the surface of a synthetic mica sheet (S).
A piece of microlith glass sheet (G), designated S~20/1 from Glaswerk Sculler GmbH, was immediately placed in the bonding material and saturated, and a second synthetic mica sheet was placed on top of the glass layer. The assembled materials were placed in a press between glass surfaces and pressed under 250 psi pressure for five minutes at 170 F. After pressing was complete, the pressed composite was conditioned at 170F
for several additional minutes to remove water, giving a product which was strong and flexible.
It is noted that, due to the porous nature of the glass sheet the bonding Muriel did not have to be applied on both sidles of the glass sheet. The bonding material was capable of passing through (saturating) the glass layer under pressure such that both continuous 92 - 12 - LF~-7336 & 7341 layers of synthetic mica could be bonded to the glass through a single application of bonding material. In this, and the following examples, the saturation is indicated by (GO) or JIG). Accordingly, the structure of this example had the luminary order SAGAS.
Example 7 A process similar to what of Example 6 was repeated except that glass sheets constituted the exterior layers and the composite material had the structure (GI)S(IG). The glass sheets were bonded with the phosphate bonding material to the single internal layer of synthetic mica sheet by placing the composite in a press that was equipped with shallowly patterned embossing plates The plates provided a fine texture in 5 a desired design to the surface of the laminate.
example 8 The procedure of Example 7 was repeated, except that the composite material was placed between a foamed silicone rubber pad and male or female metal molds bearing a design. This resulted in the production of molded products with deeply embossed images.
Example 9 A series of laminates was prepared essentially as described in Example 6, each sample containing sun-Thetis mica, phosphate bonding material, and, optionally glass sheet. As in Example I the phosphate binder sat-rated the glass sheet such that, when included internally in a laminated structure, the binder served to bond con-togas layers of synthetic mica even though the binder may have been applied to only one face of the glass sheet, or to only one of toe contiguous synthetic mica sheets.
Modulus of rupture (MOW) values were determined according to ASTM D-1037 whereas modulus of elasticity MOE values were calculated by standard mathematical means from the MOW values. The structures of each laminate are indicated, top to bottom. Unless otherwise indicated, the bonding material was applied in Molly draw downy and SO ~0~1 glass sheet was used.

-- 13 -LF:!;-7336 E 73!~1 Sample Structure MOR(psi) ~OE(ksi) 9BS¦IG~S(IG)S(IG3S 1568 175 9C*S(IG~S(IG)S(IG)S 1682 211 9D~GI)SIIG)S(IG)S~IG)S~IG~ 3449 576 *I applied as a Molly draw down The results for these samples show a marked increase in strength when the laminate is faced with the glass sheet.

10 Sample Structure MOR~psi) Mecca) 9E(Gl)SISISIS(IG) 3214 58~
9F*~(GI)SISISIS(IG) 3906 568 9G(GI3SISIS(IG) 3247 610 9HtGI)SIS~IG) 3500 582 15 **ASH 50/1 glass sheet used in place of SO 20/1 glass sheet.

These results, when compared to the values obtained for sample ED, suggest that the facing scrip sheets contribute substantially more to the strength of the laminate than do the internal glass sheets.

9J S~IG~S(IG)S 2320 385 OK IS(IG)SIIG~SI 2355 471 These data are provided for comparison.
Example It This example will illustrate the results when various samples were heaved with a propane torch as described in Example 3. The results are indicated below for laminates having various components and structural arrangements.

I
- 14 - LF~:-7336 & 7341 Heating caused noticeable changes to the laminates, and these changes became more pronounced as the number of layers increased. For example, when heat was applied to a single synthetic mica sheet, only a small expansion of the sheet was seen. However, when two or more synthetic mica and phosphate bonding layers (with or without glass reinforcing) were utilized, blistering became more pronounced. The effect with the thicker samples, as shown below, was to provide good insulative effects. The table indicates the increase in thickness which was induced in each sample by the heating.
Samples were constructed of layers of SO 20/1 glass sheet and/or synthetic mica bonded together with phosphate bonding material substantially as described in Example 9. The resulting laminates were unembossed.
They were designated as Samples lo through lo and the "Structure" column lists the luminary sequence from top to bottom.
_ Thickness Change (inch) Sample Structure Initial Final Increase lo S 0~027 0.038 0.011 lob IS 0.034 0.125 0.091 lOC(GI)S(IG) 0.037 0.130 0.093 25 lo ISIS 0.055 0.150 0.095 lOE(GI)S~GI)S(IG) 0.063 0.173 0.110 lOFISISISI 0~073 0.194 0.121 log (GI)S(GI)SIS(IG) 0.085 0.210 00125 lo (GI)S(~I)S(GI)S 0.084 0.250 0.166 Temperature differentials were as follows measured at the indicated time intervals. Measurements were made by subtracting the temperature at the top-side thermocouple (To) from the flame-side thermocouple ifs) to obtain the differential (D).

I% 9 - 15 - LF.~:-7336 h 7341 Temperatures OF as Indicated Time Intervals (seconds Sample Location 15 30 60 120 130 lo Us 2163 21802196 - -To 1017 10901107 lob Us 2195 22222239 To 855 10321024 lo Us 2275 23292314 2291 2304 To 454 10641064 1074 1068 .
lo Us 1862 19972016 2038 2059 To 183 344 794 866 869 lye Us 1897 20422043 2072 2079 To 160 237 5S2 736 756 lo Us 2060 21062162 2192 2175 To 179 199 365 714 726 log Us 2182 22192216 2253 2262 To 169 182 281 658 687 lo Us 2051 20292073 2149 2166 To 158 176 221 584 622 ~2~9~94 - 16 - LF~;-7336 h &341 These results illustrate that heating causes the lam-notes to swell, thereby exhibiting in tumescent properties.
Example 11 The procedure as set forth in Example 6 was repeated using synthetic mica, Sculler 20/1 glass scrims Burlington #1653 Lyon (16x8) glass scrip (abbreviated By and/or galvanized iron wire window screen (W) having 14 strands v. 17 strands per square inch. The following samples were prepared:

Sample Structure lea SKIS
lob IS
llC SAGAS
15llD (GI)S(IG) lye SAABS
elf SWISS

The products were tested for tensile strength and also for flexibility. Tensile strengths were determined essentially according to ASTM F-152 using Type 1 specimen sizes on an Instron tensile tester at 1 inhuman crosshead speed and a chart speed OX 1 inhuman; however, the samples were not preconditioned, The samples were cut in a l/2-inch dumbbell shape, with the exception of sample elf which was cut in a l-in. dumbbell shape. The following results were obtained:

Sample Results Lobs.@ break psi lea 24.7(1 5)1030 ~106) 30llB 11.6(2.4)777 (282) llC 30.0(3.7)1~80 ~240) lid 24.5(1.8)1210 (180) lye 45.1(2.3)1880 (180) elf 146(11) 5830 (170 I
- 17 - LF~1-7336 & 73~11 the valves reported are an average of three measurements, with the numbers in parentheses being the difference between the highest and lowest numbers recorded for each set.
Flexibility was determined essentially according to ASTM F-147, commonly referred to as a "mandrel bend testily' Samples lulled failed the test using a l-in. mandrel; sample elf passed using a l-in.
mandrel; and sample lye passed using a inn. mandrel.
lo None of the samples was preconditioned.
Example 12 This example will illustrate the heat conduct live results which can be obtained by including a metal screen in a laminate. Laminate C, having the structure lo JUICES, was prepared in the usual manner, except that thermocouples were incorporated into the structure by placing them on the upper surface of the upper synthetic mica sheet They were then cured in place by applying the upper (GO) layers The thermocouples were located at measured distances from the point of flame application either in the wire direction (WE) or diagonally across the mesh (oblique), as follows:
Thermocouple Location Distance .

TO flame application point 25 TO oblique 2"
TO 3obl pique 4 "
TO oblique 5"
TO oblique 6"
TO 6 WE 41.

Laminate C was prepared using galvanized iron wire as described in Example if whereas Laminate B was prepared to contain comparable copper wire. Laminate A, which contained no wire, was prepared as a control. The following temperatures were recorded.

I Fuji 18 LF~-7336 7341 Temperatures Recorded Time (Min.) _ A _ C A B C A B C_ 0 8080 I I 80 78 81 80 7g 3 19891892 1~1116~ 191 210 99 101 96 10 19201865 1919161 219 255 100 108 10~
15 18611877 1871~00 237 261 102 110 111 A B C A B C A B C
-3 9495 89 90 92 86 1~6 156 14~
9599 96 91 I 91 11~ 163 168 These results indicate that a laminated screen will assist in dissipating the heat from the point of application, and thaw copper wire will dissipate the heat more efficiently than will galvanized iron wire.
I In addition, by comparing the results for TC5 and TC6, it is seen thaw heat is more efficiently conducted in a wire direction as opposed to an oblique direction.
Example 13 This example will illustrate the preparation of a sample which is not cured under heat and pressure.
A Molly coating of the bonding composition described in Example 1 (about 125g) was applied to a 12 in. x 12 in.
piece of 2.5X-SM Modiglass scrims and a second piece of scrip was placed on top of the coating. The layered material was briefly compressed to drive the bonding composition into the respective scrip layers and the composite was allowed to cure under ambient conditions.
Curing was effected in about 5 minute Example 14 This example will illustrate the application of a foamed bonding composition to a layer ox scrims I
19 - LFM-7336 73~1 The bonding composition was prepared as described in Example 1 and mixed for about I seconds. To the mixed material (268g) was added 10.19 t3.8%) of Millifoam surfactant from Onyx Chemical Co. and the foam was produced by mechanically mixing with an air stirrer for 40 seconds. A Molly coating was applied to both surfaces of a 12 in. x 12 in. piece of 7.5X-SM Modiglass scrims the total application by weight being about 82g.
The coated scrip was pressed fox 25 seconds at 180F to give a cured sheet.
The present invention is not restricted solely to the descriptions and illustrations provided above, but encompasses all modifications envisaged by the following claims

Claims (35)

WHAT IS CLAIMED IS:
1. A bonded composite structure comprising at least one layer of at least one type of layer material, each said layer of layer material being bonded to contiguous layers of layer material by a water-resistant phosphate bonding material obtained from the reaction of a composition comprising a metal oxide, calcium silicate and phosphoric acid.
2. The structure as set forth in claim 1 hereof wherein said metal oxide is selected from the group consisting of aluminum oxide, magnesium oxide, calcium oxide and zinc oxide, and the hydrates thereof.
3. The structure as set forth in claim 1 hereof wherein said bonding composition comprises aluminum oxide trihydrate.
4. The structure as set forth in claim 1 hereof wherein said bonding composition comprises magnesium oxide.
5. The structure as set forth in claim 2 hereof wherein said bonding composition comprises a substantially uniform layer of material.
6. The structure as set forth in claim 2 hereof wherein said bonding composition comprises a substantially discontinuous layer of material.
7. The structure as set forth in claim 2 hereof wherein said bonded composite comprises synthetic mica layer material.
8. The structure as set forth in claim 2 hereof wherein said bonded composite comprises a woven, a non-woven or a chopped glass layer material.
9. The structure as set forth in claim 2 hereof wherein said bonded composite comprises a woven, a non-woven or a chopped synthetic layer material.
10. The structure as set forth in claim 2 hereof wherein said bonded composite comprises a kraft paper layer material.
11. The structure as set forth in claim 2 hereof wherein said bonded composite comprises a wire mesh layer material.
12. A fire-resistant bonded composite comprising a plurality of layers of at least one type of layer material, and a plurality of layers of a water-resistant phosphate bonding material obtained from the reaction of a composition comprising a metal oxide, calcium silicate and phosphoric acid, each said layer of layer material being bonded to contiguous layers of layer material by said bonding material, said bonded composite being capable of exhibiting intumescent properties when exposed to flame and/or heat.
13. The composite as set forth in claim 12 hereof wherein said metal oxide is selected from the group consisting of aluminum oxide, magnesium oxide, calcium oxide and zinc oxide, and the hydrates thereof.
14. The composite as set forth in claim 12 hereof wherein said bonding composition comprises aluminum oxide trihydrate.
15. The composite as set forth in claim 12 hereof wherein said bonding composition comprises magnesium oxide.
16. The composite as set forth in claim 13 hereof wherein said bonding composition comprises a substantially continuous layer of material.
17. The composite as set forth in claim 13 hereof wherein said bonding composition comprises a substantially discontinuous layer of material.
18. The composite as set forth in claim 13 hereof wherein said bonded composite comprises a synthetic mica layer material.
19. The composite as set forth in claim 13 hereof wherein said bonded composite comprises a woven, a non-woven or a chopped glass layer material.
20. The composite as set forth in claim 13 hereof wherein said bonded composite comprises a woven, a non-woven or a chopped synthetic layer material.
21. The composite as set forth in claim 13 hereof wherein said bonded composite comprises a kraft paper layer material.
22. The composite as set forth in claim 13 hereof wherein said bonded composite comprises a wire mesh layer material.
23. A process for forming a bonded composite structure, said process comprising the steps of preparing a layered composition comprising (a) at least one layer of a phosphate bonding composition comprising a metal oxide, calcium silicate and phosphoric acid, said composition being suitable to provide a water-resistant phosphate bonding material, and (b) at least one layer of at least one type of layer material, said composite being arranged such that contiguous layers of said layer material are in contact with intervening layers of said bonding composition, and curing said layered composition, optionally by subjecting it to heat and/or pressure.
24. The process as set forth in claim 23 hereof wherein said metal oxide is selected from the group consisting of aluminum oxide, magnesium oxide, calcium oxide and zinc oxide, and the hydrates thereof.
25. The process as set forth in claim 23 hereof wherein said bonding composition comprises aluminum oxide trihydrate.
26. The process as set forth in claim 23 hereof wherein said bonding composition comprises magnesium oxide.
27. The process as set forth in claim 23 hereof wherein said bonding composition is applied at a thickness of from about 1 to about 20 mils.
28. The process as set forth in claim 23 hereof wherein said bonding composition is applied as a mechanically frothed foam.
29. The process as set forth in claim 23 hereof wherein said bonding composition is applied as a substantially continuous layer of material.
30. The process as set forth in claim 23 hereof wherein said bonding composition is applied as a substantially discontinuous layer of material.
31. The process as set forth in claim 24 hereof wherein at least one of said layer materials is a synthetic mica layer material.
32. The process as set forth in claim 24 hereof wherein at least one of said layer materials is a woven, a non-woven or a chopped glass layer material.
33. The process as set forth in claim 24 hereof wherein at least one of said layer materials is a woven, a non-woven or a chopped synthetic layer material.
34. The process as set forth in claim 24 hereof wherein at least one of said layer materials is a kraft paper layer material.
35. The process as set forth in claim 24 hereof wherein at least one of said layer materials is a wire mesh layer material.
CA000470781A 1984-03-12 1984-12-21 Laminated composites Expired CA1229294A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58857784A 1984-03-12 1984-03-12
US588,577 1996-01-18

Publications (1)

Publication Number Publication Date
CA1229294A true CA1229294A (en) 1987-11-17

Family

ID=24354423

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000470781A Expired CA1229294A (en) 1984-03-12 1984-12-21 Laminated composites

Country Status (14)

Country Link
JP (1) JPS60228142A (en)
AT (1) AT388703B (en)
AU (1) AU572943B2 (en)
BE (1) BE901902A (en)
CA (1) CA1229294A (en)
CH (1) CH667642A5 (en)
DE (1) DE3504953A1 (en)
ES (1) ES8603614A1 (en)
FR (1) FR2560820B1 (en)
GB (1) GB2155402B (en)
IT (1) IT1183129B (en)
LU (1) LU85766A1 (en)
NL (1) NL8500706A (en)
SE (1) SE8501186L (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3603493A1 (en) * 1986-02-05 1987-08-06 Kataflox Patent Flame-retardant protective material for plastics
GB8812923D0 (en) * 1988-06-01 1988-07-06 Tenmat Ltd Fibre-reinforced composite material
DE3819902A1 (en) * 1988-06-11 1989-12-21 Wolman Gmbh Dr Laminar material for fire barriers
DE4242099A1 (en) * 1992-12-14 1994-06-16 Abb Patent Gmbh Appts., esp. gas turbine appts. - having coating on its operating parts in contact with fuel gas or waste gas to reduce pollutant emissions
JP3380858B2 (en) 1999-03-31 2003-02-24 旭ファイバーグラス株式会社 Manufacturing method of inorganic moldings
US7517402B2 (en) * 2001-10-08 2009-04-14 Xexos Ltd. Composition comprising a phosphate binder and its preparation
EP2013154A2 (en) * 2006-05-02 2009-01-14 XEXOS Limited Product coated with thin phosphate binder containing layer
DE102010035037A1 (en) * 2010-08-20 2012-02-23 Poly Tec Gmbh Kunststofftechnik Fire-resistant component and method for producing the component
US9403998B2 (en) 2011-10-05 2016-08-02 Kuraray Co., Ltd. Composite structure, product using same, and method for producing composite structure
DE102013102301A1 (en) 2013-03-08 2014-09-11 Chemische Fabrik Budenheim Kg Coating system based on a combination of monoaluminum phosphate with magnesium oxide
DE102016123842A1 (en) * 2016-12-08 2018-06-14 Ibv Holding Gmbh A composition for producing a chemically bound phosphate ceramic, phosphate ceramic and moldings comprising the phosphate ceramic

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2161290A (en) * 1936-08-04 1939-06-06 Ig Farbenindustrie Ag Coating composition
US2744589A (en) * 1951-10-26 1956-05-08 Robertson Co H H Wall-panel structure
US3059046A (en) * 1958-05-16 1962-10-16 Westinghouse Electric Corp Solid inorganic insulation for metallic conductors
US3148996A (en) * 1962-03-26 1964-09-15 Horizons Inc Foamed ceramic
JPS4851031A (en) * 1971-10-28 1973-07-18
JPS4864118A (en) * 1971-11-25 1973-09-05
JPS5614621B2 (en) * 1973-03-14 1981-04-06
JPS51119726A (en) * 1975-04-14 1976-10-20 Kikusui Kagaku Kogyo Kk A liquid coating composition for use in forming a gloss surface
DE7635163U1 (en) * 1976-11-06 1977-05-26 Ihlefeld, Karl-Helmut, 6943 Birkenau LIGHTWEIGHT PANEL WITH HIGH FIRE RESISTANCE BEHAVIOR
JPS5529953A (en) * 1978-08-23 1980-03-03 Tadatoshi Kiyono Threshing method and thresher
US4239519A (en) * 1979-03-26 1980-12-16 Corning Glass Works Inorganic gels and ceramic papers, films, fibers, boards, and coatings made therefrom
DE3144006C2 (en) * 1980-11-08 1984-08-30 Hitachi Chemical Co., Ltd., Tokio/Tokyo Electrically insulating mica tape and its use
US4375516A (en) * 1982-03-02 1983-03-01 Armstrong World Industries, Inc. Rigid, water-resistant phosphate ceramic materials and process for preparing them
CA1186130A (en) * 1981-06-16 1985-04-30 Jeffery L. Barrall Rigid, water-resistant phosphate ceramic materials and processes for preparing them
DE3206218A1 (en) * 1982-02-20 1983-09-01 Wolfgang 7517 Waldbronn Jansen Non-combustible building panel and process for its manufacture
US4507355A (en) * 1984-03-02 1985-03-26 Pyro Technology Corp. Refractory-binder coated fabric

Also Published As

Publication number Publication date
JPS60228142A (en) 1985-11-13
LU85766A1 (en) 1985-07-24
SE8501186D0 (en) 1985-03-11
DE3504953A1 (en) 1985-09-19
CH667642A5 (en) 1988-10-31
FR2560820A1 (en) 1985-09-13
GB8506393D0 (en) 1985-04-11
GB2155402B (en) 1987-09-23
IT1183129B (en) 1987-10-05
ES541161A0 (en) 1985-12-16
SE8501186L (en) 1985-09-13
NL8500706A (en) 1985-10-01
AT388703B (en) 1989-08-25
GB2155402A (en) 1985-09-25
BE901902A (en) 1985-07-01
ATA23585A (en) 1989-01-15
AU572943B2 (en) 1988-05-19
ES8603614A1 (en) 1985-12-16
FR2560820B1 (en) 1988-09-16
AU3775385A (en) 1985-09-19
IT8519316A0 (en) 1985-01-31

Similar Documents

Publication Publication Date Title
US4569878A (en) Laminated composites using bonding material from reaction of metal oxide, calcium silicate and phosphoric acid
US4472478A (en) Fibrous composite materials and the production and use thereof
FI72288B (en) ELDFAST LAMINAT AV SKUMPLAST
CA1229294A (en) Laminated composites
US4315967A (en) Magnesium oxycement/fibrous web composites
FI72078C (en) ELDFAST LAMINARAD MASTIC PRODUCT.
CN107949550B (en) Sound-absorbing ceiling tile
KR101068084B1 (en) High temperature insulation member and its manufacturing method
UA56237C2 (en) Refractory stratified slab, method for making and using it
USRE34020E (en) Fibrous composite materials and the production and use thereof
JPH04185799A (en) Method for producing flame-retrardant paper or flame-retardant board, or flame-retardant molded product
US2034522A (en) Fireproof building material
JPS5869047A (en) Sheet-shaped body, its manufacture and heat insulating material
KR101973186B1 (en) High strength magnesium oxide composite panel using carbon fiber grid technology and manufacturing method thereof
JP3177546B2 (en) Flame retardant insulation
JP5981153B2 (en) Incombustible decorative board
KR20030065032A (en) Fiber resin complex panel with color stone
KR930011147B1 (en) Anti-aging articles
KR20050046262A (en) Ornament composite panel having incombustibility
JP3865897B2 (en) Fireproof ground plate
JPS6229521Y2 (en)
CA1173205A (en) Fibrous composite materials and the production and use thereof
SU889812A1 (en) Heat-insulating panel manufacturing method
JPH0243033A (en) Building panel
JP3079459B2 (en) Non-combustible composite plate or composite molded body

Legal Events

Date Code Title Description
MKEX Expiry