Patent Publication Number: US-9428864-B2

Title: Multilayered sheet

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 61/625,867, filed Apr. 18, 2012 which is herein incorporated by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of Invention 
     This invention pertains to a multilayered sheet comprising a carrier layer and an inorganic refractory layer and a method of making the multilayered sheet. Preferably, the carrier layer is a paper. 
     2. Background of the Invention 
     U.S. Pat. No. 6,322,022 to Fay et al. discloses burnthrough resistant systems for transportation especially aircraft. 
     U.S. Pat. No. 6,670,291 to Tomkins and Vogel-Martin describes a laminate sheet material for flame barrier applications. 
     U.S. Pat. No. 5,667,886 to Gough et al describes a composite sheet having a substrate layer, a coating layer and a flexible adhesive layer. The substrate layer is preferably a polyester film. The coating layer contains a mineral, preferably vermiculite. 
     There remains an ongoing need for methods to provide a thin inorganic refractory layer in a form that may be safely handled and subsequently processed into a multi-layer composite for use as a flame barrier component in a thermal and acoustic blanket for aircraft structures. 
     SUMMARY OF INVENTION 
     This invention is directed to a layered sheet comprising a paper carrier having a first and second surface and an inorganic refractory layer adjacent to at least one surface of the paper wherein the refractory layer has a dry areal weight of from 15 to 50 gsm, the bond strength between the refractory layer and the surface of the paper is at least 0.25 lb/in, preferably at least 0.8 lb/in, wherein the carrier 
     (i) comprises from 70 to 90 weight percent of aramid fibers and from 10 to 30 weight percent of polymeric binder, 
     (ii) is hydrophilic 
     (iii) has a wet tensile strength of at least 3 lb/in in a first direction and at least 2 lb/in in a second direction, the second direction being transverse to the first direction, 
     (iv) has a dry tensile strength of at least 7 lb/in in a first direction and at least 5 lb/in in a second direction, the second direction being transverse to the first direction, 
     (v) has an air permeability no greater than 100 Gurley Air Resistance (sec/100 cc, 20 oz. cyl.). 
     (vi) has a thickness of from 0.025 to 0.175 mm, 
     (vii) has a density of from 0.25 to 1.1 g/cc, and 
     (viii) has a basis weight of from 20 to 70 gsm. 
     This invention also pertains to a method of forming a layered sheet followed by subsequent treatment comprising the steps of 
     (i) depositing an aqueous slurry of inorganic refractory platelets onto one surface of a carrier to form a layered sheet wherein the refractory platelets
         comprise from 7 to 13 weight percent of the slurry,   have a particle thickness of from 5 A to 5000 A,   have an average diameter of from 15 to 25 micrometers,
 
wherein the carrier has
   (a) a wet tensile strength of at least 3 lb/in in a first direction and at least 2 lb/in in a second direction, the second direction being transverse to the first direction,   (b) a dry tensile strength of at 7 lb/in in the first direction and at least 5 lb/in in the second direction,   (c) a thickness of from 0.025 to 0.175 mm,   (d) a density of from 0.25 to 1.1 g/cc, and.   (e) an air permeability no greater than 100 Gurley Air Resistance (sec/100 cc, 20 oz. cyl),   (f) a basis weight of from 20 to 70 gsm, and wherein the carrier comprises from 70 to 90 weight percent of aramid fibers and from 10 to 30 weight percent of polymeric binder, and       

     (ii) drying the layered sheet at a temperature of from 80 to 110 degrees C. until the residual moisture content in the refractory layer is no greater than 10 percent by weight and the bond strength between the refractory layer and the surface of the carrier is no less than 0.25 lb/in. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is a schematic cross section through a multilayered sheet of this invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       FIG. 1  shows a section through a multilayered sheet  10  comprising a carrier or substrate layer  11  and an inorganic refractory layer  12  deposited onto the carrier layer. A preferred carrier material is a flame resistant high strength fiber wet-laid nonwoven carrier. A preferred nonwoven is a paper. As used herein, the terms “carrier” and “paper” are used interchangeably. 
     Carrier 
     The carrier has a first and a second surface shown respectively at  13  and  14  in  FIG. 1 . 
     In one embodiment, the carrier comprises from 70 to 90 weight percent of aramid fibers and from 10 to 30 weight percent of binder. In another embodiment, the carrier comprises from 80 to 90 weight percent of aramid fibers and from 10 to 20 weight percent of binder. A preferred binder is meta-aramid. 
     The thickness of the carrier used in this invention is dependent upon the end use or desired properties of the laminate but, to provide an overall high flexibility and the lowest possible weight, is typically from 1 to 7 mils (0.025 to 0.175 mm) or even from 1 to 4 mils (0.025 to 0.100 mm) thick. The carrier thickness may even be from 1 to 3 mil (0.025 to 0.075 mm). A carrier thickness below 1 mil would result in undesirable features such as a weaker and a less dimensionally stable sheet, especially when saturated with water. A carrier having a thickness greater than 7 mils would add undesirable weight and stiffness. 
     In some embodiments, the carrier has a density of from 0.25 to 1.1 g/cc or from 0.50 to 1.1 g/cc or even from 0.65 to 0.95 g/cc. A carrier density of below 0.25 g/cc would result in undesirable features such as a weaker fluffy and excessively open structure. A carrier density of greater than 0.5 g/cc requires additional densification at ambient, sub-ambient or above ambient temperatures by densification processes such as calendaring, pressing in a platen press or a double-belt press. In some embodiments the carrier has been exposed to a temperature of at least 280 degrees C. during the densification process or even to temperature of 330 to 360 degree Celsius. A denser paper allows for a thinner and mechanically stronger carrier, especially when densification is carried out at temperature of at least 280 degrees C. 
     Because of the low binder content, the carrier retains high air permeability even after densification without any negative impact on the drying process of the coated paper. In some embodiments, the basis weight of the carrier is from 0.59 to 2.06 ounces per square yard (20 to 70 grams per square meter). 
     The bond strength between the refractory layer and the surface of the paper is at least 0.25 lb/in, preferably at least 0.8 lb/in, If the bond strength value is less than 0.25 lb/in, the inorganic refractory layer can peel off the carrier with a risk of breaks in the refractory layer. A bond strength of at least 0.8 lb/in ensures that the inorganic refractory layer does not separate from the carrier either during subsequent process steps or, once put in service, during the life span of the intended application. Bond strength is sometimes referred to as Release Value. In this instance, it is the Release Value between the surface of the paper and the intumescent coating applied to the paper. 
     The carrier has a wet tensile strength of at least 3 lb/in in a first direction and at least 2 lb/in in a second direction, the second direction being transverse to the first direction. In another embodiment, the paper has a wet tensile strength of at least 5 lb/in in a first direction and at least 4 lb/in in a second direction, the second direction being transverse to the first direction. In a preferred embodiment the first direction is the long direction within the plane of the paper, that is, the direction in which the roll of paper has been made. This is also known as the machine direction. The second direction is sometimes known as the cross direction. By wet tensile strength we mean the tensile strength of the paper after saturation with water. If the wet tensile strength is less than 3 lb/in in a first direction, there is a high risk of frequent sheet breaks during the coating process due to the weight being deposited on the paper and the tension applied to the paper. 
     The paper has a dry tensile strength of at least 7 lb/in in a first direction and at least 5 lb/in in a second direction, the second direction being transverse to the first direction. By dry tensile strength we mean the tensile strength of a paper that has been conditioned at ambient temperature and humidity, typically 48-52% Relative Humidity and 22-24 degrees C. TAPPI T-402 sp-08 is an example specification defining ambient conditions for paper, board and pulp products. 
     A dry tensile strength of at least 7 lb/in in a first direction is required to ensure proper handling of the coated web through the subsequent process steps, in particular, to ensure tight roll formation during winding to prevent roll sagging and telescoping. 
     In some embodiments, the carrier has a dry tensile strength of at least 15 lb/in in the first direction and at least 10 lb/in in the second direction. 
     The carrier is hydrophilic. This feature aids the drying process. As the majority of the water from the refractory coating dispersion is absorbed by the carrier, this allows more efficient drying and forming of the inorganic refractory layer as well as preventing drying defects such as blisters in the refractory layer. 
     The carrier has air permeability no greater than 100 Gurley Air Resistance (sec/100 cc, 20 oz. cyl). Air permeability no greater than 100 Gurley Air Resistance allows for a very efficient drying and forming of the inorganic refractory layer as well as preventing drying defects such as blisters in the refractory layer. In some embodiments, the paper has an air permeability no greater than 30 seconds Gurley Air Resistance (sec/100 cc, 20 oz. cyl.) or even no greater than 10 seconds Gurley Air Resistance (sec/100 cc, 20 oz. cyl.). 
     The aramid fibers of the paper may be meta-aramid, para-aramid or a combination of the two. 
     The high temperature properties of the aramid fibers ensures thermal and mechanical stability of the carrier during processing steps when the carrier can be exposed to a temperature of 150 degrees C. for at least 10 minutes, that is to say, that the paper will not change dimensions when subjected to a temperature of 150 degrees C. for at least 10 minutes. 
     The aramid fibers of the paper can be in the form of floc, pulp, or a combination of thereof. As employed herein the term aramid means a polyamide wherein at least 85% of the amide (—CONH—) linkages are attached directly to two aromatic rings. Additives can be used with the aramid. In fact, it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid. 
     Floc is generally made by cutting continuous spun filaments into specific-length pieces. If the floc length is less than 2 millimeters, it is generally too short to provide a paper with adequate strength; if the floc length is more than 25 millimeters, it is very difficult to form uniform wet-laid webs. Floc having a diameter of less than 5 micrometers, and especially less than 3 micrometers, is difficult to produce with adequate cross sectional uniformity and reproducibility; if the floc diameter is more than 20 micrometers, it is very difficult to form uniform papers of light to medium basis weights. 
     The term “pulp”, as used herein, means particles of fibrous material having a stalk and fibrils extending generally therefrom, wherein the stalk is generally columnar and 10 to 50 micrometers in diameter and the fibrils are fine, hair-like members generally attached to the stalk measuring only a fraction of a micrometer or a few micrometers in diameter and 10 to 100 micrometers long. Aramid fiber floc is of a similar length to carbon fiber floc. Both meta and para aramid fibers are suitable and are available from E.I. DuPont de Nemours, Richmond, Va. under the tradenames Kevlar® and Nomex® and from Teijin Twaron, Conyers, Ga. under the tradename Twaron®. 
     A preferred pulp material is p-aramid. However a blend of p-aramid with other synthetic or natural fibers such as liquid crystal polyester, polyareneazole, meta-aramid, and cellulose can be utilized. One illustrative process for making aramid pulp is disclosed in U.S. Pat. No. 5,084,136 to Haines et al. 
     Different thermoset and thermoplastic resins can be used as a polymeric binder in the paper of this invention. These resins can be supplied in the form of fibrids, flakes, powder, and floc. The term “fibrids” as used herein, means a very finely-divided polymer product of small, filmy, essentially two-dimensional, particles known having a length and width of 100 to 1000 micrometers and a thickness of 0.1 to 1 micrometer. Preferable types of binder resins are aramids, polyimides, phenolics, and epoxies. However, other types of the resins can also be used. 
     Fibrids are typically made by streaming a polymer solution into a coagulating bath of liquid that is immiscible with the solvent of the solution. The stream of polymer solution is subjected to strenuous shearing forces and turbulence as the polymer is coagulated. The fibrid material of this invention can be selected from meta or para-aramid or blends thereof. More preferably, the fibrid is a meta-aramid. 
     The paper can include small amounts of inorganic particles including mica, vermiculite, and the like; the addition of these performance enhancing additives being to impart properties such as improved fire resistance, thermal conductivity, dimensional stability, and the like to the paper and the final laminate. 
     In one preferred embodiment, the fiber and the polymer binder in the form of fibrids can be slurried together to form a mix that is converted to paper on a wire screen or belt. Reference is made to U.S. Pat. Nos. 4,698,267 and 4,729,921 to Tokarsky; U.S. Pat. No. 5,026,456 to Hesler et al.; U.S. Pat. Nos. 5,223,094 and 5,314,742 to Kirayoglu et al for illustrative processes for forming papers from aramid fibers and aramid fibrids. 
     Inorganic Refractory Layer 
     The inorganic refractory layer is adjacent to at least one surface of the carrier. The refractory layer has a dry areal weight of from 15 to 50 gsm and a residual moisture content of no greater than 10 percent by weight. In some embodiments, the refractory layer has a dry areal weight of from 20 to 35 gsm and a residual moisture content of no greater than 3 percent by weight. The layer is shown as  12  in  FIG. 1 . 
     The refractory layer comprises platelets. Preferably at least 85% of the layer comprises platelets, more preferably at least 90% and most preferably at least 95%. In some embodiments, platelets comprise 100% of the layer. The refractory layer may comprise some residual dispersant arising from incomplete drying of the platelet dispersion during manufacture. 
     The refractory layer has a thickness of from 7.0 to 76 micrometers and more preferably from 7.0 to 50 micrometers. Preferably, the layer has a UL 94 flame classification of V-0. The function of the refractory layer, in which adjacent platelets overlap, is to provide a flame and hot gas impermeable barrier. The inorganic platelets may be clay, such as montmorillonite, vermiculite, mica, talc and combinations thereof. Preferably, the inorganic oxide platelets are stable (i.e., do not burn, melt or decompose) at about 600 degrees C. more preferably at about 800 degrees C. and most preferably at about 1000 degrees C. Vermiculite is a preferred platelet material. Vermiculite is a hydrated magnesium aluminosilicate micaceous mineral found in nature as a multilayer crystal. Vermiculite typically comprises by (dry) weight, on a theoretical oxide basis, about 38-46% SiO 2 , about 16-24% MgO, about 11-16% Al 2 O 3 ; about 8-13% Fe 2 O 3  and the remainder generally oxides of K, Ca, Ti, Mn, Cr, Na, and Ba. “Exfoliated” vermiculite refers to vermiculite that has been treated, chemically or with heat, to expand and separate the layers of the crystal, yielding high aspect ratio vermiculite platelets. Suitable vermiculite materials are available from W. R. Grace of Cambridge, Mass., under the trade designations MicroLite 963 and MicroLite HTS-XE. 
     The thickness of an individual platelet typically ranges from about 5 Angstroms to about 5,000 Angstroms more preferably from about 10 Angstroms to about 4,200 Angstroms. The mean value of the maximum width of a platelet typically ranges from about 10,000 Angstroms to about 30,000 Angstroms. The aspect ratio of an individual platelet typically ranges from 100 to 20,000. 
     Preferably, the platelets have an average diameter of from 15 to 25 micrometers. In some other embodiments, the platelets have an average diameter of from 18 to 23 micrometers. 
     In a preferred embodiment, the refractory layer further comprises cations arising from contact, at a temperature of from 10 to 50 degrees C., with an aqueous cationic rich solution at a cation concentration of from 0.25 to 2N. The contact with the cationic solution occurs prior to assembling the refractory layer into a composite laminate. This cationic treatment provides enhanced stability to the refractory layer on exposure to fluids. 
     In some embodiments of this invention, the inorganic platelet layer is reinforced by a lightweight open weave fabric scrim either laid onto a single platelet layer or placed between two layers of platelets so as to provide additional mechanical strength to the layer. The scrim can be made from natural, organic or inorganic fibers with glass, cotton, nylon or polyester being typical examples. A glass fiber scrim is particularly preferred. The scrim may be a woven or knit structure and has a typical areal weight not exceeding 40 grams per square meter. 
     In some embodiments, the refractory layer is perforated to enhance bonding to an adhesive layer during subsequent processing. The extent of perforation is determined by experimentation. Preferably, in order to prevent compromising flame barrier properties, an individual perforation should not exceed 2 millimeters in maximum dimension. In a preferable embodiment, individual perforations should be spaced at least 10 millimeters apart. The shape of the perforations is not critical, Suitable perforations include circles, squares, rectangles, ovals and chevrons. 
     Method of Forming the Multilayered Sheet 
     A method of forming a layered sheet followed by subsequent treatment comprises the steps of 
     (i) depositing an aqueous slurry of inorganic refractory platelets onto one surface of a carrier to form a layered sheet wherein the refractory platelets
         comprise from 7 to 13 weight percent of the slurry,   have a particle thickness of from 5 A to 5000 A,   have an average diameter of from 15 to 25 micrometers,
 
wherein the carrier has
   (a) a wet tensile strength of at least 3 lb/in in a first direction and at least 2 lb/in in a second direction, the second direction being transverse to the first direction,   (b) a dry tensile strength of at least 7 lb/in in the first direction and at least 5 lb/in in the second direction,   (c) a thickness of from 0.025 to 0.175 mm,   (d) a density of from 0.25 to 1.1 g/cc, and.   (e) an air permeability no greater than 100 Gurley Air Resistance (sec/100 cc, 20 oz. cyl),   (f) a basis weight of from 20 to 70 gsm, and
 
wherein the carrier comprises from 70 to 90 weight percent of aramid fibers and from 10 to 30 weight percent of polymeric binder, and
       

     (ii) drying the layered sheet at a temperature of from 80 to 110 degrees C. until the residual moisture content in the refractory layer is no greater than 10 percent by weight and the bond strength between the refractory layer and the surface of the carrier is no less than 0.25 lb/in. 
     When the refractory platelets comprise from 11.5 to 13 weight percent of the slurry, it is preferable that the slurry is de-aerated (de-gassed) prior to deposition on the carrier. This will reduce defects due to trapped air. 
     Preferably, when the platelet content of the slurry is from 7.0 to 8.5 percent and the desired coat weight is 27 gsm or higher, then the coating is applied in multiple steps. For example, a 30 gsm total coat weight could be achieved by two applications of slurry each providing 15 gsm of refractory material or by three applications at 10 gsm. 
     In some embodiments, the layered sheet is dried at a temperature of from 80 to 110 degrees C. until the residual moisture content in the refractory layer is no greater than 3 percent by weight. In some other embodiments, the method comprises an optional step of increasing the drying temperature in step (ii) to from 150 to 180 degrees C. after the residual moisture content in the refractory layer is less than 10 percent. 
     In some embodiments, the refractory platelets comprise from 10 to 11 weight percent of the slurry. 
     Preferably the layered sheet, when wet, has a shrinkage no greater than 2 percent. 
     Prior to coating the carrier with refractory material, the carrier may optionally be treated to promote better wetting. An example of such a treatment is plasma or corona treatment. 
     Use of the Refractory Layer 
     The layered sheet may be used as a component in a flame barrier layer for a thermal insulation and acoustic blanket. An example of such a blanket is described in U.S. patent application publication 2011/0094826. 
     Test Methods 
     The wet tensile strength of the carrier was measured according to TAPPI T456 om-10 Tensile Breaking Strength of Water-saturated Paper and Paperboard (“Wet Tensile Strength”). 
     The dry tensile strength of the carrier was measured according to TAPPI T494 om-06 Tensile Properties of Paper and Paperboard (Using Constant Rate of Elongation Apparatus). 
     The thickness of the carrier was measured by TAPPI T411 om-10 Thickness (Caliper) of Paper, Paperboard, and Combined Board. 
     The density of the carrier is a calculated value based on the measured values of carrier thickness and basis weight. 
     The air permeability of the carrier was measured according to TAPPI T460 om-11 Air Resistance of Paper (Gurley Method, sec/100 cc, 20 oz. cyl.). 
     The dimensional stability of the carrier was rated based on its ability to hold flat (i.e. no moisture related wrinkles or creases) for at least 2 minutes when exposed to one-sided wetting. 
     The surface smoothness of the carrier was measured according to TAPPI T538 om-08 Roughness of Paper and Paperboard (Sheffield Method), 
     The dry areal weight of the refractory layer was measured according to ISO 536 (1995) Determination of Grammage and TAPPI T 410 Grammage of Paper and Paperboard (Weight per Unit Area). 
     The moisture content of the refractory layer was measured according to ISO 287 (1985) Determination of Moisture Content—Oven Drying Method. 
     Two-layer composite sheets were subjected to a flame test that replicated the temperature and air mass flux test conditions of test method FAA FAR 25.856(b), App. F, Part VII. The somewhat lower heat flux was compensated with a higher air mass flux to replicate a required thermo-mechanical stress level to be exerted on the flame barrier composites during the burn-through test. 
     EXAMPLES 
     In the following examples, all parts and percentages are by weight and all degrees in centigrade unless otherwise indicated. Examples prepared according to the current invention are indicated by numerical values. Control or Comparative Examples are indicated by letter 
     The vermiculite used was a high solids version of an aqueous dispersion of Microlite® 963 having an as supplied solids content of 7.5 percent. The dispersion was obtained from W. R. Grace and Co, Cambridge, Mass. 
     Example 1 
     Vermiculite dispersion concentrated to a solids content of 11.6% weight percent was coated on 3 mil thick para-aramid paper using a doctor blade to form a refractory layer on the paper. The paper was a 3-mil grade paper from DuPont comprising from 10 to 30 weight percent of para-aramid fiber and 70 to 90 weight percent of polymeric binder in the form of fibrids. The paper was calendered at 360 degrees C. to produce a finished paper having a basis weight of 1.78 oz/sq. yd., an average thickness of 2.88 mil, a density of 0.83 g/cc, a Gurley Air Resistance of 6 sec/100 cc, 20 oz. cyl., a dry tensile strength of 19 lb/in, in the machine direction and 16 lb./in. in the cross direction. The wet tensile strength was 7.5 lb/in. in the machine direction and 6.3 lb./in. in the cross direction. 
     The coated paper was dried for 15 minutes in an aft flotation conventional oven at a temperature of 85 degrees C. until the inorganic refractory layer had moisture content below 5%. The refractory layer had a dry coat weight of 37 gsm. 
     The inorganic refractory layer on the aramid paper formed an effective lightweight and flexible 2-layer composite. There were no practical ways to remove any substantial sections of the refractory layer from the paper base without the aid of a reinforcing substrate bonded to the exposed side of the refractory film layer. The inorganic refractory material remained attached to the surface of the aramid paper even after substantial flexing. 
     The 2-layer composite was subjected to a flame test that replicated the temperature and air mass flux test conditions of test method FAA FAR 25.856(b), App. F, Part VII. When exposed to a flame on the inorganic refractory layer side, the sample showed a good resistance to flame propagation, with the inorganic refractory layer acting as an effective flame barrier. 
     Comparative Example A 
     This was as Example 1 except that the binder content was from 45 to 55 percent. The Nomex® meta-aramid paper from DuPont was 2 mil thick, reduced from 5 mil by calendering at 360 degrees C. to produce a finished paper having basis weight of 1.19 oz/sq. yd., an average thickness of 2.19 mil, a density of 0.75 g/cc, a Gurley Air Resistance of 450 sec/25 cc, 20 oz. cyl., a smoothness of less than 100 Sheffield units, a dry tensile strength of 24 lb/in, in the machine direction and 12 lb./in. in the cross direction. The wet tensile strength was 21.09 lb/in, in the machine direction and 6.20 lb./in. in the cross direction. 
     From inspecting a sample of the two layer composite, it was observed that the dried refractory layer easily peeled away from the aramid carrier, especially after flexing. Although the peel characteristics were good, with 0.5 lbs/in tensile strength, the unsupported inorganic refractory film-like material was extremely difficult to handle and extra care had to be taken to further process the material. 
     Example 2 
     This was as Comparative Example A except that a different densification method was used. The paper was a commercial grade paper from DuPont calendered at 200 degree Celsius to produce a finished paper having a basis weight of 1.8 oz/sq. yd., an average thickness of 2.63 mil, a density of 0.92 g/cc, a Gurley Air Resistance of 20 sec/100 cc, 20 oz. cyl., a dry tensile strength of 17.69 lb./in, in the machine direction and 13.67 lb./in. in the cross direction. The wet tensile strength was 5.49 lb/in, in the machine direction and 5.37 lb./in. in the cross direction. 
     The coated paper was dried for 15 minutes in an air flotation conventional oven at a temperature of 85 degrees C. until the inorganic refractory layer had moisture content below 5%. The refractory layer had a dry coat weight of 37 gsm. The findings were the same as for Example 1 
     Comparative Example B 
     This was as Comparative Example A except that a low temperature densification method was used. The paper was 5-mil grade Nomex® from DuPont calendered at 200 degrees C. to produce a finished paper having a basis weight of 1.18 oz/sq. yd., an average thickness of 1.66 mil, a density of 0.96 g/cc, a Gurley Air Resistance of 1865 sec/25 cc, 20 oz. cyl., a smoothness of less than 100 Sheffield units, a dry tensile strength of 15.22 in the machine direction and 7.89 in the cross direction. The wet tensile strength was 5.8 lb/in, in the machine direction and 2.22 lb/in, in the cross direction. 
     The coated paper was dried for a total of 30 minutes in two passes each of 15 minutes in an air flotation conventional oven at a temperature of 85 degrees C. until the inorganic refractory layer had moisture content below 5%. The refractory layer had a dry coat weight of 37 gsm. 
     The findings were the same as for Comparative Example A. 
     Comparative Example C 
     Vermiculite dispersion concentrated to a solids content of 10.6 weight percent was coated on 2-mil thick metallized polyester film using a slot die coating system to form a refractory layer on the film. The film was metalized on one side. The coating was applied to the metalized side of the film. The film was obtained under the tradename Mylar from E.I. DuPont de Nemours and Co., Wilmington, Del. The coated film was dried in an oven at a temperature not exceeding 110 degrees C. until the inorganic refractory layer had moisture content below 5%. The total drying time exceeded 75 minutes comprising a staged drying of 15 minutes at 60 degrees, 15 minutes at 71 degrees, 15 minutes at 82 degrees, 15 minutes at 93 degrees, and over 15 minutes at 99 degrees. The refractory layer had a dry coat weight of 35 gsm. The paper and refractory layers were wound up on as separate rolls. 
     From inspecting a sample of the two layer composite, it was observed that the dried refractory layer spontaneously peeled away from the metallized side of the film. Although the peel characteristics were good, with 0.5 lbs/in tensile strength, the unsupported inorganic refractory film-like material was extremely difficult to handle and extra care had to be taken to further process the material. 
     Comparative Example D 
     Vermiculite dispersion concentrated to a solids content of 13 weight percent was coated on a 6 micron thick polyetheretherketone (PEKK) film using a slot die coating system to form a refractory layer on the film. The film was grade DS-E obtained from Cytec Industries, Woodland Park, N.J. The coated film was dried in an oven at a temperature not exceeding 110 degrees C. until the inorganic refractory layer had moisture content below 5%. The drying time exceeded 45 minutes comprising a staged drying of 9 minutes at 71 degrees, 6 minutes at 82 degrees, 6 minutes at 93 degrees, and 25 minutes at 96 degrees. The refractory layer had a dry coat weight of 33 gsm, The two layer composite of film and refractory layer was wound up on a roll. 
     The coating process proved to be very difficult due to tendency for the film to wrinkle and crease. Further, the film had to be surface treated by a process such as corona treatment to promote wetting and give a uniform coating, Although relatively continuous refractory layer coating was obtained the refractory layer was highly non-uniform and affected by streaks and light spots related to excessive air bubbles trapped in the high viscosity solution. 
     Comparative Example E 
     Vermiculite dispersion concentrated to a solids content of 7.5 weight percent was coated on 0.5 mil thick polyimide film using a knife over roll coating system to form a refractory layer on the film. The film was obtained under the tradename Kapton from DuPont. The coated film was dried in an oven at a temperature not exceeding 110 degrees C. until the inorganic refractory layer had moisture content below 5%. The drying time exceeded 75 minutes comprising a staged drying of 20 minutes at 71 degrees, 20 minutes at 82 degrees, 20 minutes at 93 degrees, and over 25 minutes at 96 degrees. The refractory layer had a target dry coat weight of 33 gsm. The two layer composite of film and refractory layer was wound up on a roll. 
     The coating process proved to be very difficult due to an extremely low viscosity of the coating solution combined with tendency for the film to wrinkle and crease. Further, the film had to be surface treated by a process such as corona treatment to promote wetting and give a uniform coating, A uniform and continuous refractory layer coating was not obtained. 
     Comparative Example F 
     Vermiculite dispersion concentrated to a solids content of 10.8 weight percent was coated on 2 mil thick polyimide (Kapton®) film using a slot die coating system to form a refractory layer on the film. The coated film was dried in an oven at a temperature not exceeding 110 degrees C. until the inorganic refractory layer had moisture content below 5%. The drying time exceeded 75 minutes comprising a staged drying of 9 minutes at 71 degrees, 6 minutes at 82 degrees, 6 minutes at 93 degrees, and 60 minutes at 96 degrees. The refractory layer had a dry coat weight of 33 gsm. The two layer composite of film and refractory layer was wound up on a roll. 
     Once dried to below 5% moisture content, a very uniform and continuous refractory layer resulted. The layer remained on the surface of the film with enough adhesion to allow for smooth roll winding and post-processing. Refractory layer was easily peeled off the polymeric film base with a help of a reinforcing substrate that was bonded to the exposed side of the refractory film. It was also possible to peel substantial sections of the refractory layer off the polymeric film base without the aid of a reinforcing substrate; however extreme care has to be taken to prevent premature breaks of the film-like refractory layer. 
     When exposed to a flame on the inorganic refractory layer side, the sample showed a good resistance to flame propagation, with the inorganic refractory layer acting as an effective flame barrier. 
     However, the drying time for a coating process in excess of 75 minutes was too long to be of practical value. Further, the inorganic refractory material showed signs of localized delamination/detachment from the polymeric film base when flexed. 
     Comparative Example G 
     This was as Example C except that the film layer did not have a metalized surface. The findings were the same as for Comparative Example F, with the exception for flame propagation properties. When exposed to a flame on the inorganic refractory layer side, an inorganic refractory layer acted as an effective flame barrier, however the overall 2-layer composite propagated fire on the polymeric film side. 
     Comparative Example H 
     Vermiculite dispersion was coated on 5.6 mil thick reinforced polyethylene sheet using a doctor blade. The polyethylene sheet was Tyvek® grade 1056D from DuPont. The coated sheet was dried in an oven at 90 degrees C. until the refractory layer had moisture content below 5%. The drying time was 30 minutes. The dry basis weight of the refractory layer was 37 gsm. 
     The dried refractory layer could not be removed from the sheet even with the help of a reinforcing substrate bonded to the exposed side of the refractory layer. Cohesive bond failure within the refractory layer was observed. The polyethylene sheet was unsuitable for use. 
     Comparative Example I 
     Vermiculite dispersion concentrated to a solids content of 10.8% weight percent was coated on 11 mil thick hydrophilic gray RagKraft paper using a slot die coating system to form a refractory layer on the paper. The paper comprised a blend of 50 weight percent of cellulose fibers and 50 weight percent of cotton fibers and was obtained from Crocker Technical Papers. 
     The paper had a basis weight of 8.1 oz/sq. yd., an average thickness of 11.0 mil, a density of 1.0 cc, a Gurley Air Resistance of 714 sec/100 cc, 20 oz. cyl., a smoothness of 103 Sheffield units, a dry tensile strength of 122.0 lb/in. in the machine direction and 40.0 lb./in. in the cross direction. The wet tensile strength was 6.4 lb./in. in the machine direction and 2.5 lb./in. in the cross direction. 
     The coated paper was dried for 15 minutes in an air flotation oven at a temperature not exceeding 110 degrees C. until the inorganic refractory layer had moisture content below 5%. Differential drying temperatures were applied to the top (vermiculite side) and the bottom (paper side). The drying profile on the top side was 5 minutes at 49 degrees, 5 minutes at 60 degrees and 5 minutes at 71 degrees. The drying on the bottom side was maintained for 15 minutes at 99 degrees. The refractory layer had a dry coat weight of 33 gsm. The two layer composite of film and refractory layer was wound up on a roll. 
     Once dried to below 5% moisture content, a very uniform and continuous refractory layer resulted. The layer remained on the surface of the paper with enough adhesion to allow for smooth roll winding and post-processing. The refractory layer was easily peeled off the paper base with a help of reinforcing substrate that was bonded to the exposed side of the refractory film. With extreme care it was also possible to peel short sections of the refractory layer from the paper base without the aid of a reinforcing substrate. 
     When exposed to a flame on the inorganic refractory layer side, the refractory layer acted as an effective flame barrier, however the overall 2-layer composite propagated fire on the paper side.