CA1219103A - Flexible fibrous endothermic sheet material for fire protection - Google Patents

Abstract

FLEXIBLE FIBROUS ENDOTHERMIC SHEET
MATERIAL FOR FIRE PROTECTION

Abstract of Disclosure This invention relates to a non-intumescent, non-char forming, endothermic, essentially inorganic, flexible, fire-protective sheet material. The flexible sheet is made of a composition comprising:
(a) an inorganic fiber, such as alumino-silicate refractory fibers;
(b) an organic polymer binder, such as an acrylic resin; and (c) an inorganic endothermic filler, such as alumina trihydrate.
The weight ratio of organic to inorganic constituents is less than about 0.15, and the weight ratio of inorganic endothermic filler of part (c) to inorganic fiber of part (a) is in the range of about 0.5 to 5Ø
This sheet is a useful fire barrier wrap for conduits and cable trays in building construction, which provides excellent fire protection, but the current capacity derating of cables is significantly less with this new fibrous sheet than it is in the case of known fire barrier sheet materials.

Description

3~03 FLEXIBLE FIBROUS ENDOTHERMIC SHEET
~IATERIAL E~OR FIRE PROTECTIO_ rl`~chnical l~ield This invention is in the field of fire protection materials. Specifically, it relates to Eire harrie~
materials useful in protecting electrical systems during a fire.

sackground E`ire protection in areas with high concentrations of instrument, communication and power transmission wires and cables is very important, especially in such installations as large buildings and power plants. Such wires and cables are constructed with electrically insulating coverings which are combustible and can provide a pathway by which fire might spread. Fire protection Eor such wires and cables is critical when power supply is necessary for the maintenance of controls, for example, in aircraft or factories.
Intumescent sheets for fire protection are

2~ disclosed in U.S. Patent 4,273,879. These particular sheets have a significant content of organic materials (binder and char forming resin)~ During combustion, these organic materials can cause exothermic reactions increasing the temperature of the fire~
There are other fire protection materials which may be produced in a sheet Eorm and which are designed to retard the spread of fire and heat by an endothermic reaction. See, for example, U.~. Patent 4,315,075 describiny a neoprene foam containing hydrated alumina.
Alumina trihydrate (A12O3-3H2O) has 34.6~
chemically combined water of hydration. This water is liberated beginning at about 230C with complete dehydration at about 600C. This endothermic dehydration is known to have a cooling effect in compositions of which alumina trihydrate is a component. The water vapor given r . ~

off also dilutes tlle combustible gases which may be present ~uring a Ei~e to helu arrest comhustion. ~lumina trihydrate (ATH) is a known fire retardant ~iller in the plastics industry.
Inorganic materials in the form of fiber blankets have been used Eor the protection of conduits and cable trays. ~ne such fiber blanket is prepared from alumino-silicate glass fibers and marketed under the trademark Kaowool by The Babcock & Wilcox Company. In order to have one hour fire protection, the alumino-silicate fiber blankets are wrapped around cable trays in a thickness of usually two inches or more. This blanket insulation has low thermal conductivity and, therefore, not only insulates from the effects of fire but also retains in the conduit the heat generated by the current carried through electrical cables under normal conditions. With the dissipation o~ normal heat generated by the line resistance thus retarded, the cables in trays or conduit must be derated. That is, the amount of current which they are rated to carry (ampacity or amp capacity) must be decreased It is desired to provide a composition which gives good fire protection to cable trays and conduits with a minimum reduction in the ampacity ratin~ of the electrical cables in them.

Disclosure of Invention The invention is summarized as an endothermic, non-insulating, flexible, fibrous material made of a composition comprising:
(a) inorganic fiber;
(b) organic polymer binder; and (c) an inorganic, endothermic filler which undergoes an endothermic reaction between about 100 and 600C;

19~0,3 having a weiyht ratio o- oryanic to ino~ganic constit~lellts ol- less tl~
about 0.15 (preferably below 0.08); and a weight ratio oE inorqatlic endothermic filler of part (c) to inorganic fiber of part (a) in the ran~e of about 0.5 to 5Ø
This invention provides a composition which minimizes the fuel source organic content while still maintaining the necessary strength and physical integrity required of fire protection application methods. The low ratio of organic binder to inorganic material of this invention maximizes utilization of the endothermic and cooling vapor retention aspects of the inorganics (i,e.
retention of the water vapor given off in the interstices of the inorganic fiber). This low ratio minimizes fuel contribution to any fire, and therefore minimizes smoke and harmful gases from combustion.
This new endothermic material is conveniently made in the form of a sheet. It has been found that although the organic binder content is very low, relatively high sheet densities are maintained, e.g. 0.70 - 1.0 g/cc as compared to 0.1 - 0.3 g/cc for fiber blanket type systems. The more dense sheet is advantageous because it provides an increased thermal conductivity and therefore, ~5 be~er hea~ ~issipation ~or cables in normal service.
Furthermore, the sheet of this invention provides a more compact wrap to protect such items as cables, cable trays and conduits, of particular importance in areas of limited space such as airframe structures.
It is believed that the stability of the inorganic materials in ~his composition will provide superior aging qualities over the fire barrier materials of the prior art which contain larger quantities of organic materials.
These new compositions do not rely on inorganic binders (such as clays~ colloidal silica or cementitious materials) or on the insulative effect of a fibrous matrix.

They rely on the porosity and mechanical en~anglement o~
thc ~ih(-rs, and the ma~eria]s rern~ Elexi~)le wl~ he useful proportionality oE endothermic powders to fiher can be quite high.
The inorganic fiber is chosen Erom materials which can withstand very high temperatures without significant changes in physical properties, such as refractory alumino-silicate fibers.
The sheets of this invention are preferably forme~ by standard paper-makiny techni~ues, either hand laid or machine laid on a Fourdrinier or cylinder type paper machine.

Detailed Description The inorganic fibers used in the protective material of this invention are refractory materials which combine hi~h strength, good thermal resistance and the ability to retain relatively high levels of high density endothermic filler. Examples of useful inorganic fibers include graphite, silica, alumina-silica, calcium oxide-silica, asbestos, and glass fibers, Alumino-silicate fibers are preferred and are available commercially under the trademarks Fiberfrax SK-2600 from the Carborundum Company, Cerafiber from Manville Corporation and Kaowool from Babcock and Wilcox. The fiber diameter is usually less than about 6 micrometers, preferably 3 micrometers.
Larger fiber diameters result in a material with a lower number of Eibers for a given mass, yielding sheets of lower tensile strength, and are usually more difficult to handle on paper making machinery. The physical properties of a preferred inorganic fiber (~iberfrax) are: continuous use limit 1260C; melting point 1790C; normal packing density 96-192kg/m3; fiber lengths up to 102 mm; specific gravity 2.73 and fiber strength of 2.76 x 109 N/m2.
The amount of organic binder is preferably 2-6 weight percent of the total, more preferably about 5%.
Suitable binders can include various polymers and elastomers in latex form, for example, natural rubber latex, styrene-butadiene latices, butadiene acrylonitrile latices, and latices of acrylate and methacrylate polymers and copolymers (e.g., polymethyl acrylate, polyethyl acrylate, and polymethyl methacrylate). It is preferred to use halogen-free polymers to avoid decomposition ~nd release of noxious and corrosive halogen gases during a fire. Acrylic polymers are preferred because of thelr excellent heat resistance, aging properties, and noncorrosive combustion products.
The inorganic, endothermic filler raw material is preferably a powder, having a mean particle size less than about 60 micrometers, even more preferably about 8 micrometers.
Larger filler particles tend to separate the inorganic fibers during processing, resulting in a sheet of lower tensile strength. Preferably, the weight ratio of endothermic filler to inorganic fibers is in the range o~
about 1.5 to 3,0.
Typical fillers would be hydrated metal oxides and borates. The filler should be relatively insoluble in water, chemically inert, and should not require a synergist. Alumina trihydrate, magnesium hydroxide (hydrated magnesia), and æinc borate possess these properties. Alumina trihydrate is preferred. The preferred particle size for the filler is about 8 microrneters. As particle si~e decreases below that, the dewatering of the slurry in the manufacturing process can be adversely affected. The use of larger particles (greater than 60 micrometers) can reduce the tensile strength oE the sheet.
The flexible, fibrous, endothermic materials of this invention are made by mixing the ingredients together with water to form a slurry. The latex is coagulated, and the resultin~ floc suspension flows to a head box and from there onto the Fourdrinier wire screen. The dewatered floc will drain readily and knit together to yield a homogeneous mass in which the inorganic fibers are mechanically interlocked and hound to~ether by the polymer hinder, ancl the endot~hermic filler occupies the interstices between the fibers. Larger flocs are preferred for thicker sheets, to give good drainage necessary in the process. The green sheet from the Fourdrinier machine is densified by calenderin~ and dried by passin~ through heated dryincJ
rolls.
One alternative embodiment of the invention involves addiny a backing to the sheet material already described. A suitable backing material is aluminum foil having a thickness o~ about 0.08 mm and a pressure~
sensitive adhesive coated on one side. The backing is adhered to the protective sheet by means of the adhesive.
Such backing can give an added degree of strsngth to sheet material which must be bent around sharp corners or small radii, The fibrous sheets of this invention may be held in position around conduits and cable trays by being wrapped with ceramic fiber cord, wire cloth or other high temperature resistant material. It is desirable to have the wrapping restrain the sheet, holding it tightly around the cables being protected particularly when exposed to open fire. A suitable ceramic fiber cord can be made from the fibers described in U.S. Patents 3,709,705, 3,795,524 and 4,047,965. One commercially available suitable cord is sold under the trademark Nextel brand ceramic fiber cord by Minnesota Mining and Manufacturin~ Company.
This invention will be further clarified by a consideration of the following examples, which are intended to be purely exemplary. In these examples, two ASTM tests have been used to evaluate the inventive materials. ASTM
test D3286-73 measures the gross calorific value of a fuel in an isothermal-jacket bomb calorimeter. The purpose of these tests is to determine how much the fire barrier material might actually contribute as fuel to ~ fire. ASTM
test E119-78 is a standard fire test for building and construction materials, Example I
In order to produce large quanti.ties of the ~ire protective material of this invention, a 26 inch (66cm) wide L;~ourdrinier paper machine was used. 1'~2 pounds (55.3 ky) of alimino-.silicate fibers were added to 1000 gallons (3785 1) of water in a Mordon slush maker which ayitated the mixture for three minutes to produce a slurry. This slurry was purnped to a 2000 gallon (7570 1) stock chest and diluted with an additional 265 gallons (1000 1) of water.
53 pounds (24 kg) of acrylic latex obtained as Rhoplex EIA-8 latex containing about 46% solids by weight from Rohm &
Haas Company and varying amounts and sizes of alumina trihydrate obtained from Great Lakes Minerals Company were added to the fiber slurry as shown in Table 1 below.

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lJ~ 3 A dilute (about 25 weicJht percent) aqueou5 alum solution was then added to the latex-fiber-AT~l slurry while i~ was being mixed, in sufficient amount to reduce the pH
to between about 4 7 and 5.1 (prefereably about 4.9) which coagulates the latex. The latex-fiber-ATH slurry was then pumped at controlled rates to a mixing tank where a flocculant or polyelectrolyte was added in dilute solution at about 50 ml per minute for particle retention and to aid in drainage. Suitable polyelectrolytes would be Bufloc 170 from Beckamn Laboratory Inc., used in 0.2 percent solution (~0 ml of polyelectolyte solution per 50 gallons or 189 liters of slurry) or Lufax 2g5 cationic polyelectrolyte from Rohm & Haas Company.

The slurry flowed from the mixing tank to a headbox and on to the Fourdrinier wire to form a composite sheet up to 66 cm wide. The sheet, after being dewatered to about S0 weight percent water on the Fourdrinier machine, was calendered at about 0.06 N force to further dewater (less than about 30 percent water) and densify the sheet~ The wet sheet is dried by passing it through heated drying rolls to reduce the moisture content to less than about three percent. It was then wound on to rolls.
Several process parameters ~the speed at which the sheet is transported through the paper-making machinery and the force used on the calender) may be varied to produce a sheet product of varied thickness and density~ The final cornpositions of samples 1-10 are shown in Table 2.

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Several exa~ples of known fire protection materials were used for purposes of testing as controls a(~ainst the experimental samples of this invention. Some o these were available in commercial form. Others were formulated from reference patents, Those which were not in sheet form were in the form of mastics or putties which were trowelled or pressed into sheet form for comparative testing. The control samples are shown in Table 3, C Q O ~ I o I I I I I I I I I I I o H 1~ 3 (~) E oo ~D Si .~ ~ a~
c~ r o o U~ ~ ~ I I I I I I I I
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~l215~03 lnventive sarnples 1-10 and control samples Cl-C6 were evaluated using ASTM test D3286. The gross calori~ic values of several of the materials are given below in Table D,.

Gross Calorific Value Determined by ASTM D32~6 InventiveHeat ValueControl Heat Value Sample(Joules /g) Sample (Joules Jq) 1 2790 Cl 2,080 2 2560 C2 11,160 3 2410 C3 5,580

4 1280 C4 6,050 9 1190 C5 6,050 580 C6 5,5~0 The comparative test data in Table 4 show the calorific value of the control materials to be substantially greater than the composition of this invention in all but one case.
These higher values result from the greater organic content. It is preferred to select compositions of the present invention having a calorific value of no more than about 2400 Joules/g, more preferably less than about 2000 Joules /g.

Exam~le II
In order to maintain the integrity and flexible nature of the inventive sheet system during the covering or wrapping operation, several thinner layers are applied seL~erately to achieve the necessary total thickness.
Preferably a metal foil (0.08 mm thick) is laminated to one side of each such layer to provide a flexible yet tough sheet that can be conveniently taped with metal foil tape at abutting sheet edges of the wrap covering. A final wrap of high temperature ceramic fiber cords (alumina borosilicate fiber such as Nextel 4/5 cord) or stainless steel wires rnay be placecl around the fire protective sheet, spaced at ahout 20 cm intervals or in a spiral fashion to ensure the maintainance of complete coverage and prevent tlle unwindillg of the protective sheet, particularly under fire conditions.
Fire tests in accordance with ASTM E119--78 were conducted on specimens of 2.5 cm diameter conduits and 10.2 hy 30.5 cm cable trays wrapped by the above-described procedure. The quantity of sheet material used is measured by: (a) the number oE layers, (b) the total thickness, and (c) by weight. The preferred method measures the weight of protective sheet material per linear distance in kilograms per meter covering the conduit or cable tray. The test specimens were heated inside furnaces fueled with natural or propane gas, and the heating rate of the furnace interiors were in conformance with ASTM Ell9-78. The furnace hot zone lengths for the conduit and cable tray tests were 61 cm and 245 cm respectively. The time required for the surface temperature of the conduit and cable tray under the fire protective sheet wrap to reach 315C was used to compare the samples. 315C is the temperature at which electrical cables are often observed to begin to deteriorate and short circuit. This comparison is shown in Table 5 below.

TAsLE 5 A~'rM E119-78 F'lame Test of 2.54 cm Conduit :[nventive Sample ~o.

Time to 315C (min) 46 72 57 67 ~aterial wt. (Kg/m) 2.2 3.9 3.0 3.7 Control Example No. _ Cl Cl C2 C4 Time to 315C (min) 35 44 9 57 Material wt, (Kg/m) 2.4 3.9 3.0 4.0 ASTM E119-78 Flame Test of 10.2 x 30.5_cm Cable Tra~
Inventive Example ~o. Control Example No.
9 Cl C2 C7 Time to 315C (min) 61 54 40 39 ~aterial wt. (Kg/m) 12.7 12.1 21.0 8.2 These fire tests show that the composition of the inventive sheets extends the fire exposure times substan-tially over known materials. It should be noted that the putties or mastics of comparative control samples numbers C3, C5 and C6 could not be applied in a uniform thickness.
Adhesion to the conduit and cable tray surfaces was also a problem; therefore, these materials could not be tested in this manner. Only the sheet materials were fire tested, In the case of the intumescent sheet materials of control samples Cl and C2, special precautions for designing the wrapping configuration were required. Radial cracks occur in the intumesced fire protective materials around the perimeter of the conduit or at the corners of the cable tray which allows direct heat exposure to the metal surface, A loose, eye-shaped or corrugated wrap with a wire mesh overlay for containment was employed to limit the material intumescence and control such cracking in order to obtain a meaningful test. More details on wrapping intumescent fire protective sheeting around conduits can be found in commonly assigned U.S. patent ~umber 4,513,173. The sheets of the present invention remained tightly and neatly wrapped on the conduit or cable tray. Compared to the intumescent materials which undergo a significant volume increase during heat exposure, there was essentially no physical change in the inventive sheet dimensions during heat exposure.

Example III
The following flame test was performed on the inventive material and on the controls in the form of putty or mastic. The test specimens were cut or formed to 23 by 28 cm rectangles and glued or formed to one side of a metal sheet 0.3 mm thick. The test specimen weight and thickness was recorded. A thermocouple was attached to the surface in the center of the metal sheet to measure the cold side surface temperature. The test sheet was placed vertically and centered in front of a flame source generated by a propane fueled exhaust gas simulator (from Maremont Company) which provided a hot side surface temperature of 1,050 to 1,100C. The rate of temperature rise on the cold side surface was then recorded. The results obtained are shown in l'able 6 below.

~.

~g~03 Inventive Control Sample No.
Sample 9 C3 C5 ~pecimen Weight (Kg): 0.54 0.59 0-77 Specimen Thickness mm 11.0 10.2 11.4 Time (minutes): Cold Side Temperature (C) Start 23 23 23 163 213 l9a 177 262 ~07 3~ 182 290 226 183 309 23~

183 - _ The inventive sheet sample maintained a much lower temperature for a significantly longer time than either o~ the control sample mastics.

Example IV
An ampacity study of fire barrier protected electrical conduits was conducted. The fire barrier materials used in the study included: the inventive material; commercially available intumescent mats comprising acrylic resin, alumina-silica ~ibers and unexpanded vermiculite (control sample Cl); and Kaowool blankets available from Babcock and Wilcox Company. The len~ths of intumescent mat were 457mm for the Eirst layer, 572mm for the second, and 635mm for the third. The lengths of the inventive mat were 394mm for the first layer, 445rnm for the second, and 500mm for the third. The lengths of Kaowool blankets used were~ 610~m for the ~irst layer, and 749mm for the second. The Kaowool hlankets were applied hy completely wrapping around the conduit and overlapping at least 76mm. In these tests, Scotch 33 tape, a black electrical vinyl tape, was wrapped in a helical fashion around the outside of the test specimen to provide a blaclc surface solely to raise the surface emissivity in some tests. In each case, the length of wrapped conduit under test was about 2.45 meters.
All the ampacity derating factors were calculated with respect to the case of bare conduit with unaltered surface. The equation used was percent derating = (l-( T1/ T2)l/2) x lO0 where Tl i5 the conductor temperature rise above ambient in the bare conduit case and T2 is the conductor temperature rise above ambient for the protected conduit.
The conduit tested was a 4 inch (10.2 cm) internal diameter electrical grade schedule 40 steel containing four 500 MCM 600 volt XLPE insulated copper conductor cables, The thicknesses of each fire barrier layer were: for the inventive sheets about 5mm; for the intumescent mat about 5 mm; and for the Kaowool blanket about 25mm. The conductor temperatures measured for bare steel at l90, 300 and 400 amps were 39.7C, 61.2C, and ~5.1C respectively and for steel conduit covered with black tape 37.1C, 54.2C, and 76.2C at the same respective currents. Ambient temperature ranged between about 22 and 26C for these tests. The results are shown in Table 7 below:

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~ ~ ~ U~ C) oooooooooooooooooo a 3 ~ ~ O O c~ O o ~ ~ O a~ O o ~ o O ~ O o ~2~ 3 A comparison of the samples having the same number o~ fire barrier layers reveals that the ampacity derating required by the inventive material is .signifi-cantly less than that required with either Kaowool blankets or the intumescent mat material. The air space between the Eire barrier and conduit necessitated by the loose eye-shaped or corrugated wrap for the intumescent mat (see discussion after Table 5) is believed to he detrimental to ampacity rating. Even the inventive samples having 3 fire barrier layers compare favorably to the control materials having only two layers, Thus, the current carrying capacity oE the cables in conduit does not suEfer a great deal as a result of achieving adequate fire protection In addition, it can be noted that the addition of black tape to the outside helps to decrease the percent ampacity derating.
Other embodiments of this invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. Various omissions, modifications and changes to the principles described herein may be made by one skilled in the art without departing from the true scope and spirit o~ the invention which is indicated by the following claims.

Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An endothermic, flexible, fibrous sheet material made of a composition comprising:
(a) a refractory inorganic fiber;
(b) an organic polymer binder; and (c) an inorganic, endothermic filler which undergoes an endothermic reaction between about 100° and 600°C, said endothermic flexible fibrous sheet having a weight ratio of organic to inorganic constituents of less than about 0.15, and a weight ratio of inorganic endothermic filler of part (c) to inorganic fiber of part (a) in the range of about 0.5 to 5Ø

2. The fibrous sheet material of Claim 1 wherein the inorganic endothermic filler of part (c) is selected from the group consisting of alumina trihydrate and magnesium hydroxide.

3. The fibrous sheet material of Claim 2 wherein the organic polymer binder comprises about 2 to 6 weight percent of the total.

4. The fibrous sheet material of Claim 2 having a density of about 0.70 to 1.0 grams per cubic centimeter,

5. The fibrous sheet material of Claim 2 wherein the mean particle size of the inorganic endothermic filler is less than about 60 micrometers.

6. The fibrous sheet material of Claim 2 wherein the inorganic fiber of part (a) is selected from the group consisting of silica, alumino-silicate, asbestos, and glass fibers.