EP0735187B1 - A sheet of cellulosic fibers - Google Patents

A sheet of cellulosic fibers Download PDF

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Publication number
EP0735187B1
EP0735187B1 EP19960302098 EP96302098A EP0735187B1 EP 0735187 B1 EP0735187 B1 EP 0735187B1 EP 19960302098 EP19960302098 EP 19960302098 EP 96302098 A EP96302098 A EP 96302098A EP 0735187 B1 EP0735187 B1 EP 0735187B1
Authority
EP
European Patent Office
Prior art keywords
sheet
particles
intercalated graphite
graphite
pressed
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 - Lifetime
Application number
EP19960302098
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0735187A1 (en
Inventor
Robert Angelo Mercuri
Brian Mcneil Ford
Thomas William Weber
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.)
Graftech Technology LLC
Original Assignee
Ucar Carbon Technology Corp
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 Ucar Carbon Technology Corp filed Critical Ucar Carbon Technology Corp
Publication of EP0735187A1 publication Critical patent/EP0735187A1/en
Application granted granted Critical
Publication of EP0735187B1 publication Critical patent/EP0735187B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants

Definitions

  • the present invention relates to a sheet of pressed cellulosic fibers and to an article of manufacture comprising a flammable surface adhesively bonded to a sheet of pressed cellulosic fibers.
  • the present invention relates to a sheet of pressed cellulosic fibers in the form of paper containing dispersed particles of intercalated, i.e. intumescent material graphite which can be applied to a flammable article as a fire-resistant covering.
  • a continuing effort in the building supply industry is to improve the fire resistance of flammable materials of construction and related materials such as wood products (particle board, oriented strand board), wall board, shipping boxes, bags and like.
  • Such effort has involved the addition of chemicals, such as borates and phosphates to the binder system of the flammable materials, which, at times resulted in degradation of the properties and useful life of the materials.
  • DE-A-4007060 (Bayer AG) discloses an intumescent pressed sheet-material containing cellulosic fibres, expandable graphite, and optionally a binder, manufactured by a paper making technique, with up to 98% by weight of graphite being included.
  • EP-A-0408098 discloses an intumescent sheet material having a matrix whose predominant ingredient comprises ball clay reinforced by inorganic vitreous fibre and contains heat-expandable graphite as an intumescent agent and up to 10 percent by weight of an organic binder, manufactured by a paper making technique.
  • a sheet of pressed cellulosic fibres which contains a dispersion of pressed particles of intercalated graphite, said sheet having a pair of opposed outer surfaces at least a portion of which is formed of pressed particles of intercalated graphite, with a thermosetting resin dispersed in the sheet for bonding together cellulosic fibres and intercalated graphite particles, said resin being present in an amount such that a surface of the sheet can be bonded by said resin to a contacting flammable surface.
  • the present invention thus provides a sheet of pressed cellulosic fibers in the form of a paper sheet containing co-pressed particles of intercalated natural graphite particles, also known as intumescent graphite particles. These particles, upon exposure to high temperature, e.g. a flame, expand in volume more than 50 to 100 times, i.e. exfoliate into vermicular, worm-like structures (called "worms").
  • the cellulosic paper sheet containing the intumescent, i.e. intercalated graphite particles is rendered highly fire-resistant due to the decrease in thermal conductivity of the graphite particles upon the exfoliation which results from exposure to flame.
  • the exfoliated graphite vermicular particles, i.e. worms virtually cover the exposed paper surface and form a flame barrier. Any substrate to which the aforedescribed paper is bonded, or article enclosed in such paper, is provided protection from fire damage.
  • thermosetting resin incorporated in the sheet acts as an adhesive binder which also can bond the sheet to a flammable surface which the sheet then protects.
  • an article of manufacture comprising a flammable surface adhesively bonded to a sheet of pressed cellulosic fiber which contains a dispersion of pressed particles of intercalated graphite, said sheet having a pair of opposed surfaces at least a portion of which is formed of pressed particles of intercalated graphite, with a thermosetting resin dispersed in the sheet for bonding together cellulosic fibers and intercalated graphite particles, said resin being present in an amount such that a surface of the sheet is bonded by said resin to the contacting flammable surface, one of said surfaces being in contact with said flammable surface and the other of said surfaces constituting an outer surface of said article.
  • cellulosic fibers e.g. wood, straw, bagasse, flax, cotton and the like are pulped, i.e. separated and suspended in water slurry.
  • Materials such as mineral pigments, sizing, dyes and other coloring chemicals, starches and other fiber bonding materials, are added to the pulp which is then drained, i.e. dewatered, pressed and dried.
  • Fourdrinier machines and evaporative drying by pressing a heated surface on the wet paper are employed to make a cellulosic paper sheet.
  • Particles of intercalated natural graphite i.e. intumescent graphite are added to the cellulosic fiber pulp (which may contain other additives such as noted above) and dispersed in the pulp slurry.
  • the added intercalated graphite particles are mostly, i.e. 60% by weight or more, in the size range of 30 to 80 mesh (U.S. screen series) and the amount added is suitably in the range of 40 to 80 grams per square metre of the paper sheet being produced typically from 0.015 cm to 0.15 cm thick (0.006 to 0.060 inch thick).
  • the paper sheet is prepared by dewatering, pressing and drying in the usual manner.
  • the resulting product is shown in Figure 1 which is a 1:1 scale view of the surface of paper sheet.
  • Figure 2 is an enlarged representation of a sectional side, or edge view, of the paper sheet and Figure 2A is an enlarged plan view of a part of the surface of the sheet of Figure 2.
  • the paper sheet 10, shown in Figures 1-3 is formed of pressed cellulosic fiber sheet indicated at 20 which contains a dispersion of co-pressed particles of intercalated graphite indicated at 30.
  • the pressing of a wet sheet of cellulosic fibers containing intercalated graphite particles results in some flattening of the intercalated graphite particles, particularly at the surface of the sheet 10 as indicated at 300. This results in at least a portion, e.g.
  • the surface exposed intercalated graphite particles expand in volume, up to 500 times and form a thermal barrier virtually covering the surface exposed to the flame which instantly extinguishes any burning portion of the paper.
  • thermosetting resin e.g. water soluble phenolic resin
  • a thermosetting resin e.g. water soluble phenolic resin
  • the cellulosic fibers and intercalated graphite particles are adhesively bonded due to exposure to drying temperatures of 60 tc 100°C which cause a partial setting of the resin.
  • a portion of the partially set resin, in the form of flattened globules, is exposed at the surface as indicated at 400 in Figures 3) and 3(A).
  • the paper containing intercalated graphite and partially set resin is placed in contact with the surface of a flammable element, e.g. wood based, wall board and pressure is applied to the resin containing paper at temperatures of from about 70 to 120°C to fully set the resin and cause adhesive bonding of the intercalated graphite-containing paper to the surface of the flammable element.
  • a flammable wooden substrate is shown at 500 having an outer surface 510 and an overlying intercalated graphite containing paper sheet 10 which has been heated and pressed against surface 510 so that an adhesive layer 520 of thermoset resin is formed which bonds sheet 10 to wooden substrate 500.
  • the resulting article is a flammable wooden element having at its outer surface an adhesively resin bonded sheet of paper which contains a dispersion of intercalated graphite particles 300' at its outer surface.
  • the particles 300 undergo intumescence and expand to form "worms" 3000 shown in Figure 5 which suppress the flame and protect substrate 500 from fire damage.
  • the intercalated graphite included in the present invention is essentially that which is used in the graphite composite wall covering material disclosed in US-A-5,176,863.
  • graphite is a crystalline form of carbon comprising atoms bonded in flat layered planes with weaker bonds between the planes.
  • the particles of intercalated graphite Upon exposure to high temperature, the particles of intercalated graphite expand in dimension as much as 80 or more times its original volume in an accordion-like fashion in the c-direction, i.e. in the direction perpendicular to the crystalline planes of the graphite.
  • the exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms.
  • Shane et al A common method for manufacturing graphite foil from flexible graphite is described by Shane et al, in US-A-3,404,061.
  • natural graphite flakes are intercalated by dispersing the flakes in a solution containing an oxidizing agent of, e.g. a mixture of nitric and sulfuric acid.
  • the intercalation solution contains oxidizing and other intercalating agents known in the art.
  • Examples include those containing oxidizing agents and oxidizing mixtures, such a solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid.
  • a preferred intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent, i.e. nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like.
  • the intercalation solutions may contain metal halides such as ferric chloride and ferric chloride mixed with sulfuric acid, or halide, such as bromine as a solution of bromine and sulfuric acid or bromine in an organic solvent.
  • the quantity of the intercalation solution may be limited to between 10 to 50 parts of solution per hundred parts of graphite by weight (pph) which permits the washing step to be eliminated as taught and described in US-A-4,895,713.
  • Particles of exfoliated graphite of intercalated graphite flake possess substantial fire retardant properties. Thie results from a decrease in thermal conductivity when exposed to high temperature such as in the presence of a fire. This decrease in thermal conductivity is attributable to its expansion at high temperature. An expansion in thickness of 1 to 5 times the unexpanded thickness has been realized from unexfoliated particles of intercalated graphite.
  • Recycled cellulose fiber was slurried in a solution consisting of 4 % by weight w/o Ashland 72115W55 phenolic-based resin in water for 30 seconds in a Waring blender on low speed.
  • Intumescent natural graphite treated flake particles (ntercalated graphite), UCAR Grade TG-388, was added and mixed for 5 seconds; excess solution was filtered from the mixture to form a cake which was oven dried at 60°C to remove the water. The cake was then flattened to a paper approximately 0.1cm (0.04 inches) thick between heated (60°C) platens.
  • compositions consisted of 43.04, 64.56 and 86.08 grams of treated flake (intercalated flake) per square metre (4, 6, and 8 grams of treated flake (intercalated flake) per square foot) of paper sheet; cellulose 172.16 grams per square metre (16 grams/square foot) of paper sheet; and a resin content of about 21.52 grams per square metre (2 grams/square foot) of paper sheet.
  • the intercalated flake was in the form of particles sized 50% through 40 mesh (U.S. Screen Series).
  • sheets could be bonded to wood, OSB (oriented strand board), or plywood by pressing between platens at about 120°C.
  • compositions were tested in two ways:
  • the invention is amenable to standard Fourdrinier paper processing; prepared paper may be bonded to board products in the hot-pressure-cure step.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP19960302098 1995-03-29 1996-03-27 A sheet of cellulosic fibers Expired - Lifetime EP0735187B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US412914 1989-09-26
US41291495A 1995-03-29 1995-03-29

Publications (2)

Publication Number Publication Date
EP0735187A1 EP0735187A1 (en) 1996-10-02
EP0735187B1 true EP0735187B1 (en) 2001-12-05

Family

ID=23634988

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960302098 Expired - Lifetime EP0735187B1 (en) 1995-03-29 1996-03-27 A sheet of cellulosic fibers

Country Status (6)

Country Link
EP (1) EP0735187B1 (no)
JP (1) JP3034793B2 (no)
AU (1) AU700061B2 (no)
CA (1) CA2172878C (no)
DE (1) DE69617506T2 (no)
NO (1) NO961219L (no)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10808175B2 (en) 2016-01-09 2020-10-20 Fernando Tahmouresinia Flame or fire protection agent and production and use thereof, in particular for wood-, cellulose- and polyolefin-based products
US10920147B2 (en) 2015-11-12 2021-02-16 Fernando Tahmouresinia Flame or fire retarding agents and their manufacture and use

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9807028D0 (en) 1998-04-02 1998-06-03 Technical Fibre Products Limit Intumescent material
NZ516745A (en) * 1999-07-08 2004-04-30 Markus Baumann A method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
JP4098227B2 (ja) * 2003-09-02 2008-06-11 名古屋油化株式会社 難燃性繊維シートの製造方法、およびそれによって得られた難燃性繊維シートからなる成形物と積層物、並びにその積層物を用いた成形物
GB2411200A (en) * 2004-02-18 2005-08-24 Environmental Seals Ltd Fire door
CA2778183C (en) * 2009-10-20 2014-04-15 Blmh Technologies Inc. System for forming a fire resistant wall structure, and associated method
PL2663686T3 (pl) * 2011-01-13 2020-09-07 Blmh Technologies Inc. Sposób formowania ognioodpornego materiału celulozowego i związane z nim urządzenie
US9175147B2 (en) 2011-07-06 2015-11-03 National Research Council Of Canada Fire-resistant cellulosic material
CN109763369A (zh) * 2018-12-29 2019-05-17 湖北烁砺新材料科技有限公司 一种耐火工程纤维的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256801A (en) * 1979-12-14 1981-03-17 Raybestos-Manhattan, Incorporated Carbon fiber/flame-resistant organic fiber sheet as a friction material
GB2130263B (en) * 1982-11-12 1985-10-02 T & N Materials Res Ltd Non-asbestos sheet material
GB2131058B (en) * 1982-11-20 1986-08-13 T & N Materials Res Ltd Non-asbestos sheet material
GB8915893D0 (en) * 1989-07-11 1989-08-31 T & N Technology Ltd Intumescent sheet material
DE4007060A1 (de) * 1990-03-07 1991-09-12 Bayer Ag Intumeszierende flaechengebilde
DE4007075A1 (de) * 1990-03-07 1991-09-12 Bayer Ag Intumeszenzfaehige formteile
US5176863A (en) * 1991-08-06 1993-01-05 Ucar Carbon Technology Corporation Flexible graphite composite fire retardant wallpaper and method
GB2273100B (en) * 1992-11-18 1997-01-08 Environmental Seals Ltd Intumescent products

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10920147B2 (en) 2015-11-12 2021-02-16 Fernando Tahmouresinia Flame or fire retarding agents and their manufacture and use
US10808175B2 (en) 2016-01-09 2020-10-20 Fernando Tahmouresinia Flame or fire protection agent and production and use thereof, in particular for wood-, cellulose- and polyolefin-based products

Also Published As

Publication number Publication date
EP0735187A1 (en) 1996-10-02
DE69617506D1 (de) 2002-01-17
AU700061B2 (en) 1998-12-17
CA2172878A1 (en) 1996-09-30
JPH0931887A (ja) 1997-02-04
NO961219L (no) 1996-09-30
CA2172878C (en) 2002-05-28
DE69617506T2 (de) 2002-05-16
AU5034696A (en) 1996-10-10
JP3034793B2 (ja) 2000-04-17
NO961219D0 (no) 1996-03-26

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