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EP0883736B1 - Produits fibreux composites et leurs procedes de fabrication - Google Patents

Produits fibreux composites et leurs procedes de fabrication Download PDF

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Publication number
EP0883736B1
EP0883736B1 EP97905225A EP97905225A EP0883736B1 EP 0883736 B1 EP0883736 B1 EP 0883736B1 EP 97905225 A EP97905225 A EP 97905225A EP 97905225 A EP97905225 A EP 97905225A EP 0883736 B1 EP0883736 B1 EP 0883736B1
Authority
EP
European Patent Office
Prior art keywords
fibres
product
binder
composite fibre
range
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
EP97905225A
Other languages
German (de)
English (en)
Other versions
EP0883736A1 (fr
Inventor
Stuart Samuel Boffey
Paul Martin Lawford Asher
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.)
Saffil Ltd
Original Assignee
Saffil Ltd
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
Priority claimed from GBGB9604097.7A external-priority patent/GB9604097D0/en
Priority claimed from GBGB9615770.6A external-priority patent/GB9615770D0/en
Application filed by Saffil Ltd filed Critical Saffil Ltd
Publication of EP0883736A1 publication Critical patent/EP0883736A1/fr
Application granted granted Critical
Publication of EP0883736B1 publication Critical patent/EP0883736B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209Inorganic fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209Inorganic fibres
    • D04H1/4218Glass fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D04H1/645Impregnation followed by a solidification process
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00Other non-woven fabrics
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2839Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration

Definitions

  • the present invention relates to composite fibre products comprising a plurality of inorganic fibres which are bound together with a binder and to processes for their production. More particularly, the present invention relates to composite fibre mats which can be used for resiliently mounting the fragile ceramic or metal monoliths which are found in catalytic converters and diesel particulate filters in a surrounding metal casing.
  • Catalytic converters and diesel particulate filters are routinely fitted to automobiles and other road going vehicles in order to purify the exhaust gases which are generated by the engine.
  • These devices usually comprise a ceramic honeycomb monolith which is housed within a metal casing and provides a support for the catalyst.
  • the ceramic monolith comprises a plurality of tiny flow channels and is a fragile structure which is susceptible to damage when subjected to the kind of vibrational forces which prevail when any road going vehicle is in use.
  • the monolith and the surrounding metal casing are subjected to extremely high temperatures in use which causes them to expand, but not to the same extent.
  • the mounting system which is used to mount the ceramic monolith in its metal casing must insulate the monolith from the attendant vibrational forces and compensate for any difference between the expansion of the monolith and the casing. In this way, the stresses to which the monolith is subjected during use as a result of differential expansion or vibrational forces can be maintained at an acceptable level.
  • the present invention provides a composite fibre product comprising a plurality of inorganic fibres and a binder and a process for its production.
  • the composite fibre product can take the form of a flexible mat which can be used to mount ceramic or metal monoliths found in catalytic converters and diesel particulate filters in their metal casings.
  • a composite fibre product particularly a mat, which comprises a plurality of inorganic fibres and a binder which is substantially uniformly distributed throughout the fibre product, said composite fibre product having a laminar shear strength of at least 0.1 MPa.
  • the inorganic fibres may be any of the inorganic fibres known in the art.
  • the composite fibre product is a mat which is to be used for resiliently mounting the ceramic or metal monoliths contained in catalytic converters and diesel particulate filters
  • the fibres will need to be thermally stable (i.e. will not degrade) at the high operating temperatures prevailing in such devices.
  • the fibres contained in composite fibre mats which are to be used in such mounting applications will be thermally stable at temperatures in excess of 700°C, preferably in excess of 800°C and more preferably in excess of 900°C.
  • Thermally stable inorganic fibres include ceramic fibres such as alumina, mullite, aluminosilicate, aluminoborosilicate, zirconia and titania fibres as well as vitreous glass fibres.
  • the preferred thermally stable inorganic fibres are polycrystalline inorganic fibres, particularly polycrystalline inorganic oxide fibres, such as alumina, mullite, aluminosilicate, aluminoborosilicate, zirconia and titania fibres.
  • alumina fibres by which term we are also intending to include alumina fibres comprising a few weight % of silica added as a phase stabiliser, are particularly preferred.
  • the fibres are preferably short staple fibres having a length in the range of from 1 to 10 cms and a mean diameter in the range of from 1 to 10 microns.
  • Especially preferred alumina fibres are those sold in the form of a loosely bound, low density mat by Imperial Chemical Industries PLC under the trade name Saffil which are thermally stable at temperatures in excess of 1000°C.
  • the composite fibre products of the invention may comprise two or more different types of inorganic fibre.
  • the different fibre types may be intimately mixed or they may be segregated and arranged in definite patterns, e.g. in discrete layers.
  • the binder may be an inorganic material, but is preferably organic. Suitable organic binders are more particularly described in US-4,011,651 and WO-94/24425. Preferably the binder is an organic polymer.
  • One suitable binder is a copolymer based on n-butyl acrylate and acrylonitrile.
  • Preferred binders are those obtained on curing a curable polymer composition.
  • Preferred examples of curable polymer compositions are those comprising a combination of an acrylic polymer and a cross-linking agent, particular an epoxy group containing cross-linking agent such as an epoxy resin.
  • Curable polymer compositions of this type will typically comprise from 90.0 to 99.0 % by weight, preferably from 95.0 to 99.0 % by weight of the acrylic polymer and from 1.0 to 10.0 % by weight, preferably from 1.0 to 5.0 % by weight of the cross-linking agent.
  • the acrylic polymer is suitably a homopolymer or copolymer comprising monomer units derived from at least one acrylic monomer selected from the C 1-8 alkyl (C 1-4 alkyl)acrylates, and in a preferred embodiment is a homopolymer or copolymer comprising monomer units derived from at least one acrylic monomer selected from the C 1-4 alkyl (meth)acrylates, for example methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
  • An especially preferred binder is that obtained on curing a composition comprising an acrylic polymer based on butyl acrylate and an epoxy resin cross-linking agent.
  • a composite fibre mat of the invention When a composite fibre mat of the invention is to be used for mounting a ceramic or metal monolith in a catalytic converter or in a diesel particulate filter, it is preferred to use an organic binder which will be substantially pyrolysed/burned out by the high temperatures to which the mat will be subjected in use.
  • the organic binder is preferably one which will not lead to the generation of toxic emissions when it is pyrolysed/burned out and for this reason is preferably free of chlorine and nitrogen.
  • the binder contained in the composite fibre product of the present invention is substantially uniformly distributed throughout the fibre product.
  • the distribution of the binder in the composite fibre product is such that the percentage by weight of binder in each 1 mm 3 region of the product based on the total weight of the product in that region is within 40 %, more preferably within 30 % and particularly preferably within 20 % of the overall percentage by weight of binder in the product based on the total weight of the product.
  • the distribution of the binder in the composite fibre product is such that the percentage by weight of binder in each 1 mm 3 region of the product based on the total weight of the product in that region is within 10 % of the overall percentage by weight of binder in the product based on the total weight of the product.
  • the thickness of the composite fibre product will depend on the intended end use for the product. However, when the product is a composite fibre mat for mounting a ceramic or metal monolith in a catalytic converter or in a diesel particulate filter, it will typically have a thickness in the range of from 3 to 15 mm, preferably in the range of from 5 to 12 mm and more preferably in the range of from 5 to 9 mm.
  • the loading of the binder in the composite fibre product will typically be in the range of from 2 to 15 % by weight and preferably in the range of from 5 to 15 % by weight based on the total weight of the product.
  • the composite fibre product of the invention typically has a density in the range of from 30 to 700 kg/m 3 , preferably in the range of from 100 to 500 kg/m 3 and more preferably in the range of from 100 to 350 kg/m 3 .
  • the composite fibre product of the invention has a laminar shear strength, by which is meant the force which has to be applied in order to bring about delamination of the product, of at least 0.1 MPa, preferably of at least 0.2 MPa and more preferably of at least 0.3 MPa.
  • the laminar shear strength can be conveniently measured on an Instron or similar machine using a three point bend test.
  • the composite fibre product is also capable of exerting a pressure of at least 1.0 kgf/cm 2 , more preferably in the range of from 1.5 to 4.0 kgf/cm 2 when a sample of the product having a thickness in the range of from 5 to 10 mm is compressed to a thickness of 3 mm between two plates and the binder removed.
  • a process for the production of a composite fibre product which comprises impregnating a fibre mass comprising a plurality of inorganic fibres with a liquid binder system comprising a binder material and a carrier liquid and subjecting the impregnated fibre mass to a heating step, characterised in that the heating step involves the use of dielectric heating, such as microwave or radio frequency heating.
  • the impregnated fibre mass is preferably held under compression during at least a part of the heating step.
  • the fibre mass which is impregnated in the processes of the present invention may comprise a plurality of discrete fibres or it may take the form of a multi-fibre product in which the individual fibres are assembled into a low density mat or blanket which is loosely held together by fibre intertwining or perhaps more robustly consolidated by some other means such as weaving, knitting, stitching, needle-punching or vacuum packing.
  • the fibre mass which is impregnated in the processes of the present invention is a multi-fibre product having a thickness in the range of from 10 to 60 mm, more preferably in the range of from 30 to 50 mm, and an area density in the range of from 0.2 to 2.0 kg/m 2 , more preferably in the range of from 1.0 to 2.0 kg/m 2 .
  • the inorganic fibres and preferred inorganic fibres for use in the processes of the present invention are as described previously in connection with the composite fibre product.
  • the processes of the present invention may be used to prepare composite fibre products from two or more different types of inorganic fibre.
  • the different fibre types may be intimately mixed or they may be segregated and arranged in definite patterns, e.g. in discrete layers.
  • the liquid binder system may comprise an inorganic binder material, but preferably comprises an organic binder material, such as a polymer, and an organic or aqueous carrier liquid which is able to dissolve or disperse the organic binder material.
  • organic binder materials are more particularly described in US-4,011,651 and WO-94/24425, the disclosures in which are incorporated herein by way of reference, and include polymers as well as curable polymers or prepolymers which can be cured in situ on the impregnated fibre mass as part of the drying step or in a subsequent processing step.
  • the polymer may be a material which allows for the recovery of fibres from waste product generated in a process of the present invention or in subsequent processing/finishing operations.
  • One suitable binder system comprises an aqueous dispersion of a copolymer based on n-butyl acrylate and acrylonitrile.
  • Preferred binder systems are those comprising a dispersion, preferably an aqueous dispersion, of a curable polymer composition, sometimes termed a resin or latex.
  • a curable polymer composition sometimes termed a resin or latex.
  • preferred curable polymer compositions are those comprising a combination of an acrylic polymer and a cross-linking agent, particular an epoxy group containing cross-linking agent such as an epoxy resin.
  • Curable polymer compositions of this type will typically comprise from 90.0 to 99.0 % by weight, preferably from 95.0 to 99.0 % by weight of the acrylic polymer and from 1.0 to 10.0 % by weight, preferably from 1.0 to 5.0 % by weight of the cross-linking agent.
  • the acrylic polymer is suitably a homopolymer or copolymer comprising monomer units derived from at least one acrylic monomer selected from the C 1-8 alkyl (C 1-4 alkyl)acrylates, and in a preferred embodiment is a homopolymer or copolymer comprising monomer units derived from at least one acrylic monomer selected from the C 1-4 alkyl (meth)acrylates, for example methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
  • An especially preferred binder system is one comprising an aqueous dispersion of an acrylic polymer based on butyl acrylate and an epoxy resin cross-linking agent.
  • liquid binder system When the liquid binder system is one comprising a curable polymer composition, it may also comprise a catalyst to accelerate the curing process.
  • liquid binder system we are also intending to include binder systems which comprise dispersions or suspensions of finely divided solids in liquid vehicles.
  • the liquid binder system will typically comprise from 0.5 to 50.0 % by weight of the binder material and from 50.0 to 99.5 % by weight of the carrier liquid.
  • the liquid binder system will comprise from 0.5 to 10.0 % by weight, more preferably from 1.0 to 5.0 % by weight of the binder material and from 90.0 to 99.5 % by weight, more preferably from 95.0 to 99.0 % by weight of the carrier liquid.
  • the individual fibres may be thoroughly dispersed in the liquid binder system and the resulting dispersion cast into sheets using a paper making process which involves removing excess carrier liquid, e.g. by vacuum.
  • the mass of inorganic fibres may take the form of a multi-fibre product in which the individual fibres are assembled into a low density mat or blanket
  • the mat or blanket may be simply immersed or soaked in the liquid binder system.
  • the low density fibre mat may be sprayed with the liquid binder system.
  • the impregnated fibre mass Before the impregnated fibre mass is subjected to the drying/heating step, it will often be convenient to remove any excess carrier liquid. This can be achieved by pressing the impregnated fibre mass between rollers or plates, by placing it under vacuum or by centrifuging.
  • the impregnated fibre mass is subjected to a drying/heating step.
  • a drying/heating step is conducted while the impregnated fibre mass is held under compression.
  • the impregnated fibre mass should be held under compression until such time as the binder material is able to hold the fibres together and significantly limit the expansion of the composite fibre product once the compressive forces are released.
  • the whole of the drying/heating step will be performed while the impregnated fibre mass is held under compression, but it may be possible to perform just the final stages of the drying/heating step in this manner and still obtain satisfactory results.
  • substantially all and preferably all of any residual carrier liquid will be removed.
  • the pressure which is applied during the drying/heating step to compress the impregnated fibre mass will generally be in the range of from 5 to 500 KPa, preferably in the range of from 5 to 200 KPa.
  • the pressure applied is such as to produce a composite fibre product having a density in the range of from 30 to 700 kg/m 3 , preferably in the range of from 100 to 500 kg/m 3 , more preferably in the range of from 100 to 350 kg/m 3 .
  • the fibre mass which is impregnated is a multi-fibre product having a thickness in the range of from 10 to 60 mm, e.g. in the range of from 30 to 50 mm, and an area density in the range of from 0.2 to 2.0 kg/m 2 , e.g.
  • the resulting impregnated fibre mass will generally be compressed to a thickness in the range of from 2 to 5 mm during the drying/heating step.
  • This pressure is conveniently applied in a batch process by sandwiching the impregnated fibre mass between plates and then squeezing the plates together, e.g. by means of clamps, spring loaded clips or hydraulic presses.
  • a conventional oven may be employed to carry out the drying/heating step, but in a preferred embodiment dielectric heating such as microwave or radio frequency heating is employed since it tends to result in an appreciably more uniform distribution of the binder in the final composite fibre product.
  • dielectric heating such as microwave or radio frequency heating
  • the drying/heating step will involve heating the impregnated fibre mass to a temperature in the range of from 80 to 200°C, preferably in the range of from 100 to 170°C. Temperatures in the range of from 140 to 160°C are especially preferred.
  • the drying/heating step may be followed by a further processing step in which the curable polymer composition is cured.
  • This curing process preferably involves the polymer composition undergoing some form of cross-linking reaction.
  • the temperatures which are employed in the drying/heating step are usually sufficient to remove any residual carrier liquid and cure the curable polymer composition so that a separate curing step is generally unnecessary.
  • the impregnated fibre mass will generally be held under compression for the duration of the curing step.
  • the composite fibre product of the present invention may also contain one or more other materials.
  • Suitable materials for inclusion in the composite fibre product include the layer minerals, particularly the expandable layer silicate minerals such as vermiculite.
  • the incorporation of another material into the composite fibre product may be achieved by adding the material to a liquid binder system used in the preparation of such a product.
  • a composite fibre product prepared in accordance with the present processes may be post-treated with a solution or dispersion of the material to be incorporated.
  • Composite fibre products of the present invention may be used as mounting mats to mount ceramic and metal monoliths in catalytic converters and diesel particulate filters or to support the ceramic monoliths found in hot gas filtration units and coal gasification plants.
  • Composite fibre products of the invention may also be usefully employed in gasket applications and as a high temperature insulation material.
  • Samples of "Saffil" low density mat having a size of about 500 mm by 200 mm were cut from a bulk product having a known area density of from 1.2 to 1.6 kg/m 2 and a thickness of from 30 to 50 mm. These samples were weighed and then transferred to a tray where they were soaked in a latex (Acronal 35D, a 50 % aqueous dispersion of a copolymer based on n-butyl acrylate and acrylonitrile available from BASF) which had been diluted to a solids content of around 3 % w/w.
  • a latex Acronal 35D, a 50 % aqueous dispersion of a copolymer based on n-butyl acrylate and acrylonitrile available from BASF
  • the impregnated samples were then sandwiched between two sheets of PTFE-coated glass fibre mesh and these sandwiches were then placed between two sheets of glass fibre filled silicone resin board of size 500 mm by 200 mm by 12 mm.
  • the resin boards were then pressed together using G-clamps until the impregnated "Saffil" layers were reduced to a thickness of about 5 mm (equal to an applied pressure of about 0.5 bar (50 KPa)), and held in this position with clips. During this assembly excess latex drained from the samples.
  • the completed mould assemblies were then placed on the belt of an air/radio frequency (RF) assisted oven and the belt speed was adjusted to give a residence time of between 15 and 45 minutes.
  • the RF power to the oven was set at about 5.5 KW and the temperature of the air in the oven was adjusted to about 150°C.
  • the samples were removed from the oven when the latex had been fully dried and cured (cross-linked).
  • the clips and the boards were then carefully removed from the samples and the PTFE mesh peeled off to reveal the final composite fibre mats which had a thickness in the range of from 7 to 8.5 mm.
  • Samples of "Saffil" low density mat having a size of about 500 mm by 200 mm were cut from a bulk product having a known area density of from 1.0 to 2.0 kg/m 2 and a thickness of from 30 to 50 mm. These samples were weighed and then transferred to a tray where they were soaked in a latex (60 % aqueous dispersion of a butyl acrylate based polymer containing 3 % w/w of Epikote (TM) 828 epoxy resin cross-linking agent) which had been diluted to a solids content of around 5 % w/w.
  • TM Epikote
  • the impregnated samples were then sandwiched between two sheets of PTFE-coated glass fibre mesh and these sandwiches were then placed between two sheets of glass fibre filled silicone resin board of size 500 mm by 200 mm by 12 mm.
  • the resin boards were then pressed together using G-clamps until the impregnated "Saffil" layers were reduced to a thickness of about 5 mm (equal to an applied pressure of about 0.5 bar (50 KPa)), and held in this position with clips. During this assembly excess latex drained from the samples.
  • the completed mould assemblies were then placed on the belt of an air/radio frequency (RF) assisted oven and the belt speed was adjusted to give a residence time of between 15 and 45 minutes.
  • the RF power to the oven was set at about 5.5 KW and the temperature of the air in the oven was adjusted to about 150°C.
  • the samples were removed from the oven when the latex had been fully dried and cured (cross-linked).
  • the clips and the boards were then carefully removed from the samples and the PTFE mesh peeled off to reveal the final composite fibre mats which had a thickness in the range of from 7 to 8.5 mm.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nonwoven Fabrics (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Reinforced Plastic Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

Produit fibreux composite comportant plusieurs fibres inorganiques et un liant réparti de manière sensiblement uniforme dans la totalité du produit fibreux. Ce produit fibreux composite présente une résistance au cisaillement laminaire d'au moins 0,1 MPa. On a également prévu un procédé de fabrication d'un produit fibreux composite, consistant à imprégner une masse fibreuse comportant plusieurs fibres inorganiques, d'un système de liant liquide comportant une matière liante et un liquide véhicule, puis à soumettre la masse fibreuse imprégnée à une opération de chauffage mettant en oeuvre un chauffage diélectrique.

Claims (44)

  1. Produit en fibres composites qui comprend une pluralité de fibres inorganiques et un liant qui est réparti de façon très uniforme dans le produit en fibres, ledit produit en fibres composites ayant un cisaillement laminaire d'au moins 0,1 MPa.
  2. Produit en fibres composites selon la revendication 1, dans laquelle les fibres inorganiques ont une stabilité thermique pour des températures supérieures à 700°C.
  3. Produit en fibres composites selon la revendication 1 ou la revendication 2, dans laquelle les fibres inorganiques sont des fibres céramiques.
  4. Produit en fibres composites selon la revendication 2 ou la revendication 3, dans laquelle les fibres inorganiques sont des fibres d'oxydes inorganiques polycristallins choisies dans le groupe constitué par les fibres d'alumine, les fibres de mullite, les fibres d'aluminosilicate, les fibres d'aluminoborosilicate, les fibres de zircone et les fibres de titane.
  5. Produit en fibres composites selon la revendication 4, dans laquelle les fibres inorganiques sont des fibres d'alumine.
  6. Produit en fibres composites selon l'une quelconque des revendications 1 à 5, dans laquelle les fibres inorganiques sont de courtes fibres discontinues ayant une longueur allant de 1 à 10 cm et un diamètre moyen allant de 1 à 10 microns.
  7. Produit en fibres composites selon l'une quelconque des revendications 1 à 6, dans laquelle le liant est une substance organique.
  8. Produit en fibres composites selon la revendication 7, dans laquelle le liant est un polymère organique.
  9. Produit en fibres composites selon la revendication 7 ou la revendication 8, dans laquelle le liant est une substance dérivée du durcissement d'une composition polymère durcissable comprenant un polymère acrylique et un agent de liaison transversale contenant un groupement époxy.
  10. Produit en fibres composites selon la revendication 9, dans laquelle le polymère acrylique est un homopolymère ou un copolymère comprenant des monomères dérivés d'au moins un monomère acrylique choisi dans les C1 à 4 alkyl (méth)acrylates.
  11. Produit en fibres composites selon la revendication 9, dans laquelle le liant est une substance dérivée du durcissement d'une composition polymère durcissable comprenant un polymère acrylique basé sur le butyl acrylate et un agent de liaison transversale de résine époxyde.
  12. Produit en fibres composites selon l'une quelconque des revendications précédentes, dans laquelle la répartition du liant dans le produit en fibres composites est telle que le pourcentage en poids du liant dans chaque zone de 1 mm3 du produit par rapport au poids total du produit dans cette zone ne dépasse pas 40% du pourcentage total en poids du liant dans le produit par rapport au poids total du produit.
  13. Produit en fibres composites selon la revendication 12, dans laquelle la répartition du liant dans le produit de fibres composites est telle que le pourcentage en poids du liant dans chaque zone de 1 mm3 du produit par rapport au poids total du produit dans cette zone ne dépasse pas 30% du pourcentage total en poids du liant dans le produit par rapport au poids total du produit.
  14. Produit en fibres composites selon l'une quelconque des revendications précédentes qui a une épaisseur de l'ordre de 3 à 15 mm.
  15. Produit en fibres composites selon l'une quelconque des revendications précédentes, dans laquelle la charge du liant dans le produit est de l'ordre de 2 à 15% en poids par rapport au poids total du produit.
  16. Produit en fibres composites selon l'une quelconque des revendications précédentes qui a une densité de l'ordre de 30 à 700 kg/m3.
  17. Produit en fibres composites selon la revendication 16 qui a une densité située de l'ordre de 100 à 500 kg/m3.
  18. Produit en fibres composites selon l'une quelconque des revendications précédentes qui a un cisaillement laminaire d'au moins 0,2 MPa.
  19. Produit en fibres composites selon l'une quelconque des revendications précédentes qui est capable d'exercer une pression d'au moins 1,0 kgf/cm2 lorsqu'une portion du produit ayant une épaisseur située entre 5 et 10 mm est compressée jusqu'à atteindre une épaisseur de 3 mm entre deux plaques et que le liant est retiré.
  20. Produit en fibres composites selon la revendication 19 qui est capable d'exercer une pression de l'ordre de 1,5 à 4,0 kgf/cm2 lorsqu'une portion du produit ayant une épaisseur située entre 5 et 10 mm est compressée jusqu'à atteindre une épaisseur de 3 mm entre deux plaques et que le liant est retiré.
  21. Procédé pour la production d'un produit en fibres composites qui comprend l'imprégnation d'une masse de fibres comprenant une pluralité de fibres inorganiques avec un système de liaison liquide comprenant une substance liante et un liquide porteur, et le passage de la masse de fibres imprégnée à une étape de chauffage, caractérisée en ce que l'étape de chauffage fait intervenir un chauffage diélectrique.
  22. Procédé selon la revendication 21, dans laquelle la masse de fibres imprégnée est maintenue sous compression pendant au moins une partie de l'étape de chauffage.
  23. Procédé selon la revendication 21 ou la revendication 22, dans laquelle la masse de fibres qui est imprégnée est un produit multi-fibres dans lequel les fibres individuelles sont assemblées en un mat ou un tapis à faible densité.
  24. Procédé selon la revendication 23 dans laquelle le produit multi-fibres a une épaisseur de l'ordre de 10 à 60 mm et une densité superficielle de l'ordre de 0,2 à 2,0 kg/m2.
  25. Procédé selon l'une quelconque des revendications 21 à 24, dans laquelle les fibres inorganiques ont une stabilité thermique pour des températures supérieures à 700°C.
  26. Procédé selon la revendication 25, dans laquelle les fibres inorganiques sont des fibres céramiques.
  27. Procédé selon la revendication 25 ou la revendication 26, dans laquelle les fibres inorganiques sont des fibres d'oxydes inorganiques polycristallins choisies dans le groupe constitué des fibres d'alumine, des fibres de mullite, des fibres d'aluminosilicate, des fibres d'aluminoborosilicate, des fibres de zircone et des fibres de titane.
  28. Procédé selon la revendication 27, dans laquelle les fibres inorganiques sont des fibres d'alumine.
  29. Procédé selon l'une quelconque des revendications 21 à 28, dans laquelle les fibres inorganiques sont de courtes fibres discontinues ayant une longueur allant de 1 à 10 cm et un diamètre moyen allant de 1 à 10 microns.
  30. Procédé selon l'une quelconque des revendications 21 à 29, dans laquelle le système de liaison liquide comprend une substance liante organique et un liquide porteur organique ou aqueux qui est capable de dissoudre ou de disperser la substance liante organique.
  31. Procédé selon la revendication 30, dans laquelle la substance liante organique est un polymère.
  32. Procédé selon la revendication 30 ou la revendication 31, dans laquelle le système de liaison liquide comprend une dispersion d'une composition polymère durcissable comprenant un polymère acrylique et un agent de liaison transversale contenant un groupement époxy.
  33. Procédé selon la revendication 32, dans laquelle le polymère acrylique est un homopolymère ou un copolymère comprenant des monomères dérivés d'au moins un monomère acrylique choisi dans les Ci à 4alkyl (méth)acrylates.
  34. Procédé selon la revendication 32, dans laquelle le système de liaison liquide comprend une dispersion d'une composition polymère durcissable comprenant un polymère acrylique basé sur le butyl acrylate et un agent de liaison transversale de résine époxyde.
  35. Procédé selon l'une quelconque des revendications 30 à 34, dans laquelle la dispersion est une dispersion aqueuse.
  36. Procédé selon l'une quelconque des revendications 21 à 35, dans laquelle le système de liaison liquide comprend 0,5 à 50,0% en poids de substance liante et 50,0 à 99,5% en poids de liquide porteur.
  37. Procédé selon la revendication 36, dans laquelle le système de liaison liquide comprend 1,0 à 5,0% en poids de substance liante et 95,0 à 99,0% en poids de liquide porteur.
  38. Procédé selon la revendication 22, dans laquelle la totalité de l'étape de séchage/chauffage est réalisée tout en maintenant la masse de fibres imprégnée sous compression.
  39. Procédé selon la revendication 22, dans laquelle la pression qui est appliquée au cours de l'étape de séchage/chauffage pour comprimer la masse de fibres imprégnée est de l'ordre de 5 à 500 KPa.
  40. Procédé selon la revendication 39, dans laquelle la pression qui est appliquée au cours de l'étape de séchage/chauffage pour comprimer la masse de fibres imprégnée est de l'ordre de 5 à 200 KPa.
  41. Procédé selon la revendication 21, dans laquelle le chauffage diélectrique est un chauffage par micro-ondes ou par fréquences radios.
  42. Procédé selon la revendication 21, dans laquelle une combinaison de chauffage diélectrique et de chauffage conventionnel est utilisée au cours de l'étape de séchage/chauffage.
  43. Procédé selon l'une quelconque des revendications 21 à 42, dans laquelle la masse de fibres imprégnée est chauffée à une température située entre 80 et 200°C au cours de l'étape de séchage/chauffage.
  44. Procédé selon la revendication 43, dans laquelle la masse de fibres imprégnée est chauffée à une température située entre 100 et 170°C au cours de l'étape de séchage/chauffage.
EP97905225A 1996-02-27 1997-02-20 Produits fibreux composites et leurs procedes de fabrication Expired - Lifetime EP0883736B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB9604097.7A GB9604097D0 (en) 1996-02-27 1996-02-27 Production process
GB9604097 1996-02-27
GBGB9615770.6A GB9615770D0 (en) 1996-07-26 1996-07-26 Production process
GB9615770 1996-07-26
PCT/GB1997/000466 WO1997032118A1 (fr) 1996-02-27 1997-02-20 Produits fibreux composites et leurs procedes de fabrication

Publications (2)

Publication Number Publication Date
EP0883736A1 EP0883736A1 (fr) 1998-12-16
EP0883736B1 true EP0883736B1 (fr) 2000-04-26

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EP97905225A Expired - Lifetime EP0883736B1 (fr) 1996-02-27 1997-02-20 Produits fibreux composites et leurs procedes de fabrication

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EP (1) EP0883736B1 (fr)
CN (1) CN1082610C (fr)
AU (1) AU1885097A (fr)
DE (1) DE69701796T2 (fr)
ES (1) ES2146461T3 (fr)
WO (1) WO1997032118A1 (fr)

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9615720D0 (en) * 1996-07-26 1996-09-04 Ici Plc Composite mat
US20020025750A1 (en) 1996-07-26 2002-02-28 Imperial Chemical Industries Plc. Composite mat
DE60013977T2 (de) 1999-07-29 2005-10-06 Sumitomo Chemical Co. Ltd. Hitzbeständiger blattformiger Katalysator und Verfahren zu seiner Herstellung
KR20010070002A (ko) * 1999-07-29 2001-07-25 고오사이 아끼오 내산성 촉매 시트 및 이의 제조방법
AU2003212657A1 (en) * 2002-03-22 2003-10-08 Jong-Hak Lee Bio-sheet material and its manufacturing method and apparatus
US7971357B2 (en) 2004-06-29 2011-07-05 Unifrax I Llc Exhaust gas treatment device and method for making the same
WO2006057240A1 (fr) * 2004-11-24 2006-06-01 Nippon Sheet Glass Company, Limited Papier en fibres inorganiques
US9416053B2 (en) 2007-10-09 2016-08-16 3M Innovative Properties Company Mounting mat including inorganic nanoparticles and method for making the same
WO2009048859A1 (fr) * 2007-10-09 2009-04-16 3M Innovative Properties Company Procédé de fabrication de tapis de montage pour monter un élément de lutte contre la pollution
BRPI0917717A2 (pt) 2008-08-29 2016-02-16 Unifrax I Llc esteira de montagem com protetor de borda flexível e dispositivo de tratamento de gás de exaustão incorporado na esteira de montagem.
JP5796713B2 (ja) 2008-12-15 2015-10-21 ユニフラックス ワン リミテッド ライアビリティ カンパニー セラミックハニカム構造体の表皮被覆
WO2010120380A2 (fr) 2009-04-17 2010-10-21 Unifrax I Llc Dispositif de traitement des gaz d'échappement
GB0906837D0 (en) 2009-04-21 2009-06-03 Saffil Automotive Ltd Mats
KR102040742B1 (ko) 2009-07-17 2019-11-05 씨에프피 콤포지츠 리미티드 섬유 매트릭스 및 섬유 매트릭스의 제조 방법
EP2464840A4 (fr) 2009-08-10 2013-10-30 Unifrax I Llc Préforme ou tapis de montage dont la masse surfacique est variable et dispositif de traitement des gaz d échappement
CN102686843B (zh) 2009-08-14 2015-04-01 尤尼弗瑞克斯I有限责任公司 多层基底支承体和排气处理装置
US9174169B2 (en) 2009-08-14 2015-11-03 Unifrax I Llc Mounting mat for exhaust gas treatment device
US8071040B2 (en) 2009-09-23 2011-12-06 Unifax I LLC Low shear mounting mat for pollution control devices
CA2773757A1 (fr) 2009-09-24 2011-03-31 Unifrax I Llc Nappe a plusieurs couches et dispositif de traitement des gaz d'echappement
US9650935B2 (en) 2009-12-01 2017-05-16 Saffil Automotive Limited Mounting mat
US20110150717A1 (en) 2009-12-17 2011-06-23 Unifrax I Llc Mounting mat for exhaust gas treatment device
EP2513442B1 (fr) 2009-12-17 2017-11-29 Unifrax I LLC Dispositif de traitement de gaz d'échappement
KR20140130206A (ko) 2009-12-17 2014-11-07 유니프랙스 아이 엘엘씨 오염 제어 장치용 다층 장착 매트
US8765069B2 (en) 2010-08-12 2014-07-01 Unifrax I Llc Exhaust gas treatment device
EP2603676B1 (fr) 2010-08-13 2016-03-23 Unifrax I LLC Matelas de fixation présentant une protection de bord flexible et dispositif de traitement des gaz d'échappement comprenant le matelas de fixation
US9924564B2 (en) 2010-11-11 2018-03-20 Unifrax I Llc Heated mat and exhaust gas treatment device
EP2638261A4 (fr) 2010-11-11 2014-08-06 Unifrax I Llc Mat de support et dispositif de traitement des gaz d'échappement
CN102748109B (zh) * 2012-07-11 2016-03-09 中国第一汽车股份有限公司 纸质的尾气后处理用载体单元的制备方法
CN102748108B (zh) * 2012-07-11 2016-12-21 中国第一汽车股份有限公司 纸质的高强度后处理载体单元的制备方法
FR2994201B1 (fr) 2012-07-31 2014-08-08 Saint Gobain Isover Procede de cuisson d'un matelas continu de fibres minerales ou vegetales
PL3536837T3 (pl) 2013-03-27 2024-07-15 3M Innovative Properties Company Komponenty izolowane termicznie
JP6327359B2 (ja) * 2014-11-19 2018-05-23 三菱ケミカル株式会社 バインダー含有無機繊維成形体の製造方法
PL3262287T3 (pl) 2015-02-24 2020-07-27 Unifrax I Llc Mata izolacyjna odporna na wysokie temperatury
CN105672056B (zh) * 2016-01-22 2018-06-29 山东大学 用于低温深冷绝热的氧化钛纤维纸及其制备方法与应用
CN109758830A (zh) * 2019-03-06 2019-05-17 江苏康隆迪超净科技有限公司 一种防静电阻燃ptfe针刺过滤材料及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011651A (en) * 1973-03-01 1977-03-15 Imperial Chemical Industries Limited Fibre masses
WO1994024425A1 (fr) * 1993-04-22 1994-10-27 The Carborundum Company Matelas de montage pour structures fragiles telles que des convertisseurs catalytiques
US5996228A (en) * 1995-04-13 1999-12-07 Mitsubishi Chemical Corporation Monolith-holding element, process for producing the same, catalytic converter using a monolith member and process for producing the same

Also Published As

Publication number Publication date
DE69701796D1 (de) 2000-05-31
CN1216595A (zh) 1999-05-12
DE69701796T2 (de) 2000-11-09
EP0883736A1 (fr) 1998-12-16
ES2146461T3 (es) 2000-08-01
AU1885097A (en) 1997-09-16
CN1082610C (zh) 2002-04-10
WO1997032118A1 (fr) 1997-09-04

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