Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B16/04—Macromolecular compounds
  • C04B16/06—Macromolecular compounds fibrous
  • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B16/0625—Polyalkenes, e.g. polyethylene
  • C04B16/0633—Polypropylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
  • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
  • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
  • E04C5/073—Discrete reinforcing elements, e.g. fibres
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer

Definitions

• the present invention relates to the field of fibers, and more particularly relates to a filled polymer fiber.
• Polymer fibers find application in numerous fields. Reference may be made, for example, to the article entitled “Textile applications of polypropylene fibers” by M. Jambrich and P. Hodul enclosed in the book “Polypropylene—an A-Z reference” edited by J. Karger-Kocsis, published by Kluwer Academic Publisher, 1999.
• the polymer fibers are used alone for their own characteristics or also in combination with other materials and/or other fibers, incorporated into diverse matrices (mineral, polymer, etc), especially for a reinforcing purpose.
• these fibers are used for the manufacture of products of varied form: fleece, fabric, mat, unidirectional product, etc.
• catalyst residues may form micron-sized impurities that are able to decrease the properties of the end fiber.
• this filled polymer fiber was made under laboratory conditions, without taking into account the industrial constraints, especially in terms of reliability and output.
• the proposed manufacturing process is therefore not realistic for industrial production.
• the present invention proposes to supply a polymer fiber that has good mechanical properties, in particular a high Young's modulus, whilst being easy to manufacture on an industrial scale.
• the first subject of the invention is a filled polymer fiber comprising additives within it, the filled polymer fiber having a Young's modulus greater than that of an unfilled polymer fiber and the additives comprising mineral additives having at least one submicron dimension.
• the combination of a polymer and mineral additives having at least one submicron dimension according to the invention makes it possible to obtain a fiber having an increased Young's modulus relative to an unfilled fiber based on the same polymer.
• the mineral additives according to the invention are readily available in nature or are easily synthesized, and if necessary, easily purified. These additives also have the advantage of not being very expensive.
• the manufacture of the fiber according to the invention is compatible with industrial requirements.
• the term “submicron dimension” according to the invention is understood to mean the submicron dimension of the mineral additives, taken as an average.
• the submicron dimension corresponds, for example, to a diameter or a thickness.
• fiber is defined in the broad sense. Without another adjective or specification added, the term “fiber” denotes both a undrawn fiber (in the solid phase) and also a drawn fiber (drawn one or more times). The term “fiber” denotes both a yarn or monofilament and also a set of filaments (of textile fiber type), that are identical to or different from each other. The fiber may be continuous or chopped, short or long.
• the submicron dimension of the mineral additives may be less than 500 nm, and preferably less than 100 nm.
• the mineral additives may be of spherical, rod-shaped or lamellar-type structure.
• the mineral additives may have an aspect ratio greater than 5, and preferably greater than 50.
• the aspect ratio is defined as the ratio of the largest dimension to the smallest dimension.
• a high aspect ratio ensures a high tenacity, in particular when the large dimension of the additives according to the invention is approximately parallel to the axis of the fiber.
• the mineral additives may be metal oxides or clays.
• metal oxides mention may be made of aluminas, barium oxides, titanium oxides, zirconium oxides, manganese oxides, talc, magnesia and calcium carbonate.
• the clays may be lamellar, that is to say as platelets, or fibrous.
• the mineral additives may comprise an exfoliable lamellar clay preferably chosen from synthetic and natural phyllosilicates, smectite clays such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, vermiculite and the equivalents, and also magadiite, kenyaite, stevensite, halloysite, aluminate oxides, hydrotalcite and the equivalents.
• synthetic and natural phyllosilicates smectite clays such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, vermiculite and the equivalents
• magadiite kenyaite
• stevensite halloysite
• aluminate oxides aluminate oxides
• hydrotalcite hydrotalcite
• the clays may have a negative surface charge of at least 20 milliequivalents, preferentially of at least 50 milliequivalents, and more preferentially between 50 and 150 milliequivalents, per 100 grams of said additives.
• the clays may thus be modified by organic molecules that are able to be absorbed within the minerals, for example between clay platelets, which allows their exfoliation. Even though the clay may have any cationic exchange capacity, it is nevertheless preferable that the clay exfoliate correctly.
• the mineral additives may be chosen from montmorillonite and boehmite.
• Boehmite is based on alumina monohydrate Al—O—OH. Boehmite is for example in rod form.
• Montmorillonite has exfoliable platelets and may be distributed uniformly within the filled polymer fiber according to the invention.
• Montmorillonite and boehmite have, moreover, a particularly high Young's modulus, greater than 100 GPa.
• the mineral additives may be surface-modified by one at least of the following agents: cationic surfactants, amphoteric agents, derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides, and preferably ammonium, sulfonium or phosphonium salts.
• These agents are used as intercalants for clays in platelet form.
• these agents also favor the dispersion of the mineral additives according to the invention.
• the mineral additives may also be modified by an adhesion promoter that is preferably an organosilane compound, and still more preferentially a silane, an aminosilane, a vinylsilane and mixtures thereof.
• an adhesion promoter that is preferably an organosilane compound, and still more preferentially a silane, an aminosilane, a vinylsilane and mixtures thereof.
• the weight content of mineral additives relative to the total weight of the fiber may be preferably less than 10%, still more preferentially less than 5%.
• the filled polymer fiber may be based on a polymer for example chosen from polyolefins, polyamides, polyesters, polyacrylonitrile and polyvinyl alcohols and copolymers thereof.
• the filled polymer fiber may be a fiber of filled polyolefin, such as polyethylene or polypropylene, and still more preferentially of filled polypropylene.
• the fiber may contain, moreover, a blend of a polyolefin and a polyolefin having polar functional groups, which is preferably a polyolefin grafted by maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the weight content of the polyolefin having polar functional groups relative to the total weight of the filled polymer fiber being preferably less than 10% and still more preferentially less than 5%.
• a polyolefin and a polyolefin having polar functional groups which is preferably a polyolefin grafted by maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the weight content of the polyolefin having polar functional groups relative to the total weight of the filled polymer fiber being preferably less than 10% and still
• the polyolefin having polar functional groups may be grafted before or after synthesis.
• the latter favors the dispersion of a blend to be spun and the drawing of the fiber.
• the percentage of polyolefin having polar functional groups may be limited for a greater increase in the Young's modulus.
• the linear density of the filled polymer fiber may be between 0.5 to 10 dtex, more advantageously between 0.5 to 2 dtex.
• a reinforcing effect that is particularly advantageous in the composites may be obtained with a fiber (monofilament) of relatively small cross section.
• the cross section of a filled polymer fiber according to the invention is not necessarily circular and may have an irregular or multilobal shape.
• the filled polymer fiber according to the invention may have a tenacity equal to at least 80% of that of the unfilled fiber.
• the filled polymer fiber has a high tenacity of at least 4 cN/dtex, preferably at least 5 cN/dtex, very preferentially at least 7 cN/dtex, and in particular 8 to 9 cN/dtex.
• This tenacity range may be achieved by regulating the spinning and drawing process in a suitable manner.
• a polyolefin base material with a suitable molecular weight distribution may be specifically chosen.
• the filled polymer fiber may preferably contain, on the surface, a sizing that contains an amine or polyamine, phosphoric or polyphosphoric compound, more preferably an ester of phosphoric acid based on a fatty chain.
• a simple modification of the exposed surface of the fiber by a sizing makes it possible to effectively and durably improve the interaction between the fiber and a cement matrix.
• the surface properties of the polymer fiber are modified by one or more sizing agents providing the function of assisting the spinning process.
• the function of assisting the spinning process consists in facilitating the formation of the polymer fiber in at least one stage of the spinning: especially, it is to lubricate the fibers (monofilaments at this stage) so at to improve their handling by transport devices at various stages of the production, to minimize the electrostatic charges carried by the fiber.
• a product may be chosen from the products sold under the names SILASTOL Cut 5A and Cut 5B from Schill & Seilacher, SYNTHESIN 7292 from Dr Boehme, KB 144/2 from Cognis, STANTEX S6077 from Cognis and STANTEX S6087/4 from Cognis.
• the sizing may be present on the fiber at a quantity of 0.05 to 5% by weight of solids relative to the dry weight of the fiber.
• the sizing also provides a function of wettability by the hydraulic binder-based composition, of promoting adhesion to the hydraulic-setting matrix and conferring on the fiber-cement composite further improved mechanical properties.
• the function of wettability by the hydraulic binder-based composition consists in facilitating the dispersion of polymer fibers in the matrix, resulting from the good dispersion of the fibrous material within the initial binder/water mixture from which the product is manufactured. This function principally relies on the surface polarity of the fibrous material to make it hydrophilic.
• the function of promoting adhesion to the hydraulic-setting matrix consists in strengthening the interaction between the fibrous reinforcement and the hardened product matrix.
• the latter function also relies on the presence of polar functional groups on the surface of the fibers.
• agents chosen from lubricants, antistatic agents, surfactants, fatty chain compounds and polymers having polar functional groups, in which a lubricant may be a fatty chain compound, likewise a surfactant may be a fatty chain compound, or an antistatic agent may be a, polymer having polar functional groups.
• a drawn fiber may be in the form of a chopped yarn with a length of around 2 to 20 mm, in particular 5 to 12 mm.
• Another subject of the present invention is the use of a filled polymer fiber as described above, as a reinforcing fiber in a fiber-based product.
• yet another subject of the present invention is a fiber-based product characterized in that it comprises filled polymer fibers as defined above.
• the product is in the form of a fabric, fleece, long fiber mat, chopped fiber mat, unidirectional product, nonwoven product, cord, net, ribbon, webbing or strip, or else in the form of a mixture of said fibers with fibers of a different type, and preferably in commingled fiber form.
• commingled fiber is the fiber sold under the trademark TWINTEX by Saint-Gobain that contains polypropylene filaments and glass filaments.
• the filled polymer fiber according to the invention carpets, hygienic applications, ribbons, cords and twines, the textile industry (clothing, yarns, etc.), domestic textiles (nonwoven for decoration, woven for walls, etc.), geotextiles, agrotextiles, packaging, medical textiles, bioactive fibers, multicomponent fibers, high-performance yarns or high strength monofilaments (seat belts, safety nets, fishing nets, etc.).
• the filled polymer fiber according to the invention may be solid or predominantly solid, that is to say it may for example comprise a hollow core along the axis of the fiber.
• the (sized or unsized) filled polymer fiber according to the invention may be coated.
• the fiber may be incorporated, in various forms, into products derived from oil, into bitumen products and, for example in mat form, into asphalt-based products such as roofing components.
• the fiber in various forms, may also be thermoformed.
• the product comprises a mineral matrix, preferably a hydraulic-setting substance, and the product is preferably chosen from adhesives, mortars, concretes, grouts and fiber cements.
• the hydraulic-setting substance is constituted from a hydraulic-setting binder, chosen mainly from various existing cements, which possibly have inert or active filler additives.
• rheology modifiers dispersing agents, plasticizers, superplasticizers and flocculants
• mineral fillers sica, fly ash, slag, pozzolana and carbonates
• supporting or reinforcing fibers for filtration or dewatering processes natural fibers, especially cellulose, or synthetic fibers.
• the reduction in the elongation of the fibers on the side intension is obtained by the high Young's modulus of the filled fibers according to the invention.
• the increase in the Young's modulus of the filled fibers makes it possible, therefore, to limit the deformation of the lower zone. This limits the displacement of the neutral axis and therefore limits the increase of the compressive stress in the upper zone.
• the fibers according to the invention are particularly effective as reinforcement for fiber cements, in quantities of around 0.2 to 5 wt % of fibers relative to the total dry weight of the initial mixture.
• the fibers according to the invention are particularly effective as reinforcement for mortars, in quantities of around 0.01 to 0.2 wt % of fibers relative to the total dry weight of the initial mix for an “anticrack” effect and 0.2 to 5% for structural effects.
• the fibers may be chopped yarns having a length between 2 and 20 mm and more particularly between 5 and 12 mm.
• the product may have various shapes (hollow, tubular) and preferably is in the shape of a flat or corrugated sheet.
• the hydraulic binder-based articles shaped into sheets may be manufactured by a technique of filtering an aqueous suspension comprising a hydraulic-setting binder, reinforcing fibers and possibly fillers.
• a commonly used process based on this technique is known as the Hatschek process: a very dilute aqueous suspension is contained in a tank fitted with means for ensuring a homogenous distribution of the constituents within the volume of the tank; a filter drum is partially immersed in the tank and its rotation causes a thin layer of material (fibers and hydrated binder) to be deposited on its surface; this layer is carried by a felt towards a size roll onto which it is continuously wound up; when the layer has reached the desired thickness, it is cut so as to unwind from the roll an individual sheet of hydraulic-setting material.
• the sheet may then be made in the form of a shaped product and it acquires its final characteristics by the curing of the binder.
• a product of greater thickness may be obtained by superposing a suitable number of sheets and by pressing them together in order to ensure cohesion of the assembly.
• Such boards are used as roofing or facade components.
• the product may comprise a polymer matrix that is chosen preferably from a polyethylene, polypropylene, polyamide, polyester, epoxy or phenolic matrix.
• the main fields of application for composites, for example based on polypropylene, are: transport (parts under the hood, parcel shelf, etc.), electrical applications, domestic and consumer goods, buildings and public works and industrial goods.
• An additional subject of the present invention is a method of manufacturing a filled polymer fiber as defined above comprising a step of spinning a polymer composition comprising mineral additives having at least one submicron dimension.
• the additives according to the invention are easily dispersible and do not significantly modify the rheological properties (viscosity, etc.) of the polymer composition to be spun.
• the polymer composition may be obtained by extrusion.
• the extrusion temperature is to be adjusted depending on the polymer and said additives.
• the spinning temperature may be between 250° C. and 300° C. for filled polypropylene.
• the spinning step may comprise a cooling operation, preferably in suitably cooled and humidified air, for a good heat exchange capacity, and a radial cooling operation.
• the method comprises a step of drawing at below the melting point, immediately after spinning or subsequently.
• the method may comprise a fiber tapering step by continuous drawing means.
• This step may be achieved with the aid of rolls at various temperatures and with different speeds and with the aid of ovens.
• the method comprises a step of preparing said composition, comprising at least one filtration operation.
• the preparation step of the composition can include the realization of a premix transformed then in pellets, to dilute with the polymer and optionally with modified polymer.
• This premix is obtained by dilution in the polymer of a master batch in pellets and in preference non commercial which contains the mineral additives according to the invention.
• the master batch can be filtered.
• a sizing step may be added in the spinning step.
• a sizing step may be added after drawing and be followed by a step of drying with the aid of air oven(s).
• the size may be applied neat or as an aqueous solution, dispersion or emulsion, or one based on another suitable carrier liquid.
• a subject of the invention is also a method of manufacturing a product based on filled fibers as defined above and on a hydraulic-setting substance.
• an initial mixture is prepared, based on hydraulic binder, water and fibers as defined above, the fibers are filtered over a stationary or moving support in order to form a wet elementary sheet, possibly a plurality of elementary sheets are superposed to form a wet intermediate product and the board or the wet intermediate product is dried.
• a subject of the invention is also a composition for a hydraulic-setting material comprising a hydraulic binder and fibers as described above.
• These compositions may be cement preparations to be put into suspension for the dewatering process, or cement preparations for mortars for other forming processes.
• a final subject of the invention is a composition comprising a polymer matrix and fibers as described above.
• Such matrices may be preferably thermoplastic matrices, thermosetting matrices, and preferably polyethylene, polypropylene, polyamide, polyester, epoxy or phenolic matrices.
• the reference fiber was an unfilled high-tenacity small-diameter (1 dtex) fiber obtained, without mineral additives, according to the invention from polypropylene resin HF445FB from Borealis, having a melt flow index of 18 g/10 min measured at 230° C. and 2.16 kg.
• the fiber On exiting the spinneret—which has holes approximately 0.35 mm in diameter—the fiber, that is to say, all monofilament, will freeze after a rapid cooling and with a cooling air that is temperature and speed controlled.
• the fiber was then wound onto a reel, then unwound and drawn continuously in a drawing zone comprising various series of heated rolls rotating at increasing rotation speeds. Hot-air or steam ovens were interposed between the various series of rolls. At the end of the drawing zone, the fiber was cooled.
• the fiber was then chopped into 30 mm lengths to carry out the tests.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• NANOMER C44PA manufactured by Nanocor
• PP polypropylene
• Montmorillonite is a clay whose platelets have a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the polymer composition was produced in a single-screw extruder at a temperature of about 250° C. and was fed into a spinneret having holes 0.35 mm in diameter.
• the viscosity of the composition was comparable to that of the polymer used.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the premix was produced in a corotating twin-screw extruder at a temperature of 220° C., was passed through a filter having holes of about 40 ⁇ m diameter and was then fed into a spinneret having holes 3 mm in diameter in order to manufacture pellets.
• the polymer composition was produced in a single screw extruder at a temperature of about 250° C. and was fed into a spinneret having holes 0.35 mm in diameter.
• the viscosity of the composition was comparable to that of the polymer used.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the fiber was manufactured under conditions similar to those in example 3.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the fiber was manufactured under conditions similar to those in example 3.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the fiber was manufactured under conditions similar to those in example 3.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the fiber was manufactured under conditions similar to those in example 3.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• the clay platelets had a nanoscale average thickness and an average length of several hundred nanometers, giving an aspect ratio greater than 50.
• the premix was produced in a corotating twin-screw extruder at a temperature of 180° C., was passed through a filter having holes of about 40 ⁇ m diameter and was then fed into a spinneret having holes 3 mm in diameter in order to manufacture pellets.
• This premix is a diluted mix 80% of Borealis HF445FB PP, with 20% of a non commercial master batch in pellet form and which contains 50% of Borealis HF445FB PP, 25% of PPgMA of reference POLYBOND3200 from Crompton and 25% of modified montmorillonite in powder of reference Cloisite C20A sold by Southern Clay Products.
• the master batch realized in a coratating twin-screw extruder at a temperature of 180° C. was passed through a filter having holed of about 40 ⁇ m diameter and was then fed into a spinneret having holes 3 mm in diameter in order to manufacture pellets of the master batch.
• the polymer composition was produced in a single screw extruder at a temperature of about 250° C. and was fed into a spinneret having holes 0.35 mm in diameter.
• the viscosity of the composition was comparable to that of the polymer used.
• a filled polypropylene fiber was manufactured from the following polymer composition, expressed in wt % of material relative to the total weight of the fiber:
• This boehmite was in the form of rods having an average diameter of about 20 nm and an average length between 100 and 200 nm, and thus an aspect ratio greater than 5.
• the fiber was manufactured under conditions similar to those in example 3.
• the Young's modulus is defined as being the secant modulus, equal to the ratio of a stress to a nominal strain respectively 1, 5 or 10%.
• the Young's moduli were calculated from tenacity-elongation curves obtained on a single fiber using a Fafegraph tensile testing machine sold by Textechno. The diameters were measured using a Vibromat sold by Textechno. The measurement conditions were determined by the IS05079 standard. The distance between the jaws was 10 mm for the fibers before drawing and 20 mm after drawing, there being drawn continuously in the solid state to the maximum draw ratio while preventing the fibers (continuous yarns at this stage) from breaking.
• the Young's modulus of the undrawn and drawn fibers 2 to 9 is clearly higher than that of the respectively undrawn and drawn reference fiber 1. Moreover, the drawn fibers 2 to 9 retain a high tenacity.
• a cement product was manufactured by filtration, by a laboratory method reproducing quite faithfully the main characteristics of the products obtained by industrial methods such as the Hatschek technique.
• a first reference cement composition was prepared with filled polypropylene fibers identical to the reference fiber of example 1. These fibers were also manufactured in a similar way to that of example 1 but with an additional post-sizing step, carried out after drawing, in an amount of 0.4 wt % of filled polypropylene fiber solids.
• a second cement composition was prepared with filled polypropylene fibers identical to the fiber of example 5. These fibers were also manufactured in a similar way to that of example 5 but with an additional post-sizing step, carried out after drawing, in an amount of 0.4 wt % of filled polypropylene fiber solids.
• the fibers were chopped into 10 mm lengths.
• the composition was filtered through a metal grid to form a single layer of about 1 mm thickness.
• Six individual layers were superposed and subjected to a pressing cycle in order to obtain a material containing, before setting, about 50 wt % of water relative to the weight of cement, and a thickness of about 6 mm.
• This laboratory material underwent a curing of 6 days at 40° C. in a waterproof bag, before being cut into test pieces that were 20 mm wide with lengths greater than 260 mm. The test pieces were put into cold water for 24 hours in order to be mechanically stressed under tension.
• the tensile tests were carried out by fixing the test pieces between the clamps of a tensile testing machine with a distance between the clamps of 180 mm. The tensile test was carried out at a pull rate of 1.2 mm/min.
• test samples 10a correspond to the reference test pieces (with unfilled fibers).
• test pieces 10b correspond to the test pieces according to the invention (with filled fibers).
• the force-displacement curve was plotted. This had a behaviour that was typical of the results observed with products obtained by the Hatschek technique.
• the length of the multicracking plateau reflected the effect of the board reinforcement by all the fibers.
• the amount of calcium carbonate was increased to 60%, even 80%, and conversely the amount of cement was significantly reduced.
• test samples containing fibers identical to the fibers of examples 2 to 4 or 6 to 9 may also be produced.
• This example 11 illustrates the application of filled fibers according to the invention to the manufacture of a cement product by the Hatschek process.
• Aqueous suspensions based on a matrix identical to that with the filled fibers of example 10 were prepared. Each suspension was introduced into the tank of a Hatschek machine, for the formation of a film and for the winding onto a size roll of a sheet of hydrated cement material of about 1 mm thickness. After cutting, sheets of hydrated material were superposed on a former so as to form plane or corrugated sheets having a thickness of 6 mm.
• the sheets were subjected to mechanical tests after 28 days of curing at room temperature.
• Test samples having the same dimensions as those in example 10 were subjected to tensile tests under the same conditions.
• the force-displacement curves were of similar behaviour, with a multicracking plateau and a decrease after pull-out.
• test samples containing fibers that are identical to the fibers of examples 2 to 4 or 6 to 9 may also be produced.
• filled polymer fibers according to the invention for example filled polypropylene fibers similar to the fibers of examples no. 2 to no. 9 or filled polymer fibers having a greater linear titer, may be used as technical yarns or high strength monofilaments to manufacture seat belts, packaging, safety nets, fishing nets, etc.
• the filled polymer fibers according to the invention may be used to manufacture unidirectional or mat-type fabrics that are also hot compactable following the methods described in the articles entitled “The Hot Compaction behaviour of woven oriented PP fibres and tapes. I. Mechanical Properties”, by P. J. Hine et al., published in Polymer, 44, 2003, pp 1117-1131, and “The hot compaction of high modulus melt-spun polyethylene fibres” by P. J. Hine et al., published in Journal of Materials Science, 28, 1993, pp 316-324.
• the filled polypropylene fibers according to the invention may also be used to manufacture agrotextiles and geotextiles according to the method described in the article entitled “Geotextiles and geomembranes”, by K. Chan in the book “Polypropylene: an A-Z reference”, edited by J. Karger-Kocsis, published by Kluwer Academic Publisher, 1999.
• Filled polypropylene fibers according to the invention may also be used to manufacture all-polypropylene (PP) thermoformed composites, filament windings of PP yarns, all-PP sandwich panels composed at the surfaces of PP fiber fabrics or mats and at the core of a PP honeycomb or a PP foam.
• PP polypropylene
• the filled polypropylene fibers according to the invention may also be used to manufacture:
• thermosetting resin following the method described in “Melting behavior of gelspun/drawn polyolefins”, by C. W. M. Bastiaansen et al., published in Makromol. Chem., Macromol. Sym., 28, 1989, pp 73-84;
• the filled polymer fiber according to the invention may just be a fiber obtained by a continuous one-step drawing process (no subsequent operation).
• the filled polymer fiber according to the invention may just be a fiber obtained by spinning a polymer composition without prior premixing.
• the filled polymer fiber according to the invention may just be a fiber obtained by solvent spinning (gel spinning or wet spinning) starting from a polymer in solution or from polymer precursors.
• solvent spinning gel spinning or wet spinning
• the filled polymer fiber according to the invention can also be a fiber from a filled fibrillated ribbon.

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• 2004
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