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 charged polymeric fiber.
• Polymer fibers find applications in many fields.
• This charged polypropylene fiber has a titer of 1 dtex, a high tenacity and a Young's modulus greater than that of an unfilled polypropylene fiber.
• This fiber is proposed as reinforcement of mortars, concretes or cementitious pastes. It is currently difficult to have a high purity of carbon nanotubes. In fact, catalyst residues can form micronic impurities liable to degrade the properties of the final fiber. In addition, it is difficult to manufacture large quantities of carbon nanotubes, which is reflected in the cost of the fiber. Furthermore, this charged polymer fiber was produced under laboratory conditions, without taking industrial constraints into account. especially in terms of reliability and performance. The proposed manufacturing is therefore not realistic for industrial production.
• the present invention proposes to provide a polymeric fiber, which has good mechanical properties, in particular a high Young's modulus, while being easy to manufacture on an industrial scale.
• the first object of the invention is a charged polymeric fiber comprising by mass of additives, the charged polymeric fiber having a Young's modulus greater than that of an uncharged polymeric fiber and the additives comprising mineral additives having minus a 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 compared to an uncharged fiber based on the same polymer.
• the mineral additives according to the invention are readily available in nature or are easily synthesizable, and if necessary easily purifiable. These additives also have the advantage of being inexpensive.
• the manufacture of the fiber according to the invention is compatible with industrial requirements.
• the submicron dimension according to the invention is understood as the submicron dimension of the mineral additives taken on average.
• the submicron dimension corresponds for example to a diameter or a thickness.
• the term fiber is defined broadly. Without any other adjective or precision added, the term fiber designates both an unstretched fiber (in solid phase) and a drawn fiber (in one or more times).
• the fiber designates both a yarn or a monofilament, as well as a set of filaments (of textile fiber type) identical or different from each other.
• the fiber can be continuous or cut, short or long.
• the submicron dimension of the mineral additives can be less than 500 nm, and preferably less than 100 nm.
• the mineral additives can be of spherical, rod-like or lamellar type structure. Naturally, a combination of additives with different structures is possible.
• the mineral additives can have a form factor greater than 5, and preferably greater than 50. It is recalled that the form factor is defined as the ratio of the largest of the dimensions to the smallest of the dimensions.
• the mineral additives can be metal oxides or clays.
• the metal oxides mention may be made of aluminas, barium oxides, titanium oxides, zirconium oxides, manganese oxides, talc, magnesia and calcium carbonate.
• the clays can be lamellar, that is to say in sheets, or fibrous.
• the mineral additives can 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 like, as well as magadiite, kenyaite, stevensite, halloysite, aluminate oxides, hydrotalcite and the like.
• the clays can have a negative surface charge of at least 20 milliequivalents, preferably at least 50 milliequivalents, and more preferably between 50 and 150 milliequivalents, per 100 grams of said additives.
• the clays can thus be modified by organic molecules capable of being absorbed inside the minerals, for example between the sheets of the clays, which allows their exfoliation. Even if the clay can have any cation exchange capacity, it is nevertheless preferable for the clay to exfoliate properly.
• the mineral additives can be chosen from montmorillonite and boehmite. Boehmite is based on alumina monohydrate AI-O-OH. Boehmite is for example in the form of sticks. Montmorillonite has exfoliable sheets and can be distributed homogeneously in the mass of the polymeric fiber loaded according to the invention. Montmorillonite and boehmite also have a particularly high Young's modulus, greater than 100 GPa.
• the mineral additives can be surface modified by at least one of the following agents: cationic surfactants, amphoteric agents, derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides, and preferably salts of ammonium, phosphonium or sulfonium. These agents serve as a blowing agent for sheet clays. Furthermore, these agents also promote the dispersion of the mineral additives according to the invention.
• the mineral additives can also be modified by an adhesion promoter which is preferably an organosilane compound and even more preferably a silane, an amino silane, a vinyl silane and their mixtures.
• the proportion by weight of mineral additives relative to the total weight of the fiber may preferably be less than 10%, even more preferentially less than 5%.
• the charged polymeric fiber may be based on a polymer, for example chosen from polyolefins, polyamides, polyesters, polyacrylonitrile and polyvinyl alcohols and their copolymers.
• the charged polymeric fiber can be a charged polyolefin fiber, such as polyethylene or polypropylene and even more preferably filled polypropylene.
• the fiber may also comprise a mixture of a polyolefin and a polyolefin having polar functions, which is preferably a grafted polyolefin of maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the content by weight polyolefin having polar functions relative to the total weight of the charged polymer fiber preferably being less than 10% and even more preferably less than 5%.
• the polyolefin having polar functions can be grafted before or after synthesis. The latter promotes the dispersion of a spinning mixture and fiber drawing.
• the percentage of polyolefin having polar functions can be limited for a greater increase in the Young's modulus.
• the titer of the charged polymer fiber can be between 0.5 to 10 dtex, more advantageously from 0.5 to 2 dtex.
• a particularly advantageous reinforcing effect in composites can be obtained with a fiber (monofilament) of relatively small section.
• the cross section of a charged polymer fiber according to the invention is not necessarily circular and may have an irregular or multilobal shape.
• the charged polymeric fiber according to the invention may have a tenacity equal to at least 80% of that of the uncharged fiber.
• the charged polymer fiber has a high tenacity, of at least 4 cN / dtex, preferably of at least 5 cN / dtex, very preferably of at least 7 cN / dtex, and in particular from 8 to 9 cN / dtex.
• This range of toughness can be achieved by adjusting the spinning and drawing process appropriately.
• a basic polyolefin material can be specifically chosen with an appropriate molecular weight distribution.
• the charged polymeric fiber may preferably comprise, on the surface, a size which contains an amino or polyamine, phosphoric or polyphosphoric compound, more preferably an ester of phosphoric acid based on 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 polymeric fiber are modified by one or more sizing agents providing a spinning assistance function.
• the spinning assistance function consists in facilitating the constitution of the polymeric fiber at at least one spinning stage: it is in particular a question of lubricating the fibers (monofilaments at this stage) to improve the handling by transport members at different stages of manufacturing, to minimize the electrostatic charges carried by the fiber. For example, you can choose a product from the products marketed under the names SILASTOL Cut 5A and Cut 5B from SCHILL & SEILACHER, SYNTHESIN 7292 from Dr.
• the size may be present on the fiber in an amount of 0.05 to 5% by weight of dry matter relative to the dry weight of fiber.
• the sizing also provides a wettability function by the composition based on hydraulic binder, of adhesion promoter to the matrix with hydraulic setting and gives the fiber-cement composite even increased mechanical properties.
• the wettability function of the hydraulic binder composition consists in facilitating the dispersion of the polymer fibers in the matrix, resulting from the good dispersion of the fibrous material in the initial mixture of binder and water from which the product is made.
• This function mainly uses the surface polarity of the fibrous material to make it hydrophilic.
• the function of promoting adhesion to the matrix with hydraulic setting consists in reinforcing the interaction between the fibrous reinforcement and the matrix of the hardened product.
• This latter function also calls for the presence of polar functional groups at the surface of the fibers.
• These functions can be provided by one or more agents chosen from lubricants, antistatics, surfactants, fatty chain compounds and polymers with polar functions, in which a lubricant can be a fatty chain compound, as well as a surfactant can be a fatty chain compound or an antistatic can be a polymer with polar functions.
• a drawn fiber can be in the form of a wire cut to a length of the order of 2 to 20 mm, in particular from 5 to 12 mm.
• the present invention also relates to the use of a charged polymeric fiber as described above as a reinforcing fiber in a fiber-based product.
• the present invention then relates to a product based on fibers, characterized in that it comprises charged polymeric fibers as defined above.
• the product is in the form of fabric, veil, long fiber mat, cut fiber mat, unidirectional product, non-woven product, rope, net, ribbon, strap, band, or even in the form of a mixture of said products. fibers with fibers of a distinct nature and preferably in the form of a mixed fiber.
• a mixed fiber is the fiber marketed under the name Twintex by Saint-Gobain and which contains polypropylene filaments and glass filaments.
• Multiple areas of application of the charged polymer fiber according to the invention are possible: carpets, hygienic applications, ribbons, ropes and twines, the textile industry (clothing, threads), household textiles (non-woven for decoration, woven for walls, ...), geotextiles, agrotextiles, packaging, medical textiles, bioactive fibers, multicomponent fibers, high-resistance technical yarns or monofilaments (seat belts, protective nets , or fishing, etc.).
• the charged polymer fiber according to the invention can be full or essentially full, that is to say comprise for example a hollow core along the axis of the fiber.
• the charged polymer fiber (sized or not) according to the invention can be coated.
• the fiber can be incorporated in various forms in petroleum products, in bituminous products and for example in the form of masts in asphalt-based products such as roofing elements. Fiber in various forms can also be thermoformed.
• the product comprises a mineral matrix, preferably a mass with hydraulic setting and the product is preferably chosen from glues, mortars, concretes, grouts and fiber-cement.
• the mass with hydraulic setting consists of a binder with hydraulic setting, chosen mainly from the various existing cements, possibly additives of inert or active fillers.
• fillers and additives there may be mentioned rheology additives (dispersants, plasticizers, superplasticizers, flocculants), mineral fillers (silica, fly ash, dairy, pozzolans, carbonates), as well as support or reinforcing fibers for filtration or draining processes (natural fibers, especially cellulose, or synthetic).
• rheology additives disersants, plasticizers, superplasticizers, flocculants
• mineral fillers sica, fly ash, dairy, pozzolans, carbonates
• support or reinforcing fibers for filtration or draining processes natural fibers, especially cellulose, or synthetic.
• the fibers according to the invention are particularly effective as reinforcing fiber cement in proportions of the order of 0.2 to 5% by weight of the fibers relative to the total dry weight of the initial mixture.
• the fibers according to the invention are particularly effective as reinforcement of mortars, in proportions of the order of 0.01 to 0.2% by weight of the fibers relative to the total dry weight of the initial mixture for an "anticrack" and from 0.2 to 5% for structural effects.
• the fibers can be cut strands having a length of between 2 and 20 mm and more particularly between 5 and 12 mm.
• the product can have various shapes (hollow, tubular) and preferably a flat or corrugated plate shape.
• Hydraulic binder articles formed into plates can be manufactured by a technique of filtration of an aqueous suspension comprising a binder with hydraulic setting, reinforcing fibers and optionally 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 equipped with means for ensuring a homogeneous distribution of the constituents in the volume of the tank; a filter drum submerges partially in the tank, and its rotation results in the deposition on its surface of a thin film of materials (fibers and hydrated binder); this film is entrained by a felt towards a format cylinder on which it is continuously wound; when the film has reached the desired thickness, it is cut so as to unwind from the cylinder an individual sheet of material with hydraulic setting.
• the sheet can then be formed into a shaped product and acquires its final characteristics by hardening the binder.
• a product of greater thickness can be obtained by superimposing an appropriate number of sheets, and pressing them to ensure the cohesion of the whole.
• Such plates are used as a roofing or facade element.
• the product can comprise a polymer matrix which is preferably chosen from a polyethylene, polypropylene, polyamide, polyester, epoxy and phenolic matrix.
• the main fields of application of composites, for example based on polypropylene, are: transport (parts under the hood, rear board, etc.), electrical applications, household and consumer goods, buildings and public works and industrial goods.
• the invention further relates to a process for manufacturing a charged polymeric fiber as defined above comprising a step of spinning a polymeric composition comprising mineral additives having at least a 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 polymeric composition can be obtained by extrusion.
• the extrusion temperature should be adjusted depending on the polymer and said additives.
• the spinning temperature can be between 250 ° C and 300 ° C for charged polypropylene.
• the spinning step may include cooling preferably with air cooled and suitably humidified, for good heat exchange capacity, and radial cooling.
• the method comprises a step of drawing below the melting temperature, immediately after spinning or in recovery.
• the method may include a step of passing the fiber through continuous drawing means. This step can be achieved using rollers at different temperatures and different speeds and using ovens.
• the method comprises a step of preparing said composition comprising at least one filtration operation. In this way, potential impurities and aggregates are removed before spinning, for example using a filter at the extruder outlet.
• the stage of preparation of said composition can include the production of a premix then put in the form of granules to dilute with the polymer and optionally with the modified polymer.
• This premix is obtained by dilution in polymer of a master mixture in granules and preferably non-commercial which contains the mineral additives according to the invention.
• the masterbatch can be filtered.
• a sizing step can intervene in the spinning step.
• a sizing step can take place after stretching and be followed by a drying step using air oven (s).
• the size can be applied pure or from an aqueous solution, dispersion or emulsion or based on another suitable liquid vehicle.
• the invention also relates to a method of manufacturing a product based on charged fibers as defined above and a mass with hydraulic setting.
• an initial mixture based on hydraulic binder, water and fibers as defined above is prepared, the fibers are filtered on a fixed or moving support to form an elementary sheet. wet, a plurality of elementary sheets are optionally superimposed to form a wet intermediate product and the wet sheet or intermediate product is dried.
• the invention also relates to a composition for material with hydraulic setting comprising a hydraulic binder and fibers as described above. These compositions can be cement preparations to be suspended for the draining process or cement preparations for mortars for other shaping processes.
• the invention finally relates to a composition comprising a polymer matrix and fibers as described above.
• Such matrices can preferably be thermoplastic matrices, thermosetting matrices, and preferably polyethylene, polypropylene, polyamides, polyesters, epoxy, phenolic matrices.
• the reference fiber is an uncharged fiber of high tenacity and small diameter (Idtex) obtained without mineral additives according to the invention from polypropylene resin HF445FB from the company Boréalis having a flow index of the melt state called M FI (for melt flow index in English) of 18 g / 10 min measured at 230 ° C and 2.16 kg.
• M FI melt flow index in English
• the fiber that is to say all monofilament, will freeze after rapid cooling and with cooling air controlled in temperature and speed.
• Dr Boehme a size having the reference Synthesin 7292 marketed by the company Dr Boehme is deposited on the polypropylene fiber at the outlet of the die, at a rate of 0.45% by weight of dry extract of polypropylene fiber.
• the fiber is then wound, then unrolled and drawn continuously in a drawing zone comprising different series of heated rollers and having an increasing speed of rotation. Hot air or steam ovens are interposed between the different series of rollers. At the end of the stretching zone, the fiber is cooled. The fiber is then cut into 30 mm sections to carry out the tests.
• EXAMPLE 2 A polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 5.5% of the product Nanomer C44PA produced by the company Nanocor and containing approximately 45% montmorillonite and polypropylene (PP), - 94.5% PP Boréalis HF445FB.
• Montmorillonite is a clay whose sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the polymeric composition is produced in a single-screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
• the viscosity of the composition is comparable to that of the polymer used.
• a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
• a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Boréalis HF445FB and from 12.5% of Nanoblend 1001 sold by the company Polyone which contains approximately 40% of montmorillonite and of PP, - 60% of PP Boréalis HF445FB.
• the clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the pre-mixing carried out in a co-rotating twin-screw extruder at a temperature of 220 ° C. passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules.
• the polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
• the viscosity of the composition is comparable to that of the polymer used.
• a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
• a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 58% of PP Borealis HF445FB, - 2% of grafted polypropylene 1% maleic anhydride, says PPgMA, Polybond3200 reference from the Crompton Company.
• the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the fiber is produced under conditions similar to those of the example
• a polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 37% of PP Borealis HF445FB, - 3% of PPgMA reference Polybond3200 from the Company Crompton.
• the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the fiber is produced under conditions similar to those of Example 3.
• a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this pre-mixture being obtained from 87.5% of PP Boréalis HF445FB and 12.5% of Nanoblend 1012 sold by the company Polyone containing approximately 40% of montmorillonite and of PP, - 37% of PP Boréalis HF445FB, - 3% of PPgMA reference Polybond3200 from the company Crompton.
• the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• EXAMPLE 7 A polypropylene fiber loaded with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 20% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 84.5% PP Borealis HF445FB and 15.5% of the product PL19315 marketed by the company Multibase and which contains approximately 32% of montmorillonite and of the PP, - 79.5 % of PP Boréalis HF445FB, - 0.5% of PPgMA of reference Polybond3200 from the company Crompton.
• the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the fiber is produced under conditions similar to those of the example
• a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in modified montmorillonite and in the form of granules, this premix being obtained from 90% of PP, 5% of PPgMA and 5% of modified montmorillonite containing approximately 62% of montmorillonite and an alkyl ammonium, - 40% of PP Boréalis HF445FB.
• the clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
• the premix produced in a co-rotating twin-screw extruder at a temperature of 180 ° C passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules.
• This premix is a mixture diluted from 80% of PP Boréalis HF445FB, with 20% of a non-commercial masterbatch under form of granules and which contains 50% of PP Boréalis HF445FB, 25% of PPgMA reference Polybond 3200 from the company Crompton and 25% of the modified montmorillonite in reference powder Cloisite C20A sold by the company Southern Clay Products.
• the masterbatch produced in a co-rotating twin-screw extruder at a temperature of 180 ° C. passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture the granules of masterbatch.
• the polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
• the viscosity of the composition is comparable to that of the polymer used.
• a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
• a polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: 70% of a premix based on modified boehmite concentrated at 3 % and in the form of granules, this pre-mixture being obtained from 94% of PP Boréalis HF445FB, 3% of PPgMA of reference Polybond3200 and 3% of boehmite sold under the name CAM9010 by the company SAINT GOBAIN and modified in surface with 0.5% of ( ⁇ -aminopropyl) triethoxysilane sold under the name A1 100 by the company Aldrich, - 30% of PP Borealis HF445FB.
• This boehmite is in the form of rods with an average diameter of approximately 20 nm and an average length between 100 and 200 nm, ie a form factor greater than 5.
• the fiber is manufactured under conditions similar to those of Example 3.
• TESTS The results of reference fiber # 1 and loaded fibers # 2 to # 8 before drawing (cold and continuous) are reported in Table 1 below.
• the results for reference fiber # 1 and loaded fibers # 2 to # 8 after drawing (cold and continuous) are shown in Table 2 below.
• the Young's modulus is defined as being the secant modulus, equal to the ratio of a stress for a conventional deformation respectively 1, 5 or 10%.
• the Young's moduli are calculated from the toughness-elongation curves obtained on a unitary fiber using a Fafegraph marketed by the company Textechno.
• the diameters are measured using a Vibromat sold by the company Textechno.
• the measurement conditions are determined by ISO5079 standard.
• the distance between the jaws is 10 mm for the fibers before drawing and 20 mm after drawing in the solid state and continuously at a maximum drawing rate while avoiding the breaking of the fibers (continuous yarns at this stage).
• EXAMPLE 10 A cementitious product was manufactured by filtration, by a laboratory method reproducing fairly faithfully the main characteristics of the products obtained by industrial methods such as the Hatschek technique. Two cement compositions are prepared on the basis of the following cement matrix suspended with a large excess of water:
• a first cement reference composition is thus prepared with charged polypropylene fibers identical to the reference fiber of Example No. 1. These fibers are also manufactured in a similar manner to that of Example No. 1 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber.
• a second cement composition is thus prepared with charged polypropylene fibers identical to the fiber of Example No. 5. These fibers are also produced in a similar manner to that of Example No. 5 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber. The fibers are cut to 10 mm in length.
• the composition is filtered through a metal grid to form a unitary layer about 1 mm thick.
• Six unit layers are superimposed and subjected to a pressing cycle to obtain a material containing before setting about 50% water by weight relative to the weight of cement, and a thickness of about 6 mm.
• This laboratory material undergoes a cure of 6 days at 40 ° C. in a sealed bag, before being cut into a test tube 20 mm wide and longer than 260 mm, which test tubes are placed in cold water for 24 hours to be mechanically stressed in traction.
• the tensile tests were carried out by installing the test pieces between the jaws of a traction machine with a distance between jaws of 180 mm.
• the tensile test is carried out at a separation speed of 1.2 mm / min.
• the test pieces 10a correspond to the reference test pieces (with uncharged fibers).
• the test pieces 10b correspond to the test pieces according to the invention (with charged fibers).
• the force - displacement curve is plotted which has a typical appearance of the results observed with products obtained by the Hatschek technique. At the beginning of the displacement, the force increases rapidly, then there is a plateau where the force evolves slowly corresponding to the multifissuring of the test tube until the appearance of a macrocrack, after which the force drops by sliding effect during the opening of the macrocrack.
• the length of the multi-cracking plate reflects the strengthening effect of the plate by all of the fibers. It is observed in particular that the breaking force, defined as the force divided by the width of the test piece and presented in table 3, is particularly high for each test piece 10b and in addition is greater than the breaking force of the reference test pieces 10a.
• the level of calcium carbonate is increased to 60% or even 80% and conversely the rate of cement is greatly reduced. It is also possible to produce test pieces containing fibers identical to the fibers of Examples 2 to 4 or 6 to 9 in a similar manner.
• EXAMPLE 11 This example 11 illustrates the application of the fibers loaded according to the invention to the manufacture of a cementitious product by the Hatschek process. Aqueous suspensions are prepared on the basis of a matrix identical to that with charged fibers of Example 10. Each suspension is introduced into the tank of a Hatschek machine, for the formation of a film and winding on a d format cylinder '' a sheet of hydrated cementitious material about 1 mm thick.
• the charged polymer fibers according to the invention for example charged polypropylene fibers similar to the fibers of examples n ° 2 to n ° 9 or charged polymer fibers having a higher titer, can be used as technical yarns or high resistance monofilaments, to make seat belts, packaging, safety nets, fishing nets etc.
• the polypropylene fibers loaded according to the invention can be used to manufacture unidirectional fabrics or of the mat type further heat-compactable according to the methods described in the articles entitled: “The Hot Compaction behavior of woven oriented PP fibers and tapes. I. Mechanical properties ”, by PJ Hine et al.
• polypropylene fibers loaded according to the invention can 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 AZ reference” edited by J. Karger-Kocsis, published by Kluwer Académie Publisher, 1999.
• Polypropylene fibers loaded according to the invention can also be used to manufacture thermoformed all polypropylene (PP) composites, filament windings of PP yarns, all PP sandwich panels composed of fabric or mat surfaces made of PP fibers and at the heart of PP honeycomb or PP foam.
• PP polypropylene
• the polypropylene fibers loaded according to the invention can also be used to manufacture: - bundles of impregnated yarns according to the method described in "Technical impregnation for fiber bundles or tow" by A. Lutz et al.
• the charged polymer fiber according to the invention can also be a fiber obtained by a continuous drawing process in one step (without recovery).
• the charged polymeric fiber according to the invention can also be a fiber obtained by spinning a polymeric composition without prior premixing.
• the polymeric fiber loaded according to the invention can also be a fiber obtained by solvent spinning (spining gel or wet spinning in English) from a polymer dissolved, from polymer precursors.
• solvent spinning spining gel or wet spinning in English
• the charged polymeric fiber according to the invention can equally well be a fiber obtained from a charged fibrous ribbon.

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• 2004
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• 2005
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