Classifications

• • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/1025—Coating to obtain fibres used for reinforcing cement-based products
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/465—Coatings containing composite materials
  • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
• • 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
• • 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
  • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Definitions

• the present invention relates to glass threads coated with a size containing nanoparticles, in particular clay, boehmite or silica, intended for reinforcing organic and / or inorganic materials.
• the reinforcing glass threads are produced by mechanical drawing of molten glass threads flowing from the multiple orifices of a die filled with molten glass, by gravity under the effect of the hydrostatic pressure linked to the height of the liquid, to form filaments which are gathered in base son, which son are then collected on a suitable support.
• the glass filaments are coated with a sizing composition, generally aqueous, by passing on a sizing member.
• the role of the sizing is essential in many ways. During the manufacture of the yarns, it protects the filaments from the abrasion resulting from the friction of the latter, at high speed, on the drawing and winding members of the thread by acting as a lubricant. The size also gives cohesion to the wire by ensuring the connection of the filaments between them. Finally, it makes the wire sufficiently integrated to withstand the rewinding operations necessary to form including rovings "assembled" from several basic son, and also eliminates electrostatic charges generated during these operations.
• the size improves the impregnation of the yarn by the matrix to be reinforced and promotes adhesion between the glass and said matrix, thus leading to composite materials with improved mechanical properties.
• the sizing protects the wires from chemical and environmental aggressions, which contributes to increasing their durability. In applications requiring cutting the thread, the size allows to avoid the bursting and the release of the filaments, and it participates with the surensimage to disperse the electrostatic charges generated during cutting.
• the glass threads in their various forms are commonly used to effectively reinforce dies of various kinds, for example thermoplastic or thermosetting organic materials, and inorganic materials, for example cement.
• the present invention aims to improve the abrasion resistance of glass son coated with a sizing, in particular to allow them to be woven in better conditions.
• Another object of the invention is to improve the resistance to aging in wet medium of glass son coated with a size to be incorporated as reinforcing elements of polymeric materials, in particular thermoplastic or thermosetting, and / or inorganic materials.
• the subject of the invention is glass threads coated with a sizing composition, in particular obtained from a dispersion and / or a suspension and / or an aqueous emulsion, which comprises (in % in weight) :
• nanoparticles means particles of matter formed from a cluster of atoms or molecules, which have one or more dimensions that can vary between 1 and 100 nanometers, preferably between 1 and 50 nanometers.
• the shape of these particles can vary to a very large extent and for example have the appearance of a sphere, a tube, a needle ("whisker" in English), a shell or a plate .
• “son” means basic son from the gathering of a multitude of filaments, and products derived from these son, including the assemblies of these basic son in rovings. Such assemblies can be obtained by unwinding simultaneously several windings of basic son, and then gathering them in locks which are wound on a rotating support. It can also be “direct” rovings of the same title (or linear density) equivalent to that of assembled rovings, obtained by the gathering of filaments directly under the die and the winding on a rotating support.
• aqueous sizing composition means a composition capable of being deposited on the filaments being drawn and which is in the form of a suspension or a dispersion comprising at least 70 % by weight of water, preferably 75% and possibly containing up to 10% by weight, preferably up to 5% of one or more essentially organic solvents which can help to solubilize certain constituents of the composition of sizing.
• the composition does not contain any organic solvent, in particular to limit volatile organic compound (VOC) emissions into the atmosphere.
• the film-forming agent according to the invention has several roles: it confers the mechanical cohesion of the coating by adhering the nanoparticles to the glass filaments and ensuring the binding of these nanoparticles together, where appropriate with the material to be reinforced; it helps to bind the filaments to each other; lastly, it participates in the protection of wires against mechanical damage and chemical and environmental aggressions.
• the film-forming agent is a polymer chosen from vinyl polyacetates (homopolymers or copolymers, for example copolymers of vinyl acetate and ethylene), polyesters, epoxies, polyacrylics (homopolymers or copolymers), polyurethanes, polyamides (homopolymers or copolymers, for example polyamide-polystyrene or polyamide-polyoxyethylene block copolymers), cellulosic polymers and mixtures of these compounds. Vinyl polyacetates, epoxies, mixtures containing at least one epoxy and at least one polyester, and polyurethanes are preferred.
• the amount of film forming agent is 50 to 90% by weight of the sizing composition.
• the coupling agent makes it possible to ensure that the size is adhered to the surface of the glass.
• the coupling agent is chosen from hydrolysable compounds, especially in the presence of an acid such as acetic, lactic or citric acid, which belong to the group consisting of silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, poly (oxyethylene / oxypropylene) trimethoxysilane, gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane, phenylaminopropyltrimethoxysilane or styrylaminoethylaminopropyltrimethoxysilane, siloxanes, titanates, zirconates and mixtures of these compounds.
• the silanes are selected.
• the amount of coupling agent is from 5 to 18% by weight of the sizing composition.
• Nanoparticles are essential for sizing. Indeed, the incorporation of nanoparticles in the sizing has proved very interesting to reduce the effects of abrasion both in the manufacture of yarn, where the constituent filaments of the yarn scroll at high speed over a multitude of the organs used to guide and collect them, as its transformation, especially by weaving, where the wire must be able to withstand significant tension and friction.
• nanoparticles Another advantage of nanoparticles is the contribution to the barrier effect to water and gases. Indeed, nanoparticles are obstacles that oppose the rapid penetration of water and gases by creating winding paths of diffusion towards the glass which is thus better protected. The degree of protection varies depending on the amount and shape of the nanoparticles in the size.
• the nanoparticles having a high aspect ratio ratio of the largest dimension to the smallest dimension
• the nanoparticles having a high aspect ratio ratio of the largest dimension to the smallest dimension
• the substantially spherical nanoparticles such as beads may also be chosen.
• the nanoparticles according to the invention are composed of a mineral material, namely that they contain more than 30% by weight of such a material, preferably more than 40%, and advantageously more than 45%.
• the nanoparticles are based on clay, boehmite or silica.
• clay is here to be considered in its general definition accepted by those skilled in the art, namely that it defines hydrated aluminosilicates of general formula AI 2 O 3 .SiO 2 .xH 2 O, where x is the degree hydration.
• a clay consists of aluminosilicate sheets having a thickness of a few nanometers connected to each other by hydrogen or ionic bonds between the hydroxide groups present on the layers and the water and / or the cations present between said layers. .
• phyllosilicates of the mica type such as smectites, montmorillonite, hectorite, bentonites, nontronite, beidellite, volonskoite, saponite, sauconite, magadiite, vermiculite, mica, kenyaite and synthetic hectorites.
• the clay is chosen from phyllosilicates of type 2: 1, advantageously smectites.
• the most preferred clay is montmorillonite.
• the clay may be a calcined clay, for example having undergone heat treatment at a temperature of at least 750 ° C.
• the clay may also be a modified clay, for example by cation exchange in the presence of a solution of an ammonium, phosphonium, pyridinium or imidazolium salt, preferably an ammonium salt.
• the clay nanoparticles are generally in the form of platelets having a thickness of a few nanometers and a length of up to 1 micrometer, generally less than 100 nanometers, these platelets can be individualized or aggregated.
• the clay nanoparticles can be obtained by subjecting a clay, possibly calcined and / or modified as mentioned above, to the action of at least one blowing agent whose role is to remove the leaves of clay.
• the blowing agent may be tetrahydrofuran or an alcohol such as ethanol, isopropanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol and polyethylene glycols, especially of molecular weight less than 1200.
• the term "boehmite” refers to alumina monohydrates.
• boehmite is a synthetic boehmite obtained by hydrothermal reaction from aluminum hydroxide.
• the boehmite nanoparticles may be in the form of beads, needles, elipsoids or platelets, the latter form being preferred.
• the silica is preferably amorphous.
• the silica particles are preferably in the form of beads.
• the beads have a diameter of between 5 and 35 nm, and preferably an average diameter of the order of 15 to 20 nm.
• the nanoparticles are treated with an agent which contributes to slowing down the diffusion of water and gases and thus makes it possible to increase the resistance to aging of the wire in a humid medium.
• an agent which contributes to slowing down the diffusion of water and gases and thus makes it possible to increase the resistance to aging of the wire in a humid medium.
• such an agent is hydrophobic.
• the nanoparticles can be reacted with a compound of formula R a XY 4-a in the presence of water and an acid, in which: R represents a hydrogen atom or a hydrocarbon radical containing 1 to 40 carbon atoms, said radical being linear, branched or cyclic, saturated or unsaturated, which may contain one or more heteroatoms O or N or may be substituted by one or more amino, carboxylic acid, epoxy or amido groups, and the R groups being identical or different
• X represents Si, Zr or Ti Y is a hydrolyzable group such as an alkoxy containing 1 to 12 carbon atoms, optionally containing one or more heteroatoms O or N, or a halogen, preferably Cl, a is equal to 1, 2 or 3.
• the compound corresponding to the above formula is an organosilane, advantageously an organosilane containing two or three alkoxy groups.
• gamma-aminopropyltrimethoxysilane gamma-aminopropyltriethoxysilane
• N-phenyl-gamma-aminopropyltrimethoxysilane N-styrylaminoethyl-gamma-aminopropyltrimethoxysilane
• gamma-glycidoxypropyltrimethoxysilane gamma-methacryloxypropyltrimethoxysilane.
• gamma acryloxypropyltrimethoxysilane vinyltrimethoxysilane, vinyltriethoxysilane, terbutylcarbamoylpropyltrimethoxysilane and gamma (polyalkyleneoxide) propyltrimethoxysilanes.
• gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-styrylaminoethyl-gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane are selected.
• the grafting agent is added in an amount representing 15 to 75% by weight of the starting nanoparticles, preferably 30 to 70%.
• the level of nanoparticles in the sizing composition preferably varies from 2.5 to 15%, and advantageously from 4 to 14%.
• one or more other constituents may be present.
• the size may comprise a dispersing agent which aids in the dispersion of the nanoparticles and promotes the compatibility between the other constituents and the water.
• the dispersing agent may be chosen from:> organic compounds, in particular - optionally halogenated polyalkoxylated, aliphatic or aromatic compounds, such as ethoxylated / propoxylated alkyphenols, preferably containing 1 to 30 ethylene oxide groups and 0 to 15 propylene oxide groups, ethoxylated / propoxylated bisphenols, preferably containing 1 to 40 ethylene oxide groups and 0 to 20 propylene, ethoxylated / propoxylated fatty alcohols, preferably having an alkyl chain of 8 to 20 carbon atoms and containing 2 to 50 ethylene oxide groups and up to 20 propylene oxide groups.
• organic compounds in particular - optionally halogenated polyalkoxylated, aliphatic or aromatic compounds, such as ethoxylated / propoxylated alkyphenols, preferably containing 1 to 30 ethylene oxide groups and 0 to 15 propylene oxide groups, ethoxylated / propoxylated bisphenols
• polyalkoxylated compounds may be block or random copolymers, polyalkoxylated fatty acid esters, for example polyethylene glycol, preferably having an alkyl chain comprising 8 to 20 carbon atoms and containing 2 to 50 ethylene oxide groups and to 20 propylene oxide groups,
• the amine compounds for example the optionally alkoxylated amines, amine oxides, alkylamides, succinates and taurates of sodium, potassium or ammonium, the derivatives of sugars, in particular sorbitan, the alkyl sulphates, optionally alkoxylated; alkyl phosphates and ether phosphates of sodium, potassium or ammonium, optionally alkylated or alkoxylated.
• Inorganic compounds for example derivatives of silica, these compounds may be used alone or in admixture with the aforementioned organic compounds.
• cationic or nonionic surfactants In order to avoid problems of stability of the sizing composition and inhomogeneous dispersion of the nanoparticles, it is preferred to use cationic or nonionic surfactants.
• the amount of dispersing agent represents 0.01 to 60% of the weight of the nanoparticles, preferably 0.25 to 50%.
• viscosity regulating agent which makes it possible to adjust the viscosity of the composition to the conditions of application on the filaments, which viscosity is in general between 5 and 80 mPa.s, preferably at least equal to 7 mPa. .s.
• This agent also makes it possible to adapt the viscosity of the dispersions of nanoparticles in order to allow their treatment under conditions of high shear to improve their state of exfoliation as explained later in the text.
• the viscosity regulating agent is chosen from polyvinylalcohols, polyvinylpyrrolidones, hydroxymethylcelluloses, carboxymethylcelluloses and polyethylene glycols.
• the amount of regulating agent in the size is preferably between 0.5 and 25%, and preferably between 1, 5 and 18%.
• the size may further include:
• a lubricating agent for example a mineral oil, a fatty acid ester such as isopropyl palmitate or butyl stearate, an alkylamine or a polyethylene wax,
• a complexing agent such as a derivative of EDTA, gallic acid or phosphonic acid, and
• an antifoaming agent such as a silicone, a polyol or a vegetable oil.
• an antifoaming agent such as a silicone, a polyol or a vegetable oil.
• All of the compounds mentioned above are used to obtain glass threads that can be easily manufactured, can be used as reinforcements, can be incorporated without problem with the resin during the manufacture of the composites and, moreover, have a resistance. high abrasion and aging in a humid environment.
• the amount of sizing represents 0.2 to 5% of the weight of the final wire, preferably 0.35 to 3%.
• the sized yarn according to the invention may be glass of any kind, for example E, C, R, AR and reduced boron level (less than 6%). E and AR glasses are preferred.
• the diameter of the glass filaments constituting the wires may vary to a large extent, for example 5 to 30 ⁇ m. In the same way, wide variations can occur in the linear density of the yarn which can range from 11 to 4800 tex depending on the intended applications.
• the invention also relates to the sizing composition capable of being deposited on the glass filaments. It includes the constituents mentioned above and water.
• the aqueous sizing composition comprises (in% by weight):
• the amount of water to be used is determined so as to obtain a solids content (solids content) which varies from 2 to 35%, preferably from 2.5 to 25%, and more preferably from 3 to 15%.
• the preparation of the sizing composition is carried out as follows: a) a dispersion D of the nanoparticles is produced in water, preferably in the presence of a dispersing agent, b) the other components of the sizing, namely the film-forming agent, the coupling agent and the optional constituents mentioned above, in water to form an emulsion E, and c) the dispersion D and the emulsion E are mixed.
• steps a) and c) are carried out with sufficient agitation to prevent the sedimentation of the nanoparticles.
• the dispersion of nanoparticles based on a sheet material such as clay or boehmite can be obtained in various ways, all with the aim of increasing the level of exfoliation of the material.
• the nanoparticles are introduced into water containing a dispersing agent and the mixture is treated under conditions of high shear, for example in an Ultraturrax ® device, and / or is subjected to the action of ultrasound.
• a good dispersion of the nanoparticles is obtained by treating the mixture in an Ultraturax ® at a speed of 3000 to 10000 rpm for 5 to 30 minutes or by ultrasound at a power of 200 W and a frequency of 20 kHz for 15 to 120 minutes.
• a polymeric agent chosen from the above-mentioned film-forming agents is added to the mixture.
• a viscosity regulating agent is introduced into the mixture before the treatment, particularly when shearing the nanoparticles.
• the nanoparticles are mixed with granules of a thermoplastic polymer such as a polyvinyl acetate, a polyamide and a polyurethane, or thermosetting such as an epoxy, phenolic or acrylic resin, and a polyurethane, and the mixture is introduced into an extruder.
• the extrudates are then put in emulsion in a substantially aqueous medium under conditions known to those skilled in the art.
• This embodiment also applies to nanoparticles in the form of silica beads, the preferred resin being in this case an epoxy or acrylic resin.
• the aqueous sizing composition is deposited on the filaments before their gathering into base yarn (s). Water is usually removed by drying the wires after collection.
• the subject of the invention is also a composite material combining at least one organic and / or inorganic material and reinforcing threads, said threads being made up of all or part of glass threads coated with the previously described sizing composition.
• the organic material may be one or more thermoplastic or thermosetting polymers, and the inorganic material may be, for example, a cementitious material.
• the level of glass within the composite material is generally between 5 and 60% by weight.
• the properties of the wire and the composites are evaluated under the following conditions: the loss on ignition of the sized glass wire is measured under the conditions of the ISO 1887 standard. It is given in%.
• the resistance to abrasion of the yarn is evaluated by measuring the amount of flock (in the form of fibrils) formed by passing 1 kg of yarn (300 tex) from a cake or 3 kg of yarn spun from roving or assembled roving (1600 tex) on a bunch consisting of a series of 4 or 6 bars at a speed of 200 m / min.
• the amount of flock is expressed in mg / 100 g of yarn.
• the tenacity of the yarn is evaluated by measuring the tensile breaking force under the conditions of ISO 3341. It is expressed in N / tex.
• the ability of the yarn to be impregnated with a resin is measured under the following conditions: 40 m wire is cut into pieces of 30 cm long that the parallel is placed on a sheet of Mylar ®, is deposited 20 g a resin consisting of 100 parts by weight of epoxy resin (PRIME ® 20 LV marketed by SP SYSTEMES) and 25 parts by weight of hardener (PRIME ® SLOW HARDENER marketed by SP SYSTEMES), is deposited on top of a sheet of Mylar ® and the whole is compressed by means of a roller. The resulting plate is heated at 105 ° C for 2 hours.
• the stress at break of the yarn is measured after a wet aging treatment in a chamber saturated with water vapor at 80 ° C.
• the tensile stress at 3-point bending in the transverse direction is measured and the stress is calculated for a glass content equal to 100%.
• the constraints are expressed in MPa.
• the stress applied to the test pieces is equal to 700 MPa.
• silylated polyazamide sold under the reference "SILQUEST ® A-1387” by GE Silicones; solids content: 50%.
• clay montmorillonite modified by ion exchange with a quaternary ammonium, marketed under the reference "Dellite ® 67G” by the company LAVIOSA CHIMICA MINERARIA; solid content:
• clay montmorillonite
• Dellite ® HPS clay (montmorillonite), marketed under the reference “Dellite ® HPS” by the company LAVIOSA CHIMICA MINERARIA; solid content: 100%
• Boehmite A modified with an aminosilane (marketed under the reference “SILQUEST A-1100” by GE SILICONES); 1% of the weight of the nanoparticles; solid content: 100%
• Boehmite B modified with an aminosilane (sold under the reference "SILQUEST A-1100" by the company GE SILICONES); 2
• Boehmite C modified with a methacryloxysilane (marketed under the reference “SILQUEST A-174" by the company GE SILICONES); 1% of the weight of the nanoparticles; solid content: 100%
• the sizing compositions contain the raw materials listed in Table 1 (in% by weight).
• the dispersion D is prepared under the following conditions: stirring until homogenization (Example 1)
• Example 7 the clay particles are brought into contact with 1,4-butanediol for 3 hours before being dispersed under the above conditions.
• the sizing compositions are deposited on glass filaments E 13 ⁇ m in diameter before their assembly into a single wire which is wound into a cake.
• Example 1 The characteristics of the yarn obtained are given in Table 1.
• the sizing of Example 1 is adapted to the production of SMC where the quantity of fluff is an important criterion for the implementation of the product.
• the yarns of Examples 2 to 7 according to the invention have a better abrasion resistance given by a much smaller amount of flock.
• the resistance to abrasion depends on the amount of nanoparticles in the size: the yarns of Examples 2 and 3 have a smaller amount of fluff than Examples 4 to 7. TABLE 1
• the sizing compositions contain the raw materials listed in Table 2 (in% by weight relative to the total volume).
• Dispersion D is treated under the following conditions:
• the sizing compositions are deposited on glass filaments E 16 ⁇ m in diameter before their assembly into 4 threads of linear density of 100 tex rolled into a cake on a single support.
• the yarns are then extracted from 4 cakes and gathered into a single yarn (1600 tex) which is wound in the form of a roving.
• the sizing compositions contain the raw materials listed in Table 3 (in% by weight relative to the total volume).
• Dispersion D is treated under the following conditions: - mechanical stirring for 1 hour and then treatment Ultraturrax ® at 5000 rpm for 5 minutes (Examples 11 to 13)
• the sizing compositions are deposited on glass filaments E 13 ⁇ m in diameter before their assembly into a single wire which is wound into a cake.
• the glass yarns of Examples 11 to 15 according to the invention have excellent abrasion resistance compared to the reference yarns.
• the tenacity of the yarns of Examples 11 to 15 is equivalent to that of the yarns of Comparative Examples 16 and 17.
• the observed variations in toughness are related to changes in yarn integrity by nanoparticles.
• the sizing compositions contain the raw materials listed in Table 4 (in% by weight relative to the total volume).
• the dispersion D is prepared under the following conditions:
• the sizing compositions are deposited on glass filaments E 13 ⁇ m in diameter before their assembly into a single wire which is wound into a cake.
• the introduction of the nanoparticles into the sizing composition does not degrade the performance of the yarn: the tenacity is equivalent to the reference thread of Example 18 and the abrasion resistance, although higher for Examples 20 and 21, is acceptable.
• Example 19 shows a gain of 114% in the maximum number of cycles and 57% in the average number of cycles before the rupture of the test piece.
• the sizing compositions are deposited on glass filaments E 13 ⁇ m in diameter before their assembly into a single wire which is wound into a cake.
• the abrasion resistance of the yarns of Examples 23 to 25 as measured by the amount of flock formed is much greater than that of Example 22 in comparison with equivalent toughness.
• the breaking stress of these yarns is of the same order of magnitude as the comparative example 22 in the initial state and improved after 14 days of aging (gain of 11 to 72.7%).

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