Classifications

• • 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
  • C03C25/103—Organic coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
  • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
  • B29B15/10—Coating or impregnating independently of the moulding or shaping step
  • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
  • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
  • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
  • B29C70/521—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
• • 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
  • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/323—Polyesters, e.g. alkyd resins
• • 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
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/36—Epoxy resins
• • 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
  • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B18/02—Agglomerated materials, e.g. artificial aggregates
  • C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
• • 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
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/0048—Fibrous materials
  • C04B20/0068—Composite fibres, e.g. fibres with a core and sheath of different material
• • 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
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • 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
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
  • C04B2103/0077—Packaging material remaining in the mixture after the mixing step, e.g. soluble bags containing active ingredients
• • 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/34—Non-shrinking or non-cracking materials

Definitions

• TITLE USE OF GLASS-RESIN COMPOSITE FIBERS FOR CONCRETE REINFORCEMENT
• the present invention relates to glass-resin composite fibers for reinforcing concrete.
• Concrete is arguably the most widely used building material today due to its high compressive strength, durability, longevity, and resilience. Its properties make it a material of choice, particularly in the fields of building, roads and engineering structures.
• Concrete is mainly composed of aggregates held together by a binder, most often Portland cement.
• a binder most often Portland cement.
• additives such as ultrafine particles (silica fume for example), superplasticizers also called water reducers or metallic, synthetic or mineral fibres.
• mechanical fibers have the disadvantage of being sensitive to corrosion, which can be detrimental to the longevity of concrete comprising such fibers. Moreover, it has densities often greater than 7.7 and are therefore not distributed evenly in concrete with a lower density (the metal fibers tend to sink under the effect of gravity). To solve this problem it has been proposed to replace the metal fibers with synthetic fibers.
• the mechanical strength (Elastic Modulus (of Young), tensile strength for example) of these fibers is not as good as that of metal fibers.
• their operating temperature between 100°C and 160°C generally
• is much lower than that of metal fibers between 600°C and 900°C approximately), which may limit their use for certain applications.
• the Applicant has also observed numerous advantages procured by the fibers according to the invention. Their implementation is very easy compared to the fibers for concrete of the prior art, in particular during the phase of mixing the various components of the concrete (easily dispersible), but also during the phase of drying of the concrete: due to their density close to that of concrete, the fibers remain evenly distributed in the concrete (they do not tend to sink like metal fibers denser than concrete, nor to rise like synthetic fibers less dense than concrete) .
• the fibers of the invention also have a much higher maximum use temperature than the synthetic fibers currently used.
• the white color of the fibers according to the invention allows them to be used in light concretes without impacting the aesthetics of these concretes. .
• the use of the fibers according to the invention makes it possible to greatly reduce the overall CO2 emissions compared to the use of other fibers of the prior art, with a constant level of reinforcement.
• the subject of the invention is a single strand of glass-resin composite comprising glass filaments embedded in a crosslinked resin, the single strand having a length within a range ranging from 5 to 85 mm, a diameter ranging from 0.2 to 1.3 mm, and a breaking stress greater than 1,050 MPa.
• a glass-resin composite single strand comprising glass filaments embedded in a crosslinked resin, the single strand having a length within a range ranging from 5 to 85 mm, a diameter ranging from 0.2 to 1, 3 mm, and an initial modulus in extension, measured at 23°C, greater than 35 GPa.
• the invention also relates to a ballotin comprising a plurality of these single strands, the use of these single strands or of this ballotin for the reinforcement of concrete, a concrete comprising these single strands, as well as a method of manufacturing these single strands.
• composition based on means a composition comprising the mixture and/or the in situ reaction product of the various constituents used, some of these constituents being able to react and/or being intended to react with one another, less partially, during the various phases of manufacture of the composition; the composition thus possibly being in the totally or partially crosslinked state or in the non-crosslinked state.
• any interval of values denoted by the expression “between a and b” represents the domain of values going from more than a to less than b (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” signifies the range of values going from a to b (that is to say including the strict limits a and b).
• the interval represented by the expression “between a and b” is also and preferably designated. All the glass transition temperature “Tg” values described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to standard ASTM D3418 (1999).
• FIG. 1 represents a diagram of the single-strand synthesis process according to the invention before the latter is cut to a determined length.
• FIG. 2 Figure 2, not shown to scale to facilitate understanding, is a drawing showing a cross section of the single strand according to the invention.
• the invention therefore relates to a single strand (or fiber, the two terms being able to be used in an equivalent manner) made of glass-resin composite (abbreviated "CVR") comprising glass filaments embedded in a crosslinked resin, characterized in that the single strand has a length within a range ranging from 5 to 85 mm, a diameter ranging from 0.2 to 1.3 mm, and a breaking stress greater than 1050 MPa and/or an initial modulus in extension, measured at 23°C , greater than 35 GPa.
• CVR glass-resin composite
• the glass filaments are present in the form of a single multifilament fiber or several multifilament fibers associated with each other.
• the multifilament fibers are preferably essentially unidirectional.
• Each of the multifilament fibers may comprise several tens, hundreds or even thousands of individual glass filaments. These very fine individual filaments generally and preferably have an average diameter of the order of 5 to 30 ⁇ m, more preferably of 10 to 20 ⁇ m.
• the section of the individual filaments is preferably cylindrical.
• glass fiber that can be used in the context of the present invention, mention may be made of the “R25H” or “SE 1200” fibers from the company Owens Corning.
• resin is meant here the resin as such and any composition based on this resin and comprising at least one additive (that is to say one or more additives).
• crosslinked resin it is understood of course that the resin is hardened (photocured and/or thermocured), in other words in the form of a network of three-dimensional bonds, in a state specific to so-called thermosetting polymers (as opposed to so-called thermoplastic polymers).
• the single strand CVR according to the invention comprises a plurality of individual glass filaments, preferably essentially parallel to each other, embedded in a hardened resin after crosslinking.
• the CVR single strand has a Cr breaking stress greater than 1050 MPa, preferably greater than or equal to 1100 MPa, more preferably greater than or equal to 1200 MPa.
• the single strand has a breaking stress of between 1050 and 1600 MPa, preferably of 1200 to 1500 MPa.
• the CVR single strand has an initial extension modulus (denoted E23), also called Young's Modulus, measured at 23° C., greater than 36 GPa, preferably greater than or equal to 40 GPa, preferably greater than or equal to 42 GPa, preferably greater than or equal to 48 GPa.
• E23 initial extension modulus
• the mechanical properties in extension of the single strand in CVR can also be measured in a known manner using an “INSTRON” tensile machine of the type 5944 (BLUEHILL® software UNIVERSAL supplied with the tensile machine), according to the ASTM D2343 standard, on glued (ready to use) CVR single strands.
• INHTRON tensile machine of the type 5944
• ASTM D2343 ASTM D2343 standard
• these single strands are subjected to prior conditioning (storage of the single strands for at least 24 hours in a standard atmosphere according to European standard DIN EN 20139 (temperature of 23 ⁇ 2°C; humidity of 50 ⁇ 5%)).
• the tensile modulus is determined by linear regression of the stress curve as a function of the strain, between 0.1% and 0.6% strain. This deformation is recorded by the MultiXtens 1995DA801 extensometer. The 260 mm specimens tested undergo traction at a nominal speed of 5 m/min, under a pre-test preload of 0.5 MPa (reference length 50 mm, distance between the jaws: 150 mm). All results given are an average of 10 measurements. Furthermore, the single-strand CVR in accordance with the invention advantageously has the following properties:
• the glass transition temperature (denoted Tg) of the resin is equal to or greater than 180° C., preferably equal to or greater than 190° C.;
• the glass transition temperature denoted Tg of the resin is preferably greater than 190°C, more preferably greater than 195°C, in particular greater than 200°C. It is measured in a known manner by DSC (Differential Scanning Calorimetry), on the second pass, for example and unless otherwise specified in the present application, according to standard ASTM D3418 of 1999 (DSC apparatus "822-2" from Mettler Toledo; atmosphere nitrogen; samples previously brought from room temperature (23°C) to 250°C (10°C/min), then rapidly cooled to 23°C, before final recording of the DSC curve from 23°C to 250 °C, according to a ramp of 10°C/min).
• the elongation at break noted Ar of the single strand in CVR, measured at 23° C., is preferably greater than 4.0%, more preferably greater than 4.2%, in particular greater than 4.4%.
• the E’190 modulus is preferably greater than 33 GPa, more preferably greater than
• the E'(Tg'-25)/E'23 ratio is advantageously greater than 0.85, preferably greater than 0.90, E' 23 and E'(T g '-25) being the real part of the complex modulus of the single strand measured by DMTA, respectively at 23°C and at a temperature expressed in °C equal to (Tg' - 25), an expression in which Tg' represents the glass transition temperature measured this time by DMTA.
• the ratio E'(Tg'-io)/E'23 is greater than 0.80, preferably greater than 0.85, E'(Tg'-io) being the real part of the complex modulus of the single strand measured by DMTA at a temperature expressed in °C equal to (Tg' - 10).
• E' and Tg' are carried out in a known manner by DMTA ("Dynamic Mechanical Thermal Analysis"), with a “DMA + 450" viscoanalyzer from ACOEM (France), using the "Dynatest 6.83 / 2010" software piloting tests bending, pulling or twisting.
• DMTA Dynamic Mechanical Thermal Analysis
• the three-point bending test does not allow in a known way to enter the initial geometric data for a single strand of circular section, one can only introduce the geometry of a rectangular (or square) section.
• a square section with side "a" having the same surface moment of inertia is therefore introduced into the software by convention, in order to work on the same stiffness R of the specimens.
• the specimen to be tested generally of circular section and of diameter D, has a length of 35 mm. It is arranged horizontally on two supports 24 mm apart. A repeated bending stress is applied perpendicular to the center of the specimen, halfway between the two supports, in the form of a vertical displacement of amplitude equal to 0.1 mm (therefore asymmetrical deformation, the interior of the specimen being only stressed in compression and not in extension), at a frequency of 10 Hz.
• the elastic deformation in compression under bending is greater than 3.0%, more preferably greater than 3.5%, in particular greater than 4.0%.
• the breaking stress in compression under bending is greater than 1050 MPa, more preferably greater than 1200 MPa, in particular greater than 1400 MPa.
• the breaking stress in pure compression is greater than 700 MPa, more preferably greater than 900 MPa, in particular greater than 1100 MPa.
• this quantity is measured according to the method described in the publication “Critical compressive stress for continuous fiber unidirectional composites” by Thompson et al, Journal of Composite Materials, 46(26), 3231-3245 .
• the CVR single strand has a porosity rate of less than 2%, preferably less than 1%, preferably less than 0.5%.
• the porosity rate of the CVR single strand is between 0% and 2%, preferably between 0.01% and 1%, preferably between 0.05% and 0.5%.
• the porosity rate can be measured by microscopy, for example by scanning electron microscopy, preferably using surface calculation software, such as Program FIJI. To perform the measurement, the following protocol is preferably carried out:
• a cold mounting resin of the epoxy type for example, for example in a vacuum coating device (CitoVac from the company Stuers for example),
• the single strand in coated CVR is cut, for example using a hydraulic guillotine, such as the "SH-5214" from the company Baileigh,
• the section of the single strand CVR is polished, for example using a mechanical polisher, from the company Mecapol for example, preferably to a final grain of 0.25 ⁇ m,
• a deposit of 1 to 4 nm of gold is made, for example using a gold metallizer, such as Cerssington of the 108 or 208 series from the company Elo ⁇ se,
• porosity of the CVR single strand means any gas (in particular air) or vacuum present within the CVR single strand.
• the degree of alignment of the glass filaments is such that more than 85% (% by number) of the filaments have an inclination with respect to the axis of the single strand which is less than 2.0 degrees, more preferably less than 1.5 degrees, this inclination (or misalignment) being measured as described in the above publication by Thompson et al.
• the CVR single strand according to the invention is not helically deformed, that is to say it is not twisted.
• the CVR single strand has a number of turns per meter of less than 5, preferably less than 2, preferably less than 0.5, preferably from 0 to 0.5.
• the weight content of glass fibers (that is to say filaments) in the CVR single strand is within a range ranging from 65% to 85%, preferably from 70% to 80%.
• This weight rate is calculated by taking the ratio of the titer of the initial glass fiber to the titer of the single strand in final CVR.
• the titer (or linear density) is determined on at least three samples, each corresponding to a length of 50 m, by weighing this length; the title is given in tex (weight in grams of 1000 m of product - as a reminder, 0.111 tex is equivalent to 1 denier).
• the crosslinked resin represents from 15% to 35%, preferably from 20% to 30%, by weight, of the CVR single strand of the invention.
• the density (or density in g/cm 3 ) of the CVR single strand is between 1.8 and 2.1. It is measured (at 23° C.) using a specialized scale from Mettler Toledo of the “PG503 DeltaRange” type; the samples, a few cm long, are successively weighed in air and immersed in ethanol; the device software then determines the average density over three measurements.
• the diameter D of the CVR single strand of the invention is preferably within a range ranging from 0.25 and 1.25 mm, more preferably between 0.3 and 1.2 mm, in particular between 0.4 and 1, 1mm.
• This definition covers both single strands of essentially cylindrical shape (with a circular cross section) and single strands of a different shape, for example single strands that are oblong (of more or less flattened shape) or with a rectangular cross section.
• D is by convention the so-called overall diameter, i.e. the diameter of the cylinder of imaginary revolution enveloping the single strand, in other words the diameter of the circumscribed circle surrounding its cross section.
• the length L of the CVR single strand of the invention is preferably within a range ranging from 10 to 80 mm, for example from 15 to 60 mm.
• the length/diameter L/D ratio of the CVR single strands of the invention is within a range ranging from 10 to 110, for example from 11 to 90, for example from 12 to 75, preferably from 15 to 65, preferably from 20 to less than 60.
• the resin used is by definition a crosslinkable (i.e., hardenable) resin capable of being crosslinked, hardened by any known method, in particular by UV (or UV-visible) radiation, preferably emitting in a spectrum ranging from at least 300 nm to 450 nm.
• a crosslinkable resin capable of being crosslinked, hardened by any known method, in particular by UV (or UV-visible) radiation, preferably emitting in a spectrum ranging from at least 300 nm to 450 nm.
• the crosslinked resin is based:
• crosslinkable resin chosen from the group consisting of vinyl ester resins (preferably vinyl ester urethane resins), epoxy, polyester and mixtures thereof,
• cross-linking system preferably comprising a photoinitiator reactive to UV above 300 nm.
• the resin composition When we speak of the "resin composition", it is the composition from which the resin is made, that is to say before crosslinking.
• polyester or vinyl ester resin is preferably used, more preferably a vinyl ester resin.
• polymers polyethylene glycol dimethacrylate resin
• vinyl ester resins are well known in the field of composite materials.
• the vinylester resin is preferably of the epoxyvinylester type. More preferably, a vinylester resin, in particular of the epoxy type, is used, which at least in part is based (that is to say grafted onto a structure of the type) novolac (also called phenoplast) and/or bisphenolic, or preferably a vinyl ester resin based on a novolac, bisphenolic, or novolac and bisphenolic.
• the initial tensile modulus of the resin measured at 23° C., is greater than 3.0 GPa, more preferably greater than 3.5 GPa.
• a novolak-based epoxy vinyl ester resin (part in brackets in formula I below) corresponds, for example, in a known manner, to formula (I) which follows:
• a bisphenol A-based epoxy vinyl ester resin (part in square brackets of formula (II) below) corresponds for example to the formula (the "A" reminding that the product is manufactured at
• a novolak and bisphenol type epoxy vinyl ester resin has shown excellent results.
• Epoxy vinyl esters are available from other manufacturers such as, for example, AOC (USA - “VIPEL” resins).
• the crosslinking system of the resin (resin composition) for impregnation comprises a photoinitiator sensitive (reactive) to UV above 300 nm, preferably between 300 and 450 nm.
• This photoinitiator is used at a preferential rate of 0.5 to 3%, more preferentially of 1 to 2.5%.
• the resin crosslinking system also comprises a crosslinking agent, for example at a rate of between 5% and 15% (% by weight of impregnating composition), the crosslinking agent being as defined above. -above.
• this photoinitiator is from the family of phosphine compounds, more preferably a bis(acyl)phosphine oxide such as for example bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Omnirad 819" from the company IGM or "speedcureBPO" from the company Lambson) or a mono(acyl)phosphine oxide (for example "Esacure TPO" from the company IGM), such phosphine compounds being able to be used as a mixture with other photo- initiators, for example photoinitiators of the alpha-hydroxy-ketone type such as for example dimethylhydroxy-acetophenone (e.g. "Omnirad 1173" from IGM) or 1-hydroxy-cyclohexyl-phenyl-ketone (e.g.
• a bis(acyl)phosphine oxide such as for example bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("
• the crosslinking agent is preferably chosen from the group consisting of the family of triacrylates.
• the single strand in CVR can be prepared according to the method described in application WO 2015/014579 followed by a step of cutting the single strand to a desired length.
• the present invention also relates to a process for manufacturing single strands of glass-resin composite comprising glass filaments embedded in a crosslinked resin comprising the following successive steps:
• impregnation resin a photo-crosslinkable resin composition, in the liquid state
• the polymerization is carried out in an irradiation chamber comprising a tube transparent to UV, called irradiation tube, through which the single strand being formed circulates, traversed by a current of inert gas, the speed (denoted Vir) passage of the single strand in the irradiation chamber being greater than 50 m/min, the duration of irradiation (denoted D ir ) of the single strand in the irradiation chamber being equal to or greater than 1.5 seconds.
• irradiation tube a tube transparent to UV
• the method can of course include a rolling step for storage of the single strand after it has passed through the UV irradiation chamber and before being cut.
• the so-called “calibration” die makes it possible, thanks to a cross section of determined dimensions, generally and preferably circular or rectangular, to adjust the proportion of resin in relation to the glass fibers while imposing on the impregnated the shape and l target thickness for the monofilament.
• the polymerization or UV irradiation chamber then has the function of polymerizing and cross-linking the resin under the action of UV.
• the UV irradiation chamber comprises one or preferably several UV irradiators, each consisting for example of a UV lamp with a wavelength of 200 to 600 nm.
• the final CVR single strand thus formed through the UV irradiation chamber, in which the resin is now in a solid state, is then collected, for example, on a take-up spool on which it can be rolled up over a very long length.
• the tensions undergone by the glass fibers at a moderate level, preferably between 0.2 and 2.0 cN/tex, more preferably between 0.3 and 1.5 cN/tex; to check this, it is possible, for example, to measure these voltages directly at the output of the irradiation chamber, using appropriate tensiometers well known to those skilled in the art.
• the method for manufacturing the CVR single strand of the invention comprises the following essential steps:
• V ir the speed (V ir ) of passage of the single strand in the irradiation chamber is greater than 50 m/min;
• the duration (D ir ) of passage of the single strand in the irradiation chamber is equal to or greater than 1.5 s and equal to or less than 10 s;
• the irradiation chamber comprises a tube transparent to UV (such as a quartz tube or preferably glass), said irradiation tube, through which circulates the single strand being formed, this tube being traversed by a stream of inert gas, preferably nitrogen.
• a tube transparent to UV such as a quartz tube or preferably glass
• said irradiation tube through which circulates the single strand being formed, this tube being traversed by a stream of inert gas, preferably nitrogen.
• V ir a high irradiation speed (greater than 50 m/min, preferably between 50 and 150 m/min) was favorable on the one hand to an excellent alignment rate of the filaments of glass inside the single strand in CVR, on the other hand to a better maintenance of the vacuum in the vacuum chamber with a markedly reduced risk of seeing a certain fraction of impregnation resin rise from the impregnation chamber towards the chamber empty, and therefore to a better quality of impregnation.
• the diameter of the irradiation tube (preferably glass) is preferably between 10 and 80 mm, more preferably between 20 and 60 mm.
• the speed V ir ⁇ is between 50 and 150 m/min, more preferably in a range of 60 to 120 m/min.
• the irradiation time D ir is between 1.5 and 10 s, more preferably in a range of 2 to 5 s.
• the irradiation chamber comprises a plurality of UV irradiators (or radiators), that is to say at least two (two or more than two) which are arranged in line around the irradiation tube.
• Each UV irradiator typically comprises one (at least one) UV lamp (preferably emitting in a spectrum from 200 to 600 nm) and a parabolic reflector at the focus of which is the center of the irradiation tube; it delivers a linear power preferably between 2,000 and 14,000 watts per meter.
• the irradiation chamber comprises at least three, in particular at least four UV irradiators in line.
• the linear power delivered by each UV irradiator is between 2,500 and 12,000 watts per meter, in particular within a range of 3,000 to 10,000 watts per meter.
• UV radiators suitable for the method of the invention are well known to those skilled in the art, for example those marketed by the company Dr. Hönle AG (Germany) under the reference “1055 LCP AM UK", equipped with “UVAPRINT” lamps. (iron doped high pressure mercury lamps).
• the nominal (maximum) power of each radiator of this type is equal to approximately 13,000 Watts, the power delivered actually being adjustable with a potentiometer between 30 and 100% of the nominal power.
• the temperature of the resin (resin composition), in the impregnation chamber is between 50°C and 95°C, more preferably between 60°C and 90°C.
• the irradiation conditions are adjusted such that the temperature of the CVR single strand, at the outlet of the impregnation chamber, is higher than the Tg of the crosslinked resin; more preferably, this temperature is higher than the Tg of the crosslinked resin and lower than 270°C.
• Another object of the invention is a single strand in CVR capable of being obtained by a process as described above, in particular a single strand in CVR capable of being obtained by a process comprising the following successive steps:
• impregnation resin a photo-crosslinkable resin composition, in the liquid state
• the speed (Vir) of passage of the single strand in the irradiation chamber is greater than 50 m/min;
• the duration (D ir -) of passage of the single strand in the irradiation chamber is equal to or greater than 1.5 s and equal to or less than 10 s;
• the irradiation chamber comprises a tube transparent to UV (such as a quartz or preferably glass tube), called the irradiation tube, through which the single strand being formed circulates, this tube being traversed by a stream of inert gas, preferably nitrogen,
• the CVR single strand preferably having a diameter ranging from 0.2 to 1.3 mm.
• FIG. 1 very simply schematizes an example of a device 10 allowing the production of CVR single strands in accordance with the invention.
• the reel is unwound continuously by driving, so as to produce a rectilinear arrangement 12 of these fibers 11b.
• This arrangement 12 then passes through a vacuum chamber 13 (connected to a vacuum pump, not shown), arranged between an inlet pipe 13a and an outlet pipe 13b leading to an impregnation chamber 14, the two pipes preferably rigid wall having for example a minimum section greater (typically twice as much) than the total section of fibers and a much greater length (typically 50 times more) than said minimum section.
• the arrangement 12 of fibers 11b passes through an impregnation chamber 14 comprising a supply reservoir 15 (connected to a metering pump not shown) and a reservoir of Impregnation 16 sealed completely filled with impregnating composition 17 based on a curable resin of the vinyl ester type (e.g., "ALTAC® E-Nova FW 2045" from AOC).
• an impregnation chamber 14 comprising a supply reservoir 15 (connected to a metering pump not shown) and a reservoir of Impregnation 16 sealed completely filled with impregnating composition 17 based on a curable resin of the vinyl ester type (e.g., "ALTAC® E-Nova FW 2045" from AOC).
• composition 17 further comprises (at a weight rate of 1 to 2%) a photoinitiator agent suitable for UV and/or UV-visible radiation with which the composition will be subsequently treated, for example bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Omnirad 819” from the company IGM). It may also comprise (for example approximately 5% to 15%) of a crosslinking agent such as, for example, tris(2-hydroxyethyl)isocyanurate triacrylate (“SR 368” from the company Sartomer). Of course, the impregnation composition 17 is in the liquid state.
• a photoinitiator agent suitable for UV and/or UV-visible radiation with which the composition will be subsequently treated for example bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Omnirad 819” from the company IGM). It may also comprise (for example approximately 5% to 15%) of a crosslinking agent such as, for example, tris(
• the length of the impregnation chamber is several meters, for example between 2 and 10 m, in particular between 3 and 5 m.
• an impregnated material which comprises for example (% by weight) from 65% to 75% of solid fibers 11b, the remainder ( 25 to 35%) being constituted by the liquid impregnation matrix 17.
• calibration means 19 comprising at least one calibration die 20 whose channel (not shown here), for example of circular, rectangular or even conical shape, is adapted to the particular conditions of production.
• this channel has a minimum cross-section of circular shape, the downstream orifice of which has a diameter slightly greater than that of the targeted monofilament.
• Said die has a length which is typically at least 100 times greater than the minimum dimension of the minimum section. Its function is to ensure high dimensional precision in the finished product, it can also play a role in dosing the fiber content with respect to the resin.
• the die 20 can be directly integrated into the impregnation chamber 14, which avoids, for example, the use of the outlet pipe 18.
• the length of the calibration zone is several centimeters, for example between 5 and 50 cm, in particular between 5 and 20 cm.
• a "liquid” composite monofilament 21 (liquid in the sense that its impregnating resin is always liquid) is obtained at this stage, the shape of the cross-section of which is preferably essentially circular.
• the liquid composite single strand 21 thus obtained is then polymerized by passing through a UV irradiation chamber (22) comprising a sealed glass tube (23) through which the single strand circulates. compound; said tube, the diameter of which is typically a few cm (for example 2 to 3 cm), is irradiated by a plurality (here, for example 4) of UV irradiators (24) in line ("UVAprint” lamps from the company Dr Hônle, of wavelength 200 to 600 nm) arranged at a short distance (a few cm) from the glass tube.
• UVAprint lamps from the company Dr Hônle, of wavelength 200 to 600 nm
• the length of the irradiation chamber is several meters, for example between 2 and 15 m, in particular between 3 and 10 m.
• the irradiation tube (23) in this example is traversed by a stream of nitrogen.
• the irradiation conditions are preferably adjusted in such a way that, at the outlet of the impregnation chamber, the temperature of the single strand in CVR, measured at the surface of the latter (for example using a thermocouple), is higher to the Tg of the crosslinked resin (in other words greater than 190°C), and more preferably less than 270°C.
• a finished composite block is finally obtained as shown very simply in FIG. 2, in the form of a continuous CVR single strand (25), of very great length, the individual glass filaments homogeneously throughout the volume of cured resin (252). Its diameter is for example equal to about 1 mm.
• the method of the invention can be implemented at high speed, greater than 50 m / min, preferably between 50 and 150 m / min, more preferably in a range of 60 to 120 m/min.
• the continuous CVR single strand (25) can be cut to a determined length (not shown in Figure 1), for example 45 mm by any means known to those skilled in the art, for example using a hydraulic guillotine , such as "SH-5214" from Baileigh.
• This step can be carried out directly at the exit from the irradiation chamber (23). It can also be made after being packaged on a final receiving reel (26).
• the invention also relates to a ballotin comprising a plurality of single strands made of CVR according to the invention and at least one element for holding the single strands together.
• this holding element is a breakable film, for example tearable, dispersible, water-soluble.
• the at least one holding element is a water-soluble thread.
• the holding element is a water-soluble film, preferably made of a material chosen from the group consisting of polyvinyl alcohols (PVA) or any water-soluble or bioplastic polymer, such as bioplastics derived from milk casein.
• PVA polyvinyl alcohols
• the at least one water-soluble film is made of a material chosen from the group consisting of polyvinyl alcohols.
• the ballotin according to the invention advantageously comprises a number of single strands comprised in a range ranging from 300 to 20,000.
• the single strands making up the ballotin can be of identical or different dimensions.
• a ballotin can comprise single strands of different length, diameter and/or length to diameter ratio.
• the ballotin comprises single strands according to the invention having lengths and diameters not having more than 10%, preferably not more than 3%, of difference with respect to each other.
• the single strands according to the invention are particularly useful as an additive for concrete.
• the invention also relates to the use of single strands in CVR according to the invention or of a ballotin according to the invention, to reinforce concrete and/or reduce the weight of the concrete and/or reduce or prevent cracking concrete.
• the present invention also relates to a concrete comprising a plurality of CVR single strands according to the invention.
• the concrete can be prepared using any technique well known to those skilled in the art.
• the volumetric content of the single strands according to the invention in the concrete according to the invention is comprised in a range ranging from 0.1% to 6%, for example from 0.1% to 1.5% for concretes called " conventional", for example of the BPS C40/50 XA3 type, or from 1.5% to 6% for ultra-high performance fiber-reinforced concrete (UHPFRC).
• the surfaces of the two facing heels have been glued as well as the reinforcement in order to limit the "dry zones” as much as possible (without adhesive).
• the beads were held in place for the curing time (12 h at 23° C.) in a template with the dimensions of the test specimens, with weights on the beads to ensure good bead/reinforcement contact.
• these single strands were subjected to prior conditioning (storage of the single strands for at least 24 hours in a standard atmosphere according to European standard DIN EN 20139 (temperature of 23 ⁇ 2° C.; humidity of 50 ⁇ 5%)).
• the tensile modulus was determined by linear regression of the stress versus strain curve, between 0.1% and 0.6% strain.
• Single strands (M1 to M4) in CVR were manufactured according to the process described previously with a mass percentage of glass/resin of 70/30.
• the resin composition used was based on vinylester resin (“ATLAC E-NOVA FW2045” from the company), a triacrylate hardener (“SR 368” from the company Sartomer) and a photoinitiator
• the glass fibers of the single strands M1 and M2 were “R25H” fibers from the company Owens Corning and that of the single strands M3 and M4 were “SE 1200” fibers from the company Owens Corning.
• the diameter and the tex of the single strands as well as their physical characteristics and the mechanical properties are presented in Table 2 below.
• the degree of porosity and the breaking stress of these single strands were compared with reinforcing fibers for concrete of the prior art. It has been observed that these fibers of the prior art systematically have a porosity rate greater than 2% and a breaking stress less than or equal to 1050 MPa. Due to their low level of porosity and their high breaking stress, the single strands of the invention make it possible to improve the resistance to cracking of concrete. It has thus been found that the single strands in accordance with the invention have a performance compromise between in particular the mechanical strength, the corrosion resistance, the processability (in particular the dispersibility during mixing, the processing temperature and the maintenance of homogeneity during the drying of the concrete).

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