WO2017201592A1 - Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé - Google Patents

Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé Download PDF

Info

Publication number
WO2017201592A1
WO2017201592A1 PCT/BR2017/050098 BR2017050098W WO2017201592A1 WO 2017201592 A1 WO2017201592 A1 WO 2017201592A1 BR 2017050098 W BR2017050098 W BR 2017050098W WO 2017201592 A1 WO2017201592 A1 WO 2017201592A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
fiber
composite
microfilaments
composition
Prior art date
Application number
PCT/BR2017/050098
Other languages
English (en)
Portuguese (pt)
Inventor
Luciano Fusco
Original Assignee
Luciano Fusco
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Luciano Fusco filed Critical Luciano Fusco
Priority to PCT/BR2017/050098 priority Critical patent/WO2017201592A1/fr
Publication of WO2017201592A1 publication Critical patent/WO2017201592A1/fr

Links

Images

Classifications

    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/16—Slip casting, i.e. applying a slip or slurry on a perforated or porous or absorbent surface with the liquid being drained away
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/20—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. moulding inserts or for coating articles
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/24—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least three directions forming a three dimensional structure
    • 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
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • 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
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration

Definitions

  • the present invention relates to a composite material formed liquid L is for a resin composition that has been reinforced with pre-cut glass individual filaments very short, as the method of their manufacture.
  • the liquid composite according to the invention is homogeneous, three-dimensional isotropic, developed in the field of chemistry, and produces parts with excellent mechanical properties and smooth surfaces.
  • the purpose of the present invention is to develop new technology that overcomes the problems of the prior art.
  • the object of this invention is to obtain a homogeneous FRP liquid composite (fiber reinforced plastic) able to simplify most traditional molding systems while producing parts stronger and smoother than normal wearers chopped-strands.
  • Another object of the present invention is to create a method for the manufacture of said plastic composite microfilament-reinforced liquid in the form of a resin fiberglass microfilament suspension.
  • Fiberglass is produced by a combination of extrusion and pultrusion from a plurality of individual filaments. In two successive operations, said filaments are first grouped and glued together to form strands, which are then regrouped and glued together to form multi-strand or roving strands , and wound to form the known coils.
  • the glue that binds the filaments is a component of sizing . While the glue that bundles filaments into strands is relatively firm, the glue that reassembles the strands to form the roving is weak and only sufficient for its coiling.
  • the individual filaments are bundled and firmly bonded directly forming, in a single operation, the strands of "roving" in the grouping dispensing strands.
  • the filaments are arranged in the form of "filament tape” , hereinafter referred to simply as “tape” .
  • the “tape” is cut to such short sizes that the “sizing” that glued the filaments now loses its binding function and they separate themselves from each other in the cut. This process is defined as the fiber "filament” .
  • the short filaments resulting from cutting the "tape” will hereinafter be referred to as “microfilament” or simply "MF".
  • the “tape” is as thin as possible, its width being a consequence, and its rigidity allows it to be pulled as well as pushed and allows its wrapping.
  • Unique “ribbon” strands make cutting easier and lower the cost of fiber manufacturing.
  • the number of filaments that can make up the “tape” depends on the equipment available.
  • the method of manufacturing the liquid composite comprises essentially two separate and independent phases:
  • the production of the MF according to the invention, where the "filament tape” maintains its integrity during cutting and allows it to be cut to very short and substantially constant and predetermined lengths are essential factors, and - MF compounding with resin composition and additives, where, while the production phase of MF is common for both thermoset and thermoplastic resins, compounding is different for each type of resins.
  • a method of manufacturing a homogeneous liquid composite formed of a thermosetting unsaturated resin composition and fiber MF comprises the steps of: - provide a mixing tank with a coupled mixing system, - provide a resin composition and place it in the mixing tank, providing and adding fiber MFs to the resin composition until the amount of fiber in the mixture reaches a predetermined fraction corresponding to a predetermined composite viscosity, where the fraction is the fiber content or% content related to the total weight of the fiber mixture. -resin.
  • thermosetting unsaturated resin liquid composite and the MF the mixing tank can be replaced by a pump extruder of the type used in thermoplastic injection where a twin-screw thread mixes the fiber MFs with the resin composition in the pump itself.
  • the invention further relates to a liquid composite made according to the method described.
  • the The composite material comprises MF obtained by cutting filaments, and said MF are homogeneously dispersed in the resin composition forming a material capable of being molded by systems that require fluidity, such as spray, injection, RTM, rolling-continuous, casting etc.
  • THE viscosity of the mixture should allow natural or any air that may have been introduced during compounding. Once the absence of air is verified, liquid thixotropic agents may be added to prevent sedimentation of the MPs if necessary.
  • Systems of compression molding like BMC / SMC, extrusion etc. may be made possible by intentionally increasing the viscosity incorporating fillers and additives into the liquid composite in a later operation.
  • the blend of the invention is intentionally planned. to be liquid and homogeneous, resembling a resin and not of a plastic mass, providing parts with excellent mechanical strength and smooth surfaces.
  • Fiber MFs are incorporated into the resin only by dispersion, eliminating the slow, complex and costly steps required in the conventional impregnation of the fiber, making the processes of simpler and economical molding.
  • the homogeneity of mixture is a of the essential factors of the technology of the invention. Beyond In addition, viscosity characteristics, appearance, homogeneity and compounding, resemble the composite to a gelcoat.
  • the MFs become become relatively “long” because of their new aspect ratio created by its smaller diameter compared to the diameter of the strands. Unlike what happens in the composites that use strands, MFs now allow all resin and fiber particles participate in the transfer of effort, including plurality of portions resin that in the prior art would form where the strands intersect and overlap each other, so no used or wasted, just like those filaments which in the prior art would be positioned at the core of the strands, being passive. All the filaments that there were on the strands, i.e. the outer ones that formed the shell and the located inside the core, now has direct contact with the resin and can work individually.
  • the new concepts of the invention raise the question of reinforce plastics in a new light and create a new culture in composites.
  • a way to take advantage of these concepts is a method capable of maintaining the viscosity of the mixture as low as necessary, enabling moldings that require fluidity.
  • Composite fluidity is achieved limiting, at the same time, the MF aspect ratio between 10 and 35, preferably between 15 and 20 and its length between 100 ⁇ m and 1200 ⁇ m, preferably between 250 ⁇ m and 700 ⁇ m.
  • the interdependence between aspect ratio, length and diameter of the MPs determines that the diameters of the filaments are in the range of 9 to 38 ⁇ m.
  • the small size of the FM according to the invention makes them fully, randomly and uniformly oriented in all directions of space, creating a three-dimensional or omnidirectional isotropy, as shown in [Fig. 6] .
  • the perfect three-dimensional isotropy of the mixture provides desirable properties for any type of part made from said mixture, particularly for structural, 3-D shape or complex shapes, or variable thickness, or ribbed, or requested in different planes and directions, or requested by a combination of efforts.
  • high mechanical strength can be obtained by orienting or positioning the MFs in a plane parallel to the stress plane as shown in [Fig. 5] . This can be achieved by thin layer stratification, eg by spraying, or by combining different molding systems such as spray, injection and casting, or by combining different sizes of MF.
  • a slender piece made merging MF with similar aspect ratios for example 250 ⁇ m x 16 ⁇ m and 1000 ⁇ m x 33 ⁇ m, can reconcile 3-D isotropy with good mechanical properties when the part is ordered in a plane. This type of combination provides synergistic effects. physical part performance and reduces resin demand to maintain certain viscosity or flow values.
  • composite layers sprayed into an open mold until desired thickness compatible with the curing system. Even with an open mold, both sides of the part will have their smooth and level surfaces.
  • the main factors of the liquid composite are the MF aspect ratio and fiber-resin interaction at the interface, with the fiber fraction being a consequence.
  • Your performance results in each case from the best compromise between aspect ratio, length and diameter of the MF. a certain aspect ratio, for example 15, can be obtained with different length / diameter ratios such as 500/33 or 250/16. While 4 16 ⁇ m MF weighs as much as 1 33 ⁇ m MF, they double the area of the fiber-resin interface, increasing the fiber-resin grip strength and mechanical strength. As the aspect ratio increases, the fraction of the fiber that mixture is able to admit decreases. The reaglomeration of the FM dramatically damages homogeneity, affecting the interface interaction and reducing the final properties of the composite.
  • the composite obtained by the method of the present invention creates new situations and concepts, with causes and effects that differ from those established in the prior art using any other known technology.
  • the homogeneity of the composite determines the true effectiveness of the fiber fraction, as a large fraction of the fiber can be elusive if the fiber is not fully utilized or only partially worked.
  • Cutting strands so short that they spontaneously break apart in MF revolutionizes the manufacture, nature and industrial scalability of the composite.
  • Each cut slice of a tape releases thousands of imperceptible MFs that result, when mixed with the resin, into small particulate solids suspended in a liquid.
  • the smallness of the MF allows, under certain conditions, to control and neutralize the action of the forces of molecular attraction, as well as the tendency of the MF to orient in the direction of composite flow in the molding of the pieces, allowing the complete dispersion of fiber in the resin. , and making the interaction at the fiber-resin interface as complete as that of a solution, with no apparent distinction between fiber and resin.
  • the versatility of the inventive blend simplifies most traditional molding systems known in the art, and allows you to produce parts with complex shapes, no size limit, industrial scale and low cost, short lead time tooling, requiring little labor. , eliminates fiber preforms (typical of RTM), and the parts produced require minimal finishing.
  • the use of MF eliminates one of the major causes of composite failure, such as stress concentration near the fiber tips.
  • MPs are produced by cutting cleanly and perpendicular to the filament length, and said fiber to be treated with a sizing that provides maximum interface grip fiber resin; cutting must be done by a system capable of maintain a substantially consistent length and to create a predetermined composition of constant and predetermined lengths of the MF does not produce down or glass dust, and does not damage the properties of the preserving the original characteristics provided by by the fiber manufacturer, including the properties of coupling with the resin at the interface. Contrary to what happens in the milling for the production of milled-fiber, where the grinding is so destructive that it crushes and deteriorates glass.
  • Ground fiber is a dubious percentage filaments with irregular aspect ratios and not controllable and large amount of impossible glass dust be eliminated in the sieving so that as the technicians know and the composites market confirms, not able to behave as reinforcement, but only as cargo, even if resilanized.
  • Particles are subject to attractive forces. especially when said particles have the shape and the nature of glass filaments, and when they should be dispersed in a low polarity medium like resin polyester.
  • the interaction energy consists of the forces of van der Waals-London attraction and the Coulombica interaction.
  • THE fiber filament increases the area of the interface which in turn increases free surface energy at the interface or interfacial tension and the attraction / mass ratio of each filament. The higher the interfacial tension, the more strong is the tendency of fibers to reduce the area of interface. The filaments thus tend to re-cluster and form flakes or lumps.
  • MFs should be considered as particles and, as regards intermolecular forces of attraction due to polarity and surface free energy, should be able to take advantage of technologies capable of inhibiting the tendency of particle agglomeration, including the following systems, which can be used. alone or together: - Addition of conventional polymeric liquid dispersants to the resin and / or fiber prior to mixing to disperse and stabilize the MFs in the resin, preventing their re-agglomeration, preferably by steric repulsion, and - Addition of solid nanoparticle dispersants including metal oxides such as SiO2, ZnO, TiO2, Al2O3 and CaCO3. They cover their surfaces by acting as spacers between the MFs avoiding flocculation and reaglomeration.
  • conventional polymeric liquid dispersants to the resin and / or fiber prior to mixing to disperse and stabilize the MFs in the resin, preventing their re-agglomeration, preferably by steric repulsion
  • solid nanoparticle dispersants including metal oxide
  • the coupling on the interface resin can be improved by improving factors such as surface treatment, temperature, dispersion, and time of fiber-resin contact.
  • silanes are applicable in filament surface
  • zirconates and titanates are added to the resin.
  • Neoalkoxy Zirconates and Titanates Act on the protons (H +) of the glass surface and not on hydroxyls (OH). They do not require a certain pH for the reaction and do not require water for the formation of silanol. Glass has at best 15% hydroxyls, but it has about 85% protons.
  • Organometallic react in points where silanes do not act and coordinate on protons without segmentation of molecular fragment.
  • the method for manufacturing the liquid composite comprises steps for: providing an auxiliary or intermediate tank (5) having coupled a mixer (9), preferably of the Cowles type, where thermosetting unsaturated resin (6), liquid additives (7) and solid additives (8) including nanoparticles are placed, and mixing until that the additives are completely dispersed and the composition (10) formed is homogeneous, - providing a mixing or compounding tank (11) having coupled a mixer (12), providing MF (3) with an aspect ratio of between 10 and 35, preferably between 15 and 20, and with a length of between 100 and 1200 ⁇ m, preferably between 250 and 700 ⁇ m, - transfer the resin composition (10) and additives into the compounding tank (11), adding the MFs (3) to the composition (10) in the tank (11) until the amount of fiber in the tank (11) reaches a predetermined fraction that corresponds to a predetermined viscosity, said viscosity being capable of allowing natural or spontaneous exit.
  • a mixer (9) preferably of the Cowles type, where thermosetting unsaturated resin
  • the mixing tank (11) is replaced by a twin-screw extruder pump, typically used in thermoplastic injection, adapted to to do, at room temperature and no injection pressure, the resin composition mixture (10) and the MF (3), forming the liquid composite (13).
  • FIG. 1a a setup for the production of MF in a materialization of the layout for the production of liquid composite
  • FIG. 1b - a setup for mixing or compounding in a layout materialization for composite production
  • FIG. 2a example alternative fiber cutting system
  • FIG. 2b - another alternative example of fiber cutting system
  • FIG. 3 - a chopped-strand and an MF comparing the aspect ratio between a chopped-strand and an MF
  • FIG. 4 - stress-strain distribution at the interface of a chopped-strand
  • FIG. 5 - two-dimensional setup of MF dispersed in resin composition
  • FIG. 6 Three-dimensional setup of MF dispersed in resin composition.
  • FIG. 1a] and [Fig. 1b] - show an example of layout for producing the liquid composite, comprising two main parts as follows:
  • FIG. 1a] shows a roller cutter (2) for producing MF (3) by pulling the tape (1) from the spool, typically formed by a cutter roller (2a) having cutting blades and a thrust or cot roller (2b). ), preferably made of hard plastic such as nylon, while (2c) is a guide.
  • MF (3) is collected in containers (4).
  • the cutting plane is substantially perpendicular to the fiber length.
  • FIG. 1b] shows a mixing or compounding setup.
  • liquid additives (7) and / or solid additives (8) in the form of nanoparticles are dispersed in the resin, forming the primary composition. (10) which is then transferred to the main mixing tank (11). MFs (3) are added to the resin composition (10) and dispersed slowly and completely through a mixer (12) without creating vortices that could include air until the liquid composite (13) is formed.
  • the tank 11 may be rotatable and function as a concrete mixer (not shown). Since the MPs are fully dispersed and the composite (13) is free of air, liquid thixotropic agents may be added in a final step to inhibit fiber sedimentation, if necessary. [Fig.
  • FIG. 2a shows an alternative cutter with a movable blade (14) driven by any mechanism (15) capable of converting circular to linear motion, eg, an eccentric, where the rigid tape (1) is pushed for cutting by the drive rollers (20). ) sliding on the guide (21) and is cut by the blade (14) which presses it against a thrust roller (16) or "cot”; the tape advance (1) is synchronized with the rotation of the cam (15).
  • the blade (14) is a carbide blade, eg, "widia” mounted on a blade holder (23) that slides into the guides (22). The parts not mentioned are the same as in [Fig. 1a] . [Fig.
  • FIG. 2b shows another type of cutting device where one or more movable blades (17) are mounted on a rotor or rotary guillotine (18) and cut the tape against a fixed blade (19).
  • the tape advance (1) is synchronized with the rotor rotation (18).
  • the parts not mentioned are the same as in [Fig. 1a] .
  • the advance system of Figs. 2a and 2b can be replaced by any feed system such as the known sewing machine feed mechanism (not shown) by pushing the fiber ribbon at regular intervals.
  • FIG. 3 When structural failures in composites occur because tensile forces elongate resin more than fibers, such failures occur precisely on the surface of the pull-out shell. It is important to note that the comparison of [Fig. 3] counteracts a 10 mm chopped-strand on one side against several thousand 0.5 mm MF on the other, where the external stress transferred to each type of fiber of [Fig. 3] is substantially proportional to their respective sizes.
  • FIG. 4] shows the stress - strain distribution at the resin - fiber interface of composites using normal chopped - strands. All external stress “Ee” is applied to the fiber through the resin at the resin-fiber interface. The stress on each fiber strand “Ef” is the result of the external force “Ee” applied to the resin.
  • FIG. 5 shows a typical two-dimensional configuration of the MF (3), randomly distributed and positioned on a plane parallel to the stress plane, providing the uniformity of properties in all directions of this plane.
  • FIG. 6 shows a typical three-dimensional setup of the MF (3), with their randomly distributed lengths oriented in the three directions, providing the uniformity of composite properties in all directions of space.
  • cutting the slender tape of the invention allows maintain a substantially constant length and default of the MF.
  • the systems of cutting of the invention do not produce fuzz and glass dust and do not alter the original characteristics provided by the fiber manufacturer, contrary to what occurs in known milling systems for milled-fiber production.
  • the MF according to the invention can be used to advantageously reinforce thermoplastic resins and produce a liquid composite using thermoplastic resins, where the liquid thermoplastic composite is liquid. at the melting temperature of the resin.
  • the method for reinforcing thermoplastic resins comprises a sequence of steps for: - providing a compounding tank with a heating system to bring virgin material to the melting point, a mixer, and a valve outlet, - provide a thermoplastic resin granulate composition and place it in the tank, - providing MF according to the invention, - heat the resin to melting temperature, adding said MF to the liquid thermoplastic resin until the amount of fiber in the composition reaches a predetermined fraction, - mix to form a homogeneous mixture, - open the tank outlet valve and pour the mixture into shapes or molds, preferably bars or ingots, by casting; - cool the compound to solidification, and - grind the bars or ingots to thermoplastic pellets or pellets, where thermoplastic pellets or pellets are pre-reinforced with microfilaments. These pellets are used by melting them again and shaping the pieces.
  • any other resin such as epoxy and fiber such as carbon which ensure high adhesion at the fiber-resin interface can be as well as any alternative additives for deaerate, wet, disperse, mate, like silanes, zirconates and titanates, mineral fillers, curing agents and thixotropic agents, method aids, and other cutting, mixing, dispersing and curing systems can be provided that they are compatible with the method and product of the invention. Even though it's harder and smaller uniformity in lengths, some types of cutters may in some cases produce MF by cutting roving normal.
  • the fiber used in microfilament production according to the invention is selected from a group consisting of of normal roving and a filament tape in which all the filaments that would make up a roving are firmly glued each other and arranged in ribbon form forming a single Rigid strand.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

La présente invention concerne un matériau composite liquide, homogène et isotrope tridimensionnel, formé d'une composition de résine pré-renforcée de microfilaments de fibre de verre, ainsi que son procédé de fabrication. Les microfilaments sont obtenus par coupe d'une fibre continue sous forme de bande rigide de filaments, et sont ajoutés à la composition de résine jusqu'à ce que la quantité de fibre dans le mélange atteigne une fraction prédéterminée correspondant à une viscosité prédéterminée. La faible viscosité du mélange doit permettre la sortie de tout l'air ayant pu être introduit pendant le mélangeage. Le mélange peut être moulé par des systèmes requérant une fluidité, notamment par pulvérisation, injection, stratification continue, coulée, etc. Tous les types de charges et d'additifs peuvent être additionnés au composite liquide en vue de permettre la mise en oeuvre de systèmes de compression tels que le BMC/SMC, l'extrusion, la pultrusion, etc.
PCT/BR2017/050098 2016-05-25 2017-04-25 Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé WO2017201592A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/BR2017/050098 WO2017201592A1 (fr) 2016-05-25 2017-04-25 Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPCTBR102016011927-8 2016-05-25
PCT/BR2017/050098 WO2017201592A1 (fr) 2016-05-25 2017-04-25 Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé

Publications (1)

Publication Number Publication Date
WO2017201592A1 true WO2017201592A1 (fr) 2017-11-30

Family

ID=60411103

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2017/050098 WO2017201592A1 (fr) 2016-05-25 2017-04-25 Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé

Country Status (1)

Country Link
WO (1) WO2017201592A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040108051A1 (en) * 2000-12-21 2004-06-10 Andrews Albert A. Composite riser
CN1727168A (zh) * 2004-07-28 2006-02-01 上特技材有限公司 一种玻璃纤维强化塑胶复合结构体的制造方法
KR100763937B1 (ko) * 2006-10-26 2007-10-05 (주)포텍스 파티션 시트 커버용 기능성 원단의 제조 방법
KR20070119587A (ko) * 2007-10-04 2007-12-20 주식회사 코스모스엔지니어링 종이 대체용 시트재와 그 제조방법
JP2008050715A (ja) * 2006-08-23 2008-03-06 Daicel Chem Ind Ltd 微小繊維及びその製造方法
EP1995043A1 (fr) * 2007-05-22 2008-11-26 Protac Procédé de réalisation de préforme axisymétrique
KR20120101241A (ko) * 2011-02-28 2012-09-13 박재준 전기장 분산을 이용한 절연용 에폭시-마이크로 실리카-나노 유기화 층상 실리케이트 혼합 콤포지트 제조방법 및 이로부터 제조된 혼합 콤포지트
CN103111947A (zh) * 2012-11-13 2013-05-22 湖北天马研磨材料有限公司 一种稀土复合刚玉增强纤维超薄树脂切割片及其生产方法
EP2595460A1 (fr) * 2010-07-14 2013-05-22 Guangdong Shengyi Sci. Tech Co., Ltd Matériau composite et substrat de circuit à haute fréquence fabriqué à l'aide du matériau composite et procédé de fabrication associé
KR101590847B1 (ko) * 2015-08-07 2016-02-04 김홍준 방수 파우더를 이용한 방수 코어, 이를 구비한 방수 립코드 및 그 제조방법

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040108051A1 (en) * 2000-12-21 2004-06-10 Andrews Albert A. Composite riser
CN1727168A (zh) * 2004-07-28 2006-02-01 上特技材有限公司 一种玻璃纤维强化塑胶复合结构体的制造方法
JP2008050715A (ja) * 2006-08-23 2008-03-06 Daicel Chem Ind Ltd 微小繊維及びその製造方法
KR100763937B1 (ko) * 2006-10-26 2007-10-05 (주)포텍스 파티션 시트 커버용 기능성 원단의 제조 방법
EP1995043A1 (fr) * 2007-05-22 2008-11-26 Protac Procédé de réalisation de préforme axisymétrique
KR20070119587A (ko) * 2007-10-04 2007-12-20 주식회사 코스모스엔지니어링 종이 대체용 시트재와 그 제조방법
EP2595460A1 (fr) * 2010-07-14 2013-05-22 Guangdong Shengyi Sci. Tech Co., Ltd Matériau composite et substrat de circuit à haute fréquence fabriqué à l'aide du matériau composite et procédé de fabrication associé
KR20120101241A (ko) * 2011-02-28 2012-09-13 박재준 전기장 분산을 이용한 절연용 에폭시-마이크로 실리카-나노 유기화 층상 실리케이트 혼합 콤포지트 제조방법 및 이로부터 제조된 혼합 콤포지트
CN103111947A (zh) * 2012-11-13 2013-05-22 湖北天马研磨材料有限公司 一种稀土复合刚玉增强纤维超薄树脂切割片及其生产方法
KR101590847B1 (ko) * 2015-08-07 2016-02-04 김홍준 방수 파우더를 이용한 방수 코어, 이를 구비한 방수 립코드 및 그 제조방법

Similar Documents

Publication Publication Date Title
CN106479186B (zh) 用于增材制造的复合原料带材及其形成方法
EP2151418B1 (fr) Faisceau de fibres coupées, matériau de moulage, et plastique renforcé par des fibres, et leur procédé de production
CA2832823C (fr) Ame composite pour cables electriques de transmission
JP2022087205A (ja) 複合繊維および繊維を生成する方法
CN103476839B (zh) 包括纤维以及至少一种氯乙烯聚合物的复合材料的制造和用途
US9783646B2 (en) Molding material for injection molding, extrusion molding or pultrusion molding, carbon-fiber-reinforced thermoplastic resin pellet, molding product, method for producing injection molded product, and injection molded product
RU2732284C2 (ru) Композиционное волокно, покрытое диоксидом кремния, для армирования бетона
CN107249838A (zh) 用于生产纤维复合材料的方法和设备
TW201945442A (zh) Frp筋及其製造方法
Ma et al. Bioinspired composites reinforced with ordered steel fibers produced via a magnetically assisted 3D printing process
CN108192286A (zh) 复合绝缘子及其制备方法
Liu et al. Solid freeform fabrication of epoxidized soybean oil/epoxy composites with di‐, tri‐, and polyethylene amine curing agents
US20130196138A1 (en) Fiber Reinforced Putty, Device And Method For Its Manufacture, Device And Method To Make Laminates And Other Finished Parts From The Putty, And A Laminate Made From The Putty
RU2468918C1 (ru) Композиционный армированный материал и способ его получения
WO2017201592A1 (fr) Procédé de fabrication d'un composite liquide réalisé en résine et fibre de verre, et composite liquide obtenu au moyen de ce procédé
BR102016011927A2 (pt) Method for the manufacture of a liquid composite made of resin and glass fiber and a liquid composite made by the method
EP0170245A2 (fr) Granulés de matériaux composites renforcés de fibres et leur procédé de fabrication
EP3484624A2 (fr) Module de coupe et procédé pour couper un fil en morceaux individuels
CN103540154A (zh) 一种防静电高阻燃型拉挤玻璃钢电缆桥架及其制备方法
BR102014029490A2 (pt) método de fabricação de uma suspenção de microfibra em resina e suspensão produzida pelo método
CN111117068A (zh) 一种改性聚丙烯复合材料及其制备方法
EP0069539A1 (fr) Eléments structurals
WO2018026000A1 (fr) Extrudeuse à deux vis
US20210245455A1 (en) Method of producing improved composite fibers
WO2012021958A1 (fr) Procédé de fabrication de structure composite par enroulement filamentaire avec des résines thermoplastiques

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17801848

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17801848

Country of ref document: EP

Kind code of ref document: A1