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WO2025029197A1 - Traitement par induction magnétique de thermoplastiques, leurs composites et leur production - Google Patents

Traitement par induction magnétique de thermoplastiques, leurs composites et leur production Download PDF

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Publication number
WO2025029197A1
WO2025029197A1 PCT/SG2024/050489 SG2024050489W WO2025029197A1 WO 2025029197 A1 WO2025029197 A1 WO 2025029197A1 SG 2024050489 W SG2024050489 W SG 2024050489W WO 2025029197 A1 WO2025029197 A1 WO 2025029197A1
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thermoplastic
curie
sheets
nanoparticles
composite material
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Terry William Joseph STEELE
Raju V. RAMANUJAN
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Nanyang Technological University
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Nanyang Technological University
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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0063—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use in a non-magnetic matrix, e.g. granular solids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • H01F1/37—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/22—Thermoplastic resins

Definitions

  • the present invention generally relates to thermoplastics, their composites, and production thereof, and more particularly relates to magnetic induction processing of thermoplastics, their composites, and production thereof.
  • thermoset/fiber prepregs are not recyclable and are a landfill hazard at a current production rate of 4 Mkg.y 1 .
  • Thermoplastic composites have considerable benefits over thermoset composites in terms of material properties and sustainability.
  • scalable, automated production platforms for thermoplastic composites have not reached the same level as that of thermoset composites, thus limiting their usage.
  • Thermoplastic composites are composed of a thermplastic matrix (e g. polyether ether ketone- PEEK, poly-ether sulfone-PES, polyphenylene sulfide-PPS, polyphthalamide-PPA, polyetherimide-PEI, styrene acrylonitrile-SAN, polycarbonate-PC, polyamide 6/6 -PA66, polyamide 6-PA6, polyamide 12-PA12, polybutylterephthalate-PBT, polyoxymethylene-POM, polypropylene-PP) and a reinforcing material, fabric or fibre (e g. glass, carbon, synthetic, aramid, metal, basalt, flax, hybrids, and braided).
  • Thermoplastic composites are available in a number of manufacturing stages, such as semipregs, prepregs, and organosheets.
  • Semipregs are fabrics with a thermoplastic matrix powder that has been partially melted or coated to the fabric surface.
  • the semipreg is still flexible (drape) and can be easily formed, cut, and manipulated.
  • Prepreg is the subsequent processing stage of semipreg, which becomes fully impregnated with matrix, forming a relatively stiff fabric.
  • Organosheets combine semipregs or prepegs into a thermal fabric stacking process that fully consolidates and impregnates the multilayer sheets.
  • Current production lines for consolidation of semipregs and prepregs are limited to a layer by layer process (Automated Tape Laying, ATL or Advanced Fiber Placement, AFP) because rapid surface heating can only be done via direct energy sources, such as lasers and ultrasound.
  • a method of multi-layer composite consolidation is an unmet industrial need where 3-10 layers or more are often required within a finished organosheet.
  • Another unmet industrial need is a process that allows reversible consolidation of composites in order to address recycling and sustainability mandates.
  • Thermoplastics need to be heated nearer above their glass transition temperature (Tg) before they can be shaped, formed, or consolidated.
  • Thermal conduction or radiation based heating is inefficient for processing materials that have low thermal conductivity (e.g. 0.01 - 1 W.m LK 1 ) or materials that are opaque, such as foams, laminates, and most thermoplastic resins. These methods are not capable of volumetric heating and are limited to finite surface heating applications.
  • Radiation based heating offers a method of heat transfer via electromagnetic waves and is generally easier to control with respect to spatial and dynamic production processes.
  • Some of the known positive attributes include excellent resistance to flexural fatigue, high impact resistance, high abrasion resistance, excellent adhesion to both plastics and metals, low moisture absorption, and excellent dimensional stability.
  • COPES is ideal for applications and parts that require excellent flexural strength in a wide temperature range of use.
  • Some example applications include electrical & mechanical sectors, electric cars, sporting goods, boots, air ducts, water seals, foam adhesives, gaskets, belts, hoses, wire coatings, cable insulation, railpads, diaphragms, valves, caps, and closures.
  • the right dynamic energy balance results in a stable cure of resin with the monomer majority consumed while free from gas pockets. Partial curing (initiation, but incomplete monomer consumption) results if activation energy, temperature, or both is too low. Overcuring occurs when the heat produced exceeds the heat removed by the adjacent resin, substrate, endothermic reactions, or combination thereof causing a local rapid temperature rise that leads to resin volatilization. The latter process yields foamed heterogenous resins with numerous voids and trapped gas pockets whose bulk mechanical properties are relatively weak compared to stable cured resins.
  • Elium® is one such liquid resin based on a proprietary methacrylate/peroxide (thermoplastic) formulation that is marketed to replace epoxy resins (thermoset) that have a poor sustainability profile.
  • thermoplastic methacrylate/peroxide
  • thermoset epoxy resins
  • Elium® targets sustainable manufacturing of thermoplastic prepregs, organosheets, and finished composites within the wind power, sailing, concrete reinforcement, and hydrogen storage industries. Current Elium® resins cure like a thermoset in 20-30 minutes at 80 °C.
  • the composite matrix once cured, behaves like a thermoplastic (PMMA, poly-methylmethacrylate) that can be thermoformed into any shape and induction welded to other thermoplastics. Sustainable recycling are thus possible since the resin can be melted, demanufactured, removed, or combination thereof from the composite fibers.
  • PMMA poly-methylmethacrylate
  • Magneto-composite technology offers a non-contact method of consolidating prepregs and semipregs based on magnetic induction.
  • the nanotechnology is based on paramagnetic particles that have no remnant magnetization at room temperature. The particles only have magnetic properties and associated interactions if external magnetic fields are applied. This prevents magnetic agglomeration of the particles when suspended in fluids under zero-field conditions unlike permanent magnets that suffer from particle agglomeration due to attractive magnetic forces.
  • a few studies have been initiated to develop alternating magnetic field (AMF) mediated in-situ heating (induction) for the production of composites. Previous studies have investigated activation of thermoset resins based on FeCo epoxy composites (Miller, K. J. et al., J. Appl. Phys.
  • Nickel particles also rapidly oxidize, which results in limited shelf stability and loss of induction heating parameters. Nickel materials also have many toxicity concerns and are thus generally avoided if possible. In-situ polymerization has been demonstrated with iron oxide nanochains (T c s 570 °C) (Ma, M. et al., J. Colloid Interface Sei. 2012, 1 (374), 339-344). Magsilica formulations that have a core-shell nanoparticle are known, where the core is magnetite (T c 2 570°C) and the shell is a thin layer of silica on the order of a few nanometers thick, which aids in dispersion. All the paramagnetic particles employed to date lack the ability to self-regulate temperature within the known temperature range of thermoplastic processing, which is generally from 80 - 400 °C.
  • EP1326741 B1 discloses the temperature-controlled induction heating of polymeric materials.
  • EP1326741B1 presents the induction heating of thermoplastic polymeric materials by adding ferromagnetic particles.
  • Ferromagnetic hexagonal ferrite particles are, for example, SrFe ⁇ Oig, Co2Ba 2 Fei 2 O22, Mg 2 Ba 2 Fei2O22, ZniMgiBa 2 Fei 2 O22 and ZniCoiBa 2 Fei 2 O22. Loading of these materials into thermoplastics was varied from 1% to 50% by volume and explored at a magnetic field frequencies of 275 kHz and 4 MHz. Ferromagnetic particles cannot be employed in liquid resins due magnetic induced aggregation, preventing homogenous distribution and application of volumetric heating.
  • W02019090067A1 discloses the adhesive/sealant materials filled with metallic particles for induction heating.
  • the metallic filler is required to be 30% - 70% by weight of the adhesive/sealant material. Dendritic shaped fern-like particles of pure iron was mostly explored.
  • the directed energy sources include microwaves, laser/hot gas heating, and ultrasound to obtain in-situ consolidation.
  • the latter signifies bonding between prepregs and impregnation within the thermoplastic prepregs filled with carbon, glass, or aramid fibres.
  • microwave energy fields are rarely uniform and carbon fibres reflect the radiation - this method is best suited for glass fibre composites.
  • Lasers/infrared lamps/hot gas have expensive hardware and consumables, lack temperature control, and best suited for uniform resins - cannot be used for mixed materials, multi-laminate designs, or delamination.
  • Ultrasonic heating is limited due to the horn size/geometry available ( ⁇ 50 mm contact width) and best suited for narrow width advanced fibre placement designs.
  • Previous applications of magnetic induction have employed ferromagnetic materials that aggregate in liquid states or applied paramagnetic particles whose Curie temperature is above the resin degradation temperature.
  • thermoplastic resin precursor a thermoplastic resin precursor and a thermoset resin precursor, the method comprising the steps of:
  • thermoset resin precursor (a) providing a mixture comprising: one or both of a monomeric and/or oligomeric thermoplastic resin precursor and a monomeric and/or oligomeric thermoset resin precursor; at least one initiator suitable for initiating polymerisation of the monomeric and/or oligomeric thermoplastic resin precursor and the monomeric and/or oligomeric thermoset resin precursor;
  • Curie nanoparticles having a Curie temperature of from 90 to 400 °C;
  • the monomeric and/or oligomeric thermoplastic resin precursor is selected from one or more of the group consisting of acrylates, urethanes, lactones, silanes, and amides, wherein said materials are presented in the form of one or both of monomers and oligomers;
  • the monomeric and/or oligomeric thermoset resin precursor is selected from one or more of the group consisting of epoxy, oxetane, di-acrylates, tri-acrylates, tetra-acrylates, vinyl carbonates, vinyl carbamates, latex, isoprene, butyl diene, and styrene, wherein said materials are presented in the form of one or both of monomers and oligomers, as well as condensation oligomers and monomers; and
  • the at least one initiator is selected from one or more of the group consisting of azoradicals, diazirines, peroxy, diperoxy, carbonates, diacyl peroxides, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides, triazines, persulfates, iodonium salts, and sulfonium salts.
  • thermoplastic polymeric composite material comprising: a solid thermoplastic polymeric material
  • Curie nanoparticles having a Curie temperature of from 90 to 400 °C homogeneously distributed throughout the solid thermoplastic polymeric material.
  • thermoplastic polymeric composite material according to Clause 5, wherein one or both of the following apply:
  • the Curie nanoparticles are present in an amount of from 1 to 20% wt/wt (e.g. from 5 to 15% wt/wt, such as about 10 % wt/wt) relative to the solid thermoplastic polymeric material; and (aaii) the solid thermoplastic polymeric material is selected from one or more of the group consisting of polyacrylates, polyurethanes, polylactones, polysilanes, polyamides and copolymers thereof.
  • thermoplastic polymeric composite material according to Clause 5 or Clause 6, the method comprising the steps of:
  • a method of delaminating two or more sheets of a thermal insulating foam so as to separate the two or more sheets comprising the steps of:
  • thermoplastic polymeric composite material (ci) providing a laminate construct comprising at least two sheets of a thermal insulating foam and at least one sheet of a thermoplastic polymeric composite material according to Clause 5 or Clause 6, where each sheet of thermal insulating foam is separated from each other sheet of thermal insulating foam by a sheet of the thermoplastic polymeric composite material, and where the thermoplastic polymeric composite material is adhered to each of the thermal insulating foam sheets;
  • a method of consolidating a plurality of thermoplastic sheets together comprising the steps of:
  • thermoplastic sheets where each sheet has a first surface and a second surface diametrically opposed to the first surface, and either: n-1 of the sheets have a first surface that is coated with Curie nanoparticles having a Curie temperature of from 90 to 400 °C and the sheets are arranged such that each coated first surface is in contact with an uncoated second surface of a directly neighbouring thermoplastic sheet; or when n is a multiple of three, one of the thermoplastic sheets is coated on the first and second surfaces with Curie nanoparticles and is sandwiched between two uncoated sheets; and
  • thermoplastic semipreg sheets together comprising the steps of:
  • thermoplastic semipreg sheets under compression, where each sheet has a first surface and a second surface diametrically opposed to the first surface, where when a first surface of a first sheet is brought into contact with a second surface of a second sheet, they together form a mating surface, where each mating surface is coated with Curie nanoparticles having a Curie temperature of from 90 to 400 °C;
  • thermoplastic semipreg sheets subjecting the stack of m thermoplastic semipreg sheets under compression to an alternating magnetic field to provide a consolidated product, wherein m is from 2 to 30.
  • thermoplastic polymeric composite material according to Clause 5 or Clause 6 the method according to Clause 7, the method according to Clause 8, the method according to Clause 9, the method according to Clause 10 or the method according to Clause 11 , wherein the Curie nanoparticles are selected from one or more of the group consisting of Mi. x Zn x Fe 2 O4 and NaFeO 2 , where:
  • M represents Mn, Co or Ni
  • x represents 0 to 0.6 (e.g. from 0.01 to 0.6, such as from 0.1 to 0.6).
  • Curie nanoparticles are selected from one or more of the group consisting of Mno 4ZnoeFe 2 04, Mno 5Zno.5Fe 2 04, Mno eZno.4Fe 2 04, Mno.?Zno 3Fe 2 04, Mno.8Zno 2 Fe 2 04, Mno.gZno.iFe 2 04, Coo.g. Zno iFe 2 C>4, MnFe 2 O4, and NaFeO 2 .
  • Fig. 1 depicts initiation of in-situ frontal polymerization resins and ring opening polymerization.
  • A 2.5 wt% loading of CNP in resin. Rapid heating leads to exothermic volatization of resin, known as overcuring.
  • B 2.0 wt% loading of CNP in resin. Moderate heating leads to a balanced exothermic reaction with complete curing of resin.
  • C 1.5 wt% loading of CNP in resin. Insufficient heating leads to incomplete crosslinking reaction, or partial curing of resin.
  • the magnetic field had a field strength of 200 Oersted (Oe) and frequency of 400 kHz. Mno 9Zn 0 .iFe204 nanoparticles were used.
  • Fig. 2 depicts initiation of Elium® (Arekema) thermoplastic precursors and free radical polymerization.
  • A 5 and 10 wt% loading of CNP in Elium®. The composite was brought to activation temperature (> 60 °C) within 4 minutes. Continuous heating leads to exothermic volatization of resin, known as overcuring.
  • B 1 and 2 wt% loading of CNP in Elium®. Moderate heating leads to a balanced exothermic reaction with complete curing of resin, or partial curing of resin.
  • the magnetic field has a field strength of 200 Oe and frequency of 400 kHz. Mno9Zno iFe 2 04 nanoparticles were used.
  • Fig. 3 depicts induction melting and remelting of CoPES thermoplastic elastomer nurdles.
  • A Temperature profile of CoPES nurdles with 10 wt% CNP/CoPES when exposed under a field strength of 200 Oe and frequency of 400 kHz. Mno.9Zno iFe 2 04 nanoparticles were used.
  • B Shear and loss modulus of neat CoPES and CoPES/CNP composite via a thermal rheometry sweep, where temperature sweep starts from 120 °C to 25 °C.
  • C Complex viscosity of neat CoPES and CoPES/CNP composite via a thermal rheometry sweep, where temperature sweep starts from 120 °C to 25 °C.
  • the complex viscosity defined measures the resistance to flow as a function of angular frequency.
  • Fig. 4 depicts bonding of thermal insulating foam by CoPES thermoplastic elastomers. Black line: induction bonding with 10 wt% CNP/CoPES. Grey line: control sample.
  • Fig. 5 depicts (A) AMF melting and remelting of PCL thermoplastic polymer. Melting of PCL raw nurdles at 5.8 min to reach the Tm of 60 °C. Remelting of CNP/PCL composite, 3.9min@60 °C. Assuming relatively linear heating within the first minute, the corresponding temperature kinetics are 0.130, 0.137, and 0.146 °Cs- 1 . This shows remelted specimens have increased dispersion as the bulk heating is more effective than the surface heating. Mno 9Zno.iFe204 CNPs were used to melt PCL nurdles under AMF strength of 200 Oe and frequency of 400 kHz. Magnetic coil diameter was 32 mm.
  • Fig. 6 depicts thermoplastic polymers processing temperature compared to the Curie temperature (T c ) of particles with elemental composition of Mni. x Zn x Fe2O4.
  • Fig. 7 depicts (A) consolidation of semipreg fabrics through induction. (Left) 60 mm induction coil with insertion of consolidation jig. (Right) Consolidation that applies a compressive force on 3 layers of semipreg fabric. Interface between fabric was coated with CNP 0.5 mg. erm 2 surface concentration. (B) Temperature of multilayer composite under induction (CF47 + CNP) with a field strength of 110 Oe and frequency of 400 kHz. Control experiments (CF47) generated a minimal temperature when CNP is not present. (C) Photographs of multilayer organosheets prepared under induction. Multilayer organosheets could be delaminated through subsequent exposure to induction and applying a peel force of > 1 N.mm within 30 seconds of induction heating.
  • Fig. 8 depicts (A) induction curing of Elium150-15wtCNP-2wtBPO on three sheets of glass fiber cloth composite. (B) Temperature profile during cure. The specimen surpassed the 80 °C temperature set point in less than two minutes. Manufacturer recommends this temperature for optimal curing of the resin.
  • Fig. 9 depicts (A) foam substrates were bonded through thermoplastic melting of CNP/COPES. (B) Foam sandwich was attached to a non-metallic wood rod. (C) Exposure of the foam sandwich to induction field for 5 min. (D) Foam sandwich can be easily delaminated by hand with no damage to the foam substrates. Foam substrates can be recycled for sustainable manufacturing initiatives.
  • Fig. 10 depicts (A) determination of the onset temperature (95-105 °C) of three samples of CE + 1 mol% iodonium salt + 1 mol% BPO + 10 wt%CNP uncured resin via thermal Dynamic Scanning Calorimetry (DSC). (B) Dynamic field strength display temperature control at 95 ⁇ 2 °C. (C) Dynamic field strength display temperature control at 102 ⁇ 2 °C. (D) Dynamic field strength display temperature control at 107 ⁇ 2 °C.
  • the present invention provides non-contact consolidation of thermoplastic, semipreg, and prepreg matrices, and non-contact interfacial debonding of organosheets and consolidated thermoplastic composites. Further, the present invention provides a balance of heat (watts) input to achieve programmable temperature profiles suited to any desired resin activation temperature and curing profile.
  • thermoplastic resin precursor a thermoplastic resin precursor and a thermoset resin precursor, the method comprising the steps of:
  • thermoset resin precursor (a) providing a mixture comprising: one or both of a monomeric and/or oligomeric thermoplastic resin precursor and a monomeric and/or oligomeric thermoset resin precursor; at least one initiator suitable for initiating polymerisation of the monomeric and/or oligomeric thermoplastic resin precursor and the monomeric and/or oligomeric thermoset resin precursor;
  • Curie nanoparticles having a Curie temperature of from 90 to 400 °C;
  • the word “comprising” may be interpreted as requiring the features mentioned, but not limiting the presence of other features.
  • the word “comprising” may also relate to the situation where only the components/features listed are intended to be present (e.g. the word “comprising” may be replaced by the phrases “consists of” or “consists essentially of”). It is explicitly contemplated that both the broader and narrower interpretations can be applied to all aspects and embodiments of the present invention.
  • the word “comprising” and synonyms thereof may be replaced by the phrase “consisting of’ or the phrase “consists essentially of’ or synonyms thereof and vice versa.
  • frontal polymerisation refers to a polymerization process for converting monomer into polymer in a localized reaction zone which could self-propagate in the bulk monomer.
  • any suitable monomeric and/or oligomeric thermoplastic resin precursor may be used herein.
  • monomeric and/or oligomeric thermoplastic resin precursors that may be mentioned herein include, but are not limited to acrylates, urethanes, lactones, silanes, amides, and combinations thereof.
  • the monomeric and/or oligomeric thermoplastic resin precursors may be presented in the form of one or both of monomers and oligomers.
  • any suitable monomeric and/or oligomeric thermoset resin precursor may be used herein.
  • monomeric and/or oligomeric thermoset resin precursors that may be mentioned herein include, but are not limited to epoxy, oxetane, di-acrylates, tri-acrylates, tetra-acrylates, vinyl carbonates, vinyl carbamates, latex, isoprene, butyl diene, styrene, and combinations thereof.
  • the monomeric and/or oligomeric thermoset resin precursors may be presented in the form of one or both of monomers and oligomers, and condensation oligomers and monomers.
  • any suitable initiator may be used herein.
  • suitable initiators include, but are not limited to azo-radicals, diazirines, peroxy(di), carbonates, diacyl peroxides, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides, triazines, persulfates, iodonium salts, sulfonium salts, and combinations thereof.
  • the term “Curie nanoparticles” refers to nanoparticles that are paramagnetic and interact with alternating magnetic fields, resulting in heat generation by the Curie nanoparticles; the heat is dissipated and transferred to the surrounding environment.
  • the Curie nanoparticles may be selected from one or more of the group consisting of Mi. x Zn x Fe2O4 and NaFeCh, where:
  • M represents Mn, Co or Ni
  • x represents 0 to 0.6 (e.g. from 0.01 to 0.6, such as from 0.1 to 0.6).
  • the Curie nanoparticles may be selected from one or more of the group consisting of Mno 4Zno.6Fe204, Mno.sZno 5Fe204, Mno.6- Zno.4Fe2C>4, Mno.7Zno 3Fe204, Mno 8Zno.2Fe204, Mno.gZno.iFe204, Coo 9Zno.i Fe204, MnFe2C>4, and NaFeCh.
  • the Curie nanoparticles may be Mn o gZno iFe 2 O4.
  • the Curie nanoparticles may have a surface that is coated in an organic material.
  • the organic material may be a surfactant.
  • the organic material may be a fatty acid having from 15 to 20 carbon atoms (e g. oleic acid).
  • the organic material may further comprise one or both of bisphenol A diglycidyl ether, copolyester (COPES) and polycaprolactone.
  • Croe temperature refers to the temperature above which certain materials lose their permanent magnetic properties.
  • alternating magnetic field refers to fields which amplitudes vary in time.
  • the alternating magnetic field may be generated with an alternating magnetic field heating equipment which includes a F1 Driver, a magnetic coil that creates the alternating magnetic field, and optic fiber probes. Any suitable frequency and Oe field strength may be used for the alternating magnetic field used herein.
  • the alternating magnetic field may have a frequency of 400 kHz and field strength of 200 Oe.
  • the Curie nanoparticles may be provided in an amount of from 1 to 10 wt% relative to the weight of the resin precursor(s) present in the mixture.
  • the amount of Curie nanoparticles may be varied to provide partially cured, completely cured, and overly cured products of one or both of a thermoplastic resin and a thermoset resin.
  • the Curie nanoparticles may be provided in an amount of from 4 to 10 wt% (e.g. from 5 to 10 wt%) relative to the weight of the resin precursor(s) present in the mixture, where only monomeric and/or oligomeric thermoplastic resin precursors are present.
  • the Curie nanoparticles may be provided in an amount of from 1 to 3 wt% (e.g. from 1 to 2 wt%) relative to the weight of the resin precursor(s) present in the mixture, where only monomeric and/or oligomeric thermoplastic resin precursors are present.
  • the Curie nanoparticles may be provided in an amount of from 1.5 to 2.5 wt% (e.g. 2 wt%) relative to the weight of the resin precursor(s) present in the mixture, where only monomeric and/or oligomeric thermoset resin precursors are present.
  • a preset temperature or a desired preset temperature profile may be maintained through a dynamic feedback control on an induction field strength of the alternating magnetic field.
  • a preset T c temperature control allows a self-regulating temperature that avoids the limitations of prior art designs, which observed scorching - a detrimental property of other ferromagnetic nanoparticles and paramagnetic particles that cannot be tuned to the desired temperature required for thermoplastic melting or in-situ polymerization of reactive thermoplastic monomers.
  • thermoplastic polymeric composite material comprising: a solid thermoplastic polymeric material;
  • any suitable solid thermoplastic polymeric material may be used herein.
  • solid thermoplastic polymeric materials that may be mentioned herein include, but are not limited to polyacrylates, polyurethanes, polylactones, polysilanes, polyamides and copolymers thereof, and combinations thereof.
  • the Curie nanoparticles may be present in an amount of from 1 to 20% wt/wt (e.g. from 5 to 15% wt/wt, such as about 10 % wt/wt) relative to the solid thermoplastic polymeric material.
  • thermoplastic polymeric composite material in a third aspect of the invention, comprising the steps of:
  • thermoplastic polymeric composite material (bii) subjecting the mixture to an alternating magnetic field to provide the thermoplastic polymeric composite material according to the second aspect of the invention.
  • a method of laminating two or more sheets of a thermal insulating foam together comprising the steps of:
  • thermoplastic polymeric composite material (ci) providing at least two sheets of a thermal insulating foam and at least one sheet of a thermoplastic polymeric composite material according to the second aspect of the invention, where each sheet of thermal insulating foam is separated from each other sheet of thermal insulating foam by a sheet of the thermoplastic polymeric composite material;
  • thermal insulating foam refers to a foam that provides a thermal barrier around a component or between an interior space and a heat or cold source. Any suitable thermal insulating foam may be used herein. Examples of thermal insulating foams that may be mentioned here include, but are not limited to maleimide, polyamide, polyurethane, glass wool, and polyethylene.
  • a method of delaminating two or more sheets of a thermal insulating foam so as to separate the two or more sheets comprising the steps of:
  • thermoplastic polymeric composite material (ci) providing a laminate construct comprising at least two sheets of a thermal insulating foam and at least one sheet of a thermoplastic polymeric composite material according to the second aspect of the invention, where each sheet of thermal insulating foam is separated from each other sheet of thermal insulating foam by a sheet of the thermoplastic polymeric composite material, and where the thermoplastic polymeric composite material is adhered to each of the thermal insulating foam sheets; and (cii) subjecting the mixture to an alternating magnetic field to enable separation of the laminate construct to provide a delaminated product through the removal of the two or more sheets of thermal insulating foam from the thermoplastic polymeric composite material.
  • thermoplastic sheets together comprising the steps of:
  • thermoplastic sheets where each sheet has a first surface and a second surface diametrically opposed to the first surface, and either: n-1 of the sheets have a first surface that is coated with Curie nanoparticles having a Curie temperature of from 90 to 400 °C and the sheets are arranged such that each coated first surface is in contact with an uncoated second surface of a directly neighbouring thermoplastic sheet; or when n is a multiple of three, one of the thermoplastic sheets is coated on the first and second surfaces with Curie nanoparticles and is sandwiched between two uncoated sheets; and
  • thermoplastic semipreg sheets together comprising the steps of:
  • thermoplastic semipreg sheets under compression, where each sheet has a first surface and a second surface diametrically opposed to the first surface, where when a first surface of a first sheet is brought into contact with a second surface of a second sheet, they together form a mating surface, where each mating surface is coated with Curie nanoparticles having a Curie temperature of from 90 to 400 °C;
  • thermoplastic semipreg sheets subjecting the stack of m thermoplastic semipreg sheets under compression to an alternating magnetic field to provide a consolidated product, wherein m is from 2 to 30.
  • semipregs are fabrics with a thermoplastic matrix powder that has been partially melted or coated to the fabric surface.
  • thermoplastic semipreg sheets may be compressed with a 3D printed ABS jig.
  • the present invention provides a magneto-composite consolidation of thermoplastic composites through a modifier methodology, wherein multi-layers prepregs and semipregs can melt-bond simultaneously, and the peel strength of the demonstrated system may be in a range of 1-7 kN/m.
  • the present invention includes:
  • thermoplastic matrix 1) allowing a method of volumetric heating and self-regulating temperatures at the interface of thermoplastic matrix, semipreg, prepreg, or multiple thermoplastic matrices, semipreg, prepreg interfaces;
  • thermoplastic matrices and elastomers rapidly melting thermoplastic matrices and elastomers to form homogeneous resins that melt and consolidate other plastic surfaces via polymer entanglement;
  • thermoplastic consolidation may be remotely controlled, and may provide rapid and localized heating, reduced processing cost and energy by applying induction frequency in the range of 100 - 800 kHz and a magnetic field strength in the range of 100 - 200 Oe.
  • induction frequency in the range of 100 - 800 kHz
  • magnetic field strength in the range of 100 - 200 Oe.
  • the melting temperature required for consolidation was reached within 5 min and initiates resin entanglement after exceeding the glass transition temperature. Therefore, it is perfectly suitable for a range of industries;
  • CNP Curie nanoparticles
  • the present invention provides improved and advantageous methods over existing methods, comprising:
  • thermoplastic, semipreg, and prepreg matrices 1) a processing platform designed to allow non-contact consolidation of thermoplastic, semipreg, and prepreg matrices through exposure to suitable alternating magnetic field frequency and strength.
  • CNPs are paramagnetic and interact with the alternating magnetic fields, resulting in heat generation by the CNPs; the heat is dissipated and transferred to the surrounding polymers chains;
  • CNPs with a chosen preset Curie temperature may be synthesized by controlling the specific elemental composition of crystal grains within the nanoparticles.
  • T c of the CNPs is a macro property - i.e. of the bulk material and not of the individual crystal grains.
  • the CNPs are paramagnetic with the advantage of programmable temperature and power profiles capable of homogenous distribution;
  • preset T c temperature control allows a self-regulating temperature that avoids the limitations of previous designs, which observed scorching — a detrimental property of other ferromagnetic nanoparticles and paramagnetic particles that cannot be tuned to the desired temperature required for thermoplastic melting or in-situ polymerization of reactive thermoplastic monomers;
  • volumetric heating (watts applied) control is possible since magnetic fields can pass through organic resins and inorganic fibre materials with little to no attenuation, facilitating control of most material and mechanical properties of thermoplastic composites, including but not limited to polymer entanglement, multi-layer consolidation, polymer crystallinity, and setup of preplanned interface failure sites upon specific magnetic exposure;
  • a magnetic induction platform is designed to allow non-contact interfacial debonding of organosheets and consolidated thermoplastic composites, wherein CNPs have been incorporated at preplanned interface failure sites;
  • a magnetic induction platform has been designed to overcome the current limitations of Automated Tape Laying (ATL) that are based on photo- or ultrasonic heat methods; and
  • AMF heating by CNP additives within in-situ frontal polymerization resins offers a method that balances heat (watts) input to achieve programmable temperature profiles suited to any desired resin activation temperature and curing profile, including partial curing (higher viscosity and adhesive tack), homogenous stable curing (no voids with complete propagation), and over-curing (excess exothermic heat that leads to volatilization and foams).
  • the CNP nanoparticles may be represented by a formula of A x Z . x Fe 2 O4; wherein A is cobalt, manganese, or nickel; and x has a value in the range of 0.4 to 0.99.
  • the organic coating may be a surfactant.
  • the organic coating may be a fatty acid having 15 to 20 carbon atoms.
  • the organic coating may be oleic acid (OA).
  • CNPs were dispersed in deionized water and placed in a sonicating water bath.
  • OA was added to the solution and sonicated. This solution was heated (e.g. at 80 °C for 1 hour) under mechanical stirring (e.g. at 400 rpm). The resultant solution was washed 3-4 times with ethanol and the OA-coated CNPs were separated using a permanent magnet.
  • the oleic acid-coated particles (Mn x Zni. x Fe 2 O4/OA) were used as they are for the further functionalization with a monomer (e.g. bisphenol A diglycidyl ether, and polycaprolactone).
  • Mn x Zni. x Fe 2 O4/OA particles were dispersed into tetrahydrofuran (THF) and sonicated. After that, a solution of bisphenol A diglycidyl ether (BADGE) in THF was added to the above solution and sonicated again. This solution was kept until the surface of the nanoparticles was completely wetted with BADGE (e.g. for 16 hours). Next, Mn x Zni. x Fe 2 O4/OA/BADGE was obtained by washing with THF and acetone, separated using a permanent magnet and vacuum dried. Same procedure was repeated for the functionalization of Mn x Zni. x Fe 2 C>4/OA particles with polycaprolactone.
  • BADGE bisphenol A diglycidyl ether
  • CNP of composition MnogZno.iFe 2 04 nanoparticles (T c > 280°C) were synthesized via the hydrothermal method as previously described in DOI: 10.1016/j.apmt.2020.100824.
  • Mm. x Zn x Fe 2 O4 nanoparticles have a tuneable T c that ranges from 80 - 400°C based on the elemental composition.
  • CNP nanoparticles with organic coatings were mixed within the following in-situ frontal polymerization resin of CE epoxy, lodonium salt, and TPED.
  • the alternating magnetic field (AMF) heating equipment includes the F1 Driver, the S 32 magnetic coil (3 cm, water cooled copper coil) that creates the AMF, and optic fiber probe to monitor the temperature of the composites (nB Biomaterials).
  • CNP additives were thoroughly mixed with the thermosetting material in a 5 mL glass vial. The composite was then sonicated to improve the nanoparticles dispersion for 30 minutes. Afterwards, the composite was placed at the middle of a magnetic coil (110 mm length, 32 mm diameter) and optic fiber probes used to measure the temperature in-situ. An AMF of 400 kHz frequency and 200 Oe field strength was subjected to the sample for each magnetocuring experiment. Heating output (Specific Absorption Rate) of the composite with respect to CNP concentration was also calculated as previously published see: DOI: 10.1016/j.apmt.2020.100824 and these results are provided in Fig. 1.
  • Elium® resin was mixed with 1, 2, 5, and 10 wt% of CNP (composition of Mno gZno.iFe204) and dispersed within an ultrasonic bath. Magnetic induction resulted in variable heating rates and temperature plateaus dependent on the CNP wt%. At 1 and 2 wt%, partial curing (liquid to solid gelation, but still flexible) and complete curing (liquid to solid gelation, dense and inflexible) were observed (Fig. 2). These formulations would be ideal for substrates with low thermal conductivity. At 5 and 10 wt%, rapid heating led to rapid resin activation and exothermic heat evolution.
  • CNP composition of Mno gZno.iFe204
  • the resin is described as over-curing; liquid to solid gelation occurs but with resin volatilization that yields a porous and inflexible matrix.
  • These formulations would be ideal for substrates with high thermal conductivity or other situations where high thermal dissipation is needed.
  • Induction parameters magnetic coil (110 mm length, 32 mm diameter), AMF of 400 kHz frequency, and 200 Oe field strength (see Example 3 for the AMF heating equipment used).
  • COPES resin nurdles (0.5 g) of ⁇ 100 pm diameter were mixed with Mno.9Zno.iFe204 CNP at 10 w/w% by a vortex mixer. The mixture was placed in a 5 mL glass vial and exposed to an AMF (see Example 3 for the AMF heating equipment used). Temperature was constantly recorded until a viscous polymer melt was visibly observed (e g. flowed under gravity). AMF was switched off at intervals, during which the elastomer composite was allowed to solidify into homogenous composite elastomer, as shown in Fig. 3. Subsequent AMF exposure resulted in remelting of this thermoplastic in lesser time than the first heterogenous mixture.
  • the CNP/COPES elastomer composite from Example 4 was applied for melt bonding of fabric insulation (e.g. thermal/acoustic foam composed of a polyester resin).
  • the fabric sandwich was immobilized by tape. The material was subject to 400 kHz and 200 Oe AMF heating.
  • the peel strength of the AMF sample had a higher adhesive strength, as judged by the failure mode and T-peel force analysis (Fig. 4) using a static tensile tester (MTS Model 42).
  • AMF melt bonding underwent a substrate failure vs. conduction melt bonding observed interfacial failure at the adhesive/foam interface, as seen in Fig. 4.
  • Induction parameters magnetic coil (110 mm length, 32 mm diameter), AMF of 400 kHz frequency, and 200 Oe field strength.
  • Example 7 Induction melting and remelting of a thermoplastic polymer
  • thermoplastic polymers compared to the Curie temperature (T c ) of particles with elemental composition of Mni. x Zn x Fe 2 C>4.
  • T c Curie temperature
  • a sample mixture of 10 w/w% CNP (Mno 9Zno.iFe204 nanoparticles)/PCL was stored in a 5 mL glass vial and placed at the center of the magnetic coil.
  • the melting temperature (Tm) of 4 mm nurdle pellets was achieved in less than 5 min.
  • the corresponding temperature ramp rates of the melting and remelting (x2) segments are 0.130, 0.137, and 0.146 °Cs' 1 , respectively.
  • the homogenous dispersion of CNPs has a faster heat dispersion than surface heating on nurdles.
  • the complex shear modulus and complex viscosity of 10 w/w% CNP/PCL was compared to neat PCL and had similar values over the temperature range of 25 - 120 °C.
  • the rheology data was collected from a temperature sweep from 120 °C to 25 °C.
  • the complex viscosity, defined as ⁇ measures the resistance to flow as a function of angular frequency. Induction parameters; magnetic coil (110 mm length, 32 mm diameter), AMF of 400 kHz frequency, and 200 Oe field strength.
  • Thermoplastics coupons were shown to be melt bonded through induction heating, as displayed in Fig. 5.
  • the coated CNP coupon was then sandwiched to an uncoated coupon and fixed together by clear cello tape, with the CNP coating in contact with both PCL coupons.
  • the center portion of the sample ( ⁇ 50 mm in width) was then exposed to AMF (see Example 3 for the AMF heating equipment used) for 10 min to spatially selective melt bond the two thermoplastic specimens.
  • the T-peel adhesion strength was then evaluated using a static tensile tester (MTS Model 42).
  • Tecatec SAN CF47 T245 CP V02 (provided by Ensinger, Germany) is a thermoplastic semipreg. Carbon fibre with a twill 2/2 fibre architecture was sputter coated with SAN, resulting in a flexible semipreg with 47% vol. fibre content that is easily draped across complex surfaces with a mass of 245 g.m 2 .
  • SAN is a styrene (75 wt%) acrylonitrile (25 wt%) resin often used in place of polystyrene due to a better profile of thermal and chemical resistance, while retaining visible transparency. This semipreg targets the automotive, mechanical engineering, and sporting good industries.
  • Tg and Tm are 110 °C and 220 °C, which defines the semipreg process range and overlaps with the Curie temperature of the CNPs chosen (180 °C).
  • Organo-sheet could be delaminated for recycling through subsequent induction heating due to the inherent CNP layer.
  • Induction parameters magnetic coil (110 mm length, 60 mm diameter), AMF of 400 kHz frequency, and 110 Oe field strength (see Example 3 for the AMF heating equipment used).
  • Infusible thermoplastic resins are commercially available (i.e., Elium®) and consist of proprietary acrylic resins for reactive processing. In-situ polymerization of the low viscosity thermoplastic resins allows vacuum assisted infiltration of fiber-based composites and reactive transfer molding (RTM) manufacturing techniques. This allows manufacture of thermoplasticbased composites while overcoming the high viscosity of thermoplastic melts. However, there currently is no method of volumetric heating of the resin or resin/fiber composite once infiltrated.
  • the components of Elium® acrylic resin are 2-propenoic acid, 2-methyl-, methyl ester, or methylmethacrylate monomer (MMA), and acrylic copolymer. Before infusion, resin is mixed with initiator chemical(s) (e.g.
  • Infusion open time varies with peroxide initiator, initiator ratio, and concentration which ranges from 1 .5% (slow reactivity) to 3% (higher reactivity). Open time is the amount of time during which the viscosity of the resin is low enough to inject or infiltrate the resin within fiber composites.
  • Elium150 thermoplastic resin is an acrylate adhesive that cures at room temperature.
  • E-glass fiber cloth is from Saertex, which has an areal weight of 151 g/m 2 and is unidirectional.
  • Elium150® with 2 wt% benzoyl peroxide (BPO) and 10 wt% CNP (Mno gZno iFe204) was applied at a 1 :1 w/w ratio of resin and glass fiber and resin.
  • the resin soaked fibers have an area of 2.5 x 2.5 cm 2 area.
  • An uncured, three-layer laminate specimen was positioned within the center of a 3.2 cm-diameter induction coil, and the temperature of this section was monitored in-situ using an optic fiber probe under AMF field strength of 200 Oe and frequency of 400 kHz (see Example 3 for the AMF heating equipment used).
  • Example 11 Debonding of thermal insulating foams via CNP/COPES adhesive interface
  • Induction generator AMF, D5 series, 640W F1 Driver, attached with a solenoid coil (S 32 ) operating ata field strength of 200 Oe and 400 kHz frequency. Foams are bonded with CoPES thermoplastic particles are mixed with 10 wt% CNP (Mno.gZno iFe204).
  • Adhesive failure under room temperature conditions occurs via substrate failure. After 5 min of exposure to induction field strength 200 Oe, the tg was exceeded and the foam substrates can easily be separated by hand within one minute after removal of the induction field (Fig. 9). This shows a method of debonding and allows recycling of the undamaged foam substrates. Foam substrates can be recycled, reused, or repurposed for sustainable manufacturing initiatives.
  • DSC thermal Dynamic Scanning Calorimetry
  • DSC experiments were performed using a TA Instruments DSC Q10 system with a maximum temperature of 400 °C. For this analysis, each sample consists of no more than 6 mg resin to avoid excessive exothermic reactions that distort the exothermic peak. Each resin sample was tested in an aluminium hermetic pan, and three measurements were carried out for each controlled temperature.
  • One DSC run comprises of two heating ramps: 1) the first ramp was from -50 °C to +200 °C at a rate of 10 °C/min to acquire the exothermic peak from induction- cured epoxy; and 2) the second ramp was from -50 °C to +200 °C at a rate of 10 °C/min to confirm that there are no more exothermic reactions from induction-cured epoxy.
  • the data from this 2 nd ramp serves as the baseline for exothermic peak analysis.
  • An AMF generating system (D5 series, 640W F1 Driver) attached with a solenoid coil (S 32 ) operating at 200 Oe and 400 kHz was used in all experiments.
  • Liquid resin samples with dispersed CNPs were stored inside of an NMR glass vial (0.42 mm-thick wall, Wilmad®), and the samples were positioned at the centre of the solenoid.
  • In-situ temperature monitoring was conducted via an optic fibre sensor (Neoptix, T1S-01-PT15, USA) connected to the AMF generator that was submerged into the resin during cure. Prior to all experiments, samples were freshly prepared by dispersing CNPs into CE epoxy resin with sonication for 60 minutes.

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Abstract

L'invention concerne un procédé de polymérisation frontale in situ d'un précurseur de résine thermoplastique et/ou d'un précurseur de résine thermodurcie, et un matériau composite polymère thermoplastique comprenant un matériau polymère thermoplastique solide, et des nanoparticules de Curie ayant une température de Curie de 90 à 400°C réparties de manière homogène dans tout le matériau polymère thermoplastique solide. L'invention concerne également des procédés de formation du matériau composite polymère thermoplastique, de stratification conjointe de deux feuilles ou plus d'une mousse d'isolation thermique, de déstratification d'au moins deux feuilles d'une mousse d'isolation thermique de façon à séparer les deux feuilles ou plus, de consolidation d'une pluralité de feuilles thermoplastiques ensemble, et de consolidation conjointe d'une pluralité de feuilles semi-imprégnées thermoplastiques.
PCT/SG2024/050489 2023-08-01 2024-08-01 Traitement par induction magnétique de thermoplastiques, leurs composites et leur production Pending WO2025029197A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248864A (en) * 1991-07-30 1993-09-28 E. I. Du Pont De Nemours And Company Method for induction heating of composite materials
EP0498998B1 (fr) * 1990-12-28 1997-02-26 Westinghouse Electric Corporation Procédé pour chauffer, à distance, une matière polymère à une température sélectionnée
US20090133822A1 (en) * 2001-12-21 2009-05-28 Henkel Kommanditgesellschaft Auf Akitien (Henkel Kgaa) Nanoparticulate preparation
CN104531002A (zh) * 2015-01-09 2015-04-22 沈阳理工大学 一种磁热熔胶及其制备和使用方法
KR20180060487A (ko) * 2016-11-29 2018-06-07 주식회사 엘지화학 경화성 조성물
WO2022039676A1 (fr) * 2020-08-21 2022-02-24 Nanyang Technological University Adhésifs durcis par chauffage par induction

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0498998B1 (fr) * 1990-12-28 1997-02-26 Westinghouse Electric Corporation Procédé pour chauffer, à distance, une matière polymère à une température sélectionnée
US5248864A (en) * 1991-07-30 1993-09-28 E. I. Du Pont De Nemours And Company Method for induction heating of composite materials
US20090133822A1 (en) * 2001-12-21 2009-05-28 Henkel Kommanditgesellschaft Auf Akitien (Henkel Kgaa) Nanoparticulate preparation
CN104531002A (zh) * 2015-01-09 2015-04-22 沈阳理工大学 一种磁热熔胶及其制备和使用方法
KR20180060487A (ko) * 2016-11-29 2018-06-07 주식회사 엘지화학 경화성 조성물
WO2022039676A1 (fr) * 2020-08-21 2022-02-24 Nanyang Technological University Adhésifs durcis par chauffage par induction

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