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WO2024263559A2 - Procédé électrochimique rapide pour recycler des composites de fibres de carbone - Google Patents

Procédé électrochimique rapide pour recycler des composites de fibres de carbone Download PDF

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Publication number
WO2024263559A2
WO2024263559A2 PCT/US2024/034459 US2024034459W WO2024263559A2 WO 2024263559 A2 WO2024263559 A2 WO 2024263559A2 US 2024034459 W US2024034459 W US 2024034459W WO 2024263559 A2 WO2024263559 A2 WO 2024263559A2
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Prior art keywords
fibers
epoxy
fiber
polymer matrix
reinforced polymer
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WO2024263559A3 (fr
Inventor
Steven Nutt
Zehan YU
Travis J. Williams
Younghan Justin LIM
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University of Southern California USC
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University of Southern California USC
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention is related to the recycling of carbon fiber composites.
  • CFRPS Thermoset carbon fiber-reinforced polymer
  • CFRPS are top choices for lightweight structural components in the aerospace, automobile, and wind energy industries. There has been a continuous increase in global demand for CFRPS, projected to reach 285,000 tons in 2025. 1 Thermoset CFRPS are cured irreversibly to produce a solid, crosslinked polymer matrix. Once the process completes, the matrix is insoluble and inert. Thus, recycling end- of-life (EOL) CFRPS is challenging.
  • the first electrochemical method to deploy electrolysis-generated methyl radicals to depolymerize amine-epoxy CFRPS is provided.
  • fibers embedded within the CFRP are used as the anode to electrolyze CH 3 COOH and generate methyl radicals directly on the CFRP.
  • Such radicals abstract hydrogen atoms adjacent to the polymer’s linking nitrogen atom, thus ultimately enabling selective C-N bond cleavage and completely dissolving CFRP matrices (T g > 160 °C) within 20 hours while preserving the fabric architecture of CFs. Fiber fabrics were then directly remanufactured to produce second-cycle CFRPs.
  • a spin trap strategy to obtain structural information on propagating radical(s) is provided.
  • a method for recycling fiber composites using methyl radicals includes a step of providing a fiber-reinforced polymer matrix for recycling.
  • the fiber-reinforced polymer matrix includes an initial plurality of fibers dispersed in a polymeric matrix.
  • the method also includes a step of electrolytically degrading the fiber-reinforced polymer matrix by electrolysis in an electrochemical cell that includes an anode that includes the fiber- reinforced polymer matrix, a cathode, and an electrolyte that includes CH 3 COOH, NaCl, and water.
  • the anode and cathode are immersed in an electrolyte solution.
  • a recycled plurality of fibers is recovered.
  • the polymeric matrix can be an amine-linked epoxy matrix.
  • the polymeric matrix includes a component selected from the group consisting of diglycidyl ether of bisphenol A with aliphatic diamines, epoxy novolac resins with aromatic diamines, cycloaliphatic epoxy resins with cycloaliphatic diamines, acid anhydride-cured epoxy resin systems, waterborne epoxy emulsions with amine crosslinkers, and combinations thereof.
  • an electrochemical cell for recycling carbon fiber composites by electrochemical digestion of a fiber-reinforced polymer matrix with the methods set forth above.
  • the electrochemical cell includes a fiber-reinforced polymer-containing anode.
  • the fiber- reinforced polymer-containing anode includes a fiber-reinforced polymer matrix for recycling.
  • the fiber-reinforced polymer matrix that includes an initial plurality of fibers dispersed in a polymeric matrix.
  • Electrochemical cell 10 includes a vessel, which holds an electrolyte.
  • the electrochemical cell includes a cathode.
  • the electrolyte solution includes a C 1-6 carboxylic acid and sodium, a salt.
  • the fiber-reinforced polymer-containing anode and the graphite rod cathode are at least partially immersed in the electrolyte solution.
  • FIGURE Schematic of an electrochemical cell for recycling fiber composites.
  • FIGURES 2a, 2b, 2c, and 2d [0018] FIGURES 2a, 2b, 2c, and 2d.
  • Scheme 1 Approaches to cleave various CFRP matrices.
  • FIGURE 3 Scheme 2: Approaches to recycle CRFP matrices.
  • FIGURE 4 Measured voltage of Table 1, entry 5 during the electrolysis digestion
  • FIGURES 5a, 5b, and 5c SEM images of virgin CF and recovered CFs.
  • FIGURE 6 EDS spectrum of virgin CF.
  • FIGURE12. GC of electrolysis set-up headspace
  • alkyl refers to C 1-20 inclusive, linear (i.e., “straight-chain”), branched, saturated or at least partially and in some cases fully unsaturated (i.e., alkenyl and alkynyl) hydrocarbon chains, including for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, and allenyl groups.
  • Branched refers to an alkyl group in which a lower alkyl group, such as methyl, ethyl or propyl, is attached to a linear alkyl chain.
  • Lower alkyl refers to an alkyl group having 1 to about 8 carbon atoms (i.e., a C 1-8 alkyl), e.g., 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.
  • “Higher alkyl” refers to an alkyl group having about 10 to about 20 carbon atoms, e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
  • integer ranges explicitly include all intervening integers.
  • the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.
  • the range 1 to 100 includes 1, 2, 3, 4. . . . 97, 98, 99, 100.
  • intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1. to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits.
  • concentrations, temperature, and reaction conditions e.g.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, etc.
  • concentrations, temperature, and reaction conditions e.g., pH, etc.
  • concentrations, temperature, and reaction conditions e.g., pH, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 10 percent of the values indicated rounded to three significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 10 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • matrix means the polymeric material in which the fiber system of a composite is embedded.
  • a polymeric matrix is a continuous phase in a composite material in which the reinforcement material (such as fibers or particulates) is embedded.
  • the polymeric matrix binds the reinforcement material together and distributes loads applied to the composite, providing shape, stability, and protection to the reinforcing elements.
  • reinforced plastic or polymer means a plastic or polymer composition with fibers embedded therein. This can improve some mechanical properties over that of the base resin.
  • amine-linked epoxy means a type of epoxy resin that is cured or crosslinked using amines.
  • degree of polymerization means the number of monomeric units in a polymer molecule.
  • oligomer refers to a compound that has 2 to 10 monomeric repeat units.
  • prepolymer is a polymer that has reactive functional groups capable of further polymerization or cross-linking. Typically, a prepolymer has more than 10 monomeric repeat units. In a refinement, a prepolymer has 100 to 1000 or more monomeric repeat units.
  • benzoxazine-epoxy composite refers to a polymer material (e.g., a resin) created by combining (e.g., polymerizing) benzoxazine monomers with epoxy monomers.
  • DGEBA means di-glycidyl ether of bisphenol A.
  • DDS means diaminodiphenyl sulfone.
  • CFRP carbon fiber-reinforced polymers
  • DMPO means 5,5-dimethyl-l-pyrroline-N-oxide.
  • LC-QTOF means liquid chromatography-quadrupole time of flight.
  • rCF means recycled carbon fibers.
  • a method for recycling carbon fiber composites using methyl radicals includes a step of providing a fiber-reinforced polymer matrix for recycling.
  • the fiber-reinforced polymer matrix includes an initial plurality of fibers dispersed in a polymeric matrix.
  • the initial plurality of fibers includes (i.e., can be) carbon fibers.
  • the fiber-reinforced polymer matrix is electrolytically degraded by electrolysis in an electrochemical cell.
  • Figure 1 depicts electrochemical cell 10, including vessel 12, which holds electrolyte 14.
  • Electrochemical cell 10 also includes anode 16, which includes the fiber-reinforced polymer matrix 18 attached thereto, and cathode 20.
  • electrolyte 14 includes a C 2-6 carboxylic acid, a salt, and water.
  • salts include but are not limited to NaCl, KCl, NaNO 3 , K 2 SO 4 , LiCl, NH 4 CI, and combinations thereof.
  • the anode and cathode are, at least partially, immersed in an electrolyte solution.
  • a recycled plurality of fibers is recovered after electrolysis.
  • the C 1-6 alkyl carboxylic acid is selected from the group consisting of acetic acid (CH 3 COOH), propionic acid, butyric acid, valeric acid, caproic acid, and combinations thereof.
  • the C 1-6 alkyl carboxylic acid is acetic acid.
  • the polymer matrix is an epoxy resin and, in particular, an amine- cured epoxy resin.
  • the degree of polymerization for the epoxy resin is at least 2 (e.g., from 2 to 10). In another refinement, the degree of polymerization for the epoxy resin is from 2 to 10. In another refinement, the degree of polymerization for the epoxy resin is from 10 to 50. In another refinement, the degree of polymerization for the epoxy resin is from 50 to 200 or more. In some refinement, the degree of polymerization for the epoxy resin is at least 2, 10, 50, 100, 500, 1,000, or 2,000. In some further refinement, the degree of polymerization for the epoxy resin is at most 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, or 3,000.
  • the amine-cured epoxy resins include the reaction product of an epoxy monomer, epoxy oligomer, or epoxy prepolymer and an amine curing agent (i.e., a hardener).
  • epoxy monomers include but are not limited to bisphenol A diglycidyl ether (DGEBA), cycloaliphatic epoxy resins (e.g., 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate), epoxy novolac resins.
  • amine curing agents includes but are not limited to triethylenetetramine, diethylenetriamine, ethylenediamine, polyetheramine, aliphatic or aromatic amines (e.g., m-phenylenediamine), polyetheramines (e.g., jeffamine D-230), diaminodiphenyl sulfones (e.g., 3, 3 '-diaminodiphenyl sulfone), and combinations thereof.
  • DGEBA is as follows: [0063]
  • the structure of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate is as follows:
  • An example of such an amine-cured epoxy resin has the following repeat unit: where the dashed bond refers to attachment points to additional repeat units.
  • the polymer matrix is a benzoxazine-epoxy composite.
  • the benzoxazine-epoxy composite is formed by reacting a benzoxazine monomer and an epoxy anhydride monomer (e.g., copolymerized).
  • the benzoxazine monomer includes a monomer having the following formula:
  • the electrochemical cell 10 can be operated at a current density of at least 0.01 mA/cm 2 , 0.05 mA/cm 2 , 0.1 mA/cm 2 , 0.5 mA/cm 2 , 1 mA/cm 2 , 100 mA/cm 2 , 500 mA/cm 2 and at most to 1 A/cm 2 , 800 mA/cm 2 , 700 mA/cm 2 , 500 mA/cm 2 , 400 mA/cm 2 , or 300 mA/cm 2 .
  • the electrochemical cell 10 can be operated at a voltage of at least 1 V, 2 V, 3 V, or 4 V and at most 15 V, 10 V, 8 V, 6 V, or 5 V.
  • the electrolysis is performed at a predetermined temperature that is greater than 25 °C.
  • the predetermined temperature is from about 50 to 150 °C.
  • the predetermined temperature is at least 20 °C, 30 °C, 50 °C, 70 °C, or 100 °C and at most 200 °C, 180 °C, 160 °C, 150 °C, or 130 °C.
  • electrolysis is performed under reflux.
  • the C 2-6 carboxylic acid is at a concentration from about 1 M to 17.4 M and the (e.g., NaCl) is at a concentration from about 0.1 to 3 M.
  • the C 2-6 carboxylic acid is at a concentration from about 1 M to 4 M.
  • the C 2-6 carboxylic acid is at a concentration from about 4 M to 7 M.
  • the C 2-6 carboxylic acid is at a concentration from about 7 M to 10 M.
  • the C 2-6 carboxylic acid is at a concentration from about 10 M to 13 M.
  • the C 2-6 carboxylic acid is at a concentration from about 13 M to 16 M.
  • the C 2-6 carboxylic acid is at a concentration from about 16 M to 1.
  • the C 2-6 carboxylic acid is CH 3 COOH.
  • the CH 3 COOH is at a concentration from about 1 M to 17.4 M, and the (e.g., NaCl) is at a concentration from about 0.1 to 3 M.
  • the CH 3 COOH is at a concentration from about 1 M to 4 M.
  • the CH 3 COOH is at a concentration from about 4 M to 7 M.
  • the CH 3 COOH is at a concentration from about 7 M to 10 M.
  • the CH 3 COOH is at a concentration from about 10 M to 13 M.
  • the CH 3 COOH is at a concentration from about 13 M to 16 M.
  • the CH 3 COOH is at a concentration from about 16 M to 1.
  • the method further includes a step of washing the recycled plurality of fibers.
  • the recycled plurality of fibers can be incorporated into another polymer matrix.
  • Electrochemical cell 10 includes a fiber-reinforced polymer-containing anode 16.
  • the fiber- reinforced polymer-containing anode 16 includes a fiber-reinforced polymer matrix for recycling.
  • the fiber-reinforced polymer matrix 18 that includes an initial plurality of fibers dispersed in a polymeric matrix.
  • Figure 1 depicts electrochemical cell 10, including vessel 12, which holds electrolyte 14.
  • Electrochemical cell 10 includes cathode 20 (e.g., a graphite rod cathode).
  • the electrolyte solution 14 includes a C 1-6 carboxylic acid and sodium, a salt.
  • the fiber-reinforced polymer-containing anode and the graphite rod cathode are at least partially immersed in the electrolyte solution.
  • the process duration for the electrochemical digestion of the fiber-reinforced polymer matrix is up to 20 hours.
  • the electrolyte solution is maintained at a temperature of 50 to 150°C during electrolysis.
  • the details set forth above for the method apply to electrochemical cell 10.
  • DGEBA bisphenol A
  • 3,3 '-diaminodiphenyl sulfone 3,3’-DDS
  • CFRP-B samples T g 197 °C were produced using a commercial prepreg of a similar structure, Solvay CYCOM 5320-1, to demonstrate the feasibility of recovering materials from an aerospace material.
  • CFRPs laminates were cut to 50.8 x 10.2 or 76.2 x 38.1 mm for use as the anode, while a graphite rod served as the cathode ( Figure 3, Scheme 2).
  • the electrodes were immersed in an electrolyte solution that includes CH 3 COOH, NaCl, and deionized water. Electrolysis reactions were performed at constant current under reflux (0.25 A, 110 °C) with various electrolyte concentrations, respectively summarized in Table 1. Entries 1-7 test the effect of NaCl and CH 3 COOH. Entry 8 and 9 demonstrate feasibility of the method on commercial CFRPs.
  • Figure 5 shows SEM images of virgin CF and recovered CFs from entries 5 and 8.
  • Figure 5(a) shows surface grooves characteristic of the virgin fibers.
  • Figures 5b and c demonstrate that the CFs were clean and undamaged by the electrolysis process.
  • EDS composition analysis of virgin and CFs recovered from entry 5 is summarized in Table 2 and Figures 6 and 7: after 20 hours of electrolysis, EDS data show no chlorine, and oxygen increased by ⁇ 0.8 wt%, indicating no evidence of oxidation or chlorination on recovered CFs.
  • An alternative electrolysis recycling method that involved chlorine reported surface chlorine content increased by up to 8 wt%. 6
  • the difference in surface chemistry implies that the active radical in the system described herein is carbon-centered, not chlorine or oxygen, as implied elsewhere.
  • Scheme 2 ( Figure 3) also illustrates the process of recovering CF sheets from CFRP-B and remanufacturing them into second cycle CFRPs.
  • CFRP-B (76.2 x 38.1 mm) samples were electrolyzed for 25 hours under optimized conditions. Recovered CF fabrics were washed successively with acetone, deionized water, and DMSO to remove excess reactants and polyether sulfone tougheners. After drying, cleaned fabrics were hand-laminated with in-house resin (as in CFRP-A). Remanufactured CFRPs were fully consolidated, demonstrating the viability of up-cycling in-tact CF fabric from electrolysis conditions.
  • NMR spectra were recorded on a Varian Mercury 400, Vari an VNMRS 500, or VNMRS 600, spectrometers processed using MestReNova. All chemical shifts are reported in units of ppm and referenced to the residual 1 H or 13 C solvent peak and line-listed according to (s) singlet, (bs) broad singlet, (d) doublet, (t) triplet, (dd) double doublet, etc. 13 C spectra are delimited by carbon peaks, not carbon count. Air-sensitive NMR spectra were taken in 8” J-Young tubes (Wilmad or Norell) with Teflon valve plugs. Mass spectral data were acquired on an Agilent 6545 LC-QTOF instrument with electrospray set to positive ionization.
  • pre-impregnated resin-fiber substrate materials “prepregs” were fabricated in house or sourced from Solvay according to specified procedures. Cured CRFP panels were cut with a waterjet cutter (ProtoMAX) as described.
  • Epoxy equivalent weight (EEW) and amine hydrogen equivalent weight (AHEW) were used to calculate the mixing ratio of amine/epoxy.
  • a resin film was then prepared by spreading liquid resin onto a 203 x 203 mm release film (Airtech, Release Ease 236 TFNP), preheating at 50 °C on Wabash hot press. Prepreg was fabricated using 2 X 2 twill weave CF fabrics (FiberGlast 1069-B). One resin film was attached to each side of the CF fabric. Then, the stack was heated and pressed using a hot press at 50 °C with 20 kPa pressure for 1 min.
  • CFRP-A panels were then laminated via a vacuum bag-only process (VBO) using 4 plies of prepreg.
  • the curing cycle was (1) 1.5 °C /min to 120 °C, (2) hold at 120 °C for 3 hrs, (3) 1.5 °C/min to 180 °C and (4) hold at 180 °C for 3 hrs.
  • Fully cured CFRP-A panels were then cut to 50.8 x 10.2 mm using a water-jet cutter.
  • CFRP-B panels were fabricated using 4 plies of aerospace-grade VBO prepreg (Solvay CYCOM 5320-1, T650, PW). The cure cycle was (1) hold at 60 °C for 2 hrs, (2) 1 °C/min to 120 °C, (2) hold at 120 °C for 2 hrs, (3) 1.7 °C/min to 177 °C, and (4) hold at 177 at 120 °C for 2 hrs. Fully cured CFRP-B panels were cut into 50.8 x 10.2 mm or 76.2 x 38.1 mm samples on a water-jet cutter.
  • a CFRP sample was clamped by a PTFE (Teflon) platinum electrode holder and connected to a DC potentiostat as an anode, while a graphite rod served as the cathode as pictured above and diagramed in Figure 3.
  • the electrodes were immersed in the electrolyte solution including CH 3 COOH, NaCl, and DI water, according to loading details that are listed in Table 1.
  • 38.1 mm of the sample was immersed in solution and electrolyzed. Electrolysis reactions were performed in 180 mL electrolyte, using a 200 mL 5-neck glass vessel at reflux.
  • Figure 4 provides the measured voltage of Table 1, entry 5 during the electrolysis digestion
  • CFRPs were laminated using 2 x 2 twill weave CF fabrics (FiberGlast 1069-B), and Solvay CYCOM 5320-1 resin films. Fully cured panels were cut into 79.25 x 10.16 mm samples. CFRP samples were electrolyzed in 200ml electrolyte (11.6M CH 3 COOH, IM NaCl) at 110°C for 20hrs. Recovered CFs were cleaned using DI water, acetone, and DMSO. Cleaned CFs were dried in a convection oven at 120°C overnight before testing.
  • Sample mounting sheets were cut from printer paper into 25.4 x 76.2 mm strips with a 15.24 x 20.32 mm window in the center.
  • Single fibers were separated from tows and mounted across the window of the mounting papers. Both sides of single fibers were affixed using double-sided tapes and epoxy adhesive (Henkel E-120HP) to secure the fibers in place. Once the epoxy adhesive had cured, the mounted samples were examined using a light microscope (Keyence VHX-5000) using a 1000X lens to measure fiber diameter. The diameter of each sample was measured three times, and the resulting measured values were averaged to obtain the final measurement.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

Un procédé de recyclage de composites de fibres de carbone à l'aide de radicaux méthyle comprend une étape de fourniture d'une matrice polymère renforcée par des fibres pour le recyclage. La matrice polymère renforcée par des fibres comprend une pluralité initiale de fibres dispersées dans une matrice polymère. Le procédé comprend également une étape de dégradation électrolytique de la matrice polymère renforcée par des fibres par électrolyse dans une cellule électrochimique qui comprend une anode qui comprend la matrice polymère renforcée par des fibres, une cathode, et un électrolyte qui comprend du CH3 COOH, du NaCl et de l'eau. L'anode et la cathode sont immergées dans une solution électrolytique. De manière avantageuse, une pluralité recyclée de fibres est récupérée.
PCT/US2024/034459 2023-06-19 2024-06-18 Procédé électrochimique rapide pour recycler des composites de fibres de carbone Pending WO2024263559A2 (fr)

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478694A (en) * 1983-10-11 1984-10-23 Ska Associates Methods for the electrosynthesis of polyols
KR101262588B1 (ko) * 2011-07-28 2013-05-08 엘지이노텍 주식회사 에폭시 수지 조성물 및 이를 이용한 방열회로기판
WO2014017340A1 (fr) * 2012-07-25 2014-01-30 東レ株式会社 L'invention fournit un pré-imprégné, et un matériau composite renforcé par des fibres de carbone qui tout en se révélant excellent en termes d'adhérence entre des fibres de carbone et une résine de matrice et de stabilité de conservation sur le long terme, concilie une résistance aux chocs et une conductivité dans la direction de l'épaisseur qui sont excellentes. le pré-imprégné de l'invention est constitué par imprégnation dans des fibres de carbone revêtues de colle qui sont revêtues par une colle contenant un composé époxy aliphatique (a) et un composé époxy aromatique (b1), d'une composition de résine thermodurcissable contenant selon un rapport massique de 1 : 1 à 1000 des particules de résine thermoplastique (f) et des particules conductrices (g), ou des particules conductrices (h) dans lesquelles une résine thermoplastique est recouverte d'une substance conductrice. la surface desdites fibres de carbone revêtues de colle est caractéristique en ce que le rapport (a)/(b) entre la hauteur d'un composant d'énergie de liaison appartenant à (a) chx, c-c, c=c dans un spectre de noyau c1s, selon une mesure par spectroscopie de photoélectrons x, et la hauteur d'un composant d'énergie de liaison appartenant à (b) c-o, se trouve dans une plage prédéfinie.
EP3619282A1 (fr) * 2017-05-02 2020-03-11 Saudi Arabian Oil Company Consolidation de particules de formation
CN111995796A (zh) * 2020-06-24 2020-11-27 艾达索高新材料芜湖有限公司 一种碳纤维增强复合材料的电降解回收方法

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