Circulating flow reactor for recycling of carbon fiber from carbon fiber reinforced epoxy composite

For the purpose of development of a chemical recycling process for carbon fiber from carbon fiber reinforced epoxy composite, a new chemical recycling system using nitric acid aqueous solution has been proposed. The recycling system is composed of hexahedral circulating flow reactor made of quartz, Teflon supporter, acid resistance pump and auxiliaries. Epoxy matrix in the composite was effectively decomposed by nitric acid aqueous solution in the circulating flow reactor and carbon fiber could be recycled without any tangle or disturbance. Optimum conditions for the recycling process have been experimentally established. Tensile strength loss of recycled carbon fiber and composition of liquid phase decomposition products were analyzed.     

Recycling of the fibrous fraction of reinforced thermoset composites

We investigate the feasibility of reusing short fibers recovered from recycled thermoset composites for the production of new composites. Glass fibers were recovered from glass‐polyester composites, and carbon and aramide fibers from epoxy based composites. From the different fractions obtained after grinding, a specific fibrous fraction was selected for reuse. This recycled fraction was first characterized in terms of length and residual matrix content, and then incorporated into virgin polymer matrices to prepare new thermoplastic composites. To evaluate the performance of these composites, tensile tests were initially carried out, and the results were compared with similar measurements performed on pristine composites containing short unused fibers of similar length. In most cases examined, recycling does not adversely affect the mechanical performance of the new composite. This overall behavior is explained in terms of fiber length preservation, fiber dispersion mechanism and fiber‐matrix adhesion.     

The effect of mechanical recycling on the microstructure and properties of PA66 composites reinforced with carbon fibers

This article aims to prepare by injection molding recycled polymeric composites based on PA66 reinforced with short carbon fibers after artificial aging for applications in the automotive field. The aging cycles involves the combined action of UV radiation, moisture, and temperature in order to simulate the common outdoor conditions. The 100% recycled composites are obtained by the regranulation of the aged specimens followed by the remelting and re‐injection molding. The study is focused on the comparison between the mechanical behavior and the microstructure of the composites before and after mechanical recycling. The results of mechanical, thermal, and morphological investigations reveal that the recycling process had no significant effect on the final properties and microstructure of the recycled composites. Therefore the recycled PA66CF30 composites could be successfully used for structural or semi‐structural automotive applications guaranteeing good final performances and advantages from the environmental point of view. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42275.     

Recycling carbon fiber composites using microwave irradiation: Reinforcement study of the recycled fiber in new composites

With increasing use of carbon fiber reinforced polymer (CFRP) composites in transportation, sports, and many other industries, recycling of the scrap and end‐of‐life composites has presented both great challenges and opportunities. In this work, we report our study on reclaiming carbon fibers from CFRP using energy efficient microwave irradiation. Different irradiation conditions were used and the optimal conditions were determined based on the surface morphology of the recycled fiber. Polypropylene (PP) and Nylon, representing nonpolar and polar polymers, respectively, were reinforced using the recycled fiber through extrusion and injection molding. For comparison, PP and Nylon reinforced by virgin carbon fiber were also prepared using the same processing conditions. Tensile, flexural, and impact test results showed that, while both carbon fibers could improve these properties, they exhibited different reinforcing effects on the two polymers. The recycled fiber outperformed the virgin fiber in reinforcing PP whereas the virgin fiber performed better in Nylon. This was due to the differences in surface roughness, surface bonding, and fiber aspect ratio between the two fibers. This study shows the great potential of recycled carbon fiber and microwave irradiation as an effective recycling technique. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42658.     

Surface‐grafting of ground rubber tire by poly acrylic acid via self‐initiated free radical polymerization and composites with epoxy thereof

Commercially available recycled ground rubber tire (GRT) particles, found to contain persistent mechano‐free radicals confirmed by electron paramagnetic spectroscopy for the first time self‐initiates free radical polymerization of acrylic acid (AA). The poly acrylic acid (PAA) grafted GRT (PAA‐g‐GRT) was confirmed by Attenuated Total Reflection Fourier Transform Infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis (TGA). Epoxy composites using the PAA‐g‐GRT as filler were prepared and their mechanical properties were studied. The PAA‐g‐GRT/epoxy composite showed higher mechanical properties with an increase of modulus up to 180% as compared with the neat GRT/epoxy composite. Surface morphology of GRT, neat GRT/epoxy, and PAA‐g‐GRT/epoxy composites were analyzed by scanning electron microscopy. This technology introduces a new concept to functional and reactive recycling and the cost effective utilization of renewable resource green materials. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Amino‐functionalization of carbon fibers through electron‐beam irradiation technique

Amino‐functinonalized carbon fibers were achieved via electron‐beam (EB) irradiation in Diethylenetriamine (DETA) solution and triethylene tetramine (TETA) solution at 200 kGy. Different graft monomer concentrations were investigated to find the optimal concentration of each graft monomer. X‐ray photoelectron spectroscopy, scanning electron microscopy, and Raman spectroscopy were applied to investigate chemical composition and functional groups, topography and disorder degree of amino‐functionalized carbon fibers surface. Meanwhile, adsorption ability and interfacial adhesion between modified carbon fibers and epoxy resin were determined by TGA and interlaminar shear strength (ILSS). It is found that amino‐functionalized carbon fibers which had rougher and more active surface performed better adsorption ability on epoxy resin than untreated fibers. The optimal ILSS values of carbon fiber (treated with DETA and TETA) reinforced composites were 21.37 MPa and 18.28 MPa, which were much higher than that of untreated fiber reinforced composites. The comprehensive results demonstrated that in this condition, the optimal grafting concentrations of both DETA and TETA were 1.5 mol/L. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40274.     

Covalent functionalization of carbon fiber with poly(acrylamide) by reversible addition–fragmentation chain transfer polymerization for improving carbon fiber/epoxy interface

A novel method was developed for grafting poly(acrylamide) (PAAM) on to the carbon fiber (CF) surface via reversible addition–fragmentation chain transfer (RAFT) polymerization to improve the interaction between carbon fibers and epoxy matrix in the composites system. The carbon fibers were first treated with nitric acid and γ‐methacryloxypropyltrimethoxy silane (KH570). Then, the PAAM was grafting onto the carbon fiber surface via RAFT polymerization. The resulted carbon fibers functionalized with PAAM (CF‐PAAM) were characterized by FTIR, XPS, and TGA, and the results revealed that CF‐PAAM were synthesized successfully. The introduction of PAAM chains could make the fiber surface rougher and introduce a large numbers of –NH₂ groups, which can improve the interfacial adhesion in the composites. The microbond test results showed that the interfacial shear strength (IFSS) of the composites reinforced by CF‐PAAM has been enhanced about 107%. POLYM. COMPOS., 38:27–31, 2017. © 2015 Society of Plastics Engineers     

Solid freeform fabrication of epoxidized soybean oil/epoxy composites with di‐, tri‐, and polyethylene amine curing agents

Soybean oil/epoxy‐based composites are prepared by solid freeform fabrication (SFF) methods. SFF methods built materials by the repetitive addition of thin layers. The mixture of epoxidized soybean oil and epoxy resin is modified with di‐, tri‐, or polyethylene amine gelling agent to solidify the materials until curing occurs. The high strength and stiffness composites are formed through fiber reinforcement. E‐glass, carbon, and mineral fibers are used in the formulations. The type of fiber affects the properties of the composites. It was found that a combination of two types of fibers could be used to achieve higher strength and stiffness parts than can be obtained from a single fiber type. In addition, the effects of curing temperature, curing time, and fiber concentration on mechanical properties of composites are studied and reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 356–363, 2004     

Chemical recycling of glass fiber reinforced epoxy resin cured with amine using nitric acid

An approach to chemical recycling of amine cured epoxy resin using nitric acid solution has been proposed [Dang W, Kubouchi M, Yamamoto S, Sembokuya H, Tsuda K. Polymer 2002;43:2953-8. [1]]. 1,8-p-Menthanediamine cured bisphenol F type (BPF/MDA) epoxy resin was decomposed in nitric acid solution, and then the decomposed product was repolymerized with original resin. In this paper, applicability of the proposed approach to glass fiber reinforced bisphenol F type epoxy resin cured with diamino diphenyl methane (DDM) was investigated. It was concluded that the approach was applicable to BPF/DDM epoxy resin, and potentially to all of amine cured epoxy resin. Flexural strength of the recycled resin was higher than that of virgin resin until the content of the neutralized extract, which was available from degradation of BPF/DDM epoxy resin, was not more than 30 wt% of the original resin. The reinforcement of glass fiber could be separated and recovered. The existence of the reinforcement did not affect decomposition the matrix.     

Low‐velocity impact response and compression after impact assessment of recycled carbon fiber‐reinforced polymer composites for future applications

The influence of recycling on the impact damage resistance of recycled carbon fiber‐reinforced polymer (CFRP) composites was investigated using low‐velocity impact and compression after impact (CAI) tests. The relationships among load, force, and time were analyzed to gain insight into the damage characteristics of three types of composite laminate: virgin CF‐reinforced polymer (V‐CFRP), recycled CF‐reinforced polymer (R‐CFRP), and treated recycled CF‐reinforced polymer (TR‐CFRP). Special emphasis was placed on evaluating the extent of damage and the residual mechanical properties as affected by three different fiber surface states. Substantial differences were noted in the shape, area, and damage mode of impact using ultrasonic c‐scanning, photography, and scanning electron microscopy (SEM). V‐CFRP indicated significant improvement in impact damage resistance in the form of less damage, higher residual strength, and greater shear failure angle. Damage resistance was improved up to 80% of V‐CFRP by surface cleaning while R‐CFRP is 50% of V‐CFRP. Shear failure angle of 16° was attained from R‐CFRP and it was increased to 24° when the recycled fibers were cleaned. The result of SEM showed that there was less delamination of TR‐CFRP compared with R‐CFRP. This work proves that the low‐velocity impact response of recycled composites can rival that of virgin composites, while providing a basis for future applications of recycled carbon in many fields. POLYM. COMPOS., 35:1494–1506, 2014. © 2013 Society of Plastics Engineers     

Temperature effect on graphene‐filled interface between glass–carbon hybrid fibers and epoxy resin characterized by fiber‐bundle pull‐out test

The overall mechanical performance of glass–carbon hybrid fibers reinforced epoxy composites depends heavily upon fiber–matrix interfacial properties and the service temperatures. Fiber‐bundle pull‐out tests of glass (GF) and/or carbon fiber (CF) reinforced epoxy composites were carried out at room and elevated temperatures. Graphene nanoplatelets were added in the interfacial region to investigate their influence on the interfacial shear strength (IFSS). Results show that IFSS of specimens with fiber‐bundle number ratio of GF:CF = 1:2 is the largest among the hybrid composites, and a positive hybridization effect is found at elevated temperatures. IFSS of all the specimens decreases with the increasing of test temperatures, while the toughness shows a contrary tendency. As verified by scanning electron microscopy observations, graphene nanoplatelets on fiber surface could enhance the IFSS of pure glass/carbon and hybrid fibers reinforced epoxy composites at higher temperatures significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46263.     

Preparation and properties of carbon fiber/ hydroxyapatite‐poly(methyl methacrylate) biocomposites

An in situ polymerization with a later solution co‐mixing approach was used in the preparation of polymethyl methacrylate (PMMA) matrix composites using hydroxyapatite (HA) nanoparticles and short carbon fibers(C_(f)) as reinforcing materials. The microstructures and fracture surface morphologies of the prepared C_(f)/HA‐PMMA composite were characterized using XRD, FTIR, SEM, EDS, and FESEM analyses. The mechanical properties of the composites were tested by a universal testing machine. Results show that the surface of nitric acid‐oxidized carbon fibers and lecithin‐treated HA contain new functional groups. Uniform dispersion of short fibers and HA nanoparticles in PMMA matrix is successfully achieved and the mechanical properties of the composites are obviously improved. The flexural strength, flexural modulus, and Young's modulus of the composites reach the maximum value 128.12 MPa, 1.150 GPa, and 4.572 GPa when carbon fiber and HA mass fraction arrive to 4% and 8%, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Up‐cycling end‐of‐use materials: Highly filled thermoplastic composites obtained by loading waste carbon fiber composite into fluidified recycled polystyrene

Carbon fibers reinforced epoxy resins are used in a wide range of applications, such as automotive and aerospace industry. Because of their thermosetting nature, recycling at the end of the life cycle is a difficult issue. However, lack of recyclability poses environmental concerns to the use of these composite materials. In this article, a sustainable, cost‐effective technological approach aiming at recycling postconsumer carbon fibers reinforced thermosets (CFRT) is proposed. Composites containing 50 and 70 wt% of CFRT particles were prepared by incorporating the filler fraction into a fluidified postconsumer expanded polystyrene matrix. A cold mixing approach consisting in the use of a low boiling solvent as a binder to guarantee the dispersion homogeneity on micro‐ and macroscopic level was set up. For comparison, analog composites were also prepared through melt mixing process. Morphological, mechanical, and thermal analyses allowed to prove the effectiveness of the cold mixing approach and to evaluate the influence of particle size on the performance of new recycled composites. Thermogravimetric analysis and thermal conductivity tests of samples highlighted further peculiarities of the cold mixing process. The approach proposed is an effective recycling technology for CFRT and could be extended to other postconsumer materials. POLYM. COMPOS., 35:1621–1628, 2014. © 2013 Society of Plastics Engineers     

胺类固化剂固化的双酚环氧树脂回收再利用的研究

双酚F型环氧树脂的耐酸性较低，在硝酸溶液中能够被安全分解。基于这一特性，本文探讨了一种环氧树脂化学回收再利用的方法。首先，用乙酸乙酯做溶液把该树脂的硝酸分解生成物从中性环境溶液中萃取出来，干燥后，替代部分环氧树脂，混入环氧树脂中，经固化剂固化后，制得再生树脂。并对原树脂和再生树脂的机械性能进行了比较。     

An approach to chemical recycling of epoxy resin cured with amine using nitric acid

An approach to chemical recycling of epoxy resin was pursued. Bisphenol F type epoxy resin cured with 1,8-p-menthanediamine could be completely decomposed in nitric acid solution resulting from low corrosion resistance to nitric acid. Organic decomposed products of the resin with the highest yield were extracted from neutralized solution. The extract was repolymerized to prepare recycled resin, mixed with bisphenol F type epoxy resin and curing agent of phthalic anhydride. The mechanical properties of virgin resin and recycled resins were compared. It was surprising that the recycled resins were far superior to the virgin resin in strength. The results obtained from differential scanning calorimeter (DSC) showed that the glass transition temperature (T_g) of recycled resins was higher than that of virgin resin. The reason that they formed the better network structure was discussed.     

Toughening of recycled poly(ethylene terephthalate) with a maleic anhydride grafted SEBS triblock copolymer

Toughening of recycled poly(ethylene terephthalate) (PET) was carried out by blending with a maleic anhydride grafted styrene‐ethylene/butylene‐styrene triblock copolymer (SEBS‐g‐MA). With 30 wt % of the SEBS‐g‐MA, the notched Izod impact strength of the recycled PET was improved by more than 10‐fold. SEM micrographs indicated that cavitation occurred in just a small area near the notch root. Addition of 0.2 phr of a tetrafunctional epoxy monomer increased the recycled PET melt viscosity by chain extension reaction. Different from the positive effect of the epoxy monomer in toughening of nylon and PBT with elastomers, the use of the epoxy monomer in the recycled PET/SEBS‐g‐MA blends failed to further enhance dispersion quality and thus notched impact strength. This negative effect of the epoxy monomer was attributed to the faster reactivity of the epoxy group with maleic anhydride of the SEBS‐g‐MA than with the carboxyl or hydroxyl group of recycled PET. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1462–1472, 2004     

Thermal degradation of epoxy resin reinforced with polypropylene fibers

The influence of polypropylene fibers on the thermal degradation of epoxy composites was investigated with thermogravimetric analysis. Three composites with 5, 10, or 15 wt % polypropylene fibers were prepared with epoxy as a matrix material. The polypropylene fibers, used as reinforcing materials, retarded the thermal decomposition, and increasing the weight percentage of the fiber material increased the thermal stability to a certain extent. Of the three composites, the 10 wt % polypropylene fiber/epoxy resin composite showed very good thermal stability, which was indicated by the increase in the resin decomposition temperature from 280°C for the 5 wt % polypropylene fiber/epoxy resin composite to 375°C for the 10 wt % polypropylene fiber/epoxy resin composite. The Horowitz–Metzger method was used to calculate the activation energies, and the results were tabulated. A morphological analysis was carried out with scanning electron microscopy to evaluate the dispersion of the fibers in the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 500–503, 2007     

Thermal degradation of a phenolic resin,vegetable fibers,and derived composites

The thermal degradation behavior of resol, several vegetable fibers (two types of cotton fibers, sisal and sugar cane bagasse) and derived polymer composites have been investigated using thermogravimetric analysis (TGA). The initial thermal degradation temperature T_ONSET, the temperature at the maximum degradation rate TD_M, and the char left at 500°C corresponding to the crosslinked resol were higher than the values measured for the fibers and their composites. Thus, the addition of the fibers reduced the thermal resistance of the phenolic thermoset. The polymer and the fiber‐composites showed a complex degradation involving different thermal decomposition processes. For that reason, the DTG curves were deconvoluted and a phenomenological kinetic expression was found for each individual peak. The overall thermal decomposition curve was recalculated adding each degradation process weighted according to its contribution to the total weight loss. An increase in the activation energy corresponding to the cellulose degradation was observed in the composites, highlighting the protective action of the resin encapsulating the fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Incorporation of silicon dioxide nanoparticles at the carbon fiber‐epoxy matrix interphase and its effect on composite mechanical properties

Functionalized silicon dioxide nanoparticles (nano‐fSiO₂) were uniformly deposited on the surface of carbon fibers (CFs) using a coating process which consisted of immersing the fibers directly in a suspension of nano‐fSiO₂ particles and epoxy monomers in 1‐methyl‐2‐pyrrolidinone (NMP). The 0° flexural properties, 90° flexural properties, and Interlaminar shear strength (ILSS) mechanical properties of unidirectional epoxy composites made with nano‐fSiO₂+epoxy sized carbon fibers, with control fibers, and with epoxy‐only sized fibers were measured and compared. An obvious increase of the fiber/matrix adherence strength was obtained with the nano‐fSiO₂+epoxy coating. The nano‐fSiO₂+epoxy sized CF/epoxy composites showed a relative increase of 15%, 50%, and 22% in comparison to control fibers, for the Interlaminar shear strength, the 90^° flexural strength and the 90° flexural modulus, respectively, but little e difference was measured between the different systems for the 0° flexural properties. The observation of the fracture surfaces by scanning electron microscopy of composite fracture confirmed the improvement of the interfacially dependent mechanical properties. POLYM. COMPOS., 38:1474–1482, 2017. © 2015 Society of Plastics Engineers     

Investigation into the morphological and mechanical properties of date palm fiber-reinforced epoxy structural composites

This study aims to examine the morphology and mechanical properties (tensile, flexural, and compressive) of epoxy composites reinforced with epoxy date palm leaves (EDPL), epoxy date palm branch (EDPB), and epoxy/hardener date palm core shell (EDPC) fibers (particle size <1 μm depend on the date palm fibers). A three-step technique was used to obtain the composites. The EDPL composites showed a maximum tensile strength of 3.45 MPa, while the EDPB composites showed maximum compressive and flexural rigidity of 9.46 and 5.55 MPa, respectively, owing to the good compatibility of fiber-matrix bonding. In this work, epoxy composites reinforced with date palm fibers (DPF) leaves, branches, and core shell were recycled using a cost-effective and easily reproducible three-step technique. EDPC fibers fabricated with 64.65% weight carbon fibers content demonstrated improved tensile strengths and stiffness properties. The three samples of palm date composites revealed mechanical properties that could be used to trial these fibers for manufacturing purposes, and to exploit their extraordinary mechanical properties shown in current results.