Reinforcement effect of poly (methyl methacrylate)-<Emphasis Type="Italic">g</Emphasis>-cellulose nanofibers on LDPE/thermoplastic starch composites: preparation and characterization

The effect of cellulose nanofibers (CNFs) and poly [methyl methacrylate (MMA)]-grafted cellulose nanofibers (CNF-g-PMMA) on mechanical properties and degradability of a 75/25 low density polyethylene/thermoplastic starch (LDPE/TPS) blend was investigated. Graft copolymerization on CNFs was performed in an aqueous suspension by free radical polymerization using MMA as an acrylic monomer. In addition, a LDPE/TPS blend was reinforced by different amounts of CNFs (1–5 wt%) and CNF-g-PMMA (1–7 wt%) using a twin-screw extruder. A 61% grafting of PMMA on the surface of CNFs was demonstrated by gravimetric analysis. Moreover, after modification the X-ray photoelectron spectroscopy analysis showed a 20% increase of carbon atoms on the surface of CNFs and a 22.6% decrease in the oxygen content of its surface. The mechanical properties of the CNFs-modified composites were significantly improved compared to the unmodified nanocomposites. The highest tensile strength and Young’s modulus were obtained for the composites reinforced by 3 and 7 wt% CNF-g-PMMA, respectively. The degradability of cellulose nanocomposites was studied by water absorption and soil burial tests. Surface modification of CNFs lowered water absorption, and soil burial test of the LDPE/TPS blend showed improvement in biodegradability by addition of CNF-g-PMMA.     

Effect of cellulose nanofibers and acetylated cellulose nanofibers on the properties of low‐density polyethylene/thermoplastic starch blends

The aim of this study was to evaluate the effect of cellulose nanofibers (CNFs) and acetylated cellulose nanofibers (ACNFs) on the properties of low‐density polyethylene/thermoplastic starch/polyethylene‐grafted maleic anhydride (LDPE/TPS/PE‐g‐MA) blends. For this purpose, CNFs, isolated from wheat straw fibers, were first acetylated using acetic anhydride in order to modify their hydrophilicity. Afterwards, LDPE/TPS/PE‐g‐MA blends were reinforced using either CNFs or ACNFs at various concentrations (1–5 wt%) with a twin‐screw extruder. The mechanical results demonstrated that addition of ACNFs more significantly improved the ultimate tensile strength and Young's modulus of blends than addition of CNFs, albeit elongation at break of both reinforced blends decreased compared with the neat sample. Additionally, biodegradability and water absorption capacity of blends improved due to the incorporation of both nanofibers, these effects being more pronounced for CNF‐assisted blends than ACNF‐reinforced counterparts. © 2018 Society of Chemical Industry     

Effects of crystallization on dispersion of carbon nanofibers and electrical properties of polymer nanocomposites

Polymer nanocomposites filled with low volume fractions of carbon nanofibers (CNFs) were prepared by melt‐compounding. Three types of polymers with different crystallization behavior, i.e., weakly‐crystallized low density polyethylene (LDPE), strongly crystallized high density polyethylene (HDPE) and amorphous polystyrene (PS), were selected as matrices for the nanocomposites. The effects of polymer crystallization on the dispersion of CNFs were examined. Optical and electron microscopic examinations revealed that the dispersion of CNFs in the nanocomposite matrices was strongly depended on the crystallization behavior of polymer matrices. The CNFs were found to disperse uniformly in weakly crystallized LDPE and amorphous PS matrices, but agglomerated in HDPE due to its strong crystallization tendency. Such a distinct dispersion behavior of CNFs in polymers had a profound effect on the electrical properties of the nanocomposites investigated. The PS/CNF nanocomposites exhibited the lowest percolation threshold. The HDPE/CNF nanocomposites showed the largest percolation threshold due to the CNF agglomeration within the amorphous phase of HDPE. POLYM. ENG. SCI., 48:177–183, 2008. © 2007 Society of Plastics Engineers     

Effect of carbon nanofiber (CNF) silanization on the properties of CNF/epoxy nanocomposites

Carbon nanofibers (CNFs) were functionalized by a multistage process including oxidation, reduction and silanization. The chemical modifications were examined by Fourier transform infrared spectroscopy, X‐ray photoelectron spectrometry, Raman spectroscopy and thermogravimetric analysis. The silanized CNFs were then added into an epoxy resin (EPON 828) to study the effect of the surface modification of CNFs on the properties of nanocomposites. For comparison, nanocomposites containing original unmodified CNFs were also investigated. Scanning electron microscopy indicates better dispersion of modified fibers in the epoxy polymer matrix; the mechanical and thermal properties of composites are also improved; the electrical conductivity of the composites is reduced. Copyright © 2011 Society of Chemical Industry     

Surface modification of CNFs via plasma polymerization of styrene monomer and its effect on the properties of PS/CNF nanocomposites

Carbon nanofibers (CNF) were modified via plasma assisted polymerization in a specially designed reactor. The effect of the plasma reactor conditions, such as power and time, on the extent of the CNFs modification was examined. Polystyrene (PS) coated nanofibers plus PS polymer were then processed in a Brabender torque rheometer mixing chamber to obtain PS/CNF nanocomposites, with 0.5, 1.0, 3.0, and 5.0 wt % of CNF. The effect of the plasma treatment on the dispersion of the nanofibers and on the compatibility between the nanofibers and the polymer matrix was also examined. Modification of the CNFs was assessed by measuring the contact angle of water in a “bed” of nanofibers and by examining its dispersion in several solvents. The morphology of PS/CNF nanocomposites was studied through scanning electron microscopy (SEM). Contact angles decreased in all cases, indicating a change in hydrophobicity of the modified CNFs. This change was confirmed in the CNF dispersion tests in several solvents. SEM micrographs show the difference between the original and the PS coated CNF. In addition, fractured samples show the effect of this treatment, in the sense that the CNF seem to be completely embedded in the polymer matrix, which clearly indicates the high compatibility between the PS and the modified (PS coated) CNF. As a consequence, a much better dispersion of the treated CNF was observed. Finally, the tensile modulus of PS/CNF composites increased slightly with respect to PS when using untreated CNFs, but more than doubled when using plasma treated CNFs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Printability,shape-memory,and mechanical properties of PHB/PCL/CNFs composites

Shape-memory polymers have attracted attention as smart implant materials in recent years because they are lightweight, low-cost, easily processable, and because they undergo large deformation. Here, cellulose nanofibers (CNFs) were used as a reinforcement for polyhydroxybutyrate (PHB)/polycaprolactone (PCL) composites to improve mechanical properties. The composites were investigated by rheological tests, differential scanning calorimetry, dynamic mechanical analysis, mechanical property tests, and shape-memory tests. The printability of PHB/PCL/CNFs composites was demonstrated by using them to print interconnected porous structures with a gyroid surface. The results showed that the PHB/PCL (80:20) composites with 1 wt% CNF displayed the best comprehensive mechanical and shape-memory properties. As a functional verification, a model of the self-opening hand was fabricated by 3D printing, and its deformation and recovery capabilities were evaluated.     

Cellulose NANOFIBER‐polyethylene nanocomposites modified by polyvinyl alcohol

The uniform dispersion of cellulose nanofibers (CNFs) in non‐polar polymer matrices is a primary problem to overcome in creating novel nanocomposites from these materials. The aim of this study was to produce CNF‐polyethylene (PE) nanocomposites by melt compounding followed by injection molding to investigate the possibility of using polyvinyl alcohol (PVA) to improve the dispersion of CNF in the PE matrix. The tensile strength of CNF‐ filled composites was 17.4 MPa with the addition of 5 wt % CNF–PVA, which was 25% higher than the strength of neat PE. The tensile modulus of elasticity increased by 40% with 5% CNF–PVA addition. Flexural properties also significantly increased with increased CNF loading. Shear viscosity increased with increasing CNF content. The elastic moduli of the PE/CNF composites from rheological measurements were greater than those of the neat PE matrix because of the intrinsic rigidity of CNF. Melt creep compliance decreased by about 13% and 45% for the composites with 5 wt % CNF and 10 wt % CNF, respectively. It is expected that the PVA carrier system can contribute to the development of a process methodology to effectively disperse CNFs containing water in a polymer matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42933.     

Bio‐nanocomposites for food packaging applications: effect of cellulose nanofibers on morphological,mechanical, optical and barrier properties

The effect of the addition of various concentrations of cellulose nanofibers (CNF) on the thickness, solubility, morphology, mechanics, water vapor permeability and optical properties of biopolymers isolated from whey protein produced by the casting method was studied. The results show that the addition of CNF did not cause significant variation in the thickness of the films and resulted in nanocomposites with lower solubility and water vapor permeability. Scanning electron microscopy analysis showed that the films obtained with up to 4% of CNF showed good dispersion of the nanofibers in the whey protein matrix. The results of mechanical tests showed that the nanofibers acted as reinforcing material resulting in more resistant and less flexible films. © 2017 Society of Chemical Industry     

A comparison of partially acetylated nanocellulose,nanocrystalline cellulose,and nanoclay as fillers for high‐performance polylactide nanocomposites

Partially acetylated cellulose nanofibers (CNF) were chemically extracted from sisal fibers and the performance of those CNF as nanofillers for polylactide (PLA) for food packaging applications was evaluated. Three PLA nanocomposites; PLA/CNF (cellulose nanofibers), PLA/CNC (nanocrystalline cellulose), and PLA/C30B (Cloisite^TM 30B, an organically modified montmorillonite clay) were prepared and their properties were evaluated. It was found that CNF reinforced composites showed a larger decrease on oxygen transmission rate (OTR) than the clay‐based composites; (PLA/CNF 1% nanocomposite showed a 63% of reduction at 23°C and 50% RH while PLA/C30B 1% showed a 26% decrease) and similar behavior on terms of water vapor barrier properties with 46 and 43%, respectively of decrease on water vapor transmission rate at 23°C and 50% RH (relative humidity). In terms of mechanical and thermomechanical properties, CNF‐based nanocomposites showed better performance than clay‐based composites without affecting significantly the optical transparency. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43257.     

Thermotropic LCP/CNF nanocomposites prepared with aid of ultrasonic waves

Ultrasound assisted twin screw extrusion process was developed to disperse carbon nanofibers (CNFs) in a polymer matrix. CNFs were separately added into the melt stage to reduce the breakage of CNFs and to avoid intense stresses in the feed zone. The effect of ultrasound and CNFs loading on die pressure, rheological, mechanical, electrical and morphological properties of liquid crystalline polymer (LCP) filled with 0-20 wt% CNFs was studied. Ultrasonic treatment caused a reduction in die pressure and a decrease in electrical percolation threshold value of treated samples. It was also found that mechanical properties of ultrasonically treated LCP/CNF nanocomposite moldings were preserved, improved or slightly decreased in comparison with those of LCP. This is in contrast to available literature typically showing a deterioration of mechanical properties with addition of CNFs. SEM studies have indicated an improved dispersion of CNFs and a reduction of LCP rich area in nanocomposites upon ultrasonic treatment.     

Effects of surface modification,carbon nanofiber concentration,and dispersion time on the mechanical properties of carbon‐nanofiber–polycarbonate composites

The time effect of ultrasonication was investigated for dispersing carbon nanofibers (CNFs) into a polycarbonate (PC) matrix on the mechanical properties of thus‐produced composites. The effects of CNF surface modification by plasma treatment and the CNF concentration in composites on their mechanical properties were also explored. The plasma coating was characterized by HRTEM and FT‐IR. Furthermore, the plasma polymerization (10 w) treatment on the CNF enhanced the CNF dispersion in the polymer matrix. The mechanical properties of the CNF–PC composites varied with the dispersion time, at first increasing to a maximum value and then dropping down. After a long ultrasonic treatment (24 h), the properties increased again. At a high concentration, the CNF‐PC suspension became difficult to disperse. Additionally, the possible mechanisms for these behaviors are simply proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3792–3797, 2007     

Completely biodegradable composites reinforced by the cellulose nanofibers of pineapple leaves modified by eco-friendly methods

In this study, cellulose nanofibers (CNF) derived from waste pineapple leaves (PALF) were incorporated into poly (lactic acid) (PLA) with the aim of developing completely biodegradable and sustainable composites. CNF was first prepared by the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) method, and then, different surface modifications of the eco-friendly method were carried out for better dispersion in the PLA matrix. Then, a series of eco-friendly modified CNF/PLA composites were prepared by melt-blending. According to the contact angle experiment, the values of eco-friendly modified CNFs increased from 12.02° to 61.49 and 57.45°, respectively. DSC thermograms show that eco-friendly modified CNFs have a significant nucleating effect for the crystallization of PLA compared to the original CNF. Mechanical testing reveals that the tensile and impact strengths of eco-friendly modified CNF containing composites are improved by 5.4~22.7% and 17.5~56.1%, respectively, through the addition of only 1~3 wt% of modified CNF, and are all higher than that of the original CNF containing composite. Moreover, eco-friendly modified CNF containing composites can allow good light transmittance due to better dispersity of the modified CNF. Consequently, the addition of modified CNFs to the PLA matrix results in increased mechanical and thermal properties of the composites, as well as transparency. Moreover, the addition of CNFs extracted from pineapple leaves by eco-friendly methods can not only reduce the amount of agriculture waste but also avoid the usage of an organic solvent and meet the requirements of environmental protection.     

Cellulose nanofibers produced from various agricultural residues and their reinforcement effects in polymer nanocomposites

Cellulose nanofibers (CNFs) have gained widespread attention due to their extraordinary potential as superior reinforcement to improve physical and mechanical properties of polymer matrix nanocomposites. Biomass residues from local North Dakota represent a potential source for these high value structural constituents. Two types of soybean hull, wheat straw, and softwood flour were subjected to chemical pretreatments followed by mechanical fibrillation to produce CNFs. Atomic force microscopy and scanning electron microscopy results show that nanofibers with uniform diameters in the nanometer range can be easily synthesized. The nanofibers reinforcement potential was then explored via integration of the fibers into a poly(ethylene oxide) polymer matrix. Significant reinforcement effect of the nanofibers was observed from the nanocomposites: tensile modulus and yield strength of the nanocomposites were increased up to 154% and 103%, respectively. The CNFs extracted from the two types of soybean hull and wood flour showed stronger reinforcement (in terms of both modulus and yield strength) than that of the traditional wood pulp based CNFs. The nanofibers extracted from wheat straw showed higher strength but lower modulus compared with those of the traditional CNFs. More work is however needed to improve production reliability/repeatability of the agricultural residue based nanofibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46304.     

Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.     

Thermal,morphological, and mechanical characterization of novel carbon nanofiber‐filled bismaleimide composites

Novel carbon nanofiber (CNF) ‐filled bismalemide composites were fabricated by a thermokinetic mixing method. The thermal and mechanical properties of composites containing 1 wt % and 2 wt % CNFs were investigated. Thermogravimetric analysis demonstrated that minimal improvement in thermal stability of the nanocomposites was obtained by the addition of CNFs. Dynamic mechanical analysis showed an increase in storage modulus (E′) and glass transition temperature (T_g) upon incorporation of nanofibers. Limiting oxygen index (LOI) has also been found to increase with incorporation of CNFs. Morphological studies of fractured surfaces of the composites has been carried out by scanning electron microscopy to determine the effect of fiber content and dispersion on the failure mechanism. In general, good dispersion was observed, along with agglomeration at some points and some fiber matrix interfacial debonding. A decrease in mechanical strength has been observed and debonding was found as the main failure mechanism. Further research outlook is also presented. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Carbon nanofiber type and content dependence of the physical properties of carbon nanofiber reinforced polypropylene composites

The variation of the physical properties of four different carbon nanofibers (CNFs), based‐polymer nanocomposites incorporated in the same polypropylene (PP) matrix by twin‐screw extrusion process was investigated. Nanocomposites fabricated with CNFs with highly graphitic outer layer revealed electrical isolation‐to‐conducting behaviors as function of CNF's content. Nanocomposites fabricated with CNFs with an outer layer consisting on a disordered pyrolitically stripped layer, in contrast, revealed better mechanical performance and enhanced thermal stability. Further, CNF's incorporation into the polymer increased the thermal stability and the degree of crystallinity of the polymer, independently on the filler content and type. In addition, dispersion of the CNFs' clusters in PP was analyzed by transmitted light optical microscopy, and grayscale analysis (GSA). The results showed a correlation between the filler concentration and the variance, a parameter which measures quantitatively the dispersion, for all composites. This method indicated a value of 1.4 vol% above which large clusters of CNFs cannot be dispersed effectively and as a consequence only slight changes in mechanical performance are observed. Finally, this study establishes that for tailoring the physical properties of CNF based‐polymer nanocomposites, both adequate CNFs structure and content have to be chosen. POLYM. ENG. SCI., 54:117–128, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of carbon nanofiber reinforced thermoplastic polyurethane nanocomposites

The effect of CNFs on hard and soft segments of TPU matrix was evaluated using Fourier transform infrared (FTIR) spectroscope. The dispersion and distribution of the CNFs in the TPU matrix were investigated through wide angle X‐ray diffraction (WAXD), field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), polarizing optical microscope (POM), and atomic force microscope (AFM). The thermogravimetric analysis (TGA) showed that the inclusion of CNF improved the thermal stability of virgin TPU. The glass transition temperature (T_g), crystallization, and melting behaviors of the TPU matrix in the presence of dispersed CNF were observed by differential scanning calorimetry (DSC). The dynamic viscoelastic behavior of the nanocomposites was studied by dynamical mechanical thermal analysis (DMTA) and substantial improvement in storage modulus (E') was achieved with the addition of CNF to TPU matrix. The rheological behavior of TPU nanocomposites were tested by rubber processing analyzer (RPA) in dynamic frequency sweep and the storage modulus (G') of the nanocomposites was enhanced with increase in CNF loading. The dielectric properties of the nanocomposites exhibited significant improvement with incorporation of CNF. The TPU matrix exhibits remarkable improvement of mechanical properties with addition of CNF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt compounded nanocomposites with semi‐interpenetrated network structure based on natural rubber,polyethylene, and carrot nanofibers

The present study deals with the processing and characterization of cellulose nanocomposites natural rubber (NR), low‐density polyethylene (LDPE) reinforced with carrot nanofibers (CNF) with the semi‐interpenetrated network (S‐IPN) structure. The nanocomposites were compounded using a co‐rotating twin‐screw extruder where a master‐batch of NR and CNF was fed to the LDPE melt, and the NR phase was crosslinked with dicumyl peroxide. The prepared S‐IPN nanocomposites exhibited a significant improvement in tensile modulus and yield strength with 5 wt % CNF content. These improvements are due to a better phase dispersion in the S‐IPN nanocomposites compared with the normal blend materials, as demonstrated by optical microscopy, electron microscopy and ultraviolet–visible spectroscopy. The S‐IPN nanocomposite also displayed an improved crystallinity and higher thermal resistance compared with NR, CNF, and the normal blend materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45961.     

Effect of amine functionalization of CNF on electrical, thermal, and mechanical properties of epoxy/CNF composites

This paper presents experimental results of the effect of amine functionalization of carbon nanofibers (CNF) on the electrical, thermal, and mechanical properties of CNF/epoxy composites. The functionalized and non-functionalized CNFs (up to 3 wt%) were dispersed into epoxy using twin screw extruder. The specimens were characterized for electrical resistivities, thermal conductivity (K), UTS, and Vicker’s microhardness. The properties of the nanocomposites were compared with that of neat epoxy. The volume conductivity of the specimens increased by E12 S/cm and E09 S/cm in f-CNF/epoxy and CNF/epoxy, respectively, at 3 wt% filler loading. The increase in K for former was 106% at 150 °C, while for the latter it was only 64%. Similarly, UTS increased by 61% vs. 45% and hardness 65% vs. 43%. T _g increased with increase in filler content. SEM examinations showed that functionalization resulted in better dispersion of the nanofibers and hence greater improvement in the studied properties of the nanocomposites.     

Thermally stable electromagnetic interference shielding material from polysulfone nanocomposites: Comparison on carbon nanotube and nanofiber reinforcement

The present investigation aims to develop thermally stable electromagnetic interference shielding materials from polysulfone (PSU) nanocomposites filled with multiwall carbon nanotubes (MWCNT) or carbon nanofibers (CNF). The effect of filler type and their structural features such as aspect ratio (length/diameter) and wall integrity on the different properties of nanocomposites has been investigated. Nanocomposite filled with MWCNT/CNF exhibits higher thermal stability compared with the neat PSU matrix. The onset degradation temperature of PSU at 532°C enhances to 537 and 538°C at 3 wt% MWCNT and 3 wt% CNF loading, respectively. CNFs filled nanocomposite shows higher electromagnetic interference shielding effectiveness (EMISE) compared with MWCNT filled one at the same filler loading. Compared with MWCNT, CNF imparts lower electrical percolation threshold. Nanocomposite filled with MWCNTs possesses percolation threshold at 1.5 wt%, whereas nanocomposite filled with CNFs possesses the same at 0.9 wt%. The EMISE of 20–45 dB are obtained from only 1 mm thick CNF filled nanocomposites from the filler loading 3 to 10 wt%. This value of EMISE above 40 dB suggests that the prepared nanocomposite can be used as an effective lightweight EMI shielding material for high frequency (8.2–12.4 GHz) applications, where high thermal stability is required. POLYM. COMPOS. 36:566–575, 2015. © 2014 Society of Plastics Engineers