Optical and mechanical anisotropies of aligned electrospun nanofibers reinforced transparent PMMA nanocomposites

This study aims to assess the nanofiber directionality effects on optomechanical properties of a widely used transparent thermoplastic poly(methyl methacrylate) (PMMA). Aligned fiber-hybrid mats consisted of nylon-6 (PA-6) nanofibers and PMMA microfibers are prepared using a self-blending co-electrospinning method, followed by hot press molding to fabricate into transparent nanocomposites. Effects of nanofiber orientation degree in two orthogonal directions and loading fraction on the optomechanical behavior of the nanocomposites are examined. Optical transmittance differences parallel and perpendicular to the nanofibers’ orientation are found to vary in a range of 3.9–5.4% at 589 nm, and strong mechanical anisotropy is observed with the 1% PA-6/PMMA nanocomposites. A maximal of 3% PA-6 nanofiber loading maintains the nanocomposite high transmittance (>75%) with improved strength and toughness along the nanofiber axis. This study reveals evident anisotropic optomechanical properties of transparent nanocomposites, and highlights the great designability of transparent nanocomposites by using aligned nanofibers as the designing elements.     

Effect of carbon nanofibers (CNFs) content on thermal and mechanical properties of CNFs/SiC nanocomposites

Carbon nanofibers dispersed β-SiC (CNFs/SiC) nanocomposites were prepared by hot-pressing via a transient eutectic phase route at 1900 °C for 1 h under 20 MPa in Ar. The effects of additional CNFs content between 1 and 10 wt.% were investigated, based on densification, microstructure, thermal and mechanical properties. The CNFs/SiC nanocomposites by the CNFs contents below 5 wt.% exhibited excellent relative densities over 98% with well dispersed CNFs. However, the CNFs/SiC nanocomposites containing the CNFs of 10 wt.% possessed a relative density of 92%, accompanying CNFs agglomerates and many pores located inside the agglomerates. The three point bending strength gradually decreased with the increase of CNFs content, but the indentation fracture toughness increased to 5.7 MPa m^1/2 by the CNFs content of 5 wt.%. The thermal conductivity was enchanced with the increase of CNFs content and represented a maximum value of 80 W/mK at the CNFs content of 5 wt.%.     

Structural characterization, thermal and mechanical properties of polyurethane/CoAl layered double hydroxide nanocomposites prepared via in situ polymerization

Dodecyl sulfate (DS), one kind of sulfate anion, was intercalated in the interlayer space between CoAl layered double hydroxide (CoAl-LDH) layers, and then polyurethane (PU) based nanocomposites were prepared by in situ intercalation polymerization with different amounts of the organo-modified CoAl-LDH. An exfoliated dispersion of CoAl-LDH layers in PU matrix was verified by the disappearance of the (0 0 3) reflection of the XRD results when the LDH loading was less than 2.0 wt%. Tensile testing indicated that excellent mechanical properties of PU/LDH nanocomposites were achieved. The weak alkaline catalysis of DS to polyurethane chains, combined with the dehydration and structural degradation of the LDH below 300 °C, accounted for the process of proceeded degradation as shown in TGA results. The real-time FTIR revealed that the as-prepared nanocomposites had a slower thermo-oxidative rate than neat PU from 160 °C to 340 °C, probably due to the barrier effect of LDH layers. These results suggested potential applications of CoAl-LDH as a promising flame retardant in PUs.     

High performance polyimide composite films prepared by homogeneity reinforcement of electrospun nanofibers

Highly aligned polyimide (PI) and PI nanocomposite fibers containing carbon nanotubes (CNTs) were produced by electrospinning. Scanning electron microscopy showed the electrospun nanofibers were uniform and almost free of defects. Transmission electron microscopy indicated that the CNTs were finely dispersed and highly oriented along the CNT/PI nanofiber axis at a relatively low concentration. The as-prepared well-aligned electrospun nanofibers were then directly used as homogeneity reinforcement to enhance the tensile strength and toughness of PI films. The neat PI nanofiber reinforced PI films showed good transparency, decreased bulk density and significantly improved mechanical properties. Compared with neat PI film prepared by solution casting, the tensile strength and elongation at break for the PI film reinforced with 2 wt.% CNT/PI nanofibers were remarkably increased by 138% and 104%, respectively. The significant increases in the overall mechanical properties of the nanofibers reinforced polyimide films can be ascribed to good compatibility between the electrospun nanofibers and the matrix as well as high nanofiber orientation in the matrix. Our study demonstrates a good example for fabricating high performance and high toughness polyimide nanocomposites by using this facile homogeneity self-reinforcement method.     

Flow induced orientated morphology and properties of nanocomposites of polypropylene/vapor grown carbon fibers

Nanocomposite filaments composed of isotactic polypropylene (iPP) and vapor grown carbon fibers (VGCF) were prepared by melt mixing extrusion, followed by melt drawing. The effect of composition and flow on the morphology was investigated by X-ray diffraction and high resolution scanning electron microscopy. Apparently in the drawn filaments, the presence of nanofibers resulted in a higher degree of orientated morphology and - as revealed by differential scanning calorimetry - higher degrees of crystallinity and crystallization kinetics enhancement. The amount of the orientated crystals increased as a result of VGCF addition, suggesting that the nanofibers obstructed the motion of polymer chains after the cessation of stretching force resulting in the delayed relaxation of stretched polymer segments. Significant stiffness improvements were observed due to the nanofibers and high draw ratios of the filaments. These results indicate that the orientated VGCF aligned in the flow direction, joined by fiber-induced crystallization of the surrounding iPP matrix, generate a strong stiffening effect.     

Aramid fibers reinforced silica aerogel composites with low thermal conductivity and improved mechanical performance

Aramid fibers reinforced silica aerogel composites (AF/aerogels) for thermal insulation were prepared successfully under ambient pressure drying. The microstructure showed that the aramid fibers were inlaid in the aerogel matrix, acting as the supporting skeletons, to strengthen the aerogel matrix. FTIR revealed AF/aerogels was physical combination between aramid fibers and aerogel matrix without chemical bonds. The as prepared AF/aerogels possessed extremely low thermal conductivity of 0.0227 ± 0.0007 W m⁻¹ K⁻¹ with the fiber content ranging from 1.5% to 6.6%. Due to the softness, low density and remarkable mechanical strength of aramid fibers and the layered structure of the fiber distribution, the AF/aerogels presented nice elasticity and flexibility. TG–DSC indicated the thermal stability reaching approximately 290 °C, can meet the general usage conditions, which was mainly depended on the pure silica aerogels. From mentioned above, AF/aerogels present huge application prospects in heat preservation field, especially in piping insulation.     

Characteristics of nanoclay and calcined nanoclay-cement nanocomposites

The influence of nanoclay (NC) and calcined nanoclay (CNC) on the mechanical and thermal properties of cement nano-composites presented. Calcined nanoclay is prepared by heating nanoclay (Cloisite 30B) at 900 °C for 2 h. Characterisation of microstructure is investigated using Quantitative X-ray Diffraction Analysis (QXDA) and High Resolution Transmission Electron Microscopy (HRTEM). Estimation of Ca(OH)₂ content in the cement nanocomposite is studied by the combination of QXDA and thermogravimetry analysis (TGA) techniques. Results showed that the mechanical and thermal properties of the cement nanocomposites are improved as a result of NC and CNC addition. An optimum replacement of ordinary Portland cement with 1 wt% CNC is observed through reduced porosity and water absorption as well as increased density, compressive strength, flexural strength, fracture toughness, impact strength, hardness and thermal stability of cement nanocomposites. The microstructural analyses from QXRA and SEM indicate that the CNC acted not only as a filler to improve the microstructure, but also as the activator to support the pozzolanic reaction. Cost-benefit analysis indicates that nanoparticles are expensive but from economic point of view nanoclay is used in very small amount (i.e. 1 wt. %) in cementitious materials. As a result nanoclay does not add any significant cost but improves the mechanical properties significantly.     

Morphology,thermal and mechanical properties of PVC/MMT nanocomposites prepared by solution blending and solution blending + melt compounding

Two types of montmorillonite (MMT), natural sodium montmorillonite (Na-MMT) and organically modified montmorillonite (OMMT), in different amounts of 1, 2, 5, 10 and 25 phr (parts per hundred resin), were dispersed in rigid poly (vinyl chloride) by two different methods: solution blending and solution blending + melt compounding. The effects on morphology, thermal and mechanical properties of the PVC/MMT nanocomposites were studied by varying the amount of Na-MMT and OMMT in both methods. SEM and XRD analysis revealed that possible intercalated and exfoliated structures were obtained in all of the PVC/MMT nanocomposites. Thermogravimetric analysis revealed that PVC/Na-MMT nanocomposites have better thermal stability than PVC/OMMT nanocomposites and PVC. In general, PVC/MMT nanocomposites prepared by solution blending + melt compounding revealed improved thermal properties compared to PVC/MMT nanocomposites prepared by solution blending. Vicat tests revealed a significant decrease in Vicat softening temperature of PVC/MMT nanocomposites prepared by solution blending + melt compounding compared to unfilled PVC.     

Structure and properties of hybrid PLA nanocomposites with inorganic nanofillers and cellulose fibers

Polylactide reinforced with 3 wt% of organo-modified montmorillonite, 5 wt% of stearic acid-modified calcium carbonate nanoparticles, 15 wt% of cellulose fibers (PLA/MMT, PLA/NCC, PLA/CF) and hybrid composites containing 15 wt% of fibers in addition to montmorillonite (PLA/MMT/CF) or calcium carbonate (PLA/NCC/CF) were prepared and examined. The nanoparticles were dispersed in polylactide almost homogeneously; montmorillonite was exfoliated during processing. T_g of polylactide remained unaffected but its cold crystallization was enhanced; the cold-crystallization behavior of the hybrid composites was dominated by nanofillers nucleating ability. The fibers and calcium carbonate decreased whereas exfoliated montmorillonite improved the thermal stability of the materials. Polylactide, PLA/NCC and PLA/MMT exhibited ability to plastic deformation, although the latter the weakest. Tensile behavior of the hybrid composites was strongly influenced by the fibers and similar to that of PLA/CF. All the fillers increased the storage modulus below T_g; that of PLA/MMT/CF and PLA/NCC/CF was improved with respect to polylactide by 50% and 45%, respectively.     

A novel approach to fabricate high volume fraction nanocomposites with long aligned carbon nanotubes

Conventional micro-fiber-reinforced composites provide insight into critical structural features needed for obtaining maximum composite strength and stiffness: the reinforcements should be long, well aligned in a unidirectional orientation, and should have a high reinforcement volume fraction. It has long been a challenge for researchers to process CNT composites with such structural features. Here we report a method to quickly produce macroscopic CNT composites with a high volume fraction of millimeter long, well aligned CNTs. Specifically, we use the novel method, shear pressing, to process tall, vertically aligned CNT arrays into dense aligned CNT preforms, which are subsequently processed into composites. Alignment was confirmed through SEM analysis while a CNT volume fraction in the composites was calculated to be 27%, based on thermogravimetric analysis data. Tensile testing of the preforms and composites showed promising mechanical properties with tensile strengths reaching 400 MPa.     

Influence of silica fillers on the ageing by gamma radiation of EDPM nanocomposites

This study evidences that the presence of silica fillers as well as their surface treatment influences the impact of gamma irradiation on the mechanical properties of the filled materials. It influences it both chemically, by a modification of the kinetics of the degradation reactions, and physically, through the complex modification of the filler–filler and filler–matrix interactions involved in the mechanical properties of the filler network.     

Effects of organic chain length of layered zirconium phosphonate on the structure and properties of castor oil-based polyurethane nanocomposites

Three novel organic–inorganic hybrid molecules, layered zirconium phosphates or phosphonates, were synthesized. To study the effects of organic chain length of them on the structure and properties of polymer nanocomposites, the polyurethane/α-zirconium phosphate (PU/ZrP), polyurethane/zirconium 2-aminoethylphosphonate (PU/ZrAEP) and polyurethane/zirconium 2-(2-(2-(2-aminoethylamino)ethylamino)ethylamino) ethylphosphonate (PU/Zr(AE)₄P) nanocomposites were prepared, and characterized by Fourier Transform Infrared (FT-IR) spectroscopy, wide-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and tensile testing. It was revealed that morphological, mechanical, and thermal properties of these nanocomposites were strongly dependent on the organic chain length of the layered zirconium phosphonates. The results showed that the fillers with longer chain length exhibited better dispersion in the PU matrix. As expected, the mechanical properties and water resistance were improved with the increasing of organic chain length of fillers, which attributed to better interfacial adhesion between fillers and PU matrix.     

PHBV nanocomposites based on organomodified montmorillonite and halloysite: The effect of clay type on the morphology and thermal and mechanical properties

The aim of this study was to evaluate the effect of the addition of two types of nanoparticles, organomodified montmorillonite Cloisite® 30B (C-30B), and a tubular like clay, halloysite (HNT), on the morphology and thermal and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) – PHBV nanocomposites. TEM and WAXD results showed a combination of a few tactoids and a partially exfoliated structure for PHBV/C-30B nanocomposites and a good dispersion of HNT in the PHBV matrix. DSC analysis indicated a lower nucleation density with the addition of nanoparticles. Furthermore, the presence of C-30B led to the formation of double melting peaks, related to different crystalline phases. However, a higher melting temperature was obtained for PHBV/HNT nanocomposites. A general increase in the Young’s modulus was observed. However, for PHBV/C-30B nanocomposites, this enhancement was at the expense of the strain at break and impact strength, probably due to the degradation of the polymer during processing.     

Phenolic matrix nanocomposites based on commercial grade resols: Synthesis and characterization

Polymer Layered Silicate Nanocomposites based on a commercial grade resol were produced using a simple, low labor cost, mechanical approach which allowed to avoid the process of intercalative polymerization of phenol and formaldehyde. Commercial compatibilized montmorillonite was selected as the main nanoreinforcement, while the matrix was a resol diluted in methanol. The aim of this work was to optimize the production technique of the above mentioned nanocomposites. Therefore intercalation of the resin was promoted by high speed mixing, and the processing parameters were varied in order to find the optimum dispersion. The produced nanocomposites were characterized and compared by means of X-ray diffraction, SEM and thermogravimetric analysis. The results of the characterization tests indicated that it was possible to obtain a good degree of dispersion as well as and uniform distribution of the nanoclay platelets. However, TGA measurements showed that the introduction of well dispersed nanoclays did not result in a consistent improvement of thermal stability respect that of the neat resol.     

Effect of crystallite size of zinc oxide on the mechanical,thermal and flow properties of polypropylene/zinc oxide nanocomposites

ZnO nanoparticles were prepared using zinc chloride and sodium hydroxide in chitosan medium. Prepared ZnO (NZO) and commercial ZnO (CZO) was characterized by scanning electron microscopic and X-ray diffraction studies. PP/ZnO nanocomposites were prepared using 0–5 wt% of zinc oxide by melt mixing. It was then compression moulded into films. Transparency of the composite films were improved by reducing the crystallite size of ZnO. Melt flow index studies revealed that NZO increased the flow characteristics of PP while CZO decreased. X-ray diffraction studies indicated α-form of isotactic polypropylene. An increase in mechanical properties, dynamic mechanical properties and thermal stability of the composites were observed by the addition of ZnO. Uniform dispersion of the ZnO was observed in the scanning electron micrographs of the tensile fractured surface of composites.     

Characterization of epoxy functionalized graphite nanoparticles and the physical properties of epoxy matrix nanocomposites

This work presents a novel approach to the functionalization of graphite nanoparticles. The technique provides a mechanism for covalent bonding between the filler and matrix, with minimal disruption to the sp² hybridization of the pristine graphene sheet. Functionalization proceeded by covalently bonding an epoxy monomer to the surface of expanded graphite, via a coupling agent, such that the epoxy concentration was measured as approximately 4 wt.%. The impact of dispersing this material into an epoxy resin was evaluated with respect to the mechanical properties and electrical conductivity of the graphite–epoxy nanocomposite. At a loading as low as 0.5 wt.%, the electrical conductivity was increased by five orders of magnitude relative to the base resin. The material yield strength was increased by 30% and Young’s modulus by 50%. These results were realized without compromise to the resin toughness.     

Effects of loading rate and temperature on tensile yielding and deformation mechanisms of nylon 6-based nanocomposites

Tensile tests were conducted on nylon 6/organoclay nanocomposites, with and without POE-g-MA rubber particles, over a range of temperatures and strain rates 10⁻⁴–10⁻¹ s⁻¹. It was shown that the 0.2% offset yield strength varied with both temperature and strain rate which could be described by the Eyring equation thus providing results on the activation energy and activation volume for the physical processes involved. In addition, their tensile deformation mechanisms were characterized using the tensile dilatometry technique to differentiate the dilatational processes (e.g., voiding/debonding caused by the organoclay and rubber particles or matrix) and shear yielding (e.g., matrix with zero volume change). Dilatometric responses indicated that the presence of POE-g-MA rubber particles did not alter the shear deformation mode of neat nylon 6. In contrast, the presence of organoclay layers changed the tensile yield deformation behavior of nylon 6 matrix from dominant shear yielding to combined shear yield plus dilatation associated with delaminations of nanoclay platelets. In nylon 6/organoclay/POE-g-MA ternary nanocomposite, the volume strain response indicated that the POE-g-MA rubber particles promoted shear deformation and suppressed delamination of the organoclay layers. Supports for the deformation mechanisms deduced from the tensile dilatometry tests were corroborated by optical microscopy and transmission electron microscopy micrographs of the studied materials.     

Improving the mechanical properties of multiwalled carbon nanotube/epoxy nanocomposites using polymerization in a stirring plasma system

Uniform treatment of multiwalled carbon nanotubes by plasma treatment has been investigated using a custom-built stirring plasma system. A thin plasma polymer with high levels of amine groups has been deposited on MWCNTs using a combination of continuous wave and pulsed plasma polymerization of heptylamine in the stirring plasma system. Scanning electron microscopy showed that the plasma polymerization improved the dispersion and interfacial bonding of the MWCNTs with an epoxy resin at loadings of 0.1, 0.3 and 0.5 wt%. The flexural and thermal mechanical properties of plasma polymerized MWCNT/epoxy nanocomposites were also significantly improved while untreated MWCNT/epoxy nanocomposites showed an opposite trend. The epoxy with 0.5 wt% plasma polymerized MWCNTs had the greatest increase in flexural properties, with the flexural modulus, flexural strength and toughness increasing by about 22%, 17% and 70%, respectively.     

Toughening and reinforcement of poly(vinylidene fluoride) nanocomposites with “bud-branched” nanotubes

Bud-branched nanotubes, fabricated by growing metal particles on the surface of multi-wall carbon nanotubes (MWCNTs), were used to prepare poly(vinylidene fluoride) (PVDF) based nanocomposites. The results of differential scanning calorimetry (DSC) showed that the introduction of the MWCNTs and bud-branched nanotubes both increased the crystallization temperature, while no significant variation of T_m (melting temperature), ΔH_c (melting enthalpy) and ΔH_m (crystallization enthalpy) occurred. The results of wide angle X-ray diffraction (WAXD) tests showed that α-phase was the dominated phase for both pure PVDF and its nanocomposites, indicating the addition of the MWCNTs and bud-branched nanotubes did not alter the crystal structures. Dynamic mechanical analysis (DMA) tests showed that bud-branched nanotubes were much more efficient in increasing storage modulus than the smooth MWCNTs. In addition, no significant variation of the T_g (glass transition temperature) was observed with the addition of MWCNTs and bud-branched nanotubes. Tensile tests showed that the introduction of MWCNTs and bud-branched nanotubes increased the modulus. However, a dramatic decrease in the fracture toughness was observed for PVDF/MWCNTs nanocomposites. For PVDF/bud-branched nanotubes nanocomposites, a significant improvement in the fracture toughness was observed compared with PVDF/MWCNTs nanocomposites.     

Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes

We herein report the effects of interfacial reinforcement on mechanical and electrical properties of nanocomposites based on polylactide (PLA) and multi-walled carbon nanotube (MWCNT). For this purpose, a series of MWCNTs grafted with PLA chains of various lengths (MWCNT-g-PLAs) were prepared by ring-opening polymerization of l-lactide with carboxylic acid-functionalized MWCNT (MWCNT-COOH). MWCNT-g-PLAs were then mixed with commercial PLA to obtain PLA/MWCNT-g-PLA nanocomposites with 1.0 wt.% MWCNT content. It was revealed that morphological, mechanical, and electrical properties of PLA/MWCNT-g-PLA nanocomposites were strongly dependent on the PLA chain length of MWCNT-g-PLAs. FE-SEM images exhibited that the nanocomposites containing MWCNT-g-PLA with longer PLA chain length exhibited better dispersion of MWCNTs in the PLA matrix. Initial moduli and tensile strengths of PLA/MWCNT-g-PLA composites increased with the increment of chain length of PLA grafted on MWCNTs, which attributes to the improved interfacial adhesion between the grafted PLA chains of MWCNT-g-PLA and the PLA matrix. As a result, the experimental initial modulus (2775 ± 193 MPa) of the nanocomposite including MWCNT-g-PLA with PLA chains of average molecular weight of 530 g/mol was quite close to the theoretical value (2911 MPa) predicted for the nanocomposite with perfect interfacial adhesion. Unexpectedly, electrical resistivities of PLA/MWCNT-g-PLA nanocomposites were found to increase from ∼10⁴ to ∼10¹² Ω/sq with increasing the PLA chain length of MWCNT-g-PLA, which is due to the fact that the PLA chains grafted on MWCNTs prevent the formation of the electrical conduction path of MWCNTs in the PLA matrix.