Influence of Carbon Micro- and Nano-Fillers on the Viscoelastic Properties of Polyethylene Terephthalate.

In this research study, three carbon fillers of varying dimensionality in the form of graphite (3D), graphite nano-platelets (2D), and multiwall carbon nanotubes (1D) were incorporated into a matrix of poly (ethylene terephthalate), forming carbon-reinforced polymer composites. Melt compounding was followed by compression moulding and then a quenching process for some of the samples to inhibit crystallization. The samples were analysed using dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM), considering the dimensionality and loading of the carbon fillers. The dynamic mechanical analysis revealed a similar decline of storage moduli for all composites during the glassy to rubbery transition. However, storage moduli values at room temperature increased with higher loading of nano-fillers but only to a certain level; followed by a reduction attributed to the formation of agglomerates of nanotubes and/or rolled up of nano-platelets, as observed by SEM. Much greater reinforcement was observed for the carbon nanotubes compared to the graphite and or the graphite nano-platelets. The quenched PET samples showed significant changes in their dynamic mechanical properties due to both filler addition and to cold crystallization during the DMTA heating cycle. The magnitude of changes due to filler dimensionality was found to follow the order: 1D > 2D > 3D, this carbon filler with lower dimensionality have a more significant effect on the viscoelastic properties of polymer composite materials.

Optimization of Glass Transition Temperature and Pot Life of Epoxy Blends Using Response Surface Methodology (RSM).

The aim of this work was to improve the processability of triglycidyl-p-aminophenol (TGPAP) epoxy resin. To achieve this improvement, a diluent, the diglycidyl ether of bisphenol F (DGEBF or BPF), was added to TGPAP, and the blended epoxy was then cured with 4, 4'-diaminodiphenyl sulfones (DDS). A response surface methodology (RSM) was used, with the target response being to achieve a blended resin with a high glass transition temperature (Tg) and maximum pot life (or processing window, PW). Characterization through dynamic mechanical thermal analysis (DMTA) and using a rheometer indicated that the optimum formulation was obtained at 55.6 wt.% of BPF and a stoichiometric ratio of 0.60. Both values were predicted to give Tg at 180 °C and a processing window of up to 136.1 min. The predicted values were verified, with the obtained Tg and processing window (PW) being 181.2 ± 0.8 °C and 140 min, respectively, which is close to the values predicted using the RSM.

Addition of Graphite Filler to Enhance Electrical, Morphological, Thermal, and Mechanical Properties in Poly (Ethylene Terephthalate): Experimental Characterization and Material Modeling.

Poly(ethylene terephthalate)/graphite (PET/G) micro-composites were fabricated by the melt compounding method using a minilab extruder. The carbon fillers were found to act as nucleating agents for the PET matrix and hence accelerated crystallization and increased the degree of crystallinity. TGA showed that carbon fillers improved the resistance to thermal and thermo-oxidative degradation under both air and nitrogen atmospheres. However, a poor agreement was observed at higher loadings of the filler where the composites displayed reduced reinforcement efficiency. The results demonstrate that the addition of graphite at loading >14.5 wt.% made electrically conductive composites. It was calculated that the electric conductivities of PET/graphite micro-composites were enhanced, above the percolation threshold values by two orders of magnitudes compared to the PET matrix. The minimum value of conductivity required to avoid electrostatic charge application of an insulating polymer was achieved, just above the threshold values. The addition of graphite also improved thermal stability of PET, accelerated its crystallization process and increased the degree of crystallinity. Microscopic results exhibit no indication of aggregations at 2 wt.% graphite, whereas more agglomeration and rolling up could be seen as the graphite content was increased in the PET matrix (in particular, above the percolation threshold value). Furthermore, based on the mechanical experimental characterization of the PET/graphite micro-composites, a large deformation-based mathematical model is proposed for material behavior predictions. The model fits well the experimental data and predicts other mechanical data that are not included in the parameter identification.

Deformation micromechanics of all-cellulose nanocomposites: comparing matrix and reinforcing components.

All-cellulose nanocomposites, comprising two different forms of cellulose nanowhiskers dispersed in two different matrix systems, are produced. Acid hydrolysis of both tunicate (T-CNWs) and cotton cellulose (CNWs) is carried out to produce the nanowhiskers. These nanowhiskers are then dispersed in a cellulose matrix material, produced using two dissolution methods; namely lithium chloride/N,N-dimethyl acetamide (LiCl/DMAc) and sodium hydroxide/urea (NaOH/urea). Crystallinity of both nanocomposite systems increases with the addition of nanowhiskers up to a volume fraction of 15 v/v%, after which a plateau is reached. Stress-transfer mechanisms, between the matrix and the nanowhiskers in both of these nanocomposites are reported. This is achieved by following both the mechanical deformation of the materials, and by following the molecular deformation of both the nanowhiskers and matrix phases using Raman spectroscopy. In order to carry out the latter of these analyses, two spectral peaks are used which correspond to different crystal allomorphs; cellulose-I for the nanowhiskers and cellulose-II for the matrix. It is shown that composites comprising a LiCl/DMAc based matrix perform better than NaOH/urea based systems, the T-CNWs provide better reinforcement than CNWs and that an optimum loading of nanowhiskers (at 15 v/v%) is required to obtain maximum tensile strength and modulus.

Influence of magnetic field alignment of cellulose whiskers on the mechanics of all-cellulose nanocomposites.

Orientation of cellulose nanowhiskers (CNWs) derived from tunicates, in an all-cellulose nanocomposite, is achieved through the application of a magnetic field. CNWs are incorporated into a dissolved cellulose matrix system and during solvent casting of the nanocomposite a magnetic field is applied to induce their alignment. Unoriented CNW samples, without the presence of a magnetic field, are also produced. The CNWs are found to orient under the action of the magnetic field, leading to enhanced stiffness and strength of the composites, but not to the level that is theoretically predicted for a fully aligned system. Lowering the volume fraction of the CNWs is shown to allow them to orient more readily in the magnetic field, leading to larger relative increases in the mechanical properties. It is shown, using polarized light microscopy, that the all-cellulose composites have a domain structure, with some domains showing pronounced orientation of CNWs and others where no preferred orientation occurs. Raman spectroscopy is used to both follow the position of bands located at ~1095 and ~895 cm(-1) with deformation and also their intensity as a function rotation angle of the specimens. It is shown that these approaches give valuable independent information on the respective molecular deformation and orientation of the CNWs, and the molecules in the matrix phase, in oriented and nonoriented domains of all-cellulose composites. These data are then related to an increase in the level of molecular deformation in the axial direction, as revealed by the Raman technique. Little orientation of the matrix phase is observed under the action of the magnetic field indicating the dominance of the stiff CNWs in governing mechanical properties.

Interfacial interactions in polymer-layered silicate nanocomposites.

Interactions between sodium montmorillonite (Na-MMT) and a variety of probes, some of which are intended to model components of a polyurethane system, have been studied. Particular attention was given to the effect of preadsorbed water on the adsorption behavior of the probes. Flow microcalorimetry (FMC), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), and wide-angle X-ray scattering (WAXS) were used to monitor the adsorption process. The probe set included alcohols, amines, ethers, poly(propylene glycol) monobutyl ethers (PPG), and 4-ethylphenyl isocyanate (4-EPI). FMC revealed that the preadsorbed water molecules on undried Na-MMT hindered the adsorption of alcohol and ether probes, but had little effect on the adsorption of amines. Drying of Na-MMT to less than 0.3% w/w H2O led to an increase in heat of adsorption and generally greater retention of the probes. PPG showed strong interaction with Na-MMT due to multipoint adsorption. With dried Na-MMT, WAXS revealed that PPG of molecular weight (MW) 1000 was partly intercalated into the gallery while lower molecular weight PPG (MW 340) did not intercalate the Na-MMT. DRIFTS spectra of 4-EPI adsorbed on undried Na-MMT revealed urea linkages, indicating formation of N,N'-bis(4-ethylphenyl) urea. In contrast, with dried Na-MMT the 4-EPI formed a urethane linkage with hydroxyl groups present at the edges of the silicate platelets.