Conformational changes in monolayers of a cationic amphiphilic porphyrin on saline subphases

Langmuir monolayer films of the tetracationic porphyrin tetrakis(octadecyl-4-pyridin ium)porphyrinatozinc(II) bromide on various salt containing subphases were analyzed using surface pressure-area isotherms and X-ray reflectivity. The use of these complementary techniques showed that the porphyrin molecules undergo changes in conformation upon compression. Two main phases were identified, one in which the porphyrin moiety is parallel to the subphase and one in which the porphyrin moiety is tilted out of the plane. The addition of different salts into the subphase brought about changes in film behaviour, which are explained in terms of a lyotropic series. Copyright (C) 2002 Society of Porphyrins,& Phthalocyanines.

Polymer product engineering utilising oscillatory baffled reactors

The Oscillatory baffled reactor (OBR) can be used to produce particles with controlled size and morphology, in batch or continuous flow. This is due to the effect of the superimposed oscillations that radially mixes fluid but still allows plug-flow (or close to plug flow) behaviour in a continuous system. This mixing, combined with a close to a constant level of turbulence intensity in the reactor, leads to tight droplet and subsequent product particle size distributions. By applying population balance equations together with experimental droplet size distributions, breakage rates of droplets can be determined and this is a useful tool for understanding the product engineering in OBRs. (C) 2002 Elsevier Science B.V All rights reserved.

Experimental study of drop-interface coalescence in the presence of polymer stabilisers

An experimental study has been carried out to characterise the performance of polymer stabilisers, partially hydrolysed polyvinyl acetate (PVAc), used in suspension polymerisation processes. The stabilisers are ranked by their ability to stabilise the dispersion characterised by the median coalescence time of a single drop with its homophase at a planar liquid/liquid interface. Results show that the stability of the dispersion relates closely to the molecular properties of the PVAcs. Other conditions being equal, PVAcs with higher molecular weights or lower degrees of hydrolysis can better stabilise a liquid-liquid dispersion. The stability of the dispersion also depends strongly on where the PVAc resides. The presence of a PVAc in the dispersed phase significantly reduces stability. Consistent with results reported in the literature, considerable scatter has been observed on the coalescence times of identical drops under the same conditions. An explanation for the scatter is also proposed in the paper, based on the classical Reynolds model for film thinning. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis of polymer-montmorillonite nanocomposites by in situ intercalative polymerization

Two polymer-montmorillonite (MMT) nanocomposites have been synthesized by in situ intercalative polymerization. The styrene monomer is intercalated into the interlayer space of organically modified MMT, a layered clay mineral. Upon the intercalation, the complex is subsequently polymerized in the confinement environment of the interlayer space with a free radical initiator, 2,2-azobis isobutyronitrile. The aniline monomer is also intercalated and then polymerized within the interlayer space of sodium- and copper-MMT initiated by ammonium peroxodisulphate and interlayer copper cations respectively. X-ray diffraction indicates that the MMT layers are completely dispersed in the polystyrene matrix and an exfoliated structure has been obtained. The resulting polyaniline-MMT nanocomposites show a highly ordered structure of a single polyaniline layer stacked with the MMT layers. Fourier transform infrared spectra further confirm the intercalation and formation of both polymer-MMT nanocomposites.

Investigation of ultrasonic properties of PAG and MAGIC polymer gel dosimeters

Ultrasonic speed of propagation and attenuation were investigated as a function of absorbed radiation dose in PAG and MAGIC polymer gel dosimeters. Both PAG and MAGIC gel dosimeters displayed a dependence of ultrasonic parameters on absorbed dose with attenuation displaying significant changes in the dose range investigated. The ultrasonic attenuation dose sensitivity at 4 MHz in MAGIC gels was determined to be 4.7 +/- 0.3 dB m(-1) Gy(-1) and for PAG 3.9 +/- 0.3 dB m(-1) Gy(-1). Ultrasonic speed dose sensitivities were 0.178 +/- 0.006 m s(-1) Gy(-1) for MAGIC gel and -0.44 +/- 0.02 m s(-1) Gy(-1) for PAG. Density and compressional elastic modulus were investigated to explain the different sensitivities of ultrasonic speed to radiation for PAG and MAGIC gels. The different sensitivities were found to be due to differences in the compressional elastic modulus as a function of dose for the two formulations. To understand the physical phenomena underlying the increase in ultrasonic attenuation with dose, the viscoelastic properties of the gels were studied. Results suggest that at ultrasonic frequencies, attenuation in polymer gel dosimeters is primarily due to volume viscosity. It is concluded that ultrasonic attenuation significantly increases with absorbed dose. Also, the ultrasonic speed in polymer gel dosimeters is affected by changes in dosimeter elastic modulus that are likely to be a result of polymerization. It is suggested that ultrasound is a sufficiently sensitive technique for polymer gel dosimetry.

Ultrasonic absorption in polymer gel dosimeters

Ultrasonic absorption in polymer gel dosimeters was investigated. An ultrasonic interferometer was used to study the frequency (f) dependence of the absorption coefficient (alpha) in a polyacrylamide gel dosimeter (PAG) in the frequency range 5-20 MHz. The frequency dependence of ultrasonic absorption deviated from that of an ideal viscous fluid. The presence of relaxation mechanisms was evidenced by the frequency dependence of alpha/f(2) and the dispersion in ultrasonic velocity. It was concluded that absorption in polymer gel dosimeters is due to a number of relaxation processes which may include polymer-solvent interactions as well as relaxation due to motion of polymer side groups. The dependence of ultrasonic absorption on absorbed dose and formulation was also investigated in polymer gel dosimeters as a function of pH and chemical composition. Changes in dosimeter pH and chemical composition resulted in a variation in ultrasonic dose response curves. The observed dependence on pH was considered to be due to pH induced modifications in the radiation yield while changes in chemical composition resulted in differences in polymerisation kinetics. (C) 2003 Elsevier B.V. All rights reserved.

Polymer indentation with mesoscopic molecular dynamics

Indentation tests are used to determine the hardness of a material, e.g., Rockwell, Vickers, or Knoop. The indentation process is empirically observed in the laboratory during these tests; the mechanics of indentation is insufficiently understood. We have performed first molecular dynamics computer simulations of indentation resistance of polymers with a chain structure similar to that of high density polyethylene (HDPE). A coarse grain model of HDPE is used to simulate how the interconnected segments respond to an external force imposed by an indenter. Results include the time-dependent measurement of penetration depth, recovery depth, and recovery percentage, with respect to indenter force, indenter size, and indentation time parameters. The simulations provide results that are inaccessible experimentally, including continuous evolution of the pertinent tribological parameters during the entire indentation process.

Modeling Carbon Nanotube Electrical Properties in CNT/Polymer Composites

In this work it is demonstrated that the capacitance between two cylinders increases with the rotation angle and it has a fundamental influence on the composite dielectric constant. The dielectric constant is lower for nematic materials than for isotropic ones and this can be attributed to the effect of the filler alignment in the capacitance. The effect of aspect ratio in the conductivity is also studied in this work. Finally, based on previous work and by comparing to results from the literature it is found that the electrical conductivity in this type of composites is due to hopping between nearest fillers resulting in a weak disorder regime that is similar to the single junction expression.

Multi-scale modeling of the mechanical behavior of polymer-based materials

Polymers have become the reference material for high reliability and performance applications. In this work, a multi-scale approach is proposed to investigate the mechanical properties of polymeric based material under strain. To achieve a better understanding of phenomena occurring at the smaller scales, a coupling of a Finite Element Method (FEM) and Molecular Dynamics (MD) modeling in an iterative procedure was employed, enabling the prediction of the macroscopic constitutive response. As the mechanical response can be related to the local microstructure, which in turn depends on the nano-scale structure, the previous described multi-scale method computes the stress-strain relationship at every analysis point of the macro-structure by detailed modeling of the underlying micro- and meso-scale deformation phenomena. The proposed multi-scale approach can enable prediction of properties at the macroscale while taking into consideration phenomena that occur at the mesoscale, thus offering an increased potential accuracy compared to traditional methods.

Modelling the Mechanical Behavior of Polymer-Based Nanocomposites

Molecular dynamics simulations were employed to analyze the mechanical properties of polymer-based nanocomposites with varying nanofiber network parameters. The study was focused on nanofiber aspect ratio, concentration and initial orientation. The reinforcing phase affects the behavior of the polymeric nanocomposite. Simulations have shown that the fiber concentration has a significant effect on the properties, with higher loadings resulting in higher stress levels and higher stiffness, matching the general behavior from experimental knowledge in this field. The results also indicate that, within the studied range, the observed effect of the aspect ratio and initial orientation is smaller than that of the concentration, and that these two parameters are interrelated.

Coupling Mechanical and Electrical Behavior in the Multi-scale Simulation of Polymer-based CNT Nanocomposites

A numeric model has been proposed to investigate the mechanical and electrical properties of a polymeric/carbon nanotube (CNT) composite material subjected to a deformation force. The reinforcing phase affects the behavior of the polymeric matrix and depends on the nanofiber aspect ratio and preferential orientation. The simulations show that the mechanical behavior of a computer generated material (CGM) depends on fiber length and initial orientation in the polymeric matrix. It is also shown how the conductivity of the polymer/CNT composite can be calculated for each time step of applied stress, effectively providing the ability to simulate and predict strain-dependent electrical behavior of CNT nanocomposites.

The influence of matrix mediated hopping conductivity, filler concentration, aspect ratio and orientation on the electrical response of carbon nanotube/polymer nanocomposites

A model to simulate the conductivity of carbon nanotube/polymer nanocomposites is presented. The proposed model is based on hopping between the fillers. A parameter related to the influence of the matrix in the overall composite conductivity is defined. It is demonstrated that increasing the aspect ratio of the fillers will increase the conductivity. Finally, it is demonstrated that the alignment of the filler rods parallel to the measurement direction results in higher conductivity values, in agreement with results from recent experimental work.

Energy harvesting performance of piezoelectric electrospun polymer fibers and polymer/ceramic composites

The energy harvesting efficiency of electrospun poly(vinylidene fluoride), its copolymer vinylidene fluoride-trifluoroethylene and composites of the later with piezoelectric BaTiOon interdigitated electrodes has been investigated. Further, a study of the influence of the electrospinning processing parameters on the size and distribution of the composites fibers has been performed. It is found that the best energy harvesting performance is obtained for the pure poly(vinylidene fluoride) fibers, with power outputs up to 0.03 W and 25 W under low and high mechanical deformation. The copolymer and the composites show reduced power output due to increased mechanical stiffness. The obtained values, among the largest found in the literature, the easy processing and the low cost and robustness of the polymer, demonstrate the applicability of the developed system.

Re-use assessment of thermoset composite wastes as aggregate and filler replacement for concrete-polymer composite materials: a case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.