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.

Development of fire-resistant (B1 & B2) winter 1 KPU foams applied by gun or straw adapter and optimization of a gun applied winter 1 KPU foam

A realização do presente trabalho teve como principais objectivos o desenvolvimento de espumas de poliuretano de um componente com propriedades de resistência à chama superiores (B1 & B2), aplicadas por pistola ou por adaptador/tubo e a optimização de uma espuma de poliuretano de um componente de inverno aplicada por pistola. Todo o trabalho desenvolvido está dividido em dois projectos distintos: i. O primeiro projecto consistiu em desenvolver espumas de um componente com propriedades de resistência à chama (classificadas como B1 e B2 de acordo com a norma alemã DIN 4102), aplicadas por pistola (GWB1 e GWB2) ou por adaptador/tubo (AWB), utilizando polióis poliésteres aromáticos modificados e aditivos retardantes de chama halogenados. Estas espumas deveriam apresentar também propriedades aceitáveis a baixas temperaturas. Após realizar várias formulações foi possível desenvolver uma espuma AWB2 com apenas 3,3% de poliol poliéster no pré-polímero e com propriedades equivalentes às da melhor espuma comercial mesmo a 5/-10 (temperatura da lata/cura da espuma em °C) e também com uma altura de chama de apenas 11 cm. A partir de duas formulações (AWB2) que passaram o Teste B2, foram obtidas também, uma espuma GWB2 e outra GWB1 com propriedades equivalentes às da melhor espuma da concorrência a -10/-10 e a 23/5, respectivamente, embora não tenham sido submetidas ao teste B2 e B1 após as modificações efectuadas. ii. O segundo projecto consistiu em optimizar uma espuma de poliuretano de um componente de inverno aplicada por pistola (GWB3). A espuma inicial tinha problemas de glass bubbles quando esta era dispensada a partir de uma lata cheia, sendo necessário ultrapassar este problema. Este problema foi resolvido diminuindo a razão de GPL/DME através do aumento da percentagem em volume de DME no pré-polímero para 14% no entanto, a estabilidade dimensional piorou um pouco. O reagente FCA 400 foi removido da formulação anterior (6925) numa tentativa de diminuir o custo da espuma, obtendo-se uma espuma aceitável a 23/23 e a 5/5, com uma redução de 4% no custo da produção e com uma redução de 5,5% no custo por litro de espuma dispensada, quando comparada com a sua antecessora. Por último, foi avaliada a influência da concentração de diferentes surfactantes na formulação 6925, verificando-se o melhoramento da estrutura celular da espuma para concentrções mais elevadas de surfactante, sendo este efeito mais notório a temperaturas mais baixas (5/5). Dos surfactantes estudados, o B 8871 mostrou o melhor desempenho a 5/5 com a concentração mais baixa, sendo portanto o melhor surfactante, enquanto o Struksilon 8003 demonstrou ser o menos adequado para esta formulação específica, apresentando piores resultados globais. Pode-se ainda acrescentar que os surfactantes L-5351, L-5352 e B 8526 também não são adequados para esta formulação uma vez que as espumas resultantes apresentam cell collapse, especialmente a 5/5. No caso dos surfactantes L-5351 e L-5352, esta propriedade piora com concentrações mais elevadas. Em cada projecto foram também efectuados testes de benchmark em determinadas espumas comerciais com o principal objectivo de comparar todos os resultados das espumas desenvolvidas, em ambos os projectos, com espumas da concorrência.

Cyclic deformation of bidisperse two-dimensional foams

In-plane deformation of foams was studied experimentally by subjecting bidisperse foams to cycles of traction and compression at a prescribed rate. Each foam contained bubbles of two sizes with given area ratio and one of three initial arrangements: sorted perpendicular to the axis of deformation (iso-strain), sorted parallel to the axis of deformation (iso-stress), or randomly mixed. Image analysis was used to measure the characteristics of the foams, including the number of edges separating small from large bubbles N-sl, the perimeter (surface energy), the distribution of the number of sides of the bubbles, and the topological disorder mu(2)(N). Foams that were initially mixed were found to remain mixed after the deformation. The response of sorted foams, however, depended on the initial geometry, including the area fraction of small bubbles and the total number of bubbles. For a given experiment we found that (i) the perimeter of a sorted foam varied little; (ii) each foam tended towards a mixed state, measured through the saturation of N-sl; and (iii) the topological disorder mu(2)(N) increased up to an "equilibrium" value. The results of different experiments showed that (i) the change in disorder, Delta mu(2)(N), decreased with the area fraction of small bubbles under iso-strain, but was independent of it under iso-stress; and (ii) Delta mu(2)(N) increased with Delta N-sl under iso-strain, but was again independent of it under iso-stress. We offer explanations for these effects in terms of elementary topological processes induced by the deformations that occur at the bubble scale.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

Electrodeposition and characterization of nickel–copper metallic foams for application as electrodes for supercapacitors

Nickel-copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm(-2)) the nickel-copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel-copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge-discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni-Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge-discharge data and the best value (105 F g(-1) at 1 mA cm(-2)) was obtained for nickel-copper foams deposited at 1.8 A cm(-2) for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm(-2).