Third Day Poster Session, 17 June 2010 - NanoTR-VI

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P P Department P P Chemistry Poster Session, Thursday, June 17 Theme F686 - N1123 Application of Artificial Neural Networks for Kinetic Investigation of Thermal Degradation Process in Nanocomposites 1 1 1,2 1 UM. KhanmohammadiUP P*, M. Ahmadi AzqandiP P, A. Bagheri GarmarudiP P, N. KhoddamiP 2 1 Department, Faculty of Science, IKIU, Qazvin, Iran of Chemistry & Polymer Laboratories, Engineering Research Institute, Tehran, Iran Abstract-Polyimide-Silica Hybrid nanocomposite samples were prepared by sol-gel technique. Specimens from the hybrid nanocomposite were submitted to thermogravimetric afnalysis and thermal degradation kinetics of hybrid nanocomposite was investigated by thermogravimetric analysis. The kinetic parameters were obtained via the chemometric data processing of mass loss curves. The non-linear fitting method based on Particle Swarm Optimization (PSO) algorithm was used to fit the mass loss curves at three heating rates and to adjust the non-linear curves. PSO is a population based stochastic optimization technique inspired by social behavior of bird flocking or fish schooling. PSO shares many similarities with evolutionary computation techniques such as Genetic Algorithms (GA). The system is initialized with a population of random solutions and searches for optima by updating generations. However, unlike GA, PSO has no evolution operators such as crossover and mutation. Moreover, the activation energy, order of reaction and pre-exponential factor of degradation for the nanocomposite containing different amount of inorganic filler was determined by PSO-ANN and then being compared with other methods e.g. pseudo first-order. It was concluded that PSO algorithm is stronger and more efficient in comparison with other methods for predication of kinetic parameters. Particle swarm optimization (PSO) is a population based stochastic optimization technique inspired by social behavior of bird flocking or fish schooling [1]. PSO shares many similarities with evolutionary computation techniques such as Genetic Algorithms (GA). The system is initialized with a population of random solutions and searches for optima by updating generations [2,3]. However, unlike GA, PSO has no evolution operators such as crossover and mutation. In PSO, the potential solutions, called particles, fly through the problem space by following the current optimum particles. Each particle keeps track of its coordinates in the problem space which are associated with the best solution (fitness) it has achieved so far. (The fitness value is also stored.) This value is called pbest. Another "best" value that is tracked by the particle swarm optimizer is the best value, obtained so far by any particle in the neighbors of the particle. This location is called lbest. When a particle takes all the population as its topological neighbors, the best value is a global best and is called gbest. The particle swarm optimization concept consists of, at each time step, changing the velocity of (accelerating) each particle toward its pbest and lbest locations (local version of PSO). Acceleration is weighted by a random term, with separate random numbers being generated for acceleration toward pbest and lbest locations. Nanocomposite was prepared by sol-gel technique. In this method, tetraethoxysilane (TEOS), 10% wt solution of polyamic acid in DMAc and water was used as precursors. Specimens from the Polyimide-Silica Hybrid nanocomposite were submitted to thermogravimetric analysis using the TA2100 (TA Instruments) thermal analyzer. The mass of the samples ranged from 5 to 10 mg and the analysis was done in a flowing of nitrogen atmosphere (50 ml/min). The experiment was conducted by heating samples at a constant linear heating rates of 5 °C/min, 10 °C /min, 20 °C /min up to 700 °C.The resulting curves are percentages of remaining nano composite. PSO algorithm was used in fitting of non-linear curves that were used in order to obtain the kinetic parameters as function of temperature and different heating rates, which could fit the weight loss curves. In this way, the mathematical modeling was based on bellow equation: AW . inEa( n 1) w R 10 . Ea 2.3150.4567 RT (1 W 1 1n 1n f ) W f where: w is residual mass fraction (g); Win is initial mass of specimen (g); A is pre-exponential factor; Ea is activation energy (J/mol); n is order of reaction; b is heating rate (°C /min); R is gas constant (8.31451 J/mol.K); T is temperature (K) and wRf Ris final mass fraction (g). The method is based on linear fitting of model related to the obtained parameters. PSO has been successfully applied in many research and application areas. It was demonstrated that PSO gives reliable results in kinetic investigation of thertmal degradation. Another reason of PSO attraction is the few parameters which are needed to be adjusted. One version, with slight variations, works well in a wide variety of applications. We found PSO algorithm is more efficient than other methods in the predication of kinetic parameters. *Corresponding author: mrkhanmohammadi@gmail.com [1] Zhang C, Li Y and Shao H, Proceedings of the World Congress on Intelligent Control and Automation (WCICA), 2, 1065-1068, 2000. [2] Peng J, Chen Y, and Eberhart R, Proceedings of the Fifteenth Annual Battery Conference on Applications and Advances, 173-177, 2000. [3] Chatterjee A and Siarry P, Computers & Operations Research, 33, 859-871, 2006 6th Nanoscience and Nanotechnology Conference, zmir, 2010 711
Poster Session, Thursday, June 17 Theme F686 - N1123 Fabrication and physical properties of EPDM/NBR/organoclay Nanocomposites M. Ersali 1 *, N. Fazeli 1 , Gh. Naderi 2 1 Islamic Azad University, Science and Research Branch, Polymer Engineering Group,P.O.Box 14155/4933,Tehran, Iran 2 Iran Polymer and Petrochemical Institute, Polymer Processing Society , P.O.Box 14965/115, Tehran, Iran Abstract Different blends based on 70 %(wt) ethylene propylene diene monomer rubber (EPDM) and 30 %(wt) acrylonitrile butadiene rubber (NBR) with various amount of organoclay (OC) were prepared. The effect of organoclay on structures of the samples was investigated by X- ray Diffraction (XRD). The obtained results show an intercalated structure. The effect of organoclay on cure characteristics and physical properties of the samples was investigated. It has been observed that incorporation of organoclay into polymeric matrix increases the viscosity and crosslink density and shortens the scorch time and optimum cure time of the compounds. Significant improvement in abrasion resistance and compression set of EPDM/NBR nanocomposites were observed. The rebound resilience of nanocomposites decreased with increasing of the organoclay content. It has been long years that elastomeric blends have attracted the attentions. Some of their advantages are ease of process ability, better properties and manufacturing more inexpensive product. EPDM/NBR blends have both properties of each rubber such as oil and hydrocarbon resistance, ozone, heat and good process ability since it contains two types of polar and non polar rubbers [1]. nanoclay addition to polymer blends causes more improvements in their properties. This group of materials has attracted the attentions because of improving mechanical and thermal properties[2], diffusivity [3] and flammability resistance [4]. Since EPDM based nanocomposites have good oxygen, heat and ozone resistance and can be applied in different applications such as profiles, cable insulation, jackets, weather and heat resistant products[5]. On the other hand, NBR based nanocomposites have attracted attentions because of NBR excellent oil resistance, good tensile strength and abrasion resistance and also its applications such as static gaskets, oring, seal for valves, shafts for crankshafts, high pressure resistant hoses for hydraulic applications[6]. The aim of this article was developing and making EPDM/NBR nano-composites through a melt compounding process by using organo-clay in the above blend and also studying the effect of organo-clay on curing characteristics, morphology and properties of the blend. Figure 1 shows XRD patterns for pure organoclay(OC) and nanocomposites. Figure 1- X-ray diffraction patterns of (a) OC 20A, (b) EPDM-NBR-7%OC, (c) EPDM-NBR-5%OC, (d) EPDM-NBR-3%OC. As it can be seen, the characteristic diffraction peak of cloisite 20A is located at 2 =3.4 corresponding to a basal interlayer spacing of 25.98 A. For nanocomposite samples the mentioned peak has been shifted to lower angle at 2 =2.59 (equals to d 001 =34.09 A). The increase in basal spacing of layers denotes the introduction of rubber chains inside the layers of nanoclay and presentation of an intercalated structure in nanocomposites. Obviously, the increase in the amount of organoclay has not changed the location of the peak (and consequently the space between the layers) but caused the intensity of peak to be increased. As it can be seen, the optimum curing time and scorch time decreased when organoclay was increased. In fact, the existing ammonium in organoclay facilitated the vulcanization and decrease curing time[7]. The maximum and minimum torque increased with organoclay. Rebound resilience decreased when organoclay content increased. Abrasion resistance improved by addition of organoclay. This improvement was observed in all nanocomposites. When the content of organoclay increased, higher abrasion resistance was obtained and Relative volume loss decreased. Improvement in abrasion resistance is probably due to improvement in polymer chains crosslink density and decrement of the free chains. Compression set increases with organoclay, this means that permanent set decreased. In this research work, different samples of EPDM/NBR nanocomposites were prepared. XRD results showed that in all nanocomposites, rubber chains have been introduced into the organo-clay layers and extended the spaces, so that intercalated structures have been obtained. Study of curing characteristics of the samples showed that the addition of organoclays to the blends reduces optimum curing and scorch time. This is due to the formation of complexes between quaternary amine groups in organoclay and zinc salt or sulfur which accelerates the curing process. Moreover, it has been concluded that the more the amount of nano-clays, the higher the crosslink density. Finally, physical properties of the nanocomposites were measured. It has been shown that the addition of organoclay to the blends increaseds abrasion resistance and compression set of the samples and decreases their Rebound resilience. This is due to the intercalation of chains inside the layers in addition to the higher crosslink density of nanocomposites. *Corresponding author: Mohammad.Ersali@gmail.com [1] Mitchell. J. M, J Elast and Plast., 9, 329-340 (1977) [2] A. Usuki, Y. Kojima, M. Kawasumi, A. Okada, A. Fukushima, T. Kurauchi, O. Kamigaito, J Mater Res. 8 (1993) 1179. [3] G. Choudalakis and A.D. Gotsis, Eur. Polym. J. 45 (2009) 967-984. [4] A.B. Morgan, Polym. Adv. Technol. 17 (2006) 206-217. [5] Y.W. Chang, Yang, Y., Ryu, S. and Nah, C. Polymer International, 51(4) (2002) 319 324. [6] W. G. Hwang, K. H. Wei, C.M. Wu, Polymer 45 (2004) 5729 5734. [7] M. Arroyo, M.A. Lopez-Manchado, B. Herrero, Polymer. 44 (2003) 2447. 6th Nanoscience and Nanotechnology Conference, zmir, 2010 712
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