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Estudo da reação de modificação química da poliacrilonitrila com grupos 2-oxazolina / Study of chemical modified reaction of polyacrilonitrile with 2-oxazoline groupsOdemar Cardoso Silva 21 June 2007 (has links)
Neste trabalho a reação de modificação química da poliacrilonitrila pela incorporação de grupos 2-oxazolina foi estudada através da interação dos grupos nitrila do polímero com 2-amino-etanol catalisada por acetato de cádmio. Os copolímeros foram obtidos em diferentes condições reacionais para alcançar a reação de incorporação do heterocíclico preferencialmente à reação de ciclização dos grupos nitrila que ocorre na presença de catalisador. O grau de modificação química obtido foi relacionado às alterações nas propriedades dos polímeros modificados, que foram caracterizados por espectroscopias na região do infravermelho com transformada de Fourier, do ultravioleta-visível e de ressonância magnética nuclear de hidrogênio, e por calorimetria diferencial de varredura e termogravimetria. As condições ótimas de reação foram alcançadas a 70C após 35h. E o polímero obtido a partir destas condições foi avaliado como inibidor de corrosão para aço-carbono em solução de ácido clorídrico. Sob estas condições experimentais, uma eficiência de inibição de 63 % foi obtida / In this work the chemical modification reaction of polyacrylonitrile by the incorporation of 2-oxazoline groups was obtained through the interaction of the polymer nitrile groups with 2-amino-ethanol, catalyzed by cadmium acetate. The copolymer were obtained from different reaction condictions, in order to achieve the incorporation reaction of the heterocycle rather than the cyclization reaction of nitrile groups, which occurs in the presence of the catalist. The chemical modification degree obtained was related to changes in the properties of the modified polymers, which were characterized by Fourier transform infrared, and ultraviolet-visible spectroscopy, hydrogen nuclear magnetic ressonance and differential scanning calorimetry and thermogravimetric analysis. The optimum reaction condiction condictions were achieved after 35 h at 70C and the polymer obtained from such condictions was evaluated as a corrosion inhibitor for carbon-steel in chloridric acid solution. Under these experimental condictions as inhibition efficiency of 63 % was obtained
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Single Wall Carbon Nanotube/Polyacrylonitrile Composite FiberLiang, Jianghong 01 November 2004 (has links)
Single Wall Carbon Nanotubes (SWNTs), discovered in 1993, have good mechanical, electrical and thermal properties. Polyacrylonitrile (PAN) is an important fiber for textiles as well as a precursor for carbon fibers. PAN has been produced since 1930s.
In this study, we have processed SWNT/PAN fibers by dry-jet wet spinning. Purified SWNT, nitric acid treated SWNTs, and benzonitrile functionalized SWNTs have been used. Fiber processing was done in Dimethyl Formamide (DMF) and coagulation was done in DMF/water mixture. The coagulated fibers were drawn (draw ratio of 6) at 95 oC.
Structure, orientation, and mechanical properties of these fibers have been studied. The cross-sections for all the fibers are not circular. Incorporation of SWNT in PAN results in improved mechanical properties, tensile modulus increased from 7.9 GPa for control PAN to 13.7 GPa for SWNT/PAN composite fiber, and functionalized SWNTs result in higher improvements with tensile modulus reaching 17.8 GPa for acid treated SWNT/PAN composite fibers. The theoretical analysis suggests that observed moduli of the composite fibers are consistent with the predicted values.
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Polyacrylonitrile / carbon nanotube composite fibers: effect of various processing parameters on fiber structure and propertiesChoi, Young Ho 15 November 2010 (has links)
This study elucidates the effect of various processing parameters on polyacrylonitrile (PAN) /carbon nanotube (CNT) composite fiber structure and properties. Interaction between PAN and MWNT enabled the gel-spun PAN/MWNT composite fiber to be drawn to a higher draw ratio, than the control PAN fiber, resulting in the composite fiber tensile strength value as high as 1.3 GPa. PAN/MWNT composite fibers were stabilized and carbonized, and the resulting fibers have been characterized for their structure and properties. The effect of precursor fiber shelf-time on the mechanical properties of the gel-spun PAN/MWNT composite fibers is also reported. A rheological study of PAN-co-MAA/few wall nanotube (FWNT) composite solution has been conducted. At low shear rates, the network of FWNTs contributes to elastic response, resulting in higher viscosity and storage modulus for the composite solution as compared to the control solution. On the other hand, at high shear rates, the network of FWNTs can be broken, resulting in lower viscosity for the composite solution than that for the control solution. Larger PAN crystal size (~16.2 nm) and enhanced mechanical properties are observed when the fiber was drawn at room temperature (cold-drawing) prior to being drawn at elevated temperature (~ 165 °C; hot-drawing). Azimuthal scan of wide angle X-ray diffraction (WAXD) and Raman G-band intensities were used for the evaluation of Herman's orientation factor for PAN crystal (fPAN) and FWNT (fFWNT), respectively. Significantly higher nanotube orientation was observed than PAN orientation at an early stage of fiber processing (i.e during spinning, cold-drawing). Differential scanning calorimetry (DSC) revealed that PAN-co-MAA fiber can be converted into cyclic structure at milder conditions than those for PAN. Continuous in-line stabilization, carbonization, and characterization of the resulting carbon fibers were carried out. Rheological and fiber spinning studies have also been carried out on PAN-co-MAA/VGCNF (vapor grown carbon nano fiber). The diameter of PAN-co-MAA/VGCNF composite fiber is smaller than that of the PAN-co-MAA control fiber with same draw ratio due to the suppressed die-swell in the presence of VGCNF. The mechanical properties of PAN-co-MAA control and PAN-co-MAA/VGCNF composite fibers were characterized. Crystalline structure and morphology of the solution-spun PAN-co-MAA/VGCNF fibers are characterized using WAXD and scanning electron microscopy (SEM), respectively. The volume fraction of PAN-CNT interphase in PAN matrix has been calculated to illustrate the impact of CNTs on structural change in PAN matrix, when ordered PAN molecules are developed in the vicinity of CNTs during fiber processing. The effect of PAN-CNT interphase thickness, CNT diameter, and mass density of CNT on volume fraction of PAN-CNT interphase has been explored.
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Stabilization and carbonization studies of polyacrylonitrile /carbon nanotube composite fibersLiu, Yaodong 15 November 2010 (has links)
Carbon fibers contain more than 90 wt. % carbon. They have low density, high specific strength and modulus, and good temperature and chemical resistance. Therefore, they are important candidate as reinforcement materials. Carbon fiber is made by pyrolysing precursor polymers. Polyacrylonitrile (PAN) which has been used as precursor to produce high strength carbon fiber is used as precursor in this study. The theoretical tensile strength of carbon fibers can reach over 100 GPa. Currently, the best commercial carbon fibers reach only 7.5 GPa. To make good quality carbon fiber and to narrow the gap between theoretical values and currently achieved experimental properties, the entire manufacturing process including fiber spinning, stabilization and carbonization, needs to be improved optimized. In this dissertation, the stabilization processes of gel-spun PAN/carbon nanotubes (CNTs) composite fibers are studied.
PAN/CNT (1 wt. % CNT) composite fibers are spun by dry-jet gel-spinning. Three types of CNTs with different number of walls and varying catalyst content are used as additives. The effect of different types of CNTs on the properties of the stabilized fibers was compared. It is found that the CNTs with the highest surface area shows the best reinforcement efficiency on the tensile modulus, and reduces the formation of β-amino nitrile. The residual catalyst in the range of 1 to 4 wt. % shows little effect on the mechanical properties of the stabilized fibers.
Stabilization involves complex chemical reactions, including cyclization, oxidation, dehydration, and cross-linking. These complex reactions are separated by using different gas environments during stabilization. The cross-linking reaction has the highest activation energy among all stabilization reactions, and requires a temperature higher than 300 DegC to be completed. The effect of applied tension on the stabilized fiber properties are investigated, and it is found that higher tension leads to better properties for the stabilized fiber, including higher Young's modulus, higher orientation, less formation of β-amino nitrile, and less shrinkage.
The relationship between stabilization conditions and the mechanical properties of the carbonized fiber is investigated, and the methods to identify optimum stabilization conditions are proposed. It is observed that the highest tension should be applied during both stabilization and carbonization, and the mechanical properties of the resulting carbon fibers are increased if fibers are further stabilized at a temperature of ~ 320 DegC to improve the cross-linking degree as compared with the fibers only stabilized at 255 DegC. The optimum stabilization time depends on both the stabilization temperature and on the applied tension. A new characterization method by monitoring the dynamic mechanical properties, while stabilization is in progress is used to narrow down the range of the optimum stabilization time. Also, the effect of carbonization temperature on the ultimate carbon fiber properties is studied in the batch process carbonization. Preliminary studies are carried out to find the relationship between the structure and properties of precursor fibers and the tensile strength of carbon fibers, including mechanical properties and co-monomers of precursor fibers.
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Understanding Production and Regeneration Of Hybrid Fiber-Ferric Hydroxide Adsorbents For Arsenic Removal From Drinking WaterChaudhary, Binod K. January 2014 (has links)
Drinking water contaminated with arsenic is a worldwide problem, especially in developing nations. The research presented in this dissertation describes two major goals: development of hybrid homopolymer polyacrylonitrile (PAN)-based sorbents for arsenate removal from drinking water and understanding regeneration of arsenate from ferric hydroxide-based adsorbents. The homopolymer PAN fiber was chemically modified to introduce functional groups using NaOH and hydrazine hydrate (HH) separately, or in combination of both. The modified fibers were characterized using Fourier transform infrared spectroscopy (FTIR) and ion exchange measurements. The ferric hydroxides were impregnated onto functionalized fibers using two iron loading procedures. The best arsenate removal performance was obtained using the simplest pretreatment procedure of soaking in 10% NaOH at 95 °C for ninety min, followed by precipitation coating of ferric hydroxide. This suggests that adsorbents based on a low-cost PAN fabric may be produced in developing areas of the world where commercial products may not be available. A density functional theory (DFT) molecular modeling was used to compare free energies of reactions and activation barriers in the formation of arsenate-ferric hydroxide complexes. Slow kinetics associated with arsenate adsorption and desorption attributed to the high activation barriers in forming and breaking bonds with the ferric hydroxides. Another aspect of regeneration study focused on the effects of underlying properties of the ferric hydroxides-loaded adsorbents on arsenate recovery. The arsenate loaded ferric hydroxide adsorbent containing no or weak base functionalities can be regenerated using NaOH, while addition of NaCl to NaOH solution is required for same recovery of arsenate from the adsorbents containing strong base anion exchange functionalities. Moreover, the irreversible fraction of arsenate on the adsorbent can be reduced by increasing the concentration of NaOH. Thus, understanding arsenate desorption kinetics and effects of support properties of ferric hydroxide-based adsorbents are important for environmental fate of arsenate and in designing adsorption systems for removing arsenate from potable water.
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Development of sulfur-polyacrylonitrile/graphene composite cathode for lithium batteriesLi, Jing January 2013 (has links)
Rechargeable lithium sulfur (Li-S) batteries are potentially safe, environmentally friendly and economical alternative energy storage systems that can potentially be combined with renewable sources including wind solar and wave energy. Sulfur has a high theoretical specific capacity of ~1680 mAh/g, attainable through the reversible redox reaction denoted as S8+16Li ↔8Li¬2S, which yields an average cell voltage of ~2.2 V. However, two detrimental factors prevent the achievement of the full potential of the Li-S batteries. First, the poor electrical/ionic conductivity of elemental sulfur and Li2S severely hampers the utilization of active material. Second, dissolution of intermediate long-chain polysulfides (Li2Sn, 2<n<7) into the electrolyte and their shuttle between cathode and anode lead to fast capacity degradation and low Coulombic efficiency. As a result of this shuttle process, insoluble and insulating Li2S/Li2S2 precipitate on the surface of electrodes causing loss of active material and rendering the electrode surface electrochemically inactive.
Extensive research efforts have been devoted to overcome the aforementioned problems, such as combination of sulfur with conductive polymers, and encapsulation or coating of elemental sulfur in different nanostructured carbonaceous materials. Noteworthy, sulfur-polyacrylonitrile (SPAN) composites, wherein sulfur is chemically bond to the polymer backbone and PAN acts as a conducting matrix, have shown some success in suppressing the shuttle effect. However, due to the limited electrical conductivity of polyacrylonitrile, the capacity retention and rate performance of the SPAN systems are still very modest, which shows only 67 % retention of the initial capacity after 50 cycles for the binary system.
Recently, graphene has been intensively investigated for enhancing the rate and cycling performance of lithium sulfur batteries. Graphene, which has a two-dimensional, one-atom-thick nanosheet structure, offers extraordinary electronic, thermal and mechanical properties. Herein, a sulfur-polyacrylonitrile/reduced graphene oxide (SPAN/RGO) composite with unique electrochemical properties was prepared. PAN is deposited on the surface of RGO sheets followed by ball milling with sulfur and heat treatment. Infrared spectroscopy and microscopy studies indicate that the composite consists of RGO decorated with SPAN particles of 100 nm average size. The PAN/RGO composite shows good overall electrochemical performance when used in Li/S batteries. It exhibits ~85% retention of the initial reversible capacity of 1467 mAh/g over 100 cycles at a constant current rate of 0.1 C and retains 1100 mAh/g after 200 cycles. In addition, the composite displays excellent Coulombic efficiency and rate capability, delivering up to 828 mAh/g reversible capacity at 2 C. The improved performance stems from composition and structure of the composite, wherein RGO renders a robust electron transport framework and PAN acts as sulfur/polysulfide absorber.
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Development of sulfur-polyacrylonitrile/graphene composite cathode for lithium batteriesLi, Jing January 2013 (has links)
Rechargeable lithium sulfur (Li-S) batteries are potentially safe, environmentally friendly and economical alternative energy storage systems that can potentially be combined with renewable sources including wind solar and wave energy. Sulfur has a high theoretical specific capacity of ~1680 mAh/g, attainable through the reversible redox reaction denoted as S8+16Li ↔8Li¬2S, which yields an average cell voltage of ~2.2 V. However, two detrimental factors prevent the achievement of the full potential of the Li-S batteries. First, the poor electrical/ionic conductivity of elemental sulfur and Li2S severely hampers the utilization of active material. Second, dissolution of intermediate long-chain polysulfides (Li2Sn, 2<n<7) into the electrolyte and their shuttle between cathode and anode lead to fast capacity degradation and low Coulombic efficiency. As a result of this shuttle process, insoluble and insulating Li2S/Li2S2 precipitate on the surface of electrodes causing loss of active material and rendering the electrode surface electrochemically inactive.
Extensive research efforts have been devoted to overcome the aforementioned problems, such as combination of sulfur with conductive polymers, and encapsulation or coating of elemental sulfur in different nanostructured carbonaceous materials. Noteworthy, sulfur-polyacrylonitrile (SPAN) composites, wherein sulfur is chemically bond to the polymer backbone and PAN acts as a conducting matrix, have shown some success in suppressing the shuttle effect. However, due to the limited electrical conductivity of polyacrylonitrile, the capacity retention and rate performance of the SPAN systems are still very modest, which shows only 67 % retention of the initial capacity after 50 cycles for the binary system.
Recently, graphene has been intensively investigated for enhancing the rate and cycling performance of lithium sulfur batteries. Graphene, which has a two-dimensional, one-atom-thick nanosheet structure, offers extraordinary electronic, thermal and mechanical properties. Herein, a sulfur-polyacrylonitrile/reduced graphene oxide (SPAN/RGO) composite with unique electrochemical properties was prepared. PAN is deposited on the surface of RGO sheets followed by ball milling with sulfur and heat treatment. Infrared spectroscopy and microscopy studies indicate that the composite consists of RGO decorated with SPAN particles of 100 nm average size. The PAN/RGO composite shows good overall electrochemical performance when used in Li/S batteries. It exhibits ~85% retention of the initial reversible capacity of 1467 mAh/g over 100 cycles at a constant current rate of 0.1 C and retains 1100 mAh/g after 200 cycles. In addition, the composite displays excellent Coulombic efficiency and rate capability, delivering up to 828 mAh/g reversible capacity at 2 C. The improved performance stems from composition and structure of the composite, wherein RGO renders a robust electron transport framework and PAN acts as sulfur/polysulfide absorber.
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Pyrolysis Mass Spectrometric Analysis Of Copolymer Of Polyacrylonitrile And PolythiopheneOguz, Gulcan 01 June 2004 (has links) (PDF)
In the first part of this work, the structural and thermal characteristics of polyacrylonitrile, polyacrylonitrile films treated under the electrolysis conditions in the absence of thiophene, polythiophene and the mechanical mixture and a conducting copolymer of polyacrylonitrile/polythiophene have been studied by pyrolysis mass spectrometry technique.
The thermal degradation of polyacrylonitrile occurs in three steps / evolution of HCN, monomer, low molecular weight oligomers due to random chain cleavages are followed by cyclization and dehydrogenation reactions yielding crosslinked and unsaturated segments. Pyrolysis of the treated polyacrylonitrile films indicated decrease in the yields of monomer and oligomers, and increase in the amount of products stabilized by cyclization reactions were detected. Polythiophene degrades in two steps / the loss of the dopant and degradation of polymer backbone.
The evolution profiles of polythiophene based products from polythiophene/polyacrylonitrile showed nearly identical trends with those recorded during the pyrolysis of pure polythiophene. However, evolution of HCN and the degradation products due to the homolytic cleavages of the polymer backbone continued through out the pyrolysis indicating a significant increase in their production. Furthermore, the yield of thermal degradation products associated with decomposition of the unsaturated cyclic imine segments decreased. A careful analysis of the data pointed out presence of mixed dimers confirming copolymer formation.
In the second part of this work, a poly(acrylonitrile-co-butadiene) sample involving monomer units having quite similar molecular weights have been analyzed to investigate the limits of the pyrolysis mass spectrometry technique. Pyrolysis of aged poly(acrylonitrile-co-butadiene) indicated oxidative degradation of the sample.
Keywords: conducting copolymer, polyacrylonitrile, polythiophene, polybutadiene, direct pyrolysis mass spectrometry
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Process, structure and electrochemical properties of carbon nanotube containing films and fibersJagannathan, Sudhakar 13 May 2009 (has links)
The objective of this thesis is to study the effect of process conditions on structure and electrochemical properties of polyacrylonitrile (PAN)/carbon nanotube (CNT) composite film based electrodes developed for electrochemical capacitors. The process parameters like activation temperature, CNT loading in the composite films are varied to determine optimum process conditions for physical (CO2) and chemical (KOH) activation methods. The PAN/CNT precursors are stabilized in air, carbonized in inert atmosphere (argon), and activated by physical (CO2) and chemical (KOH) methods. The physical activation process is carried out by heat treating the carbon precursors in CO2 atmosphere at activation temperatures. In the chemical activation process, stabilized carbon precursors are immersed in aqueous solutions of activating media (KOH), dried, and subsequently heat treated in an inert atmosphere at the activation temperature. The structure and morphology are probed using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The specific capacitance, power and energy density of the activated electrodes are evaluated with aqueous electrolytes (KOH) as well as organic electrolyte (ionic liquid in acetonitrile) in Cell Test. The surface area and pore size distribution of the activated composite electrodes are evaluated using nitrogen absorption. Specific capacitance dependence on factors such as surface area and pore size distribution are studied. A maximum specific capacitance of 300 F/g in KOH electrolyte and maximum energy density of 22 wh/kg in ionic liquid has been achieved. BET surface areas in excess of 2500 m2/g with controlled pore sizes in 1 - 5 nm range has been attained in this work.
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Avaliação do copolímero de acrilonitrila e 2-vinil-2-oxazolina na eficiência de Iinibição de corrosão química / Evaluation of copolymer of acrylonitrile and 2-vinyl-2-oxazoline in the efficiency of corrosion inhibition chemicalWemerson Vieira de Paula 30 March 2010 (has links)
Polímeros heterocíclicos são macromoléculas de elevado desempenho que incluem uma grande variedade de materiais, desde simples polímeros lineares preparados a partir de monômeros do tipo heterocíclicos vinílicos, até polímeros funcionalizados e reticulados. Neste trabalho realizou-se a modificação química da poliacrilonitrila com a incorporação de grupos 2-vinil-2-oxazolina em diferentes teores (10% e 20%). Os copolímeros de acrilonitrila e 2-vinil-2-oxazolina obtidos foram caracterizados por espectroscopia na região do infravermelho e o seu comportamento térmico analisado por calorimetria diferencial de varredura e análise termogravimétrica. Os copolímeros heterocíclicos foram avaliados como inibidores de corrosão para aço-carbono em solução aquosa de HCl 10%, alcançando, em alguns casos, uma eficiência de inibição superior a 75%, com diferença estatisticamente significativa (P < 0,05, ANOVA) para a poliacrilonitrila não modificada. / Heterocyclic polymers are high-performance macromolecules that include a variety of materials, from simple linear polymers which are prepared from heterocyclic monomers like vinyl, to functionalized polymers or lattices. In this work polyacrylonitrile was chemically modified with incorporation of 2-vinyl-2-oxazoline groups at different contents (10% and 20%). Copolymers of acrylonitrile and 2-vinyl-2-oxazoline were characterized by spectroscopy in the infrared region, differential scanning calorimetry and thermogravimetric analysis. The synthesized heterocyclic copolymers were evaluated as corrosion inhibitor on carbon steel against aqueous solution of HCl 10%, and in some cases inhibition efficiencies more than 75% were determined, with statistically significant difference (P < 0.05, ANOVA) to the unmodified polyacrylonitrile.
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