Zeolite A-type membranes are usually synthesized from hydrogels and rarely synthesized from clear solutions mostly in batch systems. Few studies were carried out using semi-continuous systems for zeolite A membrane synthesis. Zeolite A membranes are mainly used in pervaporation processes for separation of water from water/organic mixtures because of their hydrophilic property. In this study, zeolite A membranes were synthesized on -alumina supports from a clear solution with a molar composition of 49Na2O: 1Al2O: 5SiO2: 980H2O. Synthesis was done both in a batch system and in a flow system in which solution was circulated through the support under atmospheric pressure. Effects of synthesis temperature, time, flow rate and seeding on membrane formation were investigated. The membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), single gas permeation measurements and pervaporation tests. In batch system, pure zeolite A membranes having cubic form of zeolite A was obtained for the syntheses carried out at 60&deg / C for 24 h and 80&deg / C for 8 h. Thicknesses of the membranes synthesized at 80&deg / C and 60&deg / C were about 2 &micro / m and 4 &micro / m, respectively. N2 permeances were 2*10-8 mol/m2sPa and 8*10-8 mol/m2sPa for of the membranes synthesized in the batch system at 60&deg / C and 80&deg / C, respectively. When synthesis was carried out in flow system pure and continuous zeolite A membranes were obtained for all conditions. Membranes synthesized at 60&deg / C and 80&deg / C had thicknesses of about 1.5 and 2 &micro / m, respectively. Lower N2 permeations were obtained for the membranes synthesized in flow system. It was observed that flow rate and seeding did not significantly affect the thickness of the membrane layer. The membranes synthesized in this study are significantly thinner than the membranes reported in the literature. Single gas permeation tests at 25&deg / C for the membranes showed that comparable membranes with the ones in literature were obtained in this study. For a double layer membrane synthesized in flow system at 80&deg / C for 8h separation factor about 3700 was obtained for the separation of 92:8 (wt.%) ethanol/water mixture at 45&deg / C.

Inferential control of boric acid production system using the reaction of colemanite with sulfuric acid in four continuously stirred tank reactors (CSTR) connected in series is aimed. In this control scheme, pH of the product is measured on-line instead of boric acid concentration for control purposes. An empirical correlation between pH and boric acid concentration is developed using the collected data in a batch reacting system in laboratory-scale and this correlation is utilized in the control system for estimator design. The transfer function model of the 4-CSTR system previously obtained is used in the MPC controller design. In the experiments done previously for the modelling of 4-CSTR system, it was observed that the reaction goes complete within the first reactor. Therefore, the control is based on the measurements of pH of the second reactor by manipulating the flow rate of sulfuric acid given to the first reactor, while the flow rate of colemanite fed to the system is considered as disturbance. The designed controller&rsquo / s performance is tested for set point tracking, disturbance rejection and robustness issues using a simulation program. It is found that, the designed controller is performing satisfactorily, using the inferential control strategy for this complex reacting system.

Fast depletion of oil reserves necessitates the development of novel alternative motor vehicle fuels. Global warming problems also initiated new research to develop new fuels creating less CO2 emission. Nowadays, dimethyl ether (DME) and diethyl ether (DEE) are considered as important alternative clean energy sources. These valuable ethers are produced by the dehydration reaction of methanol and ethanol, respectively, in the presence of acidic catalysts. Besides DEE, ethylene which is very important in petrochemical industry, can also be produced by ethanol dehydration reaction. In the first part of this study, the catalytic activity of tungstophosphoric acid (TPA), silicotungstic acid (STA) and molybdophosphoric acid (MPA), which are well-known heteropolyacids were tested in ethanol dehydration reaction. The activities of other solid acid catalysts, such as Nafion and mesoporous aluminosilicate, were also tested in the dehydration reaction of ethanol. In the case of DME production by dehydration of methanol, activities of STA, TPA and aluminosilicate catalysts were tested. Among the heteropolyacid catalysts, STA showed the highest activity in both ethanol and methanol dehydration reactions. With an increase of temperature from 180oC to 250oC, Ethylene selectivities increased while DEE selectivities decreased. Ethylene yield values over 0.70 were obtained at 250oC. The presence of water in the feed stream caused some reduction in the activity of TPA catalyst. Very high DME yields were obtained using mesoporous aluminosilicate catalyst at about 450oC. The surface area of heteropolyacids are very low and they are soluble in polar solvents such as water and alcohols. Considering these drawbacks of heteropolyacid catalysts, novel mesoporous STA based high surface area catalysts were synthesized following a hydrothermal synthesis route. These novel catalysts were highly stable and they did not dissolve in polar solvents. The catalysts containing W/Si ratios of 0.19 (STA62(550)) and 0.34 (STA82(550)) have BJH surface area values of 481 m2/g and 210 m2/g, respectively, with pore size distributions ranging in between 2-15 nm. These catalysts were characterized by XRD, EDS, SEM, TGA, DTA, DSC, FTIR and Nitrogen Adsorption techniques and their activities were tested in ethanol dehydration reaction. Calcination temperature of the catalysts was shown to be a very important parameter for the activities of these catalysts. Considering the partial decomposition and proton lost of the catalysts over 375oC, they are calcined at 350oC and 550oC before testing them in ethanol dehydration reaction. The catalysts calcined at 350oC showed much higher activity at temperature as low as 180oC. However, the catalysts calcined at 550oC showed activity over 280oC. Ethylene yield values approaching to 0.90 were obtained at about 350oC with catalysts calcined at 350oC. DEE yield past through a maximum with an increase in temperature indicating its decomposition to Ethylene at higher temperatures. However, at lower temperatures (&lt / 300oC) Ethylene and DEE were concluded to be formed through parallel routes. Formation of some acetaldehyde at lower temperatures indicated a possible reaction path through acetaldehyde in the formation of DEE. DRIFTS results also proved the presence of ethoxy, acetate and ethyl like species in addition to adsorbed ethanol molecules on the catalyst surface and gave additional information related to the mechanism.

Boron carbide was produced on tungsten substrate in a dual impinging-jet CVD reactor from a gas mixture of BCl3, CH4, and H2. The experimental setup was designed to minimise the effect of mass transfer on reaction kinetics, which, together with the on-line analysis of the reactor effluent by FTIR, allowed a detailed kinetic investigation possible. The phase and morphology studies of the products were made by XPS, XRD,micro hardness and SEM methods. XPS analysis showed the existence of chemical states attributed to the boron carbide phase, together with the existence of oxy-boron carbide species. SEM pictures revealed the formation of 5-fold icosahedral boron carbide crystals up to 30 micron sizes for the samples produced at 1300oC. Microhardness tests showed change of boron carbide hardness with the temperature of tungsten substrate. The hardness values (Vickers Hardness) observed were between 3850 kg/mm2 and 4750 kg/mm2 corresponding to substrate temperatures of 1100 and 1300 C, respectively. The FTIR analysis of the reaction products proved the formation of reaction intermediate BHCl2, which is proposed to occur mainly in the gaseous boundary layer next to the substrate surface. The experimental parameters are the temperature of the substrate, and the molar fractions of methane and borontrichloride at the reactor inlet. The effects of those parameters on the reaction rates, conversions and selectivities were analysed and such analyses were used in mechanism determination studies. An Arrhenius type of a rate expression was obtained for rate of formation of boron carbide with an energy of activation 56.1 kjoule/mol and the exponents of methane and boron trichloride in the reaction rate expression were 0.64 and 0.34, respectively, implying complexity of reaction. In all of the experiments conducted, the rate of formation of boron carbide was less than that of dichloroborane. Among a large number of reaction mechanisms proposed only the ones considering the molecular adsorption of boron trichloride on the substrate surface and formation of dichloroborane in the gaseous phase gave reasonable fits to the experimental data. Multiple non-linear regression analysis was carried out to predict the deposition rate of boron carbide as well as formation rate of dichloroborane simultaneously.

Second Constitutional Era (1908-1918) was a period within which great changes occurred in the Ottoman Empire. On the one hand, it was a part of the modernization process that began in late eighteenth century / on the other hand, it was the last period of the Empire that had its own dynamics. This study is to examine changes and continuities in a locality, the Sivas Province, during the Second Constitutional Regime. The Sivas Province was one of the largest and most populated Anatolian provinces. It located in the middle of Anatolia therefore it had a geopolitical importance. Moreover, it was one of the six Eastern Provinces with a considerable Armenian population. Sivas had the biggest Armenian and Greek population among these provinces. Thus, both geopolitical importance and population characteristics make the province an appropriate place to examine change and continuity during the Second Constitutional Regime. In this study, transformation of the province is examined over some topics such as demographic characteristics, political life, administrative, educational and economic structures. The research about these topics indicates that three main dynamics of the Second Constitutional Regime were influential on developments in the Sivas case. These dynamics are war, population movements especially the Armenian Deportation and nationalism. These dynamics also determined implementation of the modernization policies in the Sivas Province during the Constitutional Regime. Therefore, transformation/change of the province is examined over these dynamics.

Methane activation with bromine followed by the condensation of the methyl bromide into higher hydrocarbons or oxygenates is a novel route. However, the selective production of monobrominated methane (CH3Br) at high conversions is a crucial prerequisite. A reaction model was developed according to the kinetic data available in the literature and thoroughly studied to investigate the optimum reactor conditions for selective methane bromination in gas phase. It was concluded that at high methane (&gt / 90%) conversions dibromomethane synthesis was favored at high selectivity (~90%) under the following conditions: T=330 &deg / C, Br:CH4 = 3. Sulfated zirconia included SBA-15 catalysts were prepared and characterized for the catalytic methane activation via bromination. The SBA-15 sol-gel preparation technique was followed and the zirconium was added during the preparation in the form of ZrOCl2&middot / 8H2O with 5-30 mol % ZrO2 with respect to the SiO2 content simultaneously with the silicon source (TEOS). The catalysts were sulfated in 0.25 M H2SO4 solution. The zirconium contents of the catalysts were determined by elemental analysis and 15 wt. % Zr was determined as the highest amount. XRD analysis showed the crystalline zirconia peaks only for high zirconia loadings (&gt / 25 mol % ZrO2) indicating the good distribution of Zr in silica framework at lower loadings. BET surface areas of the sulfated catalysts are in the range of 313-246 m2/g. The porous structures of the catalysts were determined by TEM pictures, which revealed that the increase in Zr content decreased the long range order of pore structure of SBA-15 in agreement with XRD results. The acidities of the catalysts were determined by 1H MAS NMR experiments. Br&oslash / nsted acidity was identified by a sharp 1H MAS NMR line at 10.6 ppm. The highest acidity was observed at 5.2 wt. % Zr loading according to 1H MAS NMR experiments. 29Si MAS NMR analysis showed the formation of Si-O-X linkages (X=H, Zr). Further characterization of Br&oslash / nsted acidity was performed by FT-IR spectroscopy of adsorbed CO at 82 K. The analysis revealed that the Br&oslash / nsted acidity of sulfated catalysts were similar to the acid strength of the conventional sulfated zirconia. In TPD experiments, the basic molecule isopropylamine (IPAm) was adsorbed and decomposition temperature of IPAm was monitored. The temperature decreased from 340 &deg / C to 310 &deg / C in sulfated catalysts, indicating the acidic character of these samples. Catalytic methane bromination reaction tests were performed in a quartz tubular reactor. The results showed that 69% methane conversion was attainable over SZr(25)SBA-15 catalyst at 340 &deg / C. The liquid 1H NMR measurements of the products revealed that &gt / 99% methyl bromide selectivity was achieved.

Polymer-clay nanocomposites have received a lot of attention because of outstanding improvements in properties when compared with neat polymeric materials. The aim of this study was to prepare epoxy-clay nanocomposites by mixing organically modified montmorillonite with an epoxy resin and to investigate the effects of clay content on the mechanical, thermal and flammability properties of the resultant nanocomposites. The production of the epoxy-clay nanocomposites was accomplished by in-situ polymerization. In the nanocomposite synthesis, organically modified clay content was varied from 1 wt.% to 9 wt.%. Araldite LY556 epoxy resin, Aradur 918 anhydride hardener, and DY070 imidazole type accelerator were used in the epoxy system. Closite 30B, an organoclay modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH), was used as the clay material. X-ray diffraction results showed that d-spacing between the platelets of organoclay increased from 1.80 nm to 4.4 nm. The microstructures of nanocomposites were investigated by scanning electron microscopy (SEM). The SEM micrographs indicated that at 1 wt.% clay loading, no clay aggregates were observed. On the other hand, beyond 1 wt.% clay loading, formation of clay agglomerations was observed. Tensile strength and tensile strain values of nanocomposites decreased with clay loading. The tensile strength value of neat epoxy resin decreased from 55 MPa to 29 MPa with 9 % clay loading. On the other hand, Young&amp / #8217 / s modulus increased with clay content and a maximum value was obtained at 5 wt. % clay loading. At 9 % clay loading, Young&amp / #8217 / s modulus value was 26 % higher than that of the neat epoxy resin. Impact strength property had a minimum value at 7 wt. % clay content. Flexural strength and flexural strain at break property behaved in a similar trend. They had a minimum value at 5 % clay loading. At this clay loading, flexural strength value became approximately 43 % lower compared to the flexural strength of the neat epoxy resin. On the other hand, at 9 wt.% clay loading flexural modulus value increased approximately 48 % compared to the pure epoxy resin. Up to 7 wt.% clay ratio, initial decomposition temperature of epoxy resin was slightly improved. Also, according to TGA results, amount of char formation increased with clay loading. DSC results indicate that Tg of the cured nanocomposite resins decreased from 147 oC to 129 oC with 9 wt. % clay loading. The flammability of neat epoxy resin was not significantly affected with Cloisite 30B addition.

In this study two polychelatogens for borate and a polyelectrolyte for chromate retention (R) were designed for investigating the effect of pH and loading (g metal /g polymer) on the separation performances of the synthesized polymers using continuous polymer enhanced ultrafiltration. Increase in pH increased the retention of borate for all of the synthesized polymers. Decrease in the loading resulted in an enhancement in boron retention with PNSM and PNSL. When COP was utilized, retentions remained almost constant after a certain loading, probably due to possible adverse effects of high polymer concentrations on polymer conformation in aqueous solutions. Decrease in loading caused an increase in the retention of chromate until a loading of 0.01. After that a slight decrease was observed. Maximum Cr (VI) retention was obtained as 0.70 for a loading of 0.01 and a pH of 4. Effect of crowding on Cr(VI) retention was also investigated. It was observed that retention does not only depend on the loading but also on the concentrations of both Cr (VI) and PDAM. Effect of the presence of competing anions such as chloride and sulfate on the retention of chromate was investigated to see the effect of competing anion charge to the selectivity of the synthesized polyelectrolyte. Addition of both anions decreased the retention of Cr(VI) . Divalent sulfate decreased the retention more than monovalent chloride indicating that charge of the anion may be the predominant variable in the retention of chromate using PDAM. Finally, dynamic and static light scattering measurements were performed to investigate the conformational changes in the structure of the synthesized polymers at different pH values as well as in the presence of boron in the solution. In this study, it is shown that PEUF can be successfully applied to for boron and Cr (VI) retention with the synthesized polymers. Satisfactory retention values were obtained both for boron and Cr (VI). Even if the retention of Cr (VI) decreased with the addition of high amount of competing anions, significant Cr (VI) retentions could be obtained.

Nanofibers, which have high surface area to volume ratio and better mechanical properties, are nanomaterials that both industry and scientists have started to show great attention in the last two decades. They are used in many areas such as life and filtration sciences, sensors, and composite reinforcement etc. Among five main production types, electrospinning is the best candidate for further development with a wide range of opportunities to be applied to all types of polymers and ceramics. This method uses electrically charged jet of polymers or liquid states of polymers to produce fibers from micro dimensions down to nano dimensions. Electrospinning setup has mainly three parts / (i) an AC/DC high voltage equipment which creates high electrical potential, (ii) a syringe, and (iii) a collecting screen. The purpose of this study is to electrospin polystyrene/butyl rubber blends and to investigate the effects of electrospinning parameters on the fibers produced. In this study, polystyrene/butyl rubber blends were electrospun by changing the applied voltage, the tip-to-collector distance, the flowrate, and the butyl rubber content in the fiber. Finally, morphology of electrospun fibers was characterized by SEM. The average fiber diameters varied from 760 nm to nearly 10 &micro / m. Increasing butyl rubber content in the fiber resulted in a decrease in the final fiber diameter. Increasing applied voltage also caused a decrease in the final fiber diameter. The tip-to-collector distance did not affect the average fiber diameter. Increasing flowrate yielded fibers with larger diameters. Finally, the addition of non-ionic surfactant decreased the average fiber diameter.

Sustainability and green engineering are two main concepts considered throughout this study. Sustainability deals with the utilization of renewable and replaceable sugar-based twelve most promising building blocks included in the report prepared by U.S. Department of Energy and green engineering concept is related with the incorporation of environmental performance criteria to chemical process design. Process performance criteria at the conceptual design stage are selected as persistence, bioaccumulation and aquatic toxicity, economical potential of the processes, atom &amp / mass efficiency of the processes and the relationship between Gibbs free energy of reaction values and economical potential. It is observed that bioaccumulation potentials of both the raw materials and products are low. Petrochemical raw materials are more persistent in air than the bio-based ones. The aquatic toxicity of bio-based raw materials is low / whereas some of the petrochemicals are moderately toxic and allyl alcohol and acrylonitrile among the petrochemicals are classified as highly toxic. Bio -based routes are not economically feasible with 2002 market prices. Atom and mass efficiencies of petrochemical reactions for a group of chemicals are higher than bio-based ones due to mostly addition or substitution reactions. Among high number of products, 1,3 propanediol production from glycerol with two microorganisms is analyzed at preliminary design stage. Process performance criteria are selected as material and energy consumption, cooling water requirement, CO, CO2, SO2 and NOX emissions to the atmosphere per unit of 1,3 propanediol production. Klebsiella pneumoniae process requires less cooling water, but it is less energy efficient and causes higher emissions.