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Publication Metadata only 1,3-bis(gamma-aminopropyl)tetramethyldisiloxane modified epoxy resins: curing and characterization(Elsevier, 1998) Department of Chemistry; Department of Chemistry; Yılgör, Emel; Yılgör, İskender; Researcher; Faculty Member; Department of Chemistry; College of Sciences; College of Sciences; 40527; 24181Incorporation of siloxane oligomers with reactive organofunctional terminal groups, such as amine, epoxy and carboxy, into the structure of epoxy networks, provides improvements in the fracture toughness, water absorption and surface properties of the resultant systems. 1,3-bis(gamma-aminopropyl) tetramethyldisiloxane (DSX) was used as a model curing agent and modifier in bis(4-aminocyclohexyl)methane (PACM-20) cured diglycidyl ether of bisphenol-A (DGEBA) based epoxy resins. Curing reactions followed by differential scanning calorimetry indicated faster reaction rates between DSX and DGEBA as compared with PACM-20 and DGEBA. Mechanical characterization of the modified products showed improvements in tensile and impact strengths as expected. Glass transition temperatures of these materials showed a decrease with an increase in DSX content.Publication Metadata only A comparative study of the structure-property behavior of highly branched segmented poly(urethane urea) copolymers and their linear analogs(Elsevier Sci Ltd, 2005) Sheth, JP; Unal, S; Beyer, FL; Long, TE; Wilkes, GL; Department of Chemistry; Department of Chemistry; Yılgör, Emel; Yılgör, İskender; Researcher; Faculty Member; Department of Chemistry; College of Sciences; College of Sciences; N/A; 24181The solid-state structure-property behavior of highly branched segmented poly(urethane urea) (PUU) copolymers and their linear analog was investigated. A limited study of their solution theological behavior was also undertaken. The linear PUUs were synthesized by the two-step prepolymer method, whereas the oligomeric A(2) + B-3 methodology was utilized to synthesize the highly branched materials. The soft segments (SS) were either poly(tetramethylene oxide) (PTMO) or poly(propylene oxide) (PPO). All copolymers utilized in this study, with one exception, contained 28 wt% hard segment (HS) content. DMA, SAXS, and AFM studies indicated that the linear as well as the highly branched PUUs were microphase separated. The SS T-g of the highly branched PUUs was nearly identical to that of their respective linear analogs. However, the linear copolymers exhibited broader and less temperature sensitive rubbery plateaus, both attributed to one or both of two reasons. The first is better hydrogen bonding organization of the HS phase as well as greater HS lengths than in the highly branched analogs. The second parameter is that of a potentially higher chain entanglement for the linear systems relative to the branched analogs. Tapping-mode AFM phase images confirmed the microphase morphology indicated by SAXS and DMA. Ambient temperature strain-induced crystallization was observed in the PUU based on PTMO 2040 g/mol at a uniaxial strain of ca. 400%, irrespective of the chain architecture. Stress-strain, stress relaxation, and mechanical hysteresis of the highly branched copolymers were in general slightly poorer than that of their linear analogs. Ambient temperature solution viscosity of the highly branched materials in dimethyl formamide was substantially lower that that of the linear samples of nearly equal molecular weight.Publication Metadata only A DFT study of polymerization mechanisms of indole(Elsevier Sci Ltd, 2002) Yurtsever, Mine; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129Polymerization of unsubstituted indoles is studied by accurate density functional theory calculations. Relative stability of all possible dimers of indole is computed in order to understand the thermodynamics of polymerization. It is observed that 2-position is the most likely site to enhance polymerization. A selected set of trimers and tetramers which use a 2-position for linkages are generated to understand the further growth of polyindole. A study of local minima arising from different distributions of the torsional angles reveals that there are two equally probable conformations and the one with the torsional angle changing signs alternatively is slightly favored. The cyclic structures are also investigated and it is shown that it is possible to generate stable three- and four-membered cyclic structures. Finally, the structures of radical cations and intermediate states are fully optimized and the energetics of these metastable species are used to explain the competing mechanisms of radical-radical and radical-neutral pathways.Publication Metadata only Anomalous dilute solution properties of segmented polydimethylsiloxane-polyurea copolymers in isopropyl alcohol(Elsevier, 2006) Ward, Thomas C.; Department of Chemistry; Department of Chemistry; Department of Chemistry; Yılgör, İskender; Yılgör, Emel; Gökçümen, Güneş Ekin Atilla; Faculty Member; Researcher; Undergraduate Student; Department of Chemistry; College of Sciences; College of Sciences; College of Sciences; 24181; 40527; N/APreliminary characterization of amphiphilic segmented copolymers of polydimethylsiloxane and urea 'hard blocks' was conducted by measuring isopropyl alcohol (primarily) dilute solution viscosities via capillary viscometry. The traditional data analysis techniques, which provide for extrapolation of intrinsic viscosities from these experiments, revealed that increasing concentrations of polymer produced lower reduced viscosities rather than the expected higher values. A very approximate data fit reveals negative Huggins and Kraemer constants from these analyses, which are highly unusual. In a solvent such as DMF, a similar polymer having poly(tetramethylene oxide) and urea blocks and measured with identical conditions exhibited the expected behavior, showing increasing reduced viscosities over concentrations in the same range. However, the non-linearity of the data is suggestive of much more complex hydrodynamic, or supramolecular, interactions that are not clarified by the initial research.Publication Metadata only Comparison of hydrogen bonding in polydimethylsiloxane and polyether based urethane and urea copolymers(Elsevier, 2000) Department of Chemistry; Department of Chemistry; Department of Chemistry; Department of Chemistry; Yılgör, Emel; Burgaz, Engin; Yurtsever, İsmail Ersin; Yılgör, İskender; Researcher; Undergraduate Student; Faculty Member; Faculty Member; Department of Chemistry; College of Sciences; College of Sciences; College of Sciences; College of Sciences; 40527; N/A; 7129; 24181Hydrogen bonding in polydimethylsiloxane and polyether based urethane and urea type segmented copolymers was investigated by infrared spectroscopy, differential scanning calorimetry and quantum mechanical calculations. Hydrogen bonding in model urethane and urea compounds was compared with those of the copolymers, in order to determine the extent of interaction and resulting phase mixing between hard and soft segments in these copolymers. Quantum mechanical calculations were also used to determine the interaction energies due to hydrogen bonding in model urethane and urea compounds. Further, similar calculations were also performed to quantify the interactions between silicone and ether type soft segments, and urea and urethane type hard segments. As expected, these calculations clearly indicated the absence of any interaction between silicones and urea groups, while there was substantial hydrogen bonding between urea groups and the oxygen in the ether type soft segments. Results of FTIR studies and quantum mechanical calculations were in good agreement with thermomechanical behavior and mechanical properties of these copolymers.Publication Metadata only Conformational analysis of model poly(ether urethane) chains in the unperturbed state and under external forces(Amer Chemical Soc, 2002) Department of Chemistry; Department of Chemistry; Department of Chemical and Biological Engineering; Yılgör, İskender; Yurtsever, İsmail Ersin; Erman, Burak; Faculty Member; Faculty Member; Faculty Member; Department of Chemistry; Department of Chemical and Biological Engineering; College of Sciences; College of Sciences; College of Engineering; 24181; 7129Conformational features of model poly(ether urethane) (PEU) single chains are investigated in the unperturbed state and under external force. Model PEUs consisting of symmetrical, aromatic, 1,4-phenylene diisocyanate (PDI) hard segments and poly(tetramethylene oxide) (PTMO) soft segments with varying lengths are considered. Rotational potential maps are calculated quantum mechanically using the AM1 parametrization with Gaussian98. Configurations of the chains are generated by the Monte Carlo technique, using the rotational isomeric state formalism and successive matrix multiplication scheme. Unperturbed dimensions, the change in dimensions when a force acts along the end-to-end vector, the stiffness, and toughness of the chain and orientability of segments under external force are characterized and compared with properties of polyethylene. The characteristic ratio of along PEU chain is 5.0, and the Kuhn length for a single block is 9.2 Angstrom, both of which are smaller than the corresponding polyethylene values. The model chains are significantly more ductile and tougher than polyethylene. The orientability of the backbones exhibits a strong even-odd effect, with strongly orientable bonds neighbored by weakly orienting ones. The degree of rigidity of the phenyl group does not propagate far along the chain. The projection of the bond vectors on the phenyl axis decay rapidly with increasing distance of the bond along the chain.Publication Metadata only Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents(Elsevier Sci Ltd, 2009) Wilkes, Garth L.; Department of Chemistry; N/A; Department of Chemistry; Yılgör, İskender; Eynur, Tuğba; Yılgör, Emel; Faculty Member; Master Student; Researcher; Department of Chemistry; College of Sciences; Graduate School of Sciences and Engineering; College of Sciences; 24181; N/A; N/ANovel, segmented thermoplastic silicone-urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments ( 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43-14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone-urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone-urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (M(e)) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone-urea copolymers.Publication Metadata only Critical parameters in designing segmented polyurethanes and their effect on morphology and properties: a comprehensive review(Elsevier Sci Ltd, 2015) Wilkes, Garth L.; Department of Chemistry; Department of Chemistry; Yılgör, İskender; Yılgör, Emel; Faculty Member; Researcher; Department of Chemistry; College of Sciences; College of Sciences; 24181; N/AA comprehensive discussion is provided of the critical physical, chemical and structural parameters, such as soft and hard segment structures and their molecular weights, polymer composition, solubility parameters, competitive intermolecular interactions and others, which strongly affect the morphology and bulk and surface properties of segmented thermoplastic polyurethanes, polyureas and poly-urethaneureas (TPUs). Important developments related to the design, synthesis and structure-property behavior of segmented polyurethanes are discussed. Although the main emphasis is placed on linear materials, some brief comments are also given on the effect of chemical crosslinking on the structure property behavior of segmented polyurethanes.Publication Metadata only Density functional theory study of the electrochemical oligomerization of thiophene: transition states for radical-radical and radical-neutral pathways(Elsevier, 2004) Yurtsever, Mine; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129Accurate density-functional-theory (DFT) calculations on oligothiophenes containing up to 6 units have been performed in order to understand the various possible mechanisms of growth. There are two possible mechanisms for this process which involve the coupling of cationic radicals with either another cationic radical or with a neutral oligomer. Most of the electronic properties of these oligomers are well understood, but there is very little known about the nature of the intermediates and the transition states leading to polymerization. The initial oxidation, forming stable intermediates, releasing protons and/or further oxidations are studied in terms of the energetics, changes in the geometry, charge distributions and possible signatures in the vibrational spectra. The radical-radical pathway is found to be the more probable one between two mechanisms. Also the attack of monomers/or shorter oligomers on the longer ones is found to be faster than the coupling of equal size chains.Publication Metadata only Effect of chemical composition on large deformation mechanooptical properties of high strength thermoplastic poly(urethane urea)s(Amer Chemical Soc, 2004) Curgul, Sezen; Çakmak, Miko; Department of Chemistry; Department of Chemistry; Department of Chemical and Biological Engineering; Yılgör, İskender; Yılgör, Emel; Erman, Burak; Faculty Member; Researcher; Faculty Member; Department of Chemistry; Department of Chemical and Biological Engineering; College of Sciences; College of Sciences; College of Engineering; 24181; 40527; 179997The effect of composition on the true mechanooptical properties of thermoplastic poly(urethane urea)s was investigated by selectively varying the type and content of soft and hard segments. Real-time stress-strain-birefringence data together with off-line wide-angle X-ray scattering measurements revealed that soft segment and chain extender play dominant roles on the chemical structures of the poly(urethane urea)s. All poly(tetramethylene oxide) glycol-based samples showed the same crystal structure. The samples containing ethylenediamine as the chain extender showed enhanced crystallizability as compared to those with 1,6-diaminohexane no matter which soft segment was used. In general, samples with lower fraction of hard segment exhibited higher crystallizability than their high hard segment counterparts. Long-term holding of poly(ethylene oxide) samples in stretched state was found to increase crystallinity. The strain-induced crystallization in low hard segment content poly(tetramethylene oxide)based samples was only observed at very high deformation levels. on the other hand, crystallization in the samples containing high hard segment was found to evolve gradually over large deformation range. The strain rate has a considerable effect on the crystallization behavior of poly(tetramethylene oxide)based samples. While the low hard segment content poly(tetramethylene oxide) sample experiences decreasing crystallizability as the strain rate increases, its counterpart containing higher fraction of hard segments exhibits opposite behavior. We have investigated linear and nonlinear stress optical behavior and observed that the span of the initial linear stress optical region varied primarily with composition (slope ranging from 0.1 to 2.2 GPa(-1)) and secondarily with the deformation rate. Hysteresis experiments show that there is a considerable loss of energy in cyclic loading of these materials, and hysteresis increases as the chain extender is changed from 1,6-diaminohexane to ethylenediamine.