Chemical Engineering Commons^™

Yieldlike Constitutive Transition In Shear Flow Of Entangled Polymeric Fluids, Prashant Tapadia, Shi-Qing Wang

College of Polymer Science and Polymer Engineering

We describe an unexpected constitutive transition in entangled polymer solutions. At and beyond a critical stress, the initial spatially homogeneous and well-entangled sample transforms from its entangled (coiled) state into a fully disentangled (stretched) state over a period during which the resulting shear rate increases in a spatially inhomogeneous fashion. In the mode of controlled shear rate, the sample exhibits a stress plateau over three decades. Flow birefringence and normal stress observations unravel additional features of these flow phenomena.

Observation Of Novel Liquid-Crystalline Phase Above The Bulk-Melting Temperature, Keshav S. Gautam, Satyendra Kumar, Didier Wermeille, Doug Robinson, Ali Dhinojwala

College of Polymer Science and Polymer Engineering

In this paper, we show that a noncrystalline but ordered smectic-like phase exists above the bulk-melting temperature (T-m) at poly(n-alkyl acrylates)-air interface. The surface ordered phase is one monolayer thick and undergoes a sharp transition from order to disorder 10degreesC above T-m for n=22. The presence of a surface phase that does not exist in the bulk has important implications in the design of thermally responsive adhesives.

Relaxation Of A Rubbed Polystyrene Surface, Alexander D. Schwab, Ali Dhinojwala

College of Polymer Science and Polymer Engineering

The relaxation dynamics of a rubbed polystyrene (PS) surface have been characterized using infrared-visible sum frequency generation spectroscopy (SFG). The SFG results were compared with previous relaxation of retardation measurements, and the results show that the rubbed PS surface has the same T(g) as the bulk where T(g) is defined as tau(T(g))=5 s, however, the surface has a lower activation energy (DeltaE) and a larger stretching exponent (beta(KWW)) than bulk PS. This indicates that the surface region relaxes more quickly than the bulk. The thickness of this region of lower DeltaE and larger beta(KWW) is estimated to be roughly 12 …

Poly(Meta-Phenylene Isophthalamide) Nanofibers: Coating And Post Processing, Wenxia Liu, Mathew Graham, Edward A. Evans, Darrell Hyson Reneker

College of Polymer Science and Polymer Engineering

Electrospun nanofibers have applications in the areas of filtration, composites; biomaterials, and electronics. Controlling the surface properties of these nanofibers is important for many applications. Nanofibers can also be used as unique substrates for observing the growth of deposited films and creating nanoscale structures. In this work, electrospun poly(meta-phenylene isophthalamide) (MPD-I) nanofibers were used as substrates for creating nanoscale structures out of carbon-based materials and metals. MPD-I was used because it can be electrospun into nanofibers with diameters smaller than 10 nm and it has good thermal stability. MPD-I nanofibers were coated with carbon, copper, and aluminum using plasma enhanced …

A Device For Surface Study Of Confined Micron Thin Films In A Total Internal Reflection Geometry, Sergey Mamedov, Alexander D. Schwab, Ali Dhinojwala

College of Polymer Science and Polymer Engineering

A device to probe the molecular structure of materials next to a solid interface in a thin film geometry has been developed. The device can produce controlled thicknesses as small as 1 mum with parallelity better than 0.003degrees. We have shown that the thickness and the parallelity of the film produced between two optical surfaces can be quantified using white light and monochromatic light interferometry, respectively. In addition, this apparatus allows the study of these films in a static state or under shear using spectroscopic techniques involving transmission or reflection measurements. (C) 2002 American Institute of Physics.

Melting At Alkyl Side Chain Comb Polymer Interfaces, K. S. Gautam, Ali Dhinojwala

College of Polymer Science and Polymer Engineering

Infrared visible sum frequency generation (SFG) spectroscopy has been used to study structure and melting transition temperatures of alkyl-side chain-acrylate comb polymers at air and solid interfaces. At the air interface, the SFG spectra show methyl bands and two transitions are observed: the first, near the bulk melting temperature, T-m, and the second 10-20degreesC higher than T-m. The shorter the alkyl side chain, the larger the difference between the two transition temperatures. In contrast, methylene bands are observed at sapphire interface with a single transition near T-m (C18).

Motion Of Droplets Along Thin Fibers With Temperature Gradient, Alexander L. Yarin, Wenxia Liu, Darrell Hyson Reneker

College of Polymer Science and Polymer Engineering

Liquid n-decane, n-undecane, n-dodecane, and n-hexadecane formed tiny symmetrical droplets on a partially wettable cylindrical fiber. When a temperature gradient was created along the fiber, the droplets began to move along the fiber toward the cold region. An explanation of the phenomenon is related to the thermocapillary motion. Other possible mechanisms were ruled out. The theoretical results and experimental data agree reasonably well. (C) 2002 American Institute of Physics.

Two-Photon-Excited Green Emission And Its Dichroic Shift Of Oriented Thin-Film Cds On Glass Formed By Laser Deposition, B. Ullrich, R. Schroeder, H. Sakai, A. Zhang, Stephen Z. D. Cheng

College of Polymer Science and Polymer Engineering

The photoluminescence of oriented thin-film CdS on glass formed by laser deposition was investigated employing 200 fs, 1.54 eV laser pulses at room temperature. The ultrafast excitation caused a two-photon absorption process, which results in purely green emission at the band gap. The spectra are fitted very well by the application of the van Roosbroeck-Shockley relation, density of states, and Urbach's rule demonstrating the intrinsic character of the radiative recombination. It is further shown that the energy position of the emission peak depends on the polarization of the impinging laser beam due to the dichroism of the highly oriented films. …

Taylor Cone And Jetting From Liquid Droplets In Electrospinning Of Nanofibers, Alexander L. Yarin, S Koombhongse, Darrell Hyson Reneker

College of Polymer Science and Polymer Engineering

Sessile and pendant droplets of polymer solutions acquire stable shapes when they are electrically charged by applying an electrical potential difference between the droplet and a flat plate, if the potential is not too large. These stable shapes result only from equilibrium of the electric forces and surface tension in the cases of inviscid, Newtonian, and viscoelastic liquids. In liquids with a nonrelaxing elastic force, that force also affects the shapes. It is widely assumed that when the critical potential phi (0*) has been reached and any further increase will destroy the equilibrium, the liquid body acquires a conical shape …

Dislocation-Controlled Perforated Layer Phase In A Peo-B-Ps Diblock Copolymer, Lei Zhu, Ping Huang, Stephen Z. D. Cheng, Qing Ge, Roderic P. Quirk, Edwin L. Thomas, Bernard Lotz, Jean-Claude Wittmann, Benjamin S. Hsiao, Fengji Yeh, Lizhi Liu

College of Polymer Science and Polymer Engineering

Small angle x-ray analyses show that the shear-induced hexagonal perforated layer phase in a poly(ethylene oxide)-b-polystyrene diblock copolymer consists of trigonal (R3(overbar)m) twins and a hexagonal (P6(3)/mmc) structure, with trigonal twins being majority components. Transmission electron microscopy reveals that the hexagonal structure is generated through sequential intrinsic stacking faults on the second layer from a previous edge dislocation line, while the trigonal twins are formed by successive intrinsic stacking faults on neighboring layers due to the plastic deformation under mechanical shear.

Bending Instability In Electrospinning Of Nanofibers, A. L. Yarin, S. Koombhongse, Darrell Hyson Reneker

College of Polymer Science and Polymer Engineering

A localized approximation was developed to calculate the bending electric force acting on an electrified polymer jet, which is a key element of the electrospinning process for manufacturing of nanofibers. Using this force, a far reaching analogy between the electrically driven bending instability and the aerodynamically driven instability was established. Continuous, quasi-one-dimensional, partial differential equations were derived and used to predict the growth rate of small electrically driven bending perturbations of a liquid column. A discretized form of these equations, that accounts for solvent evaporation and polymer solidification, was used to calculate the jet paths during the course of nonlinear …

The Effects Of Incorporation Of Polyethylene Glycol On Properties Of Silica-Carbon Black-Filled Rubber Compound, Yoke Cheng Tang

Student Works (2000-2009)

The use of polyethylene glycol (PEG) to modify the surface of precipitated silica by means of physical adsorption was investigated. The effects of adding PEG on processing, cure and physical properties of a silica-carbon black-filled natural rubber truck tread compound were examined. For each series of investigation, two sets of experiments were conducted. Set I was to check the effects of both physical adsorption due to PEG and chemical modification due to a silane coupling agent, Si-69 on the surface of silica. Set 2 was to check the effects of physical adsorption due to PEG alone on the surface of …

Effects Of Compression Processing Parameters And Antioxidants On Molecular Degradation Of Biodegradable Poly-L-Lactide (Plla), Thomas J. Hannan Jr.

Masters Theses

The purpose of this research was to find a combination of poly (L-lactic acid), also known as poly-L-lactide or (PLLA) and antioxidants that would, together, produce a product whose degradation rate would be advantageous for use in biodegradable medical implants. Intrinsic viscosity tests were conducted on compression molded samples of PLLA that were molded at various processing parameters in order to find optimal parameters. The optimal processing parameters were found to be time 10 minutes, temperature 220°C, and pressure 1000 psi.

The molecular weight of PLLA sample was taken while pressure, time, and temperature were varied. As pressure increased, no …

Molecular Structure Of Polystyrene At Air/Polymer And Solid/Polymer Interfaces, K. S. Gautam, Alexander D. Schwab, Ali Dhinojwala, D. Zhang, S. M. Dougal, M. S. Yeganeh

College of Polymer Science and Polymer Engineering

IR-visible sum-frequency generation(SFG) spectroscopy has been used in a total internal reflection geometry to study the molecular structure of polystyrene (PS) at PS/sapphire and PS/air interfaces, simultaneously. The symmetric vibrational modes of the phenyl rings dominate the SFG spectra at the PS/air interface as compared to the antisymmetric vibrational modes at the PS/sapphire interface. This indicates approximately parallel orientation of the phenyl rings at the PS/air interface while nearly perpendicular orientation at the PS/sapphire interface, with respect to the surface normal.

Theoretical Investigation On Dynamics Of Photopolymerization-Induced Phase Separation And Morphology Development In Nematic Liquid Crystal/Polymer Mixtures, Domasius Nwabunma, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

A theoretical investigation of the dynamics of photopolymerization-induced phase separation (PIPS) and morphology development in a nematic liquid crystal (LC) polymer network mixture has been undertaken by incorporating photopolymerization kinetics into the coupled time-dependent Ginzburg-Landau (TDGL-Model C) equations. The simulation on the spatio-temporal evolution of the coupled LC concentration and orientation order parameters reveals that both morphological and scattering patterns for the orientation order parameter initially lag behind those of the concentration order parameter. However, the two fields evolve to the same spatial topologies with the progression of time. The PIPS dynamics is characterized only by the late stage of …

Bending Instability Of Electrically Charged Liquid Jets Of Polymer Solutions In Electrospinning, Darrell Hyson Reneker, Alexander L. Yarin, Hao Fong, Sureeporn Koombhongse

College of Polymer Science and Polymer Engineering

Nanofibers of polymers were electrospun by creating an electrically charged jet of polymer solution at a pendent droplet. After the jet flowed away from the droplet in a nearly straight line, it bent into a complex path and other changes in shape occurred, during which electrical forces stretched and thinned it by very large ratios. After the solvent evaporated, birefringent nanofibers were left. In this article the reasons for the instability are analyzed and explained using a mathematical model. The rheological complexity of the polymer solution is included, which allows consideration of viscoelastic jets. It is shown that the longitudinal …

Spatiotemporal Growth Of Faceted And Curved Single Crystals, Thein Kyu, Rujul Mehta, Hao-Wen Chiu

College of Polymer Science and Polymer Engineering

The spatiotemporal growth of single crystals in a crystalline polymer has been investigated theoretically based on a nonconserved time dependent Ginzburg-Landau equation (known as TDGL model A). In the description of the total free energy, a double-well local foe energy density signifying metastability of crystal ordering is combined with a nonlocal free energy term representing an interface gradient. The resulting nonlinear reaction diffusion equation after renormalization possesses a solitary wave property. Two-dimensional numerical calculations were performed to elucidate the faceted single crystal growth including square, rectangular, diamond-shaped, and curved single crystals. A three-dimensional simulation was also undertaken for the emergence …

Double Twist In Helical Polymer "Soft" Crystals, Christopher Y. Li, Stephen Z. D. Cheng, Jason J. Ge, Feng Bai, John Z. Zhang, Ian K. Mann, Frank W. Harris, Lang-Chy Chien, Donghang Yan, Tianbai He, Bernard Lotz

College of Polymer Science and Polymer Engineering

In natural and synthetic materials having non-racemic chiral centers, chirality and structural ordering each play a distinct role in the formation of ordered states. Configurational chirality can be extended to morphological chirality when the phase, structures possess low liquid crystalline order. In the crystalline states the crystallization process suppresses the chiral helical morphology due to strong ordering interactions, In this Letter, we report the first observation of helical single lamellar crystals of synthetic non-racemic chiral polymers. Experimental evidence shows that the molecular chains twist along both the long and short axes of the helical lamellar crystals, which is the first …

Helical Single-Lamellar Crystals Thermotropically Formed In A Synthetic Nonracemic Chiral Main-Chain Polyester, Christopher Y. Li, Donghang Yan, Stephen Z. D. Cheng, Feng Bai, Jason J. Ge, Bret H. Calhoun, Tianbai He, Liang-Chy Chien, Frank W. Harris, Bernard Lotz

College of Polymer Science and Polymer Engineering

Phase structures and transformation mechanisms of nonracemic chiral biological and synthetic polymers are fundamentally important topics in understanding their macroscopic responses in different environments. It has been known for many years that helical structures and morphologies can exist in low-ordered chiral liquid crystalline (LC) phases. However, when the chiral liquid crystals form highly ordered smectic liquid crystal phases, the helical morphology is suppressed due to the crystallization process. A double-twisted morphology has been observed in many liquid crystalline biopolymers such as dinoflaggellate chromosomes (in Prorocentrum micans) in an in vivo arrangement. Helical crystals grown from solution have been reported in …

Phase Structures And Morphologies Determined By Competitions Among Self-Organization, Crystallization, And Vitrification In A Disordered Poly(Ethylene Oxide)-B-Polystyrene Diblock Copolymer, Lei Zhu, Yan Chen, Anqui-Q. Zhang, Bret. H. Calhoun, Moonseok Chun, Stephen Z. D. Cheng, Benjamin S. Hsiao, Fengji Yeh, Takeji Hashimoto

College of Polymer Science and Polymer Engineering

A poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymer having a number-average molecular weight ((M) over bar(n)) of 11000 g/mol in the PEO blocks and an (M) over bar(n) of 5200 g/mol in the PS blocks has been synthesized (with a volume fraction of the PEO blocks of 0.66 in the molten state). Differential scanning calorimetry results show that this copolymer possesses a single endotherm, which is attributed to the melting of the PEG-block crystals. Based on real-time resolved synchrotron small-angle x-ray scattering (SAXS) observations, the diblock copolymer is in a disordered state above the glass transition temperature of the PS-rich phase (T-g(PS)) …

Rhythmic Growth Of Target And Spiral Spherulites Of Crystalline Polymer Blends, Thein Kyu, Hw Chiu, Aj Guenthner, Y Okabe, H Saito, T Inoue

College of Polymer Science and Polymer Engineering

Numerical calculations reveal that the target and spiral growth patterns in spherulites can be generated from the time-dependent Ginzburg-Landau equations (model C) by coupling a conserved compositional order parameter and a nonconserved crystal ordering parameter. Of particular interest is that the periodic concentric rings (target) or the spirals at the spherulitic core remain stationary in both the crystal (orientational) ordering field and the concentration field. Another intriguing observation is that the growth of target and spiral spherulites occurs in a stepwise fashion in synchronism with the rhythmic energy dissipation during crystallization.

Spatio-Temporal Growth Of Nematic Domains In Liquid Crystal Polymer Mixtures, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

Dynamics of phase separation and morphology development in mixtures of a low molar mass liquid crystal (LC) and a polymer have been investigated theoretically in comparison with experimental results. In the theoretical model, the combined free-energy densities of Flory-Huggins theory for isotropic mixing and Maier-Saupe theory for nematic ordering have been incorporated into the time-dependent Ginzburg-Landau equation (type C). The temporal evolution of the structure factor and the emergence of phase-separated liquid crystal domains have been simulated on the basis of an explicit central difference method based on a square lattice (128 x 128) with a periodic boundary condition. Of …

Kinetics Of Phase Transition In An Anticlinic Liquid Crystal Induced By A Uniform Temperature Field: Growth In One Dimension, X. Y. Wang, Jian-Feng Li, Eliezer Gurarie, S. Fan, Thein Kyu, S. S. Keast, Charles Rosenblatt

College of Polymer Science and Polymer Engineering

It is experimentally demonstrated that a transition from a synclinic to an anticlinic liquid crystal phase occurs via stable domain wall propagation after quenching in a uniform temperature field. Such a one-dimensional growth may be explained in terms of a nonlinear diffusion equation. The experiment provides the first example of free, one-dimensional growth in a system subjected to a pure and uniform temperature field.

Phase Equilibria Of A Nematic And Smectic-A Mixture, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

A phase diagram of a mixture consisting of nematic and smectic liquid crystals has been calculated self-consistently by combining Flory-Huggins (FH) theory for isotropic mixing and Maier-Saupe-McMillan (MSM) theory for smectic-A ordering. However, the MSM theory can be deduced to the original Maier-Saupe (MS) theory for nematic ordering. To describe the phase transitions involving induced smectic phase and nematic + smectic equilibrium, two nematic and two smectic order parameters for the nematic/smectic mixtures have been coupled through the normalized partition function and the orientation distribution function. Self-consistent numerical solution has been sought in establishing nematic/smectic phase diagrams involving (i) phase …

Phase Diagrams Of A Binary Smectic-A Mixture, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

A variety of smectic phase diagrams involving smectic-isotropic and smectic-nematic-isotropic transitions have been calculated based on a combination of Flory-Huggins (FH) theory for isotropic mixing and Maier-Saupe-McMillan (MSM) theory for smectic-A ordering of liquid crystals (LC). To describe the mesophase transitions, two nematic order parameters and two smectic order parameters have been coupled through the normalized orientation distribution and partition functions. Flory-Huggins interaction parameter (chi) for isotropic mixing and the coupling term involving the nematic interaction parameter (nu) and the McMillan smectic interaction parameter (alpha) for phase transitions of liquid crystals have been incorporated in the calculation. The predictive capability …

Nucleation Initiated Spinodal Decomposition In A Polymerizing System, Thein Kyu, Jae Hyung Lee

College of Polymer Science and Polymer Engineering

Dynamics of phase separation in a polymerizing system, consisting of carboxyl terminated polybutadiene acrylonitrile/epoxy/methylene dianiline, was investigated by means of time-resolved light scattering. The initial length scale was found to decrease for some early periods of the reaction which has been explained in the context of nucleation initiated spinodal decomposition We have combined the Cahn-Hilliard kinetic equation and polymerization kinetics, and predicted the initial reduction of the length scale triggered by nucleation.

Non-Markovian Brownian Motion In A Viscoelastic Fluid, V. S. Volkov, Arkadii I. Leonov

College of Polymer Science and Polymer Engineering

A theory of non-Markovian translational Brownian motion in a Maxwell fluid is developed. A universal kinetic equation for the joint probability distribution of position, velocity, and acceleration of a Brownian particle is derived directly from the extended dynamic equations for the system. Unlike the extended Fokker-Planck equation which corresponds to Mori-Kubo generalized Langevin equation and provides only with calculations of one-time moments, the universal kinetic equation obtained gives complete statistical description of the process. In particular, an exact generalized Fokker-Planck equation in the velocity space valid for any time instant is derived for the free non-Markovian Brownian motion. It shows …

Equilibrium Phase-Behavior Of Nematic Mixtures, Hao-Wen Chiu, Thein Kyu

College of Polymer Science and Polymer Engineering

A phenomenological model for predicting phase diagrams of a binary nematic mixture containing side chain liquid crystalline polymers and/or low molar mass liquid crystals has been proposed by combining Flory-Huggins free energy of isotropic mixing and Maier-Saupe free energy for nematic ordering of the nematogens. Two orientational order parameters, s(1) and S-2, Of the two components in the mixtures having two different clearing temperatures are taken into consideration in the calculation. The Flory-Huggins interaction parameter, chi, and the nematic interaction parameter of the Maier-Saupe theory, nu(1) and nu(22), are assumed to be functions of inverse absolute temperature. Further the cross-nematic …

Spinodals In A Polymer-Dispersed Liquid-Crystal, Chungsea Shen, Thein Kyu

College of Polymer Science and Polymer Engineering

Thermodynamic phase equilibria of a polymer dispersed liquid crystal (PDLC) consisting of
monomeric liquid crystals and a polymer have been investigated theoretically and experimentally.
The equilibrium limits of phase separation as well as phase transition of a PDLC system were
calculated by taking into consideration the Flory–Huggins (FH) theory for the free energy of mixing
of isotropic phases in conjunction with the Maier–Saupe ~MS! theory for phase transition of a
nematic liquid crystal. The correspondence between the Landau–de Gennes expansion and the
Maier–Saupe theory was found and the coefficients were evaluated. The calculation based on the
combined FH-MS theory predicted …

Polymerization-Induced Phase-Separation In A Liquid-Crystal-Polymer Mixture, J. Y, Kim, C. H. Cho, P. Palffy-Muhoray, M. Mustafa, Thein Kyu

College of Polymer Science and Polymer Engineering

We have used light scattering to study the kinetics of polymerization-induced phase separation in a liquid-crystal-polymer mixture. The evolution of the structure factor is compared with scaling predictions for thermally quenched systems. We have also observed a cascading phenomenon where phase separated domains become unstable and undergo phase separation for a second time.