Engineering Commons^™

Recent Approaches In Designing Bioadhesive Materials Inspired By Mussel Adhesive Protein, Pegah Kord Forooshani, Bruce P. Lee

Bruce Lee

Marine mussels secret protein-based adhesives, which enable them to anchor to various surfaces in a saline, intertidal zone. Mussel foot proteins (Mfps) contain a large abundance of a unique, catecholic amino acid, Dopa, in their protein sequences. Catechol offers robust and durable adhe-sion to various substrate surfaces and contributes to the curing of the adhesive plaques. In this article, we review the unique features and the key functionalities of Mfps, catechol chemistry, and strategies for preparing catechol-functionalized poly- mers. Specifically, we reviewed recent findings on the contributions of various features of Mfps on interfacial binding, which include coacervate formation, surface …

Chapter 2 - Thermoplastic-Thermoset Nanostructured Polymer Blends.Pdf, Amos Adeniyi, Oluranti Agboola, Emmanuel R. Sadiku, M. O. Durowoju, P. A. Olubambi, A. B. Reddy, I. D. Ibrahim, W. K. Kupolati

Chongwen Huang

Improvement Of Mechanical Properties And Water Stability Of Vegetable Protein Based Plastics, Gowrishankar Srinivasan

Gowrishankar Srinivasan

Bio-renewable bio-degradable plastics are a potential solution to the growing problems of pollution caused by petroleum plastics and dependency on foreign nations for petroleum resources. One possible feed stock for these materials are vegetable proteins, especially from soy bean and corn. These proteins have relatively high molecular weights and have the potential of being processed with standard polymer processing technologies. But some issues that need to be addressed are their water instability (soy protein) and inferior mechanical properties as compared to petroleum derived plastics. In this study, soy protein isolates (SPI) and zein protein was processed with various additives and …

Improvement Of Mechanical Properties And Water Stability Of Vegetable Protein Based Plastics, Gowrishankar Srinivasan

Gowrishankar Srinivasan

Bio-renewable bio-degradable plastics are a potential solution to the growing problems of pollution caused by petroleum plastics and dependency on foreign nations for petroleum resources. One possible feed stock for these materials are vegetable proteins, especially from soy bean and corn. These proteins have relatively high molecular weights and have the potential of being processed with standard polymer processing technologies. But some issues that need to be addressed are their water instability (soy protein) and inferior mechanical properties as compared to petroleum derived plastics. In this study, soy protein isolates (SPI) and zein protein was processed with various additives and …

Sticky Gecko Feet: The Role Of Temperature And Humidity, Peter H. Niewiarowski, Stephanie Lopez, Liehui Ge, Emily Hagan, Ali Dhinojwala

Dr. Peter H. Niewiarowski

Gecko adhesion is expected to be temperature insensitive over the range of temperatures typically experienced by geckos. Previous work is limited and equivocal on whether this expectation holds. We tested the temperature dependence of adhesion in Tokay and Day geckos and found that clinging ability at 12 degrees C was nearly double the clinging ability at 32 degrees C. However, rather than confirming a simple temperature effect, our data reveal a complex interaction between temperature and humidity that can drive differences in adhesion by as much as two-fold. Our findings have important implications for inferences about the mechanisms underlying the …

From Elastic Deformation To Terminal Flow Of A Monodisperse Entangled Melt In Uniaxial Extension, Yangyang Wang, Shi-Qing Wang

Shi-Qing Wang

Using a well-entangled monodisperse styrene-butadiene random-copolymer (SBR) melt as a model system, we illustrate generic features of uniaxial extension behavior that may be shared by all well-entangled thermoplastic and elastomeric materials. Depending on the imposed extensional rate, the same sample may behave like a viscous liquid or an elastic "solid." Analogous to the recently revealed shear inhomogeneity, the SBR melt inevitably undergoes cohesive failure in the form of sample breakage whenever the Weissenberg number is much greater than unity, making it challenging to reach steady state. In the elastic deformation regime where the external deformation rate is faster than Rouse …

Interfacial Stick-Slip Transition In Simple Shear Of Entangled Melts, Pouyan E. Boukany, Prashant Tapadia, Shi-Qing Wang

Shi-Qing Wang

This article describes a systematic investigation of a discontinuous interfacial stick-slip transition (SST) in simple shear of monodisperse entangled 1,4-polybutadiene (PBD) and polyisoprene (PIP) melts with different molecular weights and architecture, using a specially designed controlled-force shear rheometer. The magnitude of the transition is found to be determined by the level of chain entanglement. Specifically, the dependence of extrapolation length b on molecular weight as b similar to M-w(3.4) and of the melt viscosity as b similar to eta is consistent with the observations based on capillary rheometric studies [X. Yang et al., Rheol. Acta 37, 415-423 (1998)]. The interfacial …

Shear Banding Or Not In Entangled Dna Solutions Depending On The Level Of Entanglement, Pouyan E. Boukany, Shi-Qing Wang

Shi-Qing Wang

Entangled DNA solutions are ideal as a model system to examine nonlinear shear flow behavior. Even when the number of entanglements per chain, Z, is higher than 100, the solution is still soft enough with an elastic plateau modulus under 100 Pa and is thus amenable to experimental study by commercial rotational rheometry without ambiguity and uncertainty. We have investigated nonlinear flow behavior of three entangled DNA solutions with Z=24, 60, and 156, respectively, using a combination of particle-tracking velocimetric (PTV) and conventional rheometric measurements. We explore questions such as (a) whether shear banding also occurs in moderately entangled solutions, …

Elastic Breakup In Uniaxial Extension Of Entangled Polymer Melts, Yangyang Wang, Pouyan Boukany, Shi-Qing Wang, Xiaorong Wang

Shi-Qing Wang

Five entangled melts, with the number of entanglements per chain ranging from 25 to 160, have been studied to illustrate how cohesive strength can be overcome in either continuous or interrupted extension (i.e., during or after uniaxial stretching). The internal elastic stress due to chain deformation from imposed strain appears to be the cause of the observed yielding behavior that reveals scaling laws. The visual signature of the elastic breakup is the occurrence of nonuniform extension. The yield phenomena may be understood at a force level.

Nature Of Steady Flow In Entangled Fluids Revealed By Superimposed Small Amplitude Oscillatory Shear, Pouyan E. Boukany, Shi-Qing Wang

Shi-Qing Wang

We carry out a systematic investigation into steady-state shear behavior of six entangled solutions based on a superposition of continuous shear and small amplitude oscillatory shear (SAOS). During steady shear in the shear thinning regime, the superimposed SAOS frequency sweep measurements reveal characteristics of viscous liquids, e. g., terminal dynamics, on the experimental time scale of the reciprocal shear rate. The residual entanglement network retains the same level of elastic stiffness as the equilibrium system does. Consistent with the convective constraint release idea, chains in the network are forced to pass around each other as they must do so to …

A Correlation Between Velocity Profile And Molecular Weight Distribution In Sheared Entangled Polymer Solutions, Pouyan E. Boukany, Shi-Qing Wang

Shi-Qing Wang

In this work we attempt to answer several questions concerning the flow characteristics of entangled polymer solutions in a sliding plate shearing cell. We explore (a) how the molecular weight distribution affects the velocity profile in simple shear, (b) whether the observed shear banding is consistent with a nonmonotonic constitutive model, (c) whether the flow response and velocity profiles are different in simple shear depending on the different modes of shear. Our results provide a comparison with recent reports on a polydisperse polymer sample [Tapadia and Wang, Phys. Rev. Lett. 96, 016001 (2006); Tapadia, et al., Phys. Rev. Lett. 96, …

Steady State Measurements In Stress Plateau Region Of Entangled Polymer Solutions: Controlled-Rate And Controlled-Stress Modes, Sham Ravindranath, Shi-Qing Wang

Shi-Qing Wang

Despite decades of efforts, reliable measurements of nonlinear flow behavior of well-entangled polymers in continuous shear have been challenging to obtain. The present work attempts to accomplish three important tasks: (A) overcome this challenge by adopting a strategy of decoupling theological measurements from the outer meniscus region in a cone-partitioned plate (C/PP) setup; (B) determine whether well-entangled solutions indeed undergo a flow transformation under creep that can be taken to phenomenologically define an entanglement-disentanglement transition (EDT); (C) provide the velocity profiles of such solutions undergoing either controlled-stress or controlled-rate shear by carrying out in situ particle-tracking velocimetric (PTV) measurements. Upon …

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

Shi-Qing Wang

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.

Nonlinearity In Large Amplitude Oscillatory Shear (Laos) Of Different Viscoelastic Materials, Xin Li, Shi-Qing Wang, Xiaorong Wang

Shi-Qing Wang

The present work investigates nonlinear behavior in large amplitude oscillatory shear (LAOS) of four different polymeric materials using simultaneous conventional rheometric measurements and particle-tracking velocimetric observations. In contrast to most studies in the literature that treat nonlinearity in LAOS in steady state, we emphasize by the present four examples that nonlinearity in LAOS often arise in complex fluids due to time-dependent rearrangement of their microstructures in response to LAOS. Consequently, no correlation is obvious between strain dependence of the steady-state stress response and the time-dependent characteristics of the steady-state response. For instance, a highly viscoelastic material made of nano-sized polybutadiene …

New Theoretical Considerations In Polymer Rheology: Elastic Breakdown Of Chain Entanglement Network, Shi-Qing Wang, Sham Ravindranath, Yangyang Wang, Pouyan Boukany

Shi-Qing Wang

Recent experimental evidence has motivated us to present a set of new theoretical considerations and to provide a rationale for interpreting the intriguing flow phenomena observed in entangled polymer solutions and melts [P. Tapadia and S. Q. Wang, Phys. Rev. Lett. 96, 016001 (2006); 96, 196001 (2006); S. Q. Wang , ibid. 97, 187801 (2006)]. Three forces have been recognized to play important roles in controlling the response of a strained entanglement network. During flow, an intermolecular locking force f(iml) arises and causes conformational deformation in each load-bearing strand between entanglements. The chain deformation builds up a retractive force f(retract) …

Large Amplitude Oscillatory Shear Behavior Of Entangled Polymer Solutions: Particle Tracking Velocimetric Investigation, Sham Ravindranath, Shi-Qing Wang

Shi-Qing Wang

Large amplitude oscillatory shear (LAOS) has been employed widely to probe the nonlinear behavior of complex fluids. Typically, the system undergoing LAOS has been assumed to experience homogeneous shear in each cycle so that material functions can be introduced to analyze the nonlinear dependence of these functions on the amplitude and frequency. Using particle-tracking velocimetric technique, we have carried a more systematic investigation on four different entangled polybutadiene (PBD) solutions with the number of entanglements per chain Z=13, 27, 64 and 119, extending well beyond the initial observations of shear banding in entangled PBD solutions under LAOS [Tapadia , Phys. …

Did Mineral Surface Chemistry And Toxicity Contribute To Evolution Of Microbial Extracellular Polymeric Substances?, Jie Xu, Jay M. Campbell, Nianli Zhang, William J. Hickey, Nita Sahai

Nita Sahai

Modern ecological niches are teeming with an astonishing diversity of microbial life in biofilms closely associated with mineral surfaces, which highlights the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral-water interface. Biofilm formation capability likely evolved on early Earth because biofilms provide crucial cell survival functions. The potential toxicity of mineral surfaces toward cells and the complexities of the mineral-water-cell interface in determining the toxicity mechanisms, however, have not been fully appreciated. Here, we report a previously unrecognized role for extracellular polymeric substances (EPS), which form biofilms in shielding cells against …

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

Darrell Hyson Reneker

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 …

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

Darrell Hyson Reneker

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.

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

Darrell Hyson Reneker

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 …

Branching In Electrospinning Of Nanofibers, A. L. Yarin, W. Kataphinan, Darrell Hyson Reneker

Darrell Hyson Reneker

Electrospinning of polymer nanofibers often begins with a single, straight, elongating, and electrified fluid jet that emanates from a droplet tip when the electric field at the surface is high enough. After some distance an electrically driven bending instability of the elongating jet occurs. For a polymer solution suitable for electrospinning, capillary instability does not cause the jet to become a spray of droplets. Under some conditions, a sequence of secondary jet branches emanates from the primary jet. This paper describes an experiment in which many closely spaced branches along the jet were observed during the electrospinning of a polycaprolactone …

Electrospinning Route For The Fabrication Of P-N Junction Using Nanofiber Yarns, A. F. Lotus, S. Bhargava, E. T. Bender, E. A. Evans, R. D. Ramsier, Darrell Hyson Reneker, G. G. Chase

Darrell Hyson Reneker

Electrospinning is a simple, versatile, and cost effective method for generating nanoscale fibers, wires, and tubes. Nanowires and nanotubes could be important building blocks for nanoscale electronics, optoelectronics, and sensors as they can function as miniaturized devices as well as electrical interconnects. We report on a simple method to fabricate free standing ceramic nanofiber heterostructures, which exhibit rectifying behavior of a p-n junction.

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

Darrell Hyson Reneker

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 …

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

Arkady I. Leonov

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 …

Molecular Engineering Of Side-Chain Liquid Crystalline Polymers By Living Polymerizations, Coleen Pugh, Alan L. Kiste

Coleen Pugh

“Living” anionic, cationic, metalloporphyrin and ring-opening metathesis polymerizations have been used to prepare well-defined side-chain liquid crystalline homopolymers, block and graft copolymers and statistical copolymers. This paper analyzes their successes and failures by reviewing the mechanistic aspects and experimental conditions of each type of polymerization, and identifies other classes of mesogenic monomers that could be polymerized in a controlled manner in the future. The emerging structure/property relationships are then identified using well-defined SCLCPs in which only one structural feature is varied while all others remain constant. The thermal transitions of liquid crystalline polymethacrylates, polynorbomenes and poly(viny1 ether)s reach their limiting …

Modification Of Statistical Threading In Two-Component Pseudorotaxane Melts Using The Amphiphilic Approach And Variations In The Confinement Geometry, Sagar S. Rane, Wayne L. Mattice, Coleen Pugh

Coleen Pugh

Recently we described a coarse-grained model of poly(ethylene oxide) and then employed that model to study the amount of spontaneous threading of cyclic molecules by linear chains in the melt [C. A. Helfer, G. Xu, W. L. Mattice, and C. Pugh, Macromolecules 36, 10071 (2003)]. Since the amount of statistical threading at equilibrium is small, there is interest in identifying physical changes in the system that will increase the threading. We now use that coarse-grained model to investigate the effect on threading of various hypothetical (but feasible) modifications to the two-component system of macrocycles and linear chains in the melt, …

Growth Dynamics Of Isotactic Polypropylene Single Crystals During Isothermal Crystallization From A Miscible Polymeric Solvent, Rujul Mehta, Wirunya Keawwattana, Thein Kyu

Thein Kyu

The present article presents a spatiotemporal growth of isotactic polypropylene (iPP) single crystals, melt crystallized from a polymeric solvent, i.e., poly (ethylene octene) copolymer that is known to be miscible with iPP. Optical and atomic force microscopic investigations reveal that the melt grown single crystals of iPP develop in the form of two parallel rows of crystal lamellae, but these crystals merge at the tips. To elucidate the mechanism of these emerging parallel rows of iPP crystals, a phase field model pertaining to solidification phenomena has been employed that involves a nonconserved crystal order parameter and a chain-tilting angle. This …

Phase-Field Modeling On Morphological Landscape Of Isotactic Polystyrene Single Crystals, Haijun Xu, Rushikesh Matkar, Thein Kyu

Thein Kyu

Spatio-temporal growth of isotactic polystyrene single crystals during isothermal crystallization has been investigated theoretically based on the phase field model by solving temporal evolution of a nonconserved phase order parameter coupled with a heat conduction equation. In the description of the total free energy, an asymmetric double-well local free energy density has been adopted to represent the metastable melt and the stable solid crystal. Unlike the small molecule systems, polymer crystallization rarely reaches thermodynamic equilibrium; most polymer crystals are kinetically stabilized in some metastable states. To capture various metastable polymer crystals, the phase field crystal order parameter at the solidification …

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

Thein Kyu

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 …

Breakup Of Spiral And Concentric Ringed Spherulites In Polymer Crystallization, Haijun Xu, Hao-Wen Chiu, Yoshifumi Okabe, Thein Kyu

Thein Kyu

Recently, the breakup of spiral and concentric ringed spherulites has been observed experimentally in isothermal crystallization of poly(vinylidene fluoride) in its blends with ethylene vinyl acetate copolymer. To elucidate the phenomenon of spiral breakup in polymer spherulites, a theoretical simulation has been undertaken in the framework of the phase field model of solidification based on time-dependent Ginzburg-Landau equations (TDGL model C) pertaining to the conserved concentration and nonconserved phase field order parameters. The concentration order parameter was described in terms of the Landau-type potential, while the crystal order parameter was expressed in terms of an asymmetric double-well potential to account …