Statistical analysis of a viscoelastic turbulent channel flow

Statiscal analysis related to a viscoelastic turbulent channel flow characterized as dilute polymer solution.

Polydispersity index from linear viscoelastic data: Unimodal and bimodal linear polymer melts

This article describes a method for determining the polydispersity index Ip2=Mz/Mw of the molecular weight distribution (MWD) of linear polymeric materials from linear viscoelastic data. The method uses the Mellin transform of the relaxation modulus of a simple molecular rheological model. One of the main features of this technique is that it enables interesting MWD information to be obtained directly from dynamic shear experiments. It is not necessary to achieve the relaxation spectrum, so the ill-posed problem is avoided. Furthermore, a determinate shape of the continuous MWD does not have to be assumed in order to obtain the polydispersity index. The technique has been developed to deal with entangled linear polymers, whatever the form of the MWD is. The rheological information required to obtain the polydispersity index is the storage G′(ω) and loss G″(ω) moduli, extending from the terminal zone to the plateau region. The method provides a good agreement between the proposed theoretical approach and the experimental polydispersity indices of several linear polymers for a wide range of average molecular weights and polydispersity indices. It is also applicable to binary blends.

Development of Bio-Based Polymers for Use in Asphalt, TR-639, 2014

Asphalt binder is typically modified with poly type (styrene-butadiene-styrene or SBS) polymers to improve its rheological properties and performance grade. The elastic and principal component of SBS polymers is butadiene. For the last decade, butadiene prices have fluctuated and significantly increased, leading state highway agencies to search for economically viable alternatives to butadiene based materials. This project reports the recent advances in polymerization techniques that have enabled the synthesis of elastomeric, thermoplastic, block-copolymers (BCPs) comprised of styrene and soybean oil, where the “B” block in SBS polymers is replaced with polymerized triglycerides derived from soybean oil. These new breeds of biopolymers have elastomeric properties comparable to well-established butadiene-based styrenic BCPs. In this report, two types of biopolymer formulations are evaluated for their ability to modify asphalt binder. Laboratory blends of asphalt modified with the biopolymers are tested for their rheological properties and performance grade. Blends of asphalt modified with the biopolymers are compared to blends of asphalt modified with two commonly used commercial polymers. The viscoelastic properties of the blends show that biopolymers improve the performance grade of the asphalt to a similar and even greater extent as the commercial SBS polymers. Results shown in this report indicate there is an excellent potential for the future of these biopolymers as economically and environmentally favorable alternatives to their petrochemically-derived analogs.

Modelling the curing process in magneto-sensitive polymers: Rate-dependence and shrinkage

This paper deals with a phenomenologically motivated magneto-viscoelastic coupled finite strain framework for simulating the curing process of polymers under the application of a coupled magneto-mechanical road. Magneto-sensitive polymers are prepared by mixing micron-sized ferromagnetic particles in uncured polymers. Application of a magnetic field during the curing process causes the particles to align and form chain-like structures lending an overall anisotropy to the material. The polymer curing is a viscoelastic complex process where a transformation from fluid. to solid occurs in the course of time. During curing, volume shrinkage also occurs due to the packing of polymer chains by chemical reactions. Such reactions impart a continuous change of magneto-mechanical properties that can be modelled by an appropriate constitutive relation where the temporal evolution of material parameters is considered. To model the shrinkage during curing, a magnetic-induction-dependent approach is proposed which is based on a multiplicative decomposition of the deformation gradient into a mechanical and a magnetic-induction-dependent volume shrinkage part. The proposed model obeys the relevant laws of thermodynamics. Numerical examples, based on a generalised Mooney-Rivlin energy function, are presented to demonstrate the model capacity in the case of a magneto-viscoelastically coupled load.

Linear viscoelasticity from molecular dynamics simulation of entangled polymers

The linear viscoelastic (LVE) spectrum is one of the primary fingerprints of polymer solutions and melts, carrying information about most relaxation processes in the system. Many single chain theories and models start with predicting the LVE spectrum to validate their assumptions. However, until now, no reliable linear stress relaxation data were available from simulations of multichain systems. In this work, we propose a new efficient way to calculate a wide variety of correlation functions and mean-square displacements during simulations without significant additional CPU cost. Using this method, we calculate stress−stress autocorrelation functions for a simple bead−spring model of polymer melt for a wide range of chain lengths, densities, temperatures, and chain stiffnesses. The obtained stress−stress autocorrelation functions were compared with the single chain slip−spring model in order to obtain entanglement related parameters, such as the plateau modulus or the molecular weight between entanglements. Then, the dependence of the plateau modulus on the packing length is discussed. We have also identified three different contributions to the stress relaxation:  bond length relaxation, colloidal and polymeric. Their dependence on the density and the temperature is demonstrated for short unentangled systems without inertia.

A stress relaxation model for the viscoelastic solids based on the steady-state creep equation

Creep and stress relaxation are inherent mechanical behaviors of viscoelastic materials. It is considered that both are different performances of one identical physical phenomenon. The relationship between the decay stress and time during stress relaxation has been derived from the power law equation of the steady-state creep. The model was used to analyse the stress relaxation curves of various different viscoelastic materials (such as pure polycrystalline ice, polymers, foods, bones, metal, animal tissues, etc.). The calculated results using the theoretical model agree with the experimental data very well. Here we show that the new mathematical formula is not only simple but its parameters have the clear physical meanings. It is suitable to materials with a very broad scope and has a strong predictive ability.

Expression of epitope-tagged LMW glutenin subunits in the starchy endosperm of transgenic wheat and their incorporation into glutenin polymers

The low-molecular-weight (LMW) glutenin subunits are components of the highly cross-linked glutenin polymers that confer viscoelastic properties to gluten and dough. They have both quantitative and qualitative effects on dough quality that may relate to differences in their ability to form the inter-chain disulphide bonds that stabilise the polymers. In order to determine the relationship between dough quality and the amounts and properties of the LMW subunits, we have transformed the pasta wheat cultivars Svevo and Ofanto with three genes encoding proteins, which differ in their numbers or positions of cysteine residues. The transgenes were delivered under control of the high-molecular-weight (HMW) subunit 1Dx5 gene promoter and terminator regions, and the encoded proteins were C-terminally tagged by the introduction of the c-myc epitope. Stable transformants were obtained with both cultivars, and the use of a specific antibody to the c-myc epitope tag allowed the transgene products to be readily detected in the complex mixture of LMW subunits. A range of transgene expression levels was observed. The addition of the epitope tag did not compromise the correct folding of the trangenic subunits and their incorporation into the glutenin polymers. Our results demonstrate that the ability to specifically epitope-tag LMW glutenin transgenes can greatly assist in the elucidation of their individual contributions to the functionality of the complex gluten system.

A Reynolds stress model for turbulent flows of viscoelastic fluids

A second-order closure is developed for predicting turbulent flows of viscoelastic fluids described by a modified generalised Newtonian fluid model incorporating a nonlinear viscosity that depends on a strain-hardening Trouton ratio as a means to handle some of the effects of viscoelasticity upon turbulent flows. Its performance is assessed by comparing its predictions for fully developed turbulent pipe flow with experimental data for four different dilute polymeric solutions and also with two sets of direct numerical simulation data for fluids theoretically described by the finitely extensible nonlinear elastic - Peterlin model. The model is based on a Newtonian Reynolds stress closure to predict Newtonian fluid flows, which incorporates low Reynolds number damping functions to properly deal with wall effects and to provide the capability to handle fluid viscoelasticity more effectively. This new turbulence model was able to capture well the drag reduction of various viscoelastic fluids over a wide range of Reynolds numbers and performed better than previously developed models for the same type of constitutive equation, even if the streamwise and wall-normal turbulence intensities were underpredicted.

MECHANICAL TESTING DEVICE FOR VISCOELASTIC BIOMATERIALS

Nearly all biologic tissues exhibit viscoelastic behavior. This behavior is characterized by hysteresis in the response of the material to load or strain. This information can be utilized in extrapolation of life expectancy of vascular implant materials including native tissues and synthetic materials. This behavior is exhibited in many engineering materials as well such as the polymers PTFE, polyamide, polyethylene, etc. While procedures have been developed for evaluating the engineering polymers the techniques for biologic tissues are not as mature. There are multiple reasons for this. A major one is a cultural divide between the medical and engineering communities. Biomedical engineers are beginning to fill that void. A digitally controlled drivetrain designed to evaluate both elastic and viscoelastic characteristics of biologic tissues has been developed. The initial impetus for the development of this device was to evaluate the potential for human umbilical tissue to serve as a vascular graft material. The consequence is that the load frame is configured for membrane type specimens with rectangular dimensions of no more than 25mm per side. The designed load capacity of the drivetrain is to impose an axial load of 40N on the specimen. This drivetrain is capable of assessing the viscoelastic response of the specimens by four different test modes: stress relaxation, creep, harmonic induced oscillations, and controlled strain rate tests. The fluorocarbon PTFE has mechanical properties commensurate with vascular tissue. In fact, it has been used for vascular grafts in patients who have been victims of various traumas. Hardware and software validation of the device was accomplished by testing PTFE and comparing the results to properties that have been published by both researchers and manufacturers.

Thermodynamic Study Of The Micellization Of Zwitterionic Surfactants And Their Interaction With Polymers In Water By Isothermal Titration Calorimetry.

The micellization of a homologous series of zwitterionic surfactants, a group of sulfobetaines, was studied using isothermal titration calorimetry (ITC) in the temperature range from 15 to 65 °C. The increase in both temperature and the alkyl chain length leads to more negative values of ΔGmic(0) , favoring the micellization. The entropic term (ΔSmic(0)) is predominant at lower temperatures, and above ca. 55-65 °C, the enthalpic term (ΔHmic(0)) becomes prevalent, figuring a jointly driven process as the temperature increases. The interaction of these sulfobetaines with different polymers was also studied by ITC. Among the polymers studied, only two induced the formation of micellar aggregates at lower surfactant concentration: poly(acrylic acid), PAA, probably due to the formation of hydrogen bonds between the carboxylic group of the polymer and the sulfonate group of the surfactant, and poly(sodium 4-styrenesulfonate), PSS, probably due to the incorporation of the hydrophobic styrene group into the micelles. The prevalence of the hydrophobic and not the electrostatic contributions to the interaction between sulfobetaine and PSS was confirmed by an increased interaction enthalpy in the presence of electrolytes (NaCl) and by the observation of a significant temperature dependence, the latter consistent with the proposed removal of hydrophobic groups from water.

Triboelectricity In Insulating Polymers: Evidence For A Mechanochemical Mechanism.

Transfer of reaction products formed on the surfaces of two mutually rubbed dielectric solids makes an important if not dominating contribution to triboelectricity. New evidence in support of this statement is presented in this report, based on analytical electron microscopy coupled to electrostatic potential mapping techniques. Mechanical action on contacting surface asperities transforms them into hot-spots for free-radical formation, followed by electron transfer producing cationic and anionic polymer fragments, according to their electronegativity. Polymer ions accumulate creating domains with excess charge because they are formed at fracture surfaces of pulled-out asperities. Another factor for charge segregation is the low polymer mixing entropy, following Flory and Huggins. The formation of fractal charge patterns that was previously described is thus the result of polymer fragment fractal scatter on both contacting surfaces. The present results contribute to the explanation of the centuries-old difficulties for understanding the triboelectric series and triboelectricity in general, as well as the dissipative nature of friction, and they may lead to better control of friction and its consequences.

Polímeros biomiméticos em química analítica. Parte 1: preparo e aplicações de MIP (Molecularly Imprinted Polymers) em técnicas de extração e separação

MIPs are synthetic polymers that are used as biomimetic materials simulating the mechanism verified in natural entities such as antibodies and enzymes. Although MIPs have been successfully used as an outstanding tool for enhancing the selectivity or different analytical approaches, such as separation science and electrochemical and optical sensors, several parameters must be optimized during their synthesis. Therefore, the state-of-the-art of MIP production as well as the different polymerization methods are discussed. The potential selectivity of MIPs in the extraction and separation techniques focusing mainly on environmental, clinical and pharmaceutical samples as applications for analytical purposes is presented.

Polímeros biomiméticos em química analítica. Parte 2: aplicações de MIP (Molecularly Imprinted Polymers) no desenvolvimento de sensores químicos

The aim of this paper is the description of the strategies and advances in the use of MIP in the development of chemical sensors. MIP has been considered an emerging technology, which allows the synthesis of materials that can mimic some highly specific natural receptors such as antibodies and enzymes. In recent years a great number of publications have demonstrated a growth in their use as sensing phases in the construction of sensors . Thus, the MIP technology became very attractive as a promising analytical tool for the development of sensors.