Rheology of nematic solutions of rodlike chains: Comparison of theory and experiment

The rheological properties of nematic solutions of rodlike polymers are discussed, giving comparisons between theoretical results and certain experiments. Most of the theoretical treatments are based on application of the Leslie-Ericksen constitutive equation. The experimental data considered include distortion in a magnetic field and flow in shearing deformation over a range of shear rate, including rheo-optical observations. In general, it appears that the available theory does not describe a number of the features observed.     

Rheology of active filament solutions

We study the viscoelasticity of an active solution of polar biofilaments and motor proteins. Using a molecular model, we derive the constitutive equations for the stress tensor in the isotropic phase and in phases with liquid crystalline order. The stress relaxation in the various phases is discussed. Contractile activity is responsible for a spectacular difference in the viscoelastic properties on opposite sides of the order-disorder transition.     

Effect of Compatibilizer Content on the Shear and Extensional Rheology of Polypropylene/Clay Nanocomposites

The shear and extensional rheology of polypropylene (PP)/organoclay nanocomposites in the presence of various maleic anhydride grafted polypropylene (PP-g-MA) compatibilizer concentrations were investigated. The PP nanocomposites were prepared via direct melt intercalation in an internal mixer. The structures of the nanocomposites were characterized by X-ray diffraction (XRD) and scanning electron microscopy. It was found that both the compatibilized and uncompatibilized nanocomposites could form an intercalated structure. However, the organoclay particles can disperse well only in the compatibilized systems. The linear viscoelastic properties, including the storage modulus G′ and complex viscosity η* were very sensitive to the microstructure of the nanocomposites. The extensional viscosities of PP nanocomposites were enhanced under a low deformation rate with increasing compatibilizer content and displayed a lack of superposition for different strain rates. It was proposed that the lack of superposition might originate from the formation of a three-dimensional organoclay network, which decreased in its complexity and strength as the deformation rate increased.     

Structural evidence of charge renormalization in semi-dilute solutions of highly charged polyelectrolytes

We show experimentally that Manning counterion condensation also leads to a renormalization of the charge density at high concentrations of highly charged, flexible, hydrophilic polyelectrolytes. Investigations by small angle neutron and X-ray scattering of semi-dilute solutions of poly(acrylamide-co-sodium-2-acrylamido-2-methylpropane sulfonate) at different charge densities above the condensation threshold, show that the scattering function is invariant with the charge density. Received 16 June 1998     

Lattice Boltzmann Simulations of Blood Flow: Non-Newtonian Rheology and Clotting Processes

The numerical simulation of thrombosis in stented aneurysms is an important issue to estimate the efficiency of a stent. In this paper, we consider a Lattice Boltzmann (LB) approach to bloodflow modeling and we implement a non-Newtonian correction in order to reproduce more realistic flow profiles. We obtain a good agreement between simulations and Casson’s model of blood rheology in a simple geometry. Finally we discuss how, by using a passive scalar suspension model with aggregation on top of the LB dynamics, we can describe the clotting processes in the aneurysm     

Precursor Based on Polyborylborazine for BN Fiber: Preparation and Rheology Properties

A polyborylborazine precursor for hexagonal boron nitride (h-BN) was obtained by reaction of boron trichloride with methylamine and its structure was characterized by ¹¹BNMR, ¹³CNMR, ¹HNMR, and FTIR. The results show that the molecular precursor consists of borazine rings connected via a cross-linked network. The results of shear rheological tests indicated that the polymer is capable of being melt spun at moderate temperature, which implies that the structure of the molecular chains of the precursor polymer is branched. The precursor polymer was spun into a continuous polymer fiber in the melt state and then subsequently heat-treated under NH₃ up to 1000°C for conversion into BN fibers. Its surface morphology was observed by scanning electron microscopy (SEM); the fiber was free of defects and cavities.     

Rheology Study of Chlorinated Polyethylene with Various Cl-Contents and Carbon Nanotube Composites

Composites of chlorinated polyethylene with various Cl-contents and carbon nanotubes (CNT) were produced and their rheological behaviors were characterized by capillary viscometry. For polyethylene (PE)/CNT composites with CNT loadings of 3 wt% and 5 wt%, the melt viscosity was higher than that of PE alone. However, the PE/CNT composite with CNT loading of 2 wt% gave a much lower melt viscosity than that of PE alone. The melt viscosity of chlorinated polyethylene (PECl)/CNT composites prepared also depended on the amount of added CNT and chlorine content. PECl/CNT composites with higher chlorine content displayed lower melt viscosities than that of PECl alone. A mechanism was proposed.     

Impact of Dose-Rate on Rheology,Structure and Wear of Irradiated UHMWPE

Ultrahigh molecular weight polyethylene (UHMWPE) is used as a bearing material in total joint replacements (TJR). UHMWPE for TJR is usually modified by irradiation and thermal treatment to increase wear resistance. We modified UHMWPE in three ways, differing in radiation dose-rate and/or atmosphere during irradiation. Rheological properties before and after irradiation were determined by means of oscillatory shear measurements. Structural changes were followed by X-ray diffraction, infrared spectroscopy, electron spin resonance, and solubility measurements. Wear resistance of selected samples was obtained by the pin-on-disk method. Rheological properties changed sensitively with modification conditions including radiation dose rate. Moreover, rheological results correlated well with both crosslinking extent and wear resistance. Finally, it was demonstrated that the optimal radiation dose, i.e. the dose leading to maximum crosslinking density and wear resistance, was different for each of the three modification procedures.     

Influence of Surfactant Functional Groups on Morphology and Rheology of Polypropylene/Organoclay Nanocomposites

Three surfactants, with the same long alkyl tail but varying in functional groups, were selected to modify two pristine clays with different cation exchange capacities (CEC). Each of the modified clays was melt-mixed with polypropylene (PP) to prepare nanocomposites. The microstructure of the resultant nanocomposites was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and rheological techniques. The results showed that the surfactant structure had remarkable effects on the morphology and shear rheology of the nanocomposites based on the high-CEC organoclay: use of benzyl functional groups led to the highest extent of intercalation and highest enhancement of shear properties, while use of 2-hydroxyethyl groups had the opposite effect. Nanocomposites based on low-CEC organoclay all exhibited poor dispersion and their shear behavior was changed only slightly in comparison to the polymer matrix. In the case of extensional rheology, strain hardening was observed only in the two nanocomposites containing surfactants with 2-hydroxyethyl groups, regardless of the dispersion state of the nanoparticles.     

SiO2 Reinforced EVM/TPU Blends: Bound Rubber and Rheology Behavior

Silica is shown to be a more active filler than carbon black for the reinforcement of EVM/TPU blends. The static rheology of EVM/TPU blends is considerably influenced by a tightly bound rubber structure developing between the TPU and silica that was identified by a tetrahydrofuran extraction test and SEM observations. Dynamic rheology behavior corroborated the development of bound rubber and indicated the existence of the Payne effect because of filler-filler networks in the blends. The silica-TPU interaction is thermally unstable at 190°C and mechanically unstable at a shear frequency of 1 Hz.     

Morphology,Rheology, and Mechanical Properties of Polylactide/Poly(Ethylene-co-octene) Blends

Polylactide (PLA)/poly(ethylene-co-octene) (POE) blends containing ethylene-glycidyl methacrylate copolymer (EGMA) as a compatibilizer were prepared by melt blending. An immiscible, two-phase structure with POE dispersed in the PLA matrix was observed by scanning electron microscopy. It was found that the POE particle size was significantly decreased by the addition of EGMA, and the POE particle size and distribution decreased with the increase of the compatibilizer content up to 2% EGMA, beyond which the POE particle size and distribution remained unchanged. The reactions between the epoxy groups of EGMA and carboxylic or hydroxyl groups of PLA were elucidated by the Fourier transform infrared spectroscopy. Rheological results showed that the G′(ω), G″(ω), and complex viscosity of PLA/POE blends significantly increased at low frequencies with the addition of EGMA. The failure mode changed from brittle fracture of the neat PLA to ductile fracture of the PLA/POE blends.     

Dynamic Rheology of Poly(3-hydroxybutyrate-co-4-Hydroxybutyrate) /Clay Biocomposites

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] composites filled with clay were prepared by a melt blending process. Dynamic rheology of the composites was measured by means of a rotational rheometer. The results showed that the interlayer spacing of the clay increased owing to the presence of the P(3HB-co-4HB) melt in the interlayer regions of the clay. The storage and the loss moduli of the composite samples increased with the increasing frequency, and decreased with the increasing temperature. The addition of the clay enhanced the oscillatory thinning behavior of the composite melts, and improved the processability of the P(3HB-co-4HB) melt. The decrease of the viscosity by increasing both frequency and temperature was feasible and effective for the composites with the clay contents of 1 and 2 wt.%.     

Gelation Rheology and Water Absorption Behavior of Semi-Interpenetrating Polymer Networks of Polyacrylamide and Carboxymethyl Cellulose

Gelation rheology and swelling behavior of novel semi-interpenetrating polymer network (semi-IPN) hydrogels based on polyacrylamide are described. These hydrogels were prepared by solution cross-linking of partially hydrolyzed polyacrylamide and carboxymethyl cellulose (CMC), using chromium triacetate. Effects of CMC content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels increased with increasing CMC content. Enhancement of storage modulus was more than two times for the semi-IPN gels containing 50 wt% CMC. It was also found that increasing the CMC content decreased the loss factor, indicating that the elastic properties of this gelling system increase more strongly than the viscous properties. The swelling ratio of the semi-IPN gels in tap water, NaCl and CaCl₂ solutions, and synthetic oil reservoir water slightly decreased as the concentration of the CMC increased. The improved storage modulus and slightly decreased swelling capacity in oil reservoir water make these semi-IPN hydrogels potentially good candidates for excess water treatment in oil recovery applications.     

Biophysical and electrochemical properties of Self-assembled noncovalent SWNT/DNA hybrid and electroactive nanostructure

DNA self-assembled hybrid nanostructures are widely used in recent research in nanobiotechnology. Combination of DNA with carbon based nanoparticles such as single-walled carbon nanotube (SWNT), multi-walled carbon nanotube (MWNT) and carbon quantum dot were applied in important biological applications. Many examples of biosensors, nanowires and nanoelectronic devices, nanomachine and drug delivery systems are fabricated by these hybrid nanostructures. In this study, a new hybrid nanostructure has been fabricated by noncovalent interactions between single or double stranded DNA and SWNT nanoparticles and biophysical properties of these structures were studied comparatively. Biophysical properties of hybrid nanostructures studied by circular dichroism, UV–vis and fluorescence spectroscopy techniques. Also, electrochemical properties studied by cyclic voltammetry, linear sweep voltammetry, square wave voltammetry, choronoamperometry and impedance spectroscopy (EIS). Results revealed that the biophysical and electrochemical properties of SWNT/DNA hybrid nanostructures were different compare to ss-DNA, ds-DNA and SWNT singly. Circular dichroism results showed that ss-DNA wrapped around the nanotubes through π-π stacking interactions. The results indicated that after adding SWNT to ss-DNA and ds-DNA intensity of CD and UV–vis spectrum peaks were decreased. Electrochemical experiments indicated that the modification of single-walled carbon nanotubes by ss-DNA improves the electron transfer rate of hybrid nanostructures. It was demonstrated SWNT/DNA hybrid nanostructures should be a good electroactive nanostructure that can be used for electrochemical detection or sensing.     

Disentangling DNA molecules

The widespread circular form of DNA molecules inside cells creates very serious topological problems during replication. Due to the helical structure of the double helix the parental strands of circular DNA form a link of very high order, and yet they have to be unlinked before the cell division. DNA topoisomerases, the enzymes that catalyze passing of one DNA segment through another, solve this problem in principle. However, it is very difficult to remove all entanglements between the replicated DNA molecules due to huge length of DNA comparing to the cell size. One strategy that nature uses to overcome this problem is to create the topoisomerases that can dramatically reduce the fraction of linked circular DNA molecules relative to the corresponding fraction at thermodynamic equilibrium. This striking property of the enzymes means that the enzymes that interact with DNA only locally can access their topology, a global property of circular DNA molecules. This review considers the experimental studies of the phenomenon and analyzes the theoretical models that have been suggested in attempts to explain it. We describe here how various models of enzyme action can be investigated computationally. There is no doubt at the moment that we understand basic principles governing enzyme action. Still, there are essential quantitative discrepancies between the experimental data and the theoretical predictions. We consider how these discrepancies can be overcome.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.     

Investigation on Properties of Polypropylene/Multi-walled Carbon Nanotubes Nanocomposites Prepared by a Novel Eccentric Rotor Extruder Based on Elongational Rheology

The properties of polymer matrix composites are related not only to the chemical composition of the materials but also to the processing equipment used for their preparation which has a direct influence on the microstructure of the composites. In this paper polypropylene (PP)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were prepared by melt blending through a self-developed, eccentric rotor extruder (ERE). The structure and elongational deformation mechanism of an ERE were described in detail. The morphological, rheological, thermal and mechanical properties of the resulting PP/MWCNTs nanocomposites were investigated. Scanning electron microscopy (SEM) and rheological analysis showed that the MWCNTs were well dispersed in the PP matrix. The thermal stability was investigated by thermogravimetric analysis (TGA) and indicated that the addition of MWCNTs could effectively improve the thermal stability of pure PP. The percentage of crystallinity and tensile strength of the composites were improved as a result of the heterogeneous nucleation effect of the MWCNTs in the PP matrix. The research results revealed that the enhancement of the properties of PP/MWCNTs composites could be attributed to a better dispersion of the MWCNTs in the matrix as compared to samples prepared by conventional extrusion.     

Microstructure,Rheology, and Potential Oil Absorbency of Poly(Butyl Methacrylate) and Poly(Hydroxyethyl Methacrylate) Blends

To prepare oil-absorptive polymers with moderate cross-linking structure, poly(butyl methacrylate) (PBMA) was synthesized as a linear hydrophobic polymer by suspension polymerization. In addition, hydroxyethyl methacrylate (HEMA), as a monomer, which could construct a network structure among the macromolecules via hydrogen bond interactions, was solution polymerized in dimethylacetamide (DMAc) with PBMA, yielding a polymer blend of PBMA and PHEMA. The solution of the polymer blend was investigated by rotational viscometry and extended rheometry. The results showed that the viscosity varied greatly with the temperature and shear rate for three different compositions. Fourier transform infrared (FTIR) spectra indicated that an entanglement or interlocking cross-linking structure of molecular chains was constructed by hydrogen bonds. The results from nuclear magnetic resonance (NMR) spectra exhibited a downfield movement of the proton peak as influenced by end groups or hydroxyls in the polymer chains. The rheological measurements demonstrated that the cross-linking structure greatly affected the rheological behavior of the blend solution. In addition, the cross-linking structure was also evaluated by oil absorbency of films.