Dynamics of thermoresponsive PNIPAM-g-PEO copolymer chains in semi-dilute solution

The effects of concentration and temperature on dynamics of poly(N-isopropylacrylamide)-graft-poly(ethylene oxide) (PNIPAM-g-PEO) chains in semi-dilute aqueous solution were studied by static and dynamic laser light scattering. The intensity-intensity time correlation function shows a fast and a slow relaxation mode, with line widths Γ_f and Γ_s, respectively. Γ_f is scaled to the scattering vector (q) as Γ_f ∝ q², revealing that it is due to the cooperative diffusion of the subchains between two neighboring entangled points. As the concentration increases, the slow relaxation becomes slower and contributes more to the total scattered light intensity, indicating that the slow relaxation is related to the chain entanglement. On the other hand, when the solution temperature increases, the PNIPAM chain backbone shrinks, but the fast relaxation remains and the slow mode slows down with a minimum rate at ∼33 °C. It indicates that the slow mode arises from inter-chain clustering, which is gradually suppressed by the intra-chain shrinking. The sample position independence of the time-averaged scattered light intensity 〈I〉_T reveals that the solution is homogeneous and the clustering is transient.     

Dynamics of amylopectin in semidilute aqueous solution

The dynamic behaviors of potato amylopectin and waxy corn amylopectin in semidilute solution were investigated by laser light scattering and viscometer. For potato amylopectin with relatively smaller molecular weight, only pure diffusion motion of amylopectin was found by LLS in dilute regime. When the concentration was above the critical overlapping concentration (C^∗), three relaxation modes were found. The line-width of fast mode (Γ_f) had a q² dependence, where q is the scattering vector, and the correlative length (〈ξ_h〉) could be scaled to concentration (C) as 〈ξ_h〉 ∼ C^−0.79±0.1 when C > 2%. This mode was attributed to the cooperative relaxation motion of the “blobs” in the transient network. The line-width of slow relaxation mode (Γ_s) could be scaled with q as Γs∼qαs, α_s varying from 2.0 to 2.66 as the concentration increased. The relaxation time of slow relaxation mode (τ_s) had a C^1.8±0.1 dependence. This mode was originated from the association of the amylopectin. The medium mode was found when C > 4%. The line-width of medium relaxation mode (Γ_m) could be scaled to q as Γm∼qαm, α_m varying from 2.7 to 2.5 with the increasing concentration. The relaxation time of medium relaxation mode (τ_m) had C^0.7±0.1 dependence. The relative intensity contribution of the medium relaxation mode decreased with a rise in the concentration. This mode was attributed to the thermally agitated density fluctuation in semidilute solution induced by heterogeneities of the transient network. For waxy corn amylopectin with relatively huge molecular weight (∼10⁸ g/mol), only the internal motion of the single amylopectin molecule was found in dilute regime when qR_g ≥ 2, where R_g is the gyration radius of amylopectin. It was also found that there were three relaxation modes in semidilute solution of waxy corn amylopectin. The fast relaxation mode was found to be caused first by the internal motion of the single amylopectin molecule, and then, with the increasing concentration, by the cooperative motion of the transient network. The medium and slow relaxations for waxy corn amylopectin have the same physical origin as those for potato amylopectin. However, the C dependence and the q dependence of the medium and slow relaxation times for waxy corn amylopectin were different from those for potato amylopectin. This was attributed to the strong dynamic coupling effect in semidilute solution of the waxy corn amylopectin. The concentration dependence of the viscosity of amylopectin in semidilute solution indicated that the topological entanglement of amylopectin was weak due to the highly branching.     

Investigation on the early and late stage phase-separation dynamics of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) blends through rheological and scattering functions

The phase-separation behavior of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) (PMMA/α-MSAN) blends with two different compositions was studied by time-resolved small angle light scattering (SALS) in the spinodal decomposition (SD) regime from 160 to 210 °C. The rheological function (WLF-like equation) was introduced into the processing of light scattering data. It was found that the WLF-like equation was applicable to describe the temperature dependence of apparent diffusion coefficient D_app and the relaxation time τ of normalized scattering intensity (I(t)−I(0))/(I_m−I(0)) at the early stage of SD, as well as the relaxation time τ of maximum scattering intensity I_m and characteristic scattering vector q_m with I_m at the late stage of SD for PMMA/α-MSAN blends with two different compositions. This is in consistence with the phase-separation behavior of PMMA/SAN reported in our previous paper.     

Shape memory and stress relaxation behaviour of oriented mono-dispersed polystyrene

The shape memory and stress relaxation behaviour of oriented samples of mono-dispersed polystyrene have been studied. It was found that the transient stress dip of Fotheringham and Cherry could successfully predict the recovery providing that the initial deformation which produces the molecular orientation is undertaken at a sufficiently fast strain rate. This means that if recovery is to be predicted, relaxation of the molecular orientation must not occur during the drawing process. This is attributed to the low fraction of the viscosity term of the total stress for polystyrene. This makes it advantageous to maximise the total stored stress, allowing the smaller component to be more accurately determined. It is proposed that the critical strain rate for maximising the stored stress is related to the smallest relaxation time in the melt, the entanglement time, τ_e.     

Raman spectroscopy study of high-modulus carbon fibres: effect of plasma-treatment on the interfacial properties of single-fibre-epoxy composites: Part II: Characterisation of the fibre-matrix interface

High-modulus carbon fibres from different precursors were submitted to an oxygen plasma-treatment under similar conditions. Single-fibre epoxy composites were prepared from them, and fragmentation tests were performed in order to characterise fibre-matrix interfacial adhesion. Raman spectroscopy has been used in the present work to map the strain along the fibre during tensile loading of the matrix. The strain distributions obtained agreed well with the prediction of analytical models used conventionally to describe load transfer at interfaces. Interfacial shear stress distributions were then obtained from these distributions according to the conventional force-balance concept. The interfacial shear strength (IFSS) and frictional shear stress (τ_f) values were calculated to quantify the degree of fibre-matrix adhesion. It was found that both parameters increased dramatically after the surface treatment, confirming the ability of cold plasma oxidation to improve the adhesion of carbon fibre to epoxy matrices. A dependence of the IFSS on the degree of surface order, as given by the structural order parameter I_D/(I_D+I_G), calculated from the relative intensities of the D and G bands of Raman spectra, was found. This supports the role played by the graphitic structure in fibre-matrix adhesion.     

Effects of structural transition on microwave dielectric properties of Sr3(Ti1-xSnx)2O7 ceramics

Sr₃(Ti_1-xSn_x)₂O₇ (x = 0–1.0) ceramics were prepared via a standard solid-state reaction method. X-ray diffraction patterns and Rietveld refinement results indicated a composition induced onset of octahedral tilting when x > 0.2, and the crystal structure transformed in sequence: tetragonal (I4/mmm) → coexistence of tetragonal and orthorhombic (I4/mmm + Amam) → orthorhombic (Amam). The τ_f value could be successfully tuned towards zero and the effects of octahedral tilting on the evolution of τ_f value were emphasized. Meanwhile, the role of tolerance factor in tailoring the resultant τ_ε of the present ceramics was revealed and compared with the empirical rule for complex perovskites. Qf value decreased monotonously with increasing x, which could be elucidated by the variations of extrinsic parameters and intrinsic dielectric loss extrapolated from the infrared reflectivity spectra. The optimum microwave dielectric properties were achieved at x = 0.8 (ε_r = 18.6, Qf = 45,250 GHz, τ_f =–14 ppm/^oC).     

Crystallization kinetics of poly(ethylene terephthalate): Cmemory effect of shear history

The memory effect of shear history was studied with poly(ethylene terephthalate) (PET) prepared under different shear conditions of 11.7 to 1168 s^?1 in a capillary rheometer. The shear history of PET resin led to a memory effect, which in turn affected the crystallization kinetics. The crystallization rate increased with increasing shear rate. Double peaks of heating crystallization exotherms and a low value of Avrami exponent appeared at low shear rates, which was attributed to the existence of crystallization processes with different rates; one was the fast process involving the disentangled molecules that persisted during melting, and the other was the slow process involving the highly entangled molecules. The change of instantanenous Avrami exponent and overall crystallization rate constant was in good agreement with the expected trends assuming coexistence of the two crystallization processes. The crystallization kinetics of PET with shear history could be regarded as a growth rate decrease problem to be interpreted by the modified Avrami equation, 1 ? V_c = exp[? K·f(t)ⁿ], when the fast process dominated the overall crystallization. The effect of shear history was reduced because of the relaxation process as the holding time in melt state before crystallization was increased.     

Strain-induced crystallization of peroxide-crosslinked natural rubber

Effect of network-chain density (ν) on the strain-induced crystallization of peroxide-crosslinked natural rubber was studied by fast time-resolved synchrotron wide-angle X-ray diffraction. It was observed that the elongation ratio at the onset of strain-induced crystallization (α_c) became smaller with the increase of ν. The difference of the entropy between the undeformed and deformed states at each α_c was nearly equal in spite of the variation of ν. The calculated melting temperature at α_c of the samples was also almost the same regardless of their ν. These observations mean that the strain-induced crystallization occurred when the deformation brought about a definite entropic state for peroxide-crosslinked natural rubber. They agreed with the prediction by Flory and were consistent with the classical theory of rubber elasticity.     

Structural and dynamic heterogeneity in a telechelic polymer solution

We utilize molecular dynamics simulations to investigate the implications of micelle formation on structural relaxation and polymer bead displacement dynamics in a model telechelic polymer solution. The transient structural heterogeneity associated with incipient micelle formation is found to lead to a ‘caging’ of the telechelic chain end-groups within dynamic clusters on times shorter than the structural relaxation time governing the cluster (micelle) lifetime. This dynamical regime is followed by ordinary diffusion on spatial scales larger than the inter-micelle separation at long times. As with associating polymers, glass-forming liquids and other complex heterogeneous fluids, the structural τ_s relaxation time increases sharply upon a lowering temperature T, but the usual measures of dynamic heterogeneity in glass-forming liquids (non-Gaussian parameter α₂(t), product of diffusion coefficient D and shear viscosity η, non-Arrhenius T-dependence of τ_s) all indicate a return to homogeneity at low T that is not normally observed in simulations of these other complex fluids. The greatest increase in dynamic heterogeneity is found on a length scale that lies intermediate to the micellar radius of gyration and intermicellar spacing. We suggest that the limited size of the clusters that form in our (low concentration) system limit the relaxation time growth and thus allows the fluid to remain in equilibrium at low T.     

On the some electrical properties of the non-ideal PPy/p-Si/Al structure

The electrical analysis of the PPy/p-Si structure has been investigated by means of I-V, C-V and C-f measurements. The diode ideality factor and the barrier height have been obtained to be n=1.78 and Φ_b=0.69 eV by applying a thermionic emission theory, respectively. At high current densities in the forward direction, the series resistance effect has been observed. In general, the barrier height obtained from C-V data is greater than obtained from the I-V. This has been explained by introducing a spatial distribution of barrier heights (BHs) due to barrier height inhomogeneities that present at the PPy/p-Si interface. The C-f measurements of the structure have been performed at various biases and it has been seen that they have a good agreement between experimental and theoretical values. The interface state density N_ss and relaxation time τ of the structure have been determined from the C-f characteristics.     

Turbulence level significance of the coalescence-dispersion rate parameter

The random coalescence-and-dispersion (C–D) models for non-ideal mixing in reactors involve a rate parameter, I, which is the frequency of the coalescence and dispersion events divided by the available number of coalescence sites per unit residence time, where residence time is a measure of reactor size. An approximate relationship between I and hydrodynamic parameters has been found by carefully comparing C–D computations, where I varies with location, with actual measurements of the turbulent energy dissipation rate, ε, and the turbulence length scale, L_s, in a tubular reactor. At each location I was determined such that the calculated conversion of a second-order reaction matched the measured conversion. The relationship found was: I≈ 1333(ε/L_s²)^{$\text{1}\text{3}$}(^?τ/N) where L_s, is the length scale of segregation, ε has dimensions of velocity squared per unit time, and (^?τN) is the residence time divided by the number of coalescence sites.The relationship above was applied to the C–D modeling of a semi-batch reactor with a consecutive-competitive reaction. The resulting yields and selectivities under the various conditions of the experimental data were very close to experimental results.     

The suppression of strain induced crystallization in PET through sub micron TiO2 particle incorporation

The effects of TiO₂ particles on the crystallization and uniaxial stress-strain behavior of poly(ethyleneterephthalate) (PET) films from amorphous precursors were investigated. The addition of small fraction of sub micron sized TiO₂ particles were found to suppress the mechanical relaxation processes associated with high temperature side of the β relaxation while enhancing the low temperature relaxation. When crystallized from unoriented precursors, TiO₂ particles act as a nucleation agent and enhance the thermally induced crystallization of the PET chains. However, when stretched from the amorphous precursors in rubbery temperature range (T_g<T_p<T_cc), the TiO₂ concentration levels as low as 0.35 wt% was found to reduce the overall stress and retard strain hardening and accompanying stress induced crystallization. As a result, under the same stretching conditions, the films containing TiO₂ were found to possess lower crystallinity and orientation levels. This was attributed to suppression of stress induced crystallization as these particles act to disrupt the formation of crystalline lattice by their physical presence. This may be as a result of the reduction of chain entanglements in the presence of these sub micron sized TiO₂ particles in the structure of the polymers that retard the formation of physical network whose nodes are made up of entanglements and small crystalline domains. The development of this long range ‘connected’ network is primarily responsible for the rapid upturn in the stresses at the onset of strain hardening observed in stress strain curves.This method represent a unique way to apply ‘anti-nucleating agent’ effect to control the development of stress induced crystallization that will help control the film and fiber forming processes.     

Stresses of cohesionless granular flows in liquids

We construct constitutive relations for friction stress, slide stress and collision stress of cohesionless granular flows. We propose that the friction stress and slide stress could be neglected when τ_c/τ_e < 0.02, where τ_c represents the interval time experienced by a given particle between two consecutive binary collisions and τ_e the particle relaxation time. We applied these constitutive relations to a simulation of solid-liquid flow in an inclined chute and found the simulation results agree with experimental data.     

Influence of a particulate nucleating agent on the quiescent and flow-induced crystallization of isotactic polypropylene

Flow induced crystallization of commercial isotactic polypropylene (iPP) and its blends with sodium 2,2′-methylene bis-(4,6-di-tert-butylphenyl) phosphate (also known as NA11) is studied by means of in-situ time resolved small-angle X-ray scattering (SAXS). The isothermal crystallization at 145 °C (i.e. well below melting temperature of polymer) is performed after the application of steady shear to probe the anisotropic structure formation. In order to separate the influence of shear rate and shear time on polymer crystallization, four different shear conditions (60 s⁻¹ for 1 s, 30 s⁻¹ for 2 s, 15 s⁻¹ for 4 s and 6 s⁻¹ for 10 s) are applied while maintaining the same imposed strain in the polymer melt. Further the effect of different concentration of nucleating agent on the crystallization kinetics of iPP is examined both under quiescent and shear flow conditions. For instance, under quiescent condition, the crystallization half-time (τ_1/2) decreases with the increasing concentration of nucleating agent in the polymer. Under shear flow conditions, our observations are as follows: In the case of neat iPP, τ_1/2 decreases significantly at higher shear rates (≥30 s⁻¹). Compared to the neat iPP, for the same concentration of NA11 in the NA11/iPP blends differences in τ_1/2 with the increase in applied shear rates are significantly smaller. In other words, the crystallization kinetics is dominated by the amount of nucleating agent in the NA11/iPP blends as opposed to shear rates in the neat iPP. The present study shows that the critical value of shear rate required for chain orientation in the molten polymer is lower in the presence of the nucleating agent compared to neat iPP. The self-nucleation process investigated with the aid of differential scanning calorimetry (DSC), indicates that the nucleating efficiency of NA11 on iPP is around 60%.     

Structural evolution and microwave dielectric properties in Sr2(Ti1-xSnx)O4 ceramics

The structure and microwave dielectric properties of Sr₂(Ti_1-xSn_x)O₄ ceramics were determined in the entire composition range of x?=?0–1.0. X-ray diffraction patterns and Raman spectra indicated a composition-induced onset of octahedral tilting at x?=?0.75, and the crystal structure transformed from tetragonal (I4/mmm) to orthorhombic (Pccn). An obvious change of grain morphology was observed in the phase transformation region as well. The variations of the microwave dielectric properties with composition were systematically investigated and the effect of octahedral tilting on the evolution of τ_f value was emphasized. Moreover, the relationship between τ_ε and tolerance factor of the present ceramics was revealed and compared with the empirical rule in perovskite structure. The role of tolerance factor in designing the materials with required performance was highlighted.     

Role of epitaxy of nucleating agent (NA) in nucleation mechanism of polymers

The role of “epitaxy” of nucleating agent (NA) in nucleation mechanism of polymers was studied to formulate the nucleation rate (I) as a function of concentration of NA (C_NA) in mixture of polymer and NA and lateral size of a NA crystal (a_NA), I ∝ C_NA/a_NA. It is proved that the epitaxy of NA controls nucleation mechanism by confirming above formula experimentally by observing nucleation by means of optical microscopy. We also clarified that heterogeneous nucleation is a probabilistic phenomenon by confirming that “induction time of nucleation (τ_i)” did not depend on C_NA. We established a method to obtain reliable I and τ_i by adding NA which has been a difficult problem in polymer science.     

Crystallization behavior of poly(l-lactic acid)

The crystallization behavior of poly(l-lactic acid) was studied in the range of 80-160 °C. The peak crystallization time (τ_p) was defined and obtained from the crystallization isotherm measured with a differential scanning calorimeter (DSC). Isothermal crystallization temperature (T_c) dependence of log(τ_p) discretely changed at 113 °C (= T_b). The linear growth rate of spherulite, G, was measured with a polarizing microscope. The T_c dependence of G and the size of the spherulite also discretely changed at T_b. Crystal structures for samples isothermally crystallized at temperatures which were higher and lower than T_b were orthorhombic (α-form) and trigonal (β-form), respectively. The discrete change of the crystallization behavior was explained by the formation of different crystal.     

A friction bond model for the effects of sinusoidal vibrations upon shear stress in particulate systems

A theoretical model has been derived which describes the effects of vibration upon Critical State shear stress for a bed of particles failing in shear and subject to vibrations. The model is based upon the concept of hypothetical friction bonds acting across a shear plane and relies predominantly upon mechanistic arguments. One solution of the resultant differential equation relates the shear stress τ_sf at frequency f to vibration velocity U in the following manner: τ_sf=τ^∞_s + (τ_s−τ^∞_s) exp(−AU) The model is compared with the experimental data of Roberts and is of similar mathematical form.     

Semidilute solutions of poly(methacrylic acid) in the absence of salt: Dynamic light-scattering study

Water solutions of poly(methacrylic acid) of molecular weight M_w = 3.0 × 10⁴ and M_w = 4.0 × 10⁵, neutralized with NaOH, were investigated by photon correlation spectroscopy. At a low degree of neutralization α, the short-time decay only is observed. When α > 0, a second, much slower, process becomes noticeable. It gains quickly in influence when α increases. The reciprocal values of characteristic relaxation times for both dynamic processes were found to decrease linearly with the square of the scattering vector, showing that both processes are diffusive. The following interpretation of these processes founded on the concentration and angle dependences of the corresponding diffusion coefficients and scattering amplitudes is given: (1) for the low-molecular-weight sample (M_w = 3.0 × 10⁴), D_∫ (fast process) and be attributed to the Nernst-Hartley diffusion coefficient of polyions, and D_s (slow process) to a diffusion of interchain domains (clusters) with a radius of gyration R_G ≈ 50 nm; (2) for the high-molecular-weight sample (M_w = 4.0 × 10⁵), where an overlap of polymer chains occurs, D_f can be attributed to a cooperative diffusion coefficient reflecting the concentration fluctuations due to the polyions and counterions, and D_s to slow concentration fluctuations having a large correlation length (≈ 100 nm). The existence of two diffusive modes in salt-free solutions of polyelectrolytes cannot be explained within the framework of the scaling approach as proposed by de Gennes and Odijk.     

Synthesis,speed of ultrasound and associated acoustical parameters of epoxy acrylate of 9,9′‐bis (4‐hydroxy phenyl) anthrone‐10 solutions

Density (ρ), viscosity (η), and speed of ultrasound (U) (2 MHz) of pure solvents (chloroform, THF, and 1,4‐dioxane) and solutions of epoxy acrylate of 9,9′‐bis(4‐hydroxy phenyl) anthrone‐10 (EAAN) have been investigated at 303, 308, and 313 K. Specific acoustical impedance (Z), isentropic compressibility (κ_s), intermolecular free path length (L_f), classical absorption coefficient (α/f²)_cl, and viscous relaxation time (τ) have been determined from ρ, η, and U data and are correlated with concentration. Z, (α/f²)_cl, and τ increased with C and decreased with T, while κ_s and L_f decreased with C and increased with T in the solvent systems studied. A fairly good to excellent correlation between a given parameter and concentration is observed in solvent systems studied. Linear increase or decrease of acoustical parameters with concentration and temperature indicated existence of strong molecular interactions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011