Buckling in polymer monolayers: Molecular-weight dependence

We present systematic investigations of buckling in Langmuir monolayers of polyvinyl acetate formed at the air-water interface. On compression the polymer monolayers are converted to a continuous membrane with a thickness of ~2–3 nm of well-defined periodicity, lambdab. Above a certain surface concentration the membrane undergoes a morphological transition buckling, leading to the formation of striped patterns. The periodicity seems to depend on molecular weight as per the predictions of the gravity-bending buckling formalism of Milner et al. for fluidlike films on water. However anomalously low values of bending rigidity and Young's modulus are obtained using this formalism. Hence we have considered an alternative model of buckling-based solidlike films on viscoelastic substrates. The values of bending rigidity and Young's modulus obtained by this method, although lower than expected, are closer to the bulk values. Remarkably, no buckling is found to occur above a certain molecular weight. We have tried to explain the observed molecular-weight dependence in terms of the variation in isothermal compressive modulus of the monolayers with surface concentration as well as provided possible explanations for the obtained low values of mechanical properties similar to that observed for ultrathin polymer films.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Transport property of polyaniline and its molecular weight dependence

The electrical conductivity of polyaniline doped with camphor sulfonic acid (PAn-CSA) was studied. The results indicate that there is a critical temperature (T-c) and the temperature dependence of PAn-CSA conductivity shows metallic and semiconductor characteristics above and below T-c, respectively. The higher the molecular weight of PAn, the lower the T-c. The conductivity was enhanced remarkably when PAn-CSA film was stretched, its room temperature conductivity is up to 750 S/cm when elogonation is 60%; however, T-c was independent of elongation.

MOLECULAR-WEIGHT DEPENDENCE OF THE GLASS-TRANSITION OF CYCLIC POLYSTYRENE

The glass transition temperature (T(g)) of cyclic polystyrene was measured by differential scanning calorimetry. There was a marked difference in the glass transition behaviour between cyclic and linear polystyrene. In the low molecular weight region (M(n) < 5 x 10(3)), the T(g) of the cyclic polystyrene increased with decreasing M(n), contrary to that of linear polystyrene. With M(n) higher than 5 x 10(3), the T(g) of cyclic polystyrene increased with increasing M(n). The T(g) of cyclic and linear polystyrene approached the same constant value when the M(n) was high enough (M(n) > 10(5)). Combining the results of specific volume, it is believed that the variation of T(g) with molecular weight does not depend only on free volume effects but that configurational entropy is also an important factor.

Structural dependence of density in high molecular weight esters

The effect of molecular structure on density has been examined in high molecular weight esters (molecular weight 300-900), having varying degrees of branching. Densities were calculated from an empirical equation, which agrees well with the experimental values (error +/-1.5%), irrespective of branching. Since density is related to molecular packing and hence to the molecular rotation, in n-alkanes, the glass transition temperature (T(g)) and density both increase with molecular weight, and hence T(g) is directly related to the density. The esters exhibit a complex behavior. In linear esters the T(g) decreases with molecular weight which is explained from group contribution and molecular interactions. In the +-branched esters, however, T(g) decreases with molecular weight until the molecular weight reaches 600 and increases sharply thereafter. The Y-branched esters show an intermediate behavior. The dependence of T(g) on molecular weight has been explained from the segmental motion.

Structural effects on the vaporization of high molecular weight esters

To understand the effect of molecular weight and branching on the heats of vaporization (AH,) and their flow behavior, AH, and viscosity (7) were measured at different temperatures in the high molecular weight ester series: linear flexible di-n-alkyl sebacates and compact branched triglycerides with molecular weight ranging from 300 to 900. AHv" values (AHv corrected to 298 K) have been obtained with experimental AH, and also computed according to the group additivity method; a smaller-CH,- group value of 3.8 kJ mol-' compared to the normal value of 5.0 kJ mol-' is found to give good agreement with the experimental data (within 2-5% error). Both ester series have the same AH," irrespective of their molecular features, namely,shape, flexibility, and polarity, suggesting the coiling of the molecules during vaporization. The segmental motion of these ester series during their flow and its dependence on their molecular features unlike AH,' are demonstrated by the correlation of the enthalpy of activation for viscous flow (AH*) and the ratio AE,/AH* = n (AE, is the energy of vaporization) with molecular weight.

Statistical thermodynamics of polydisperse polymer systems in the framework of lattice fluid model: Effect of molecular weight and its distribution on the spinodal in polymer solution

With the aid of thermodynamics of Gibbs, the expression of the spinodal was derived for the polydisperse polymer-solvent system in the framework of Sanchez-Lacombe Lattice Fluid Theory (SLLFT). For convenience, we considered that a model polydisperse polymer contains three sub-components. According to our calculation, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights of the polydisperse polymer, but the z-average molecular weight ((M) over bar (z)) dependence on the spinodal is invisible. The dependence of free volume on composition, temperature, molecular weight, and its distribution results in the effect of (M) over bar (n) on the spinodal. Moreover, it has been found that the effect of changing (M) over bar (w) on the spinodal is much bigger than that of changing (M) over bar (n) and the extrema of the spinodal increases with the rise of the weight-average molecular weight of the polymer in the solutions with upper critical solution temperature (UCST). However, the effect of polydispersity on the spinodal can be neglected for the polymer with a considerably high weight-average molecular weight. A more simple expression of the spinodal for the polydisperse polymer solution in the framework of SLLFT was also derived under the assumption of upsilon(*)=upsilon(1)(*)=upsilon(2)(*) and (1/r(1)(0))-(1/r(2i)(0))-->(1/r(1)(0)).

Effects of molecular weight and interaction parameter on the glass transition temperature of polystyrene mixtures and its blends with polystyrene/poly(2,6-dimethyl-p-phenylene oxide)

The glass transition temperature (T-g) of mixtures of polystyrene (PS) with different molecular weight and of blends of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and polystyrene with different molecular weight (DMWPS) was studied by a DSC method. For the whole range of composition, the curves of T-g vs composition obtained by experiment were compared with predictions from the Fox, Gordon-Taylor, Couchman and Lu-Weiss, equations. It was found that the experimental results were not in agreement with those from the Fox, Gordon-TayIor and Couchman equations for the binary mixtures of DMWPS, where the interaction parameter chi was approximately zero. However, for the blends PPO/DMWPS (chi < 0), with an increase of molecular weight of PS, it was shown that the experimental results fitted well with those obtained from the Couchman, Gordon-Taylor and Fox equations, respectively. Furthermore, the Gordon-Taylor equation was nearly identical to the Lu-Weiss equation when \chi\ was not very large. Further, the dependence of the change of heat capacity associated with the glass transition (Delta C-p) on the molecular weight of PS was investigated and an empirical equation was presented. (C) 1997 Elsevier Science Ltd.

Relevance of molecular weight of chitosan-N-2-hydroxypropyl trimethyl ammonium chloride and their antioxidant activities

The antioxidant potency of high/low molecular weight quatemary chitosan derivatives was investigated employing various established systems in vitro, such as superoxide (O-2(center dot-)) and hydroxyl (center dot OH) radicals scavenging, reducing power and iron ion chelating. As expected, we obtained several satisfying results, as follow: firstly, low molecular weight quaternary chitosan had stronger scavenging effect on O-2(center dot-) and center dot OH than high molecular weight quaternary chitosan. Secondly, the reducing power of low molecular weight quaternary chitosan was more pronounced than that of high molecular weight quaternary chitosan. Thirdly, ferrous ion chelating potency were showed to increase first and decrease afterwards with increasing concentration for two kinds of quaternary chitosans, namely, they have not concentration-dependence. However, the scavenging rate and reducing power of high and low molecular weight quaternary chitosans increased with their increasing conc centrations, and hence were concentration-dependent. (c) 2007 Elsevier Masson SAS. All rights reserved.

Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability (T-gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T-calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T-calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Bee) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration (C-crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Drop formation and breakup of low viscosity elastic fluids: Effects of molecular weight and concentration

The dynamics of drop formation and pinch-off have been investigated for a series of low viscosity elastic fluids possessing similar shear viscosities, but differing substantially in elastic properties. On initial approach to the pinch region, the viscoelastic fluids all exhibit the same global necking behavior that is observed for a Newtonian fluid of equivalent shear viscosity. For these low viscosity dilute polymer solutions, inertial and capillary forces form the dominant balance in this potential flow regime, with the viscous force being negligible. The approach to the pinch point, which corresponds to the point of rupture for a Newtonian fluid, is extremely rapid in such solutions, with the sudden increase in curvature producing very large extension rates at this location. In this region the polymer molecules are significantly extended, causing a localized increase in the elastic stresses, which grow to balance the capillary pressure. This prevents the necked fluid from breaking off, as would occur in the equivalent Newtonian fluid. Alternatively, a cylindrical filament forms in which elastic stresses and capillary pressure balance, and the radius decreases exponentially with time. A (0+1)-dimensional finitely extensible nonlinear elastic dumbbell theory incorporating inertial, capillary, and elastic stresses is able to capture the basic features of the experimental observations. Before the critical "pinch time" t(p), an inertial-capillary balance leads to the expected 2/3-power scaling of the minimum radius with time: R-min similar to(t(p)-t)(2/3). However, the diverging deformation rate results in large molecular deformations and rapid crossover to an elastocapillary balance for times t>t(p). In this region, the filament radius decreases exponentially with time R-min similar to exp[(t(p)-t)/lambda(1)], where lambda(1) is the characteristic time constant of the polymer molecules. Measurements of the relaxation times of polyethylene oxide solutions of varying concentrations and molecular weights obtained from high speed imaging of the rate of change of filament radius are significantly higher than the relaxation times estimated from Rouse-Zimm theory, even though the solutions are within the dilute concentration region as determined using intrinsic viscosity measurements. The effective relaxation times exhibit the expected scaling with molecular weight but with an additional dependence on the concentration of the polymer in solution. This is consistent with the expectation that the polymer molecules are in fact highly extended during the approach to the pinch region (i.e., prior to the elastocapillary filament thinning regime) and subsequently as the filament is formed they are further extended by filament stretching at a constant rate until full extension of the polymer coil is achieved. In this highly extended state, intermolecular interactions become significant, producing relaxation times far above theoretical predictions for dilute polymer solutions under equilibrium conditions. (C) 2006 American Institute of Physics

Electrospinning and crosslinking of low-molecular-weight poly(trimethylene carbonate-co-L-lactide) as an elastomeric scaffold for vascular engineering

The growth of suitable tissue to replace natural blood vessels requires a degradable scaffold material that is processable into porous structures with appropriate mechanical and cell growth properties. This study investigates the fabrication of degradable, crosslinkable prepolymers of l-lactide-co-trimethylene carbonate into porous scaffolds by electrospinning. After crosslinking by γ-radiation, dimensionally stable scaffolds were obtained with up to 56% trimethylene carbonate incorporation. The fibrous mats showed Young’s moduli closely matching human arteries (0.4–0.8 MPa). Repeated cyclic extension yielded negligible change in mechanical properties, demonstrating the potential for use under dynamic physiological conditions. The scaffolds remained elastic and resilient at 30% strain after 84 days of degradation in phosphate buffer, while the modulus and ultimate stress and strain progressively decreased. The electrospun mats are mechanically superior to solid films of the same materials. In vitro, human mesenchymal stem cells adhered to and readily proliferated on the three-dimensional fiber network, demonstrating that these polymers may find use in growing artificial blood vessels in vivo.

Bile Acid Derived PET-Based Cation Sensors: Molecular Structure Dependence of their Sensitivity

A number of bile acid derived photoinduced electron transfer (PET) based sensors for metal ions are prepared. A general strategy for designing the sensor with a modular nature allows for making different molecules capable of sensing different metal ions by a change in the fluorophore and receptor unit. Keeping the basic molecular structure the same, different bile acid base fluoroionophores were prepared inorder to achieve the highest sensitivity toward the metal ions. Thesensors showed similar binding constants for the same metal ion, but the degree Of fluorescence enhancement upon addition of the metal salts were different. The sensitivities of the sensors towards a certain metal were determined from the observed fluorescence enhancement upon addition of the metal salt.

Effect of Molecular Weight on the Thermal and Impact Sensitivity of Polymers in Propellants

Abstract is not available.