Neutron scattering and compressibility measurements for the study of hydration effects on polymeric aqueous solutions

Summary The present paper reports the results of compressibility and incoherent quasi-elastic neutron scattering measurements performed on polymeric systems and on their aqueous solutions. From the compressibility data, the temperature evolution of the polymer hydration number can be derived. On the other hand, neutron data show that the translational diffusion coefficientD _T turns out to be higher in the case of ethylene glycol + water, with respect to that of pure, suggesting that the water molecules act as a ?structure breaker? of the intermolecular connectivity existing into the pure. Furthermore the dynamical properties of the H₂O molecules in the presence of poly(ethylene glycol) deeply differ from those in the bulk, and show that we are in the presence of entangled water. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Polyelectrolyte multilayer formation: Electrostatics and short-range interactions

We investigate the phenomenon of multilayer formation via layer-by-layer deposition of alternating charged polyelectrolytes. Using mean-field theory, we find that a strong short-range attraction between the two types of polymer chains is essential for the formation of multilayers. For strong enough short-range attraction, the adsorbed amount per layer increases (after an initial decrease), and finally it stabilizes in the form of a polyelectrolyte multilayer that can be repeated hundreds of times. For weak short-range attraction between any two adjacent layers, the adsorbed amount (per added layer) decays as the distance from the surface increases, until the chains stop adsorbing altogether. The dependence of the threshold value of the short-range attraction as function of the polymer charge fraction and salt concentration is calculated.     

Theoretical and experimental approaches to kinetics at the collapse transition of a homopolymer

Summary We discuss some recent theoretical studies of the kinetics of the collapse transition in homopolymers. An isolated polymer is modelled using computer simulation, and a time-dependent mean-field theory. The mean-field theory is analysed analytically for early stages, and for short polymers the equations are studied numerically. The results of simulation and theory are compared yielding, we argue, a consistent physical picture. Quantitative comparisons are not yet given, but seem relatively promising. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4– 1994.     

Analysis of the crystallization kinetics in poly(ethylene oxide) by calorimetric measurements

Summary Differential scanning calorimetric measurements in the early stage of isothermal crystal growth of polyethylene oxide are analysed in the light of irreversible thermodynamics. An accurate evaluation of the equilibrium melting temperature is done by fitting the thermograms obtained at different undercoolings and referring to the activation energy values already known from the literature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Frequency dependence of the complex dielectric constant of poly(ethylene oxide) under hydrostatic pressure

Summary Electrical-impedance measurements have been made in the frequency range 5 Hz to10 MHz in pure poly(ethylene oxide) having a molecular weight of 600 000 from 254 K nearly up to the melting point of the crystalline phase (about 330 K). As the temperature approaches the melting point there are large increases in the realε′ and imaginaryε″ parts of the dielectric constant. The frequency dependence ofε′ is characterized by a primary-relaxation process, whose frequency increases with increasing temperature as a consequence of decrease of the average structural relaxation time. There is strong evidence that this low-frequency dispersion rises mainly from the diffusive transport of localised charge carriers rather than a purely orientation relaxation process. In addition the effects of hydrostatic pressure (0–25 Gpa) on the frequency dependences of the realε′ and imaginaryε″ parts of the dielectric constant have been measured in the same temperature range. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

The fusion of ethylene oxide polymers

Summary Calorimetric measurements by DSC technique have been made in pure polyethylene glycol (PEG) and oxide (PEO) polymers having a very wide molecular-weight range (from 600 to 4000 000) and in PEO (MW 600 000)-NaSCN complexes. It was found that the melting temperature increases with increasing molecular weight, ranging from 293 K in the polymer with MW=600 to 340 K in that with MW=4000 000. The behaviour of the heats of fusion with increasing molecular weight reflects the trend expected in systems, in which the increase of the main chain length produces a relevant growth of the degree of crystallinity. A distinct maximum of the heat of fusion has been found at about MW=10000, this result being an evidence of the high amount of crystalline regions building up the structure of that system. The dependence of the melting temperature on molecular weight has been nicely accounted for by using the expression of Flory, deduced from the statistical theory of polymers having the most probable molecular-weight distribution. The addition of sodium thiocyanate to PEO modifies the morphology of the host polymer and, for salt concentrations higher than 0.03 molar fraction, gives rise to the formation of a PEO-salt crystalline complex characterized by a high melting temperature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Dynamical mechanical measurements in dry PHEMA and its hydrogels

Summary The elastic modulus and tg δ of poly(2-hydroxyethyl methacrylate) (PHEMA) and its hydrogels have been measured over, the frequency range 0.3–30Hz and the temperature range 120–450 K. The mechanical spectra reveal the presence of a low-temperature γ-relaxation plus a shoulder (β-relaxation) that merges into the α-relaxation. The absorbed water lowers the temperature and rises the hight of the lowest temperature peak (the γ-peak for dry PHEMA) while lowering both temperature and height of the α-peak. This behaviour is interpreted in terms of hydrogen-bonding effects between water and polymer which weaken the intra- and/or interchain interactions. Furthermore, the calorimetric analysis in dry polymer is consistent with the mechanical behaviour in the higher-temeprature region. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Structural relaxation and anharmonicity in polymer electrolytes: Effect of the thermal history

Summary The effects of the storage at room temperature of PEO-KSCN polymer electrolytes have been studied by differential scanning calorimetry (DSC) and dynamical mechanical analysis. It has been revealed that, over the explored time interval, the annealing causes small variations in the anharmonic and relaxation properties of the samples, which are to be ascribed to changes in the relative amount of the phases building up the structure. The elastic and anelastic characteristics show a well-defined dependence on the degree of crystallinity of the polymer, which grows slightly with increasing annealing time. The application of a simplified version of a quasi-harmonic model and of the Kolrausch-Williams-Watts stretched exponential function permits to describe the temperature behaviour of the elastic modulusE′ and to obtain an anharmonicity parameter characterizing the polymeric system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Influence of polydispersity on the phase behavior of statistical multiblock copolymers with Schultz-Zimm block molecular weight distributions

In this paper we investigate in a systematic way the influence of polydispersity in the block lengths on the phase behavior of AB-multiblock copolymer melts. As model system we take a polydisperse multiblock copolymer for which both the A-blocks and the B-blocks satisfy a Schultz-Zimm distribution. In the limit of low polydispersity the expressions for the vertex functions are clarified by using simple physical arguments. For various values of the polydispersity the phase diagram is presented, which shows that the region of stability of the bcc phase increases considerably with increasing polydispersity. The strong dependence of the periodicity of the microstructure on the polydispersity and on the interaction strength is presented. Received 2 July 1998     

Early stages of phase separation from polydisperse polymer mixtures

We study the early stages of phase separation in a mixture of a polydisperse and a monodisperse polymer within the Cahn-Hilliard framework. We model the polydisperse component using a finite, but arbitrarily large, number of components, and show that the number of components required for convergent behaviour to be achieved is computationally undemanding. We study the growth rate of fluctuations following a quench into the two-phase region of the phase diagram. The q-dependence of the growth rate is shown to be commensurate with the behaviour of a monodisperse-monodisperse mixture, with the major difference being an effective mobility that is dependent on the quench depth. We also study the deviation of the time dependence of the scattering function from single exponential behaviour. Received 29 June 2000 and Received in final form 20 November 2000     

Density functional theory for nonuniform polymer melts: Based on the universality of the free energy density functional

A density functional theory is proposed for nonuniform freely jointed tangential hard sphere polymer melts in which the bonding interaction is treated on the basis of the properties of the Dirac δ-function, thus avoiding the use of the single chain simulation in the theory. The excess free energy is treated by making use of the universality of the free energy density functional and the Verlet-modified (VM) bridge function. To proceed numerically, one of the input parameters, the second-order direct correlation function of a uniform polymer melt is obtained by solving numerically the Polymer-RISM integral equation with the Percus-Yevick (PY) closure. The predictions of the present theory for the site density distribution, the partition coefficient and the adsorption isotherm, near a hard wall or between two hard walls are compared with computer simulation results and with those of previous theories. Comparison indicates that the present approach is more accurate than the previous integral equation theory and the most accurate Monte Carlo density functional theories. The predicted oscillations of the medium-induced force between two hard walls immersed in polymer melts are consistent with the experimental results available in the literature. Received 18 April 2000     

What can polymer crystal structure tell about polymer crystallization processes?

Contrary to most or all other materials, crystallization of chiral but racemic polymers such as isotactic polypropylene is accompanied by a conformational rearrangement which leads to helical geometries: the building units of the crystal are helical stems, -20nm long, which can be either right-handed or left-handed. Helical hand cannot be reversed within the crystal structure: it is therefore a permanent marker and an indicator of molecular processes (in particular segregation/selection of helical hands) which take place during crystal growth, and more precisely during the crucial step of “efficient” helical stem deposition. The issue of proper helical hand selection during polymer crystal growth is mainly illustrated with isotactic polypropylene. Its various crystalline polymorphs (, , and smectic) display virtually all possible combinations of helical hands, azimuthal settings and even non-parallel orientation of helix axes in space. Furthermore, a specific homoepitaxy which generates a lamellar branching in the phase “quadrites” and composite structures makes it possible a) to determine the helical hand and associated azimuthal setting of every stem in the crystalline entities and b) to determine the impact on the crystal structure and morphology of “mistakes” in helical hand of the depositing stem. Analysis of these morphologies demonstrates that the crystallization of isotactic polypropylene (and by implication of other achiral, helical polymers) is a highly sequential and “substrate-determined” process, i.e. that the depositing stem probes the topography of the growth face prior to attachment. These observations appear difficult to reconcile with crystallization schemes in which molecules (helical segments) are prearranged in a kind of pseudo-crystalline bundle (and as such, are not subjected to the high constraints of crystal symmetry) before deposition as a preassembled entity on the substrate. Received: 5 May 2000     

Kinetics of reversible surface crystallization and melting in poly(ethylene oxide): Effect of crystal thickness observed in the dynamic heat capacity

Poly(ethylene oxide) (PEO) in the semi-crystalline state shows a reversible surface crystallization and melting; a temperature decrease leads to a certain crystal thickening, a temperature increase reversely to an expansion of the amorphous intercrystallite layers. Dynamic calorimetry provides a means to investigate the kinetics of the process. The structural rearrangement in the region of the crystalline-amorphous interface can only be accomplished if the chains can slide through the crystallites. One therefore expects the associated time to change with the crystallite thickness. Variations of the crystal thickness of PEO can be achieved by choosing different crystallization temperatures. We studied the effect of the crystal thickness employing temperature-modulated differential scanning calorimetry and heat wave spectroscopy, and by carrying out small-angle X-ray scattering experiments for the structural characterization. The effect of the crystal thickness is clearly observed. Results indicate that the sliding diffusion through the crystallites takes place by helical jumps of whole stems. Data yield the activation energy per unit length of the stems. Received 20 April 2001 and Received in final form 13 August 2001     

The mobility of the amorphous phase in polyethylene as a determining factor for slow crack growth

Polyethylene (PE) pipes generally exhibit a limited lifetime, which is considerably shorter than their chemical degradation period. Slow crack growth failure occurs when pipes are used in long-distance water or gas distribution though being exposed to a pressure lower than the corresponding yield stress. This slow crack growth failure is characterized by localized craze growth and craze fibril rupture. In the literature, the lifetime of PE pipes is often considered as being determined by the density of tie chains connecting adjacent crystalline lamellae. But this consideration cannot explain the excellent durability of the recent bimodal grade PE for pipe application. We show in this paper the importance of the craze fibril length as the determining factor for the pipe lifetime. The conclusions are drawn from stress analysis. It is found that longer craze fibrils sustain lower stress and are deformed to a lesser degree. The mobility of the amorphous phase is found to control the amount of material that can be sucked in by the craze fibrils and thus the length of the craze fibrils. The mobility of the amorphous phase can be monitored by dynamic mechanical analysis measurements. Excellent agreement between the mobility thus derived and lifetimes of PE materials as derived from FNCT (full notch creep test) is given, thus providing an effective means to estimate the lifetime of PE pipes by considering well-defined physical properties.     

Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques. Received 30 January 2002     

Study on orientation mechanisms of poly(vinylidenefluoride-trifluoroethylene) molecules aligned by atomic force microscopy

We have developed a molecular orientation control technique for polymers utilizing contact-mode atomic force microscopy (AFM). In this paper, we studied the molecular alignment mechanism of this technique by applying it to poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)). The resultant alignment and formed crystal size were strongly dependent on the temperature during the modification. They also depended on the scan line spacing of the modification. These results made the alignment mechanism clear. The obtained molecular alignment was stable against the heat treatment even at the temperatures just below T_m.     

Overlap properties and adsorption transition of two Hamiltonian paths

We consider a model of two (fully) compact polymer chains, coupled through an attractive interaction. These compact chains are represented by Hamiltonian paths (HP), and the coupling favors the existence of common bonds between the chains. We use a (n=0 component) spin representation for these paths, and we evaluate the resulting partition function within a homogeneous saddle point approximation. For strong coupling (i.e. at low temperature), one finds a phase transition towards a “frozen” phase where one chain is completely adsorbed onto the other. By performing a Legendre transform, we obtain the probability distribution of overlaps. The fraction of common bonds between two HP, i.e. their overlap q, has both lower () and upper () bounds. This means in particular that two HP with overlap greater than coincide. These results may be of interest in (bio)polymers and in optimization problems. Received 4 December 1998 and Received in final form 10 March 1999     

A non-Gaussian model in polymeric network

We investigate a finite chain approximation, the non-Gaussian Tsallis distribution, to the polymeric network, which gives an improvement to the Gaussian model. This distribution presents some necessary characteristics, like a cutoff to the maximum chain length and a continuous limit to the Gaussian one for a large number of monomers. It also presents a simple quadratic structure that allows to generalize the Gaussian properties such as exact-moments calculation and Wick theorem. We obtain the free-energy density in its full tensorial structure.