Structural and dynamic single chain behaviour in a binary blend of low molecular mass poly(siloxanes) as studied by small angle neutron scattering and neutron spin echo spectroscopy

Elastic and quasi elastic neutron scattering investigations, using the small angle neutron scattering (SANS) and neutron spin echo (NSE) techniques, respectively, were performed in order to study the static and dynamic single chain behaviour in a binary blend of low molecular mass deuterated poly(dimethylsiloxane) (d-PDMS) and protonated poly(ethylmethylsiloxane) (p-PEMS) at the critical composition _c. Since the single chain observation requires that only a small amount of one of both components is labelled, the d-PDMS/p-PEMS system was modified in such a way that the major part of the protonated PEMS component was replaced by the corresponding deuterated material. Although the de-mixing of the PEMS isotopes occurs far below the de-mixing of the PDMS/PEMS system the resulting chemically binary d-PDMS/d-PEMS/p-PEMS blend with the volume composition 0.5/0.425/0.075 is strictly speaking a ternary system. This complication had to be taken into account, in particular with respect to the correct evaluation of the SANS data.The careful analysis of the SANS curves allows one to determine all three thermodynamic interaction parameters with reasonable reliability and gives evidence that the radii of gyration agree with those, which were determined in corresponding isotopic PDMS and PEMS blends. This is in contrast to the observation on real binary PDMS/PEMS blends at _c, where the collective conformational properties exhibit a considerable chain expansion. The NSE data of the ternary system follow completely the predictions of the Rouse model, which describes the dynamics of a dense low molecular mass polymeric system in a single chain approximation. The experimental observations are also in contrast to the results of former NSE measurements on binary PDMS/PEMS blends, where a transition from Rouse behaviour at short times to a much weaker relaxation at longer times became obvious.The results of the static and dynamic single chain behaviour presented here confirm the results of a computer simulation on a low molecular mass binary blend at the critical concentration, where explicitly the pure single chain behaviour was probed and no indications for chain expansion and deviations from the Rouse dynamics were found.Dedicated to Prof. Dr. Erhard W. Fischer on the occasion of the 75th anniversary of his birthday.     

nMoldyn: a program package for a neutron scattering oriented analysis of molecular dynamics simulations

We present a new implementation of the program nMoldyn, which has been developed for the computation and decomposition of neutron scattering intensities from Molecular Dynamics trajectories (Comp. Phys. Commun 1995, 91, 191-214). The new implementation extends the functionality of the original version, provides a much more convenient user interface (both graphical/interactive and batch), and can be used as a tool set for implementing new analysis modules. This was made possible by the use of a high-level language, Python, and of modern object-oriented programming techniques. The quantities that can be calculated by nMoldyn are the mean-square displacement, the velocity autocorrelation function as well as its Fourier transform (the density of states) and its memory function, the angular velocity autocorrelation function and its Fourier transform, the reorientational correlation function, and several functions specific to neutron scattering: the coherent and incoherent intermediate scattering functions with their Fourier transforms, the memory function of the coherent scattering function, and the elastic incoherent structure factor. The possibility to compute memory function is a new and powerful feature that allows to relate simulation results to theoretical studies.     

Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials

The recent (from 2010 onward) contributions of quasielastic neutron scattering techniques (time of flight, backscattering, and neutron spin echo) to the characterization and understanding of dynamical processes in soft materials based on polymers are analyzed. The selectivity provided by the combination of neutron scattering and isotopic—in particular, proton/deuterium—labeling allows the isolated study of chosen molecular groups and/or components in a system. This opportunity, together with the capability of neutrons to provide space/time resolution at the relevant length scales in soft matter, allows unraveling the nature of the large variety of molecular motions taking place in materials of increasing complexity. As a result, recent relevant works can be found dealing with dynamical process which associated characteristic lengths and nature are as diverse as, for example, phenyl motions in a glassy linear homopolymer like polystyrene and the chain dynamics of a polymer adsorbed on dispersed clay platelets. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Small-angle neutron scattering study on the miscibility and concentration fluctuation of hydrogen-bonded polymer blends

Thermal concentration fluctuation in the blends of deuterated poly(ethylene oxide) (dPEO) and poly(vinyl acetate-co-vinyl alcohol) [P(VAc-VOH)] with various VOH contents f_OH were examined by small angle neutron scattering techniques at a fixed blend composition, dPEO/P(VAc-VOH) = 20/80 which is close to the critical composition. Blends at the highest f_OH (=0.35) showed a non-Lorentzian scattering profile: specifically the scattering intensities at the low q (angle) region were suppressed compared to those expected from the random phase approximation (RPA) theory. However, for the blends at lower f_OH (≤0.28), the profiles could be represented by the RPA. Using the RPA we determined effective values of the Flory-Huggins interaction parameter χ_eff as a function of f_OH (=0–0.28). The χ_eff showed the minimum around f_OH = 0.1–0.18 meaning the highest miscibility of the blend at these f_OH. On the basis of the random copolymer theory, we evaluated the three interaction parameters χ_Ac–EO, χ_EO–OH, and χ_Ac–OH separately from the χ_eff(f_OH) and found the order of magnitude; χ_Ac–EO < 0 < χ_EO–OH < χ_Ac–OH. The largest positive χ_Ac–OH showing intrachain interaction in the P(VAc-VOH) copolymer was concluded to be the origin of the enhanced miscibility at around f_OH = 0.1–0.18. On the basis of the Coleman and Painter's theory, the effects of hydrogen bonding on these three χ_A-B were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2556–2565, 2008     

Inverse freezing in α-cyclodextrin solutions probed by quasi elastic neutron scattering

Solutions of α-cyclodextrin, 4-methylpyridine and water undergo a reversible liquid–solid phase transition on heating (“inverse freezing”). In this paper quasi elastic neutron scattering (QENS) measurements are reported, from which the diffusive dynamics of different components in the liquid and solid phases is determined. Results imply that, in solution, α-cyclodextrin is contained in a solvation shell of 4-methylpyridine molecules, while in the crystal phase, the majority of the cell contents are immobilized on the nanosecond timescale. This information will be important in evaluating the entropy of the system in its different phases and in understanding the unusual phase transition.     

Viscosity reduction in polymer nanocomposites: Insights from dynamic neutron and X-ray scattering

The addition of nanoparticles to a polymer matrix can in certain cases induce a reduction in viscosity, with respect to the pure matrix, in the resulting composites. This counterintuitive phenomenon cannot be explained using the most common rheological models. For this reason, it has been chosen as a good example in this paper to demonstrate the value and methods of dynamic X-ray and neutron scattering techniques for the investigation of polymer nanocomposites. An overview of the main results on this topic is presented together with an introduction to the basic concepts relating to X-ray photon correlation spectroscopy, neutron backscattering, and neutron spin echo measurements.     

Thermodynamic interactions in blends of poly(4-tert-butyl styrene) and polyisoprene by small-angle neutron scattering

The thermodynamic interactions between poly(4-tert-butyl styrene) [P(4tBS)] and 1,4-polyisoprene (PI; both hydrogenous) were obtained as functions of the temperature, PI molecular weight, and blend composition through the examination of miscible ternary blends of these two components with a common miscible labeled polymer [90% 1,2-deuterated polybutadiene (dPBD)] with small-angle neutron scattering. The thermodynamic interaction parameters between P(4tBS) and dPBD and between P(4tBS) and PI increased with increasing temperature and were consistent with lower critical solution temperature behavior. Although the binary blends of P(4tBS) and dPBD exhibited phase separation at elevated temperatures, the thermodynamic interaction parameters between P(4tBS) and PI remained large and negative and independent of the PI molecular weight. Finally, the thermodynamic interactions for PI and P(4tBS) depended strongly on the ratio of PI to P(4tBS) and were also sensitive to the amount of dPBD present in the ternary blend. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3204–3217, 2004     

Inelastic neutron scattering from isotactic polypropylene

We used inelastic neutron scattering to probe the low‐energy excitations in semicrystalline isotactic polypropylenes with different degrees of crystallinity. The contributions from the amorphous and crystalline regions to the total scattering intensity were extracted under the assumption of a weighted linear contribution of the two regions in a simplified two‐phase system. The resulting intensity from the amorphous region showed a peak at 1.2 meV that was in good agreement with the previously determined boson peak characteristic of atactic polypropylene. The possibility of a contribution to the boson peak region by longitudinal acoustic mode modes that are characteristic of semicrystalline polymers and appear in the same low‐frequency region is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2852–2859, 2001     

Boson peak and fast relaxation process near the glass transition in polystyrene

Atactic polystyrene, both side group and main chain deuterated, was investigated by inelastic neutron scattering in a wide temperature range around the glass transition from 2 to 450 K. In the glass the Boson peak position is only very weakly influenced by the deuteration of the phenyl group. In the neighborhood of the glass transition temperatureT _g we find a fast relaxation process similar to other glasses. The onset of the fast relaxation in polystyrene, however, is observed already at temperaturesT _g — 200 K. Results from partially deuterated polystyrene suggest a change of the phenyl ring dynamics already far belowT _g.     

Small angle neutron scattering and its application in battery systems

Small angle neutron scattering is a powerful, non-destructive technique that can provide both structural and compositional information. Recently, it has been applied to the field of battery research and has helped elucidate some of the phenomena that are traditionally difficult to probe, including lithiation mechanisms, solid electrolyte interface formation/composition, and electrode microstructure. Specific components of interest can be selectively probed through the application of targeted experiments, contrast variation, and specific composition/structural models gained from complementary data from other analytical techniques.     

An elastic neutron scattering on dynamical transition in hydrogen-bonded systems

Elastic incoherent neutron scattering measurements have been performed on trehalose and sucrose/D₂O mixtures as a function of temperature. The study provides an effective way for characterizing the dynamical behaviour, furnishing a set of parameters characterizing the ‘flexibility’ and the ‘rigidity’ that justifies the better cryptobiotic effect of trehalose with respect to sucrose. Elastic scans make evident a non-Gaussian behaviour of the intensity profiles, which is more marked for sucrose, with a dynamical transition at T253 and 250 K for trehalose/D₂O and sucrose/D₂O mixtures, respectively.     

Quantumness of correlations and Maxwell's demon in molecular excitations created by neutron scattering

Nonclassical correlations known as entanglement, quantum discord, quantum deficit, measurement‐induced disturbance, quantum Maxwell's demon, etc., may provide novel insights into quantum‐information processing, quantum‐thermodynamics processes, open‐system dynamics, quantum molecular dynamics, and general quantum chemistry. We study a new effect of quantumness of correlations accompanying collision of two distinguishable quantum systems A and B, the latter being part of a larger (interacting) system B + D. In contrast to the common assumption of a classical environment or “demon” D, the quantum case exhibits striking new qualitative features. Here, in the context of incoherent inelastic neutron scattering from H‐atoms which create molecular excitations (vibration, rotation, translation), we report theoretical and experimental evidence of a new phenomenon: a considerably reduced effective mass of H, or equivalently, an anomalous momentum‐transfer deficit in the neutron‐H collision. These findings contradict conventional theoretical expectations even qualitatively, but find a straightforward interpretation in the new theoretical frame under consideration. © 2015 Wiley Periodicals, Inc.     

Vibrational dynamics of a glass forming liquid in nanoscopic confinement as probed by inelastic neutron scattering

In this article we present incoherent inelastic neutron scattering results, as a function of temperature, on the vibrational dynamics of a glass-forming liquid, namely propylene glycol, confined to the 26 Å pores of a controlled porous glass. The aim is to elucidate the effects induced by surface interactions (chemical traps) and geometrical restrictions (physical traps) on the fast microscopic dynamics of hydrogen-bonded liquids. The most prominent effect is the appearance of the ‘boson peak’ in the vibrational spectra. It is ascribed to an excess density of vibrational states due to quasilocalized collective atomic vibrations induced by confinement. A destructuring effect on the transient aggregates with the highest degree of connectivity, promoted by PG in the bulk phase, is hypothesized under confinement as a consequence of interactions, via hydrogen bond, between the hydroxyl groups (OH) of the PG molecule and the active silanol groups (Si–OH) on the surface of the porous glass.

Interfacial and/or finite-size effects are also found to give rise to a destructuring effect, under confinement, of the disordered Longitudinal Acoustic Mode, together with a broadening of the highest frequency torsional vibration and a stabilization, vs. T, of the internal CCO bending vibration.     

Small-angle neutron scattering studies of dynamics and hierarchical pattern formation in binary mixtures of polymers and small molecules

We present the dynamics of the composition fluctuations and pattern formation of two-component systems in both single-phase and two-phase states as studied by time-resolved small-angle neutron scattering and light scattering. Two-component systems to be covered here include not only dynamically symmetric systems, in which each component has nearly identical self-diffusion coefficients, but also dynamically asymmetric systems, in which each component has different self-diffusion coefficients. We compare the dynamic behaviors of the two systems and illuminate their important differences. The scattering studies presented for dynamically asymmetric systems highlight that stress–diffusion coupling and viscoelastic effects strongly affect the dynamics and pattern formation. For dynamically symmetric systems, we examine the universality existing in both polymer systems and small-molecule systems as well as new features concerning the time evolution of hierarchical structures during phase separation via spinodal decomposition over a wide range of wave numbers (up to four orders of magnitude). For both systems, we emphasize that polymers provide good model systems for studying the dynamics and pattern formation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3027–3062, 2004     

Effect of random and block copolymer additives on a homopolymer blend studied by small-angle neutron scattering

Small-angle neutron scattering (SANS) has been employed to study a blend of polystyrene and polybutadiene modified by copolymer additives. SANS data from the one-phase region approaching the phase boundary has been acquired for blends modified by random and diblock copolymers that have equal amounts of styrene and butadiene monomers as well as a random copolymer with an unequal monomer composition. The binary blend is near the critical composition, and the copolymer concentrations are low at 2.5% (w/w). The data have been fitted with the random-phase approximation model (binary and multicomponent versions) to obtain Flory–Huggins interaction parameters (χ) for the various monomer interactions. These results are considered in the context of previous light scattering data for the same blend systems. The SANS cloud points are in good agreement with previous results from light scattering. The shifts in the phase boundary are due to the effects of the additives on the χ parameter at the spinodal. All the additives appear to lower the χ parameter between the homopolymers; this is in conflict with the predicted Flory–Huggins behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3191–3203, 2004     

Small-angle neutron scattering of polymer blends of polyvinylmethylether at dilute concentration in deuterated polystyrene

Small-angle neutron scattering was used to measure the radius of gyration and thermodynamics of blends of poly(vinylmethylether) (PVME) at dilute concentration in deuterated polystyrene (PSD). The data were analyzed using the Zimm equation and the random phase approximation theory. For PVME with a weight-average molecular weight of 38,400 the value of the radius of gyration, R_g, was found to be 47 Å in the limit of the concentration of PVME extrapolated to zero. Analysis of the temperature dependence of the Flory interaction parameter, χ/v₀, indicates that phase separation should occur at approximately 300°C for a sample with ϕ_PVME ≅ 9%. No significant temperature dependence of R_g was found over the experimental range studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 1–9, 1998     

CO2 diffusivity in LiY and NaY faujasite systems: a combination of molecular dynamics simulations and quasi-elastic neutron scattering experiments

Quasi-elastic Neutron Scattering combined with Molecular Dynamics simulations have been carried out to gain further insight into the CO₂ dynamics in LiY and NaY Faujasites. In both materials, it was pointed out that the transport diffusivity (D_T) increases with the loading whereas the self diffusivity (D_S) decreases. In addition, it was shown that LiY exhibits a significant slower CO₂ self diffusivity process due to a strong interaction between the Li⁺ cation and the adsorbate molecules at the initial stage of diffusion. This result is consistent with higher simulated activation energy in this cation exchanged faujasite form. By contrast, the transport diffusivity is revealed to be slightly faster in LiY than in NaY.     

Molecular weight determination from light scattering and refraction in solutions. A new and coherent theoretical equation

The classical theoretical equation allowing for the determination of the solute's molecular weight (M₂) from light scattering (LS) and refractive measurements in diluted solutions is reexamined. Serious theoretical and practical defects in its derivation and application are pointed out, especially about the refraction increment dn/dc. A new theoretical equation is deduced from a more consistent application of the basic molecular orientation formulae to binary liquid mixtures. More adequate additive molecular properties, the specific mean polarizability ( /M and the specific square of the mean polarizability instead of and , are considered with respect to refraction and LS, respectively. Inadequate approximations are avoided and a corrected LS intensity expression is used. The new equation is tested upon several typical mixtures of small molecules from measurements either performed in this work or collected in the literature (for LS perpendicular to the incident beam) to ensure objectivity. Examples of measurements in macromolecule solutions from other authors are also analysed. The new equation is suitable for practical applications, because it is based upon easy relative measurements only, and allows for a reliable determination of the M₂ values in macromolecules. The reasons for which the classic equation leads to realistic values, in spite of its theoretical inconsistency, are also explained.     

Molecular weight determination from light scattering and refraction in solutions. A new and coherent theoretical equation

The classical theoretical equation allowing for the determination of the solute's molecular weight (M₂) from light scattering (LS) and refractive measurements in diluted solutions is reexamined. Serious theoretical and practical defects in its derivation and application are pointed out, especially about the refraction increment dn/dc. A new theoretical equation is deduced from a more consistent application of the basic molecular orientation formulae to binary liquid mixtures. More adequate additive molecular properties, the specific mean polarizability and the specific square of the mean polarizability instead of ga and , are considered with respect to refraction and LS, respectively. Inadequate approximations are avoided and a corrected LS intensity expression is used. The new equation is tested upon several typical mixtures of small molecules from measurements either performed in this work or collected in the literature (for LS perpendicular to the incident beam) to ensure objectivity. Examples of measurements in macromolecule solutions from other authors are also analysed. The new equation is suitable for practical applications, because it is based upon easy relative measurements only, and allows for a reliable determination of the M₂ values in macromolecules. The reasons for which the classic equation leads to realistic values, in spite of its theoretical inconsistency, are also explained.