The use of scattering data in the study of the molecular organisation of polymers in the non-crystalline state

This research was funded by the Polytechnic of Leiria and FCT (Portugal) through UC4EP PTDC/CTM-POL/7133/2014) and UID/Multi/04044/2019, the University of Reading and EPSRC (UK).Scattering data for polymers in the non-crystalline state, i.e., the glassy state or the molten state, may appear to contain little information. In this work, we review recent developments in the use of scattering data to evaluate in a quantitative manner the molecular organization of such polymer systems. The focus is on the local structure of chain segments, on the details of the chain conformation and on the imprint the inherent chemical connectivity has on this structure. We show the value of tightly coupling the scattering data to atomistic-level computer models. We show how quantitative information about the details of the chain conformation can be obtained directly using a model built from definitions of relatively few parameters. We show how scattering data may be supplemented with data from specific deuteration sites and used to obtain information hidden in the data. Finally, we show how we can exploit the reverse Monte Carlo approach to use the data to drive the convergence of the scattering calculated from a 3d atomistic-level model with the experimental data. We highlight the importance of the quality of the scattering data and the value in using broad Q scattering data obtained using neutrons. We illustrate these various methods with results drawn from a diverse range of polymers.info:eu-repo/semantics/publishedVersio

Experimentally driven atomistic model of 1,2 Polybutadiene

We present an efficient method of combining wide angle neutron scattering data with detailed atomistic models, allowing us to perform a quantitative and qualitative mapping of the organisation of the chain conformation in both glass and liquid phases. The structural refinement method presented in this work is based on the exploitation of the intrachain features of the diffraction pattern and its intimate linkage with atomistic models by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Atomic connectivity is defined through these coordinates that are in turn assigned by pre-defined probability distributions, thus allowing for the models in question to be built stochastically. Incremental variation of these coordinates allows for the construction of models that minimise the differences between the observed and calculated structure factors. We present a series of neutron scattering data of 1,2 polybutadiene at the region 120-400K. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54Å and 1.35Å respectively. Valence angles of the backbone were found to be at 112° and the torsion distributions are characterised by five rotational states, a three-fold trans-skew± for the backbone and gauche± for the vinyl group. Rotational states of the vinyl group were found to be equally populated, indicating a largely atactic chan. The two backbone torsion angles exhibit different behaviour with respect to temperature of their trans population, with one of them adopting an almost all trans sequence. Consequently the resulting configuration leads to a rather persistent chain, something indicated by the value of the characteristic ratio extrapolated from the model. We compare our results with theoretical predictions, computer simulations, RIS models and previously reported experimental results

Nonlinear “oddities” at the percolation of 3D hierarchical graphene polymer nanocomposites

The nonlinear rheology of a novel 3D hierarchical graphene polymer nanocomposites was investigated in this study. Based on an isotactic polypropylene, the nanocomposites were prepared using simple melt mixing, which is an industrially relevant and scalable technique. The novel nanocomposites stand out as having an electrical percolation threshold (≈0.94 wt%) comparable to solution mixing graphene-based polymer nanocomposites. Their nonlinear flow behavior was investigated in oscillatory shear via Fourier-transform (FT) rheology and Chebyshev polynomial decomposition. It was shown that in addition to an increase in the magnitude of nonlinearities with filler concentration, the electrical percolation threshold corresponds to a unique nonlinear rheological signature. Thus, in dynamic strain sweep tests, the nonlinearities are dependent on the applied angular frequency, potentially detecting the emergence of a weakly connected network that is being disrupted by the flow. This is valid for both the third relative higher harmonic from Fourier-transform rheology, I3/1, as well as the third relative viscous, v3/1, Chebyshev coefficient. The angular frequency dependency comprised non-quadratic scaling in I3/1\ua0with the applied strain amplitude and a sign change in v3/1. The development of the nonlinear signatures was monitored up to concentrations in the conductor region to reveal the influence of a more robust percolated network

Crystallisation Kinetics and Associated Electrical Conductivity Dynamics of Poly(Ethylene Vinyl Acetate) Nanocomposites in the Melt State

Nanocomposite systems comprised of a poly(ethylene vinyl acetate) (EVA) matrix and carbon black (CB) or graphene nanoplatelets (GNPs) were used to investigate conductivity and crystallisation dynamics using a commercially relevant melt-state mixing process. Crystallisation kinetics and morphology, as investigated by DSC and SEM, turn out to depend on the interplay of (i) the interphase interactions between matrix and filler, and (ii) the degree of filler agglomeration. For the GNP-based systems, an almost constant conductivity value was observed for all compositions upon cooling, something not observed for the CB-based compositions. These conductivity changes reflect structural and morphological changes that can be associated with positive and negative thermal expansion coefficients. GNP-based systems were observed to exhibit a percolation threshold of approximately 2.2 vol%, lower than the 4.4 vol% observed for the CB-based systems

New tools for understanding complex polymer behaviour

The process of manufacturing with polymers usually involves shaping in the melt followed by a transition to the solid to preserve that shape and provide the required mechanical properties. The development of an understanding of those transitions is critical to the optimisation of materials and manufacturing technology. For synthetic polymers there are three key length scales in any phase transition such as crystallisation: the first involves the thin (∼10 nm) lamellar crystals, the second is the crystal planes in the unit cell (∼1 nm) and the third the regular local chain conformation (∼0.1 nm). We are using the extended Q range available with NIMROD at the ISIS Facility in the UK to obtain neutron scattering data which follows the transformation pathways of these three length scales simultaneously. We are using computational modelling procedures to analyse these data to develop a firm understanding of the multiscale processes involved in crystallisation. This paper describes the methodology and some of the experimental challenges using data drawn from this stud

Mechanical Behavior of Melt‐Mixed 3D Hierarchical Graphene/Polypropylene Nanocomposites

The mechanical properties of novel low percolation melt-mixed 3D hierarchical graphene/polypropylene nanocomposites are analyzed in this study. The analysis spans a broad range of techniques and time scales, from impact to tensile, dynamic mechanical behavior, and creep. The applicability of the time–temperature superposition principle and its limitations in the construction of the master curve for the isotactic polypropylene (iPP)-based graphene nanocomposites has been verified and presented. The Williams–Landel–Ferry method has been used to evaluate the dynamics and also Cole–Cole curves were presented to verify the thermorheological character of the nanocomposites. Short term (quasi-static) tensile tests, creep, and impact strength measurements were used to evaluate the load transfer efficiency. A significant increase of Young’s modulus with increasing filler content indicates reasonably good dispersion and adhesion between the iPP and the filler. The Young’s modulus results were compared with predicted modulus values using Halpin–Tsai model. An increase in brittleness resulting in lower impact strength values has also been recorded

SANS/WANS time-resolving neutron scattering studies of polymer phase transitions using NIMROD

We use new neutron scattering instrumentation to follow in a single quantitative time-resolving experiment, the three key scales of structural development which accompany the crystallisation of synthetic polymers. These length scales span 3 orders of magnitude of the scattering vector. The study of polymer crystallisation dates back to the pioneering experiments of Keller and others who discovered the chain-folded nature of the thin lamellae crystals which are normally found in synthetic polymers. The inherent connectivity of polymers makes their crystallisation a multiscale transformation. Much understanding has developed over the intervening fifty years but the process has remained something of a mystery. There are three key length scales. The chain folded lamellar thickness is ~ 10nm, the crystal unit cell is ~ 1nm and the detail of the chain conformation is ~ 0.1nm. In previous work these length scales have been addressed using different instrumention or were coupled using compromised geometries. More recently researchers have attempted to exploit coupled time-resolved small-angle and wide-angle x-ray experiments. These turned out to be challenging experiments much related to the challenge of placing the scattering intensity on an absolute scale. However, they did stimulate the possibility of new phenomena in the very early stages of crystallisation. Although there is now considerable doubt on such experiments, they drew attention to the basic question as to the process of crystallisation in long chain molecules. We have used NIMROD on the second target station at ISIS to follow all three length scales in a time-resolving manner for poly(e-caprolactone). The technique can provide a single set of data from 0.01 to 100Å-1 on the same vertical scale. We present the results using a multiple scale model of the crystallisation process in polymers to analyse the results

High-temperature creep resistant ternary blends based on polyethylene and polypropylene for thermoplastic power cable insulation

The impact of a small amount of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) on the thermomechanical and electrical properties of blends comprising low-density polyethylene (LDPE) and isotactic polypropylene (PP) is investigated. SEBS is found to assemble at the PP:LDPE interface as well as within isolated PP domains. The addition of 10\ua0wt% SEBS significantly increases the storage modulus between the melting temperatures of the two polyolefins, 110 and 160\ub0C, and results in improved resistance to creep during both tensile deformation as well as compression. Furthermore, the ternary blends display a very low direct-current (DC) conductivity as low as 3.4 7 10 \ua0S m at 70\ub0C and 30 kV mm , which is considerably lower than values measured for neat LDPE. The here presented type of ternary blend shows potential as an insulation material for high-voltage direct current power cables

Nanocomposites and polyethylene blends: two potentially synergistic strategies for HVDC insulation materials with ultra-low electrical conductivity

Among the various requirements that high voltage direct current (HVDC) insulation materials need to satisfy, sufficiently low electrical conductivity is one of the most important. The leading commercial HVDC insulation material is currently an exceptionally clean cross-linked low-density polyethylene (XLPE). Previous studies have reported that the DC-conductivity of low-density polyethylene (LDPE) can be markedly reduced either by including a fraction of high-density polyethylene (HDPE) or by adding a small amount of a well dispersed, semiconducting nanofiller such as Al2O3 coated with a silane. This study demonstrates that by combining these two strategies a synergistic effect can be achieved, resulting in an insulation material with an ultra-low electrical conductivity. The addition of both HDPE and C8–Al2O3 nanoparticles to LDPE resulted in ultra-insulating nanocomposites with a conductivity around 500 times lower than of the neat LDPE at an electric field of 32 kV/mm and 60–90 \ub0C. The new nanocomposite is thus a promising material regarding the electrical conductivity and it can be further optimized since the polyethylene blend and the nanoparticles can be improved independently