The contribution of neutron scattering to polymer science

The contribution of neutron scattering to polymer science is reviewed. A summary is given of the theory of neutron scattering followed by a review of the literature. Particular emphasis is placed on the use of small angle neutron scattering to observe the conformation of polymer chains in bulk polymers and concentrated polymer solutions and on quasi elastic neutron scattering to measure the dynamics of polymer chains.     

Determination of the conformation of polymers in the amorphous solid state and in concentrated solution by neutron diffraction

From the coherent neutron scattering on dilute solid solutions of the ordinary polymer within the deuterated polymer, conformation parameters of polymer chains in amorphous solid states can be determined. In this way vitreous poly(methyl methacrylate) (PMMA) has been investigated. The chains form unperturbed coils and the radius of gyration is very near to the corresponding value in dilute solutions of the same polymer in the low molecular θ-solvent butyl chloride. The same principle of measurement has been applied to concentrated solutions of PMMA in D-acetone. The solutions contained 50% polymer, the main part of which (98% and more) was deuterated so that the system was optically dilute for neutron scattering on H-PMMA. A monotonic dependence of the radius of gyration and of thermodynamic parameters on the concentration has been found. A first result is presented for a mixture of two polymers. A dilute solid dispersion of poly(α-methylstyrene) (PMS) within D-PMMA has been investigated at M_w = 250 000. The samples are limpid. The PMS forms micelles of 16 molecules (weight average). The radius of gyration of the micelles, r_z is 170 Å.     

Observation of single chain motion in a polymer melt

Molecular motion of single polymer chains has been investigated in a melt sample of polytetrahydrofuran and compared with results for the same polymer in dilute solution. Using a high resolution neutron scattering technique motion over distances up to 30 Å has been observed with an energy resolution of 0.01 μeV (～10⁷s^?1). The motion of the chains in the melt is described by the Rouse model and a friction factor per segment has been extracted from the data. This compares well with values obtained from viscosity and bulk relaxation measurements on similar polymers.     

A metallurgical approach to the pre-yield and yield behavior of glassy polymers

This paper discusses some new mechanical and small angle neutron scattering (SANS) data on glassy polymers, both thermoplastics and thermoset resins, from the point of view of dislocation-like defects introduced in the molecular chain arrangement by deformation. In the pre-yield stage, a new parameter, the work-hardening rate K is introduced and its measurement is defined. Experiments are reported which show that K can be used as a very sensitive probe for microstructural changes during physical aging or curing. In one hand, the theory of yielding is revisited to make clear how dislocations and their propagation in polymers depend on specific features like entanglements and chain stiffness. On this basis, experimental internal stresses and activation volumes at yield (i.e., the temperature slope of yield stress) are accounted for. On the other hand, SANS data provide us with experimental evidence at the scale of 10 to 20 Å of the dislocation nature of the molecular “shear defects” introduced in the polymer by deformation. Finally, temperature is known to have a pronounced influence on yield processes. It is shown that two distinct deformation modes exist below and above a critical temperature T_c. Above T_c, a dislocation climb, which probably involves β-processes, gives rise to a “diffusional” deformation mode where chains within a (diffuse) shear band are no longer oriented. A tentative formalization of this behavior, and its relation to the small strain creep of polymers, are then presented.     

A new method for data evaluation of small angle neutron scattering experiments and its application to amorphous polycarbonate

Summary The conformation of single chains in bulk polymer materials can be evaluated from coherent neutron scattering on mixtures of normal and deuterated polymers. It is shown that the single-chain structure factor can be also obtained from measurements of highly concentrated mixtures and the procedure of evaluation is described. The application to amorphous polycarbonate demonstrates the advantages of the method.Paper presented at the Colloque Franco-Americain sur la diffusion des rayons X et des neutrons aux petits angles par les polymers, 16. – 19. Septembre 1980, StrasbourgNeutron scattering measurements were carried out at the ILL, Grenoble     

Characterization of polymer conformation and morphology through small-angle neutron scattering—A literature review

Small-angle neutron scattering, SANS, stands forth as one of the most important of the new tools for evaluating polymer chain conformation and morphology. This paper reviews the SANS literature through 1982, with a few early 1983 references added. The theory of SANS is outlined and compared to light scattering. SANS values of polymer molecular weights and radii of gyration obtained in the bulk state were found to be in agreement with values obtained from dilute solutions by light scattering. In each case, deuterated fractions of polymer were inserted into the hydrogeneous matrix, or vice versa, to provide contrast. Several new research areas are then discussed, including unidirectional stretching of elastomers, stress-relaxation, polymer-polymer miscibility, crystallization from the melt compared with crystallization from dilute solutions, nonclassical aggregation during bulk polymerization of thermoset systems, morphology of polymer blends, block copolymers and ionomers, the core-shell structure of latexes and polymer blocks, and grafts as surfactants in emulsions and latexes. Much new and sometimes unexpected information is being provided by the SANS research now in progress.     

Polymer networks characterized by slidable crosslinks and the asynchronous dynamics of interlocked components

In mechanically interlocked molecules like rotaxanes and catenanes, each component has asynchronous microscopic motion within the topological restrictions. The motions can be expressed macroscopically by incorporating the mechanically interlocked molecules in polymers and their networks. Rotaxane develops into polyrotaxane having a polymer axis, and then polyrotaxane forms a polymer network so-called slide-ring material. Because the polymer chains in the material are topologically connected to each other via a figure-eight crosslink, the chains can slide through the crosslink. This microscopic slidability at the crosslink drastically affects the mechanical properties. This article first presents an overview of significant studies on slide-ring materials in the first decade that deal with single species material consisting of polyethylene glycol and α-cyclodextrin. These studies have revealed abnormal statics and network structures, most of which can be interpreted in terms of slidability. Next, we describe our recent designs of materials and findings in mechanical properties attributed to the slidable crosslinks that are built on a synthetic breakthrough that yields a new series of slide-ring materials composed of various backbone polymers. The finding of a sliding transition reveals the dynamics of sliding, the significance of the entropy of uncrosslinked cyclic compounds, and helps in determining the mechanical properties of slide-ring materials.     

Untersuchungen zur Synthese und den Eigenschaften von amphiphilen Polymeren

Investigations of the Synthesis and Properties of Amphiphilic Polymers By reaction of propylene/maleic anhydride copolymers with the sodium salt of α-dodecyl-ω-hydroxy-trioxyethylene ionic polymers with different shares of long aliphatic side chains were prepared. The properties of these amphiphilic polymers were studied. Like micelles they are able to solubilize nonpolar probe molecules (N,N-dimethyl-aminoazobenzene). Viscosity measurements show the dependence of the conformation of the polymeric chain in solution on the share of aliphatic side chain and the degree of protonation. The polymers from micelle-like aggregates. It is supposed that the polymer with a high share of aliphatic side chains froms several local aggregates per polymer chain, while the polymer containing only few side chains seems to form intermolecular aggregates between different polymer chains. These investigations were performed with pyrene as probe molecule. Pyrene was also used to examine the micropolarity of the aggregates. Like polyelectrolytes the amiphilic polymers are able to cause the aggregation of opposite charged dyes (thionine).     

An effect of side chain length on the solution structure of poly(9,9-dialkylfluorene)s in toluene

The effect of side chain length of π-conjugated poly(9,9-dialkylfluorene)s has been studied in semi-dilute (10 mg/mL) toluene solutions using small-angle neutron scattering (SANS) and ¹H and ²H NMR spectroscopies. Under these conditions, SANS data indicate that poly(9,9-dinonylfluorene) and poly(9,9-dioctylfluorene) are dissolved down to the molecule level and appear as elongated one-dimensional chains (length >20-30 nm). In contrast, the shorter side chain polymers exhibit a self-association so that poly(9,9-diheptylfluorene) forms thin sheet-like (∼1 nm) and poly(9,9-dihexylfluorene) thin (∼1 nm) and thick sheet-like (>6 nm) aggregates. ¹H NMR data, together with the density functional theory (DFT) calculations, however, show that this occurs without changes in the conformation of the polymer backbone.     

Computer-Aided Design of Crosslinked Polymer Membrane Using Machine Learning and Molecular Dynamics

The formation of crosslinking network between polymer chains has significant influence on polymer properties. In particular, the crosslinked structure of ionic networks like proton exchange membrane affects the conductivity performance. To further develop in this area, a framework for polymer membrane design based on the developed quantitative prediction model of the properties of crosslinked polymer is proposed. First, polymers with different crosslinking degrees are constructed by a crosslinking algorithm. Next, molecular dynamics is used to calculate the properties of crosslinked polymers. Then, the quantitative relationship between crosslinked polymer structures and macroscopical properties is developed. Subsequently, computer-aided polymer design method is integrated with the developed quantitative predict model. The crosslinked polymer design problem is expressed as an optimization problem to obtain the optimal crosslinking degree. Bayesian optimization strategy is used to solve the established optimization model. Finally, two case studies of perfluoro sulfonic acid and perfluoro imide acid design are given to illustrate the application of the proposed polymer design framework.     

Solubility of neutral and charged polymers in ionic liquids studied by laser light scattering

The solubility and chain conformation of different types of homopolymers in low viscosity ionic liquids (ILs), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]) at 50 °C and 1-butyl-3-methylimidazolium formate ([BMIM][COOH]) at 25 °C, were studied by laser light scattering (LLS). For neutral polymers, such as polyvinyl alcohol and polysulfonamide, aggregation occurred in all the cases except for polyvinyl alcohol in [BMIM][COOH]. For negative polyelectrolytes, such as DNA and polystyrene sulfonate, single chain conformation was observed. However, the hydrodynamic radius of both polymers was much smaller than that in good solvents, suggesting that the chains were condensed. Cellulose was soluble in [AMIM][Cl], and non-diffusive mode was observed by dynamic light scattering. Zeta potential analysis indicated that cellulose exhibited the feature of polyelectrolyte. The solubility of homopolymers could be qualitatively explained by treating polymer/IL as a ternary system: polymer, cation, and anion. It was the mutual interactions determined the solubility and conformation of polymers in ILs.     

Light reflection at polyaniline films and its application to a kinetic study of polymer chain conformation

Light reflection at polymer-coated electrodes is studied for polyaniline, poly(o-methylaniline), and poly(o-methoxyaniline). Reflected light intensity is found to be affected greatly by the applied potential for the two reasons: one is absorption of light due to coloring of the oxidized polymer film and the other is light scattering which is concerned with a polymer chain conformation upon oxidation. A new method based on the potential dependence of light reflection is proposed for studying kinetics of conformational changes of polymer chains. The rate constants evaluated are in the range of 0.05-8 s⁻¹ at room temperature, depending on the sort of polymers, the film thickness, and pH of the solution. Irrespective of the sort of polymers, the increase in film thickness or solution pH leads to the decrease of the rate constant. It is found that a film morphology has a significant effect on the rate constant, as confirmed by a comparison of rate constants observed with polyaniline films grown at different rates.     

Theory of correlations in partly labelled homopolymer melts

Small-angle neutron scattering by a polymer melt with partly tagged chains is considered. When several types of chain (differently labelled) are present in the system a new long-range correlation effect which modifies the scattering spectrum is predicted. This effect will arise because of the chemical polydispersity of the sample. A general formalism is developed to calculate the scattering intensity and is applied to special cases: diblock and triblock chains. It is shown that even a small chemical polydispersity leads to important long-range fluctuations and modifies the scattering spectrum substantially.     

Residual orientation in injection‐moulded plaques of atactic‐polystyrene II: The effect of molecular weight

Injection moulding of polymers is a well‐established technique for the production of increasingly complex articles, and residual molecular orientation is a matter of considerable interest. A single matrix of commercial atactic polystyrene was systematically blended with deuterated polystyrene chains of five different weight fractions and the orientation investigated using small angle neutron scattering (SANS), optical birefringence and thermal shrinkage. The strengths and limitations of the experimental techniques used to measure residual orientation are explored and highlighted the unique contribution of SANS to observe ensemble averaged molecular orientation using deuterated polymers. The residual molecular orientation was found to vary with the molecular weight of the deuterated chains with an increase with increasing molecular weight. The observed correlations lead to a better understanding of the processing parameters that influence the degree of residual orientation on the molecular scale. Such information is valuable in the selection of the polymer matrix, mould design, and processing conditions. POLYM. ENG. SCI., 58:1332–1341, 2018. © 2017 Society of Plastics Engineers     

Dynamics of polymer molecules using neutron spin—echo

The dynamics of single polymer chains have been investigated in dilute solution and in the melt using the neutron spin—echo technique. In dilute solution the intramolecular motion is described to a first approximation by that for a Rouse chain incorporating hydrodynamic interactions (Zimm). It is characterised by an inverse correlation time which may be normalised by temperature, solvent viscosity and segment size, and which for long chains varies as Q³ at small scattering angles (Q is the change in wavevector on scattering). At very low Q vectors the predicted ‘universal’ regime is observed, but over most of the accessible range chemical structure also becomes important. For short chains, deviations from this Q³ behaviour are associated with overall molecular diffusion. In the melt, chain entanglements come into play and modify the simple Rouse-type motion. The correlation functions are described by a combination of Rouse motion over short distances and times and a long-time slow-motion predicted by the reptation model of melt dynamics.     

Ceramic-reinforced polymers and polymer-modified ceramics

The composites discussed in this review are prepared using techniques similar to those used in the new sol-gel approach to ceramics. Organometallis such as silicates, titanates, and aluminates are hydrolyzed in the presence of polymer chains (for example polysiloxanes and polyimides) that typically contain hydroxyl or amino groups. The functional groups are used to bond the polymer chains onto the silica, titania, or alumina being formed in the hydrolysis, thus forming organic-inorganic composites. When the polymer chains are present in excess, they constitute the continuous phase, with the ceramic-type material appearing as reinforcing particles. When present in smaller amounts, the polymer is dispersed in the continuous ceramic phase, to give a polymer-modified ceramic. Under some conditions, bicontinuous systems are obtained. The composites thus prepared are characterized by electron microscopy, X ray, and neutron scattering intensities, density determinations, and stress-strain and impact-strength measurements.     

Computer simulation study on the shear-induced phase separation in semi-dilute polymer solutions by using Ianniruberto-Marrucci model

In our previous study, a computer simulation scheme based on Doi-Onuki theory is proposed to simulate the dynamics of the shear-induced phase separation in semi-dilute polymer solutions [KOBUNSHI RONBUNSHU 2007, 64, 324]. The scheme employs Ianniruberto-Marrucci model as a constitutive equation to express the viscoelastic behavior of the solution explicitly. The scheme enables us to simulate the time-evolution of stress as well as that of shear-induced structure upon shear-jump. In this study, we focus on the conformation of polymer chains. The dynamics of the polymer chains agrees with those in the “solvent squeeze” model which interprets the shear-induced phase separation phenomena in semi-dilute polymer solutions by Saito et al. [Macromolecules 1999, 32, 4879].     

Reflection methods for the study of polymer interfaces

The direct study of polymer Interfaces is very difficult. Small angle scattering methods have been most successfully applied to block copolymer Interfaces where the morphology is well known. Other techniques such as electron microscopy, Rutherford back scattering, and forward recoil spectroscopy generally only give resolution of the order of 10 nm. Here we describe two techniques which have only recently been applied to polymer interfaces, neutron reflection, and spectro-scopic ellipsometry. Both reflection techniques examine planar samples and give compositional information in the depth direction. Neutron reflection gives a resolution of 0.5 nm and spectroscopic ellipsometry may give better than 5 nm. We will describe experiments using neutron reflection which measure the inter-facial thickness between two immiscible polymers and experiments using both techniques which measure the interdiffusion of miscible polymers. Other applications and limitations of the techniques will also be discussed.     

Study on the Effect of Axial Vibration of Screw in Plasticating Process (Extrusion Part)

To improve the conformation of polymers, axial vibration is offered in the entire polymer process. Two sections, the axial shearing section and the axial pressing section, exert the effects of vibration on the melt. In the axial shearing section, with the effect of vibration, molecular chain orientations in the direction of flow and vibration produce the network frame, which ameliorates the mechanical properties, especially in the transverse direction, of the polymer product. The vibration can promote the disentanglement of molecular chains, which leads to a decrease in the viscosity and an increase in the flowability of melt. At the same time, it can ameliorate the blend quality of the filling system. Some experiments on extruded film, sheet, pipe, foam, and filling systems prove that the analyses are correct.