Depth-resolved molecular structure and orientation of polymer thin films by synchrotron X-ray diffraction

An exemplary system suitable for optoelectronics applications, i.e. poly(3-hexylthiophene), hereinafter P3HT, deposited by spin casting onto silicon substrates functionalised by three selected molecules and then properly annealed, has been examined. Grazing Incidence X-ray Scattering (GIXS) measurements have been performed with 4-circle diffractometer, allowing for a fine control of sample axes movement.By choosing different grazing incident angles, diffraction patterns from different layers of polymeric thin films have been recorded. Both in-plane and out-of-plane geometries have been combined in order to obtain complementary structural information. In this way structural and orientational differences of the polymer along with the film thickness (?50 nm) have been highlighted. For all P3HT films spun on functionalized Si wafer, macromolecular layers close to the substrate surface give some evidence of higher order and orientation than those outmost the surface, and this behaviour is pronounced to a different extent depending on the functionalized molecules used. Contrariwise P3HT layers deposited onto bare Si wafer display reduced orientation and decreased crystallite size, especially at buried interface.     

The effect of collector gap width on the extent of molecular orientation in polymer nanofibers

Electrospun poly(vinylidene fluoride) (PVDF) nanofibers were collected on aluminum foil across a gap with widths that varied in size from 2 to 10 mm. Scanning electron microscopy (SEM) images on fiber bundles showed that in all cases, fibers in the gap were macroscopically aligned across the gap. However, single fiber selected area electron diffraction (SAED) patterns and polarized Fourier Transform Infrared (FTIR) spectra demonstrated that fibers deposited across the gap were also highly aligned at the molecular level with the polymer backbones oriented along the fiber axis and that the extent of molecular orientation increased with the gap width. A possible explanation for this observation is based on the repulsion of similarly charged nanofibers and the simultaneous attraction of these fibers to the oppositely charged gap edges. This provides a plausible model for understanding the deposition kinetics and subsequent molecular orientation as a function of gap size when electrospinning using this method of fiber collection. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 617–623     

A modern approach to the solution and analysis of the Simha-Somcynsky model for the description of pressure-volume-temperature properties of polymer fluids

We revisit the Simha-Somcynsky model of polymer fluids with the purpose of developing novel theoretical and computational approaches to simplify and speed up its solution as well as the fitting of experimental data, and decrease its level of mathematical complexity. We report a novel method that allows us to solve one of the two equations of the model exactly, thus putting the level of mathematical difficulty on a par with the one of other models for polymer fluids. Moreover, we describe a computational algorithm capable of fitting all five parameters of the model in an unbiased way. The results obtained reproduce literature results and fit experimental pressure-volume-temperature and solubility parameter data for three polymers very accurately. Moreover, the new techniques allow for the investigation of the model at very low temperatures. Unexpectedly, the model predicts behaviors that could be interpreted as a glass transition, as routinely observed in dilatometry and differential scanning calorimetry, and a glass phase. We compared the predicted and experimental T g’s for cis poly(1,4-butadiene) and found an excellent quantitative agreement.     

Anisotropic plasticity and chain orientation in polymer glasses

The anisotropic mechanical response of oriented polymer glasses is studied through simulations with a coarse-grained model. Systems are first oriented by uniaxial compression or tension along an axis. Then the mechanical response to subsequent deformation along the same axis or along a perpendicular axis is measured. As in experiments, the flow stress and strain hardening modulus are both larger when deformation increases the degree of molecular orientation produced by prestrain, and smaller when deformation reduces the degree of orientation. All stress curves for parallel prestrains collapse when plotted against either the total integrated strain or the degree of molecular orientation. Stress curves for perpendicular prestrains can also be collapsed. The stress depends on the degree of strain or molecular orientation along the final deformation axis and is independent of the degree of orientation in the perpendicular plane. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1473–1482, 2010     

Infrared dichroism and polymer orientation in attenuated total reflection. Theoretical considerations

The orientation of molecular chains in polymers cannot be easily extracted from ATR spectra measurements. One can infer the orientation parameters by using plausible models that describe the type of the statistical distribution of the molecular chains in the sample. In this work, we are interested in the case of weakly aligned polymers. Therefore, we first adjusted the partial axial orientation model usually applied for strongly oriented polymers to the samples under our investigations and second, related the parameters describing the orientation configuration to the dichroic ratios in four particular molecular chain distributions: randomly, totally, partially, and elliptically oriented. A new method that leads to the determination of these dichroic ratios from ATR spectra is presented. This method is based only on the use of three distinct polarizations of the beam. Thus, all the practical difficulties usually encountered in the other methods are eliminated. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1361–1372, 1997     

Influence of polymer matrix composition and architecture on polymer nanocomposite formation: Coarse-grained molecular dynamics simulation

Coarse-grained molecular dynamics simulations of stacks of two-dimensional platelets immersed in a polymer melt were performed to investigate aspects of the polymer matrix that promote the formation of intercalated or exfoliated nanocomposite structures. Such factors include temperature, copolymer architecture, and blend composition. Increasing the polymer-sheet attractive interaction led to binding of the sheets, where individual beads simultaneously attract two neighboring sheets, thus kinetically blocking intercalation by occupying the perimeter of the affected gallery. Polymers with a small polymer-sheet attraction, but having a strongly attractive chain end (end-functionalized polymers) minimized the bonding of adjacent sheets. These systems exhibited some sheet sliding because a majority of the confined polymer beads only interacted weakly with adjacent sheets; however, the number density of intercalated polymer was low. Mixtures of end-functionalized and nonfunctionalized polymers, however, yielded better intercalation efficiency. For the mixed system, the reduced number of highly attractive beads provided sufficient interaction for intercalation to occur, enabling greater intercalation rates, less sheet-bridging, and incorporation of the nonfunctionalized polymers into the galleries. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3272–3284, 2003     

Atomic level picture of stress relaxation in polymer melts

We have been developing a physical picture on the atomic level of stress relaxation in polymer melts by means of computer simulation of the process in model systems. In this article we treat a melt of freely jointed chains, each with N = 200 bonds and with excluded-volume interactions between all nonbonded atoms, that has been subjected to an initial constant-volume uniaxial extension. We consider both the stress relaxation history σ(t) based on atomic interactions, and the stress history σ_e(t; N_R) based on subdividing the chain into segments with N_R bonds each, with each segment regarded as an entropic spring. It is found that at early times σ(t) > σ_e(t; N_R) for all N_R, and that, for the remainder of the simulation, there is no value of N_R for which σ(t) = σ_e(t; N_R) for an extended period; by the end of the simulation σ(t) has fallen just below the value σ_e(t; 50). The decay of segment orientation, 〈P₂(t; N_R)〉, and of bond orientation 〈P₂(t; 1)〉, is computed during the simulation. It is found that the decay of the atom-based stress σ(t) is closely related to that of 〈P₂(t; 1)〉. This result may be understood through the concept of steric shielding. The change in local structure of the polymer melt during relaxation is also studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 143–154, 1998     

The perturbation of a polymer molecular orbital

The symmetry restrictions imposed by the Born-Kármán boundary conditions on a polymer in order to calculate its electronic band structure are relaxed by the separate introduction of two types of perturbation at a site on the polymer chain. The first simulates a defect or the close approach of a molecule by modifying the segment orbital functions in the environment of the site while the second simulates a change in the distance between one pair of adjacent segments by altering the interaction between them. When applied to a molecular orbital described by a Bloch function and arbitrary energy band these perturbations generate a small number of electronic states whose energies lie above and below those of the band. The sign of the energy shift depends on the symmetry of the crystal orbital perturbed.     

Analysis of thin films and molecular orientation using cluster SIMS

A study of phenylalanine films of different thicknesses from submonolayer to 55 nm on Si wafers has been made using Bi_n⁺ and C₆₀⁺ cluster primary ions in static SIMS. This shows that the effect of film thickness on ion yield is very similar for all primary ions, with an enhanced molecular yield at approximately 1 monolayer attributed to substrate backscattering. The static SIMS ion yields of phenylalanine at different thicknesses are, in principle, the equivalent of a static SIMS depth profile, without the complication of ion beam damage and roughness resulting from sputtering to the relevant thickness. Analyzing thin films of phenylalanine of different thicknesses allows an interpretation of molecular bonding to, and orientation on, the silicon substrate that is confirmed by XPS. The large crater size for cluster ions has interesting effects on the secondary ion intensities of both the overlayer and the substrate for monolayer and submonolayer quantities. This study expands the capability of SIMS for identification of the chemical structure of molecules at surfaces. © Crown copyright 2010.     

Supercritical fluids as reaction media for molecular catalysis

Chemical transformations in supercritical fluids (SCFs) have enormous potential advantages. The possibilities of rate enhancement and adjustable selectivities will motivate the research of molecular catalysis in SCFs. Recent progress in the organometallic catalysis under supercritical conditions is reviewed with emphasis on the benefits of utilization of supercritical carbon dioxide (scCO₂) both as a reaction medium and reactant.     

Prediction of environmental stress cracking in polycarbonate by molecular modeling

Environmental stress cracking (ESC) is a premature failure of a polymer exposed to a fluid, under stress which is much less than its yield stress. Many experimental works were done before in an effort to predict experimentally the ESC potential of a fluid in different polymers. None of the previous works applied molecular modeling techniques to predict this potential so this work is a pioneering work. This study's goal was to apply atomistic molecular modeling techniques to gain a better understanding of the ESC mechanism and to predict the ESC potential of different fluids in polymers. Our model experimental system was amorphous polycarbonate (PC) with water as an ESC fluid. The computational study was expanded to include a high level ESC fluid for PC–toluene and a non ESC fluid–BD, together with the moderate ESC fluid–water. A clear distinction between ESC fluids and non ESC fluids for PC was achieved by means of molecular modeling. The experimental work approved that water is an ESC fluid for PC as predicted in the computational part. Copyright © 2014 John Wiley & Sons, Ltd.     

Predicting the location of weld line in microinjection‐molded polyethylene via molecular orientation distribution

The microstructure and molecular orientation distribution over both the length and the thickness of microinjection‐molded linear low‐density polyethylene with a weld line were characterized as a function of processing parameters using small‐angle X‐ray scattering and wide‐angle X‐ray diffraction techniques. The weld line was introduced via recombination of two separated melt streams with an angle of 180° to each other in injection molding. The lamellar structure was found to be related to the mold temperature strongly but the injection velocity and the melt temperature slightly. Furthermore, the distributions of molecular orientation at different molding conditions and different positions in the cross section of molded samples were derived from Hermans equation. The degree of orientation of polymeric chains and the thickness of oriented layers decrease considerably with an increase of both mold temperature and melt temperature, which could be explained by the stress relaxation of sheared chains and the reduced melt viscosity, respectively. The level of molecular orientation was found to be lowest in the weld line when varying injection velocity, mold temperature, and melt temperature, thus providing an effective means to identify the position of weld line induced by flow obstacles during injection‐molding process. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1705–1715     

Influence of molecular orientation on the photodissociation process of LiH molecules

Regulation of photodissociation dynamics of oriented LiH molecules in different dissociation channels is proposed based on time dependent quantum wave packet theory. The enhancement of molecular orientation on the photodissociation of LiH is obvious with our theoretical scheme. The results show that the molecular orientation in the ground state has a great effect on the angular distributions of wave packets. By using the proper laser pulses and controlling the polarization direction of the laser pulses, the enhancement of the photodissociation could be realized. After the molecular orientation, an optimal dissociation channel is observed with an improved dissociation probability. Compared with the results without molecular orientation, the maximal dissociation probability is increased by 8.1% in the indirect dissociation channel and 30.7% in the direct dissociation channel. The enhancement effect is more obvious in the direct dissociation channel, which provides a possible method to manipulate the dissociation of LiH molecules experimentally. Additionally, the photodissociation process of LiH also relies on the electric intensity and delay time of two pump pulses.     

UV-induced homeotropic orientation of nematic liquid crystals dissolving two species of monomers carrying liquid-crystalline side-chain group and anthracene group

We propose the technique for formation of the polymer orientation film (POF) by polymerisation of the monomers being dissolved in the liquid crystal (LC) material for controlling the orientation of the LC molecules. For obtaining the homeotropic orientation, combination of the two monomers, 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester (AOBBE) and 2,7-dimethacryloyl-oxy-anthracene (DMAAnth), was found to be useful. The monomer DMAAnth initiates the polymerisation under ultraviolet (UV) light exposure, and the AOBBE unit induces the homeotropic orientation. The monomer DMAAnth is useful for maintaining the high voltage holding ratio and low residual direct-current voltage after UV light exposure because the molecules of DMAAnth do not remain in the LC layer.     

Simulation of orientation of uniaxially stretched poly(vinyl phenol) by molecular dynamics

Molecular dynamics were performed for the simulation of the uniaxial deformation of poly(vinyl phenol) under periodic boundary conditions with the Parrinello–Rahman scheme followed by relaxation under NVT conditions (constant number of atoms, volume, and temperature). Changes in the orientation of the main chain, benzene segments, and hydrogen bonds were analyzed with the second‐order Legendre polynomial, 〈P₂(cos θ)〉. Conformational changes were also followed. During deformation, backbone and phenyl rings both initially orient parallel to the draw direction. After relaxation, the chain is oriented parallel to the deformation direction, and side groups orient approximately perpendicular to this direction, in agreement with experimental data reported in the literature. Orientation values are higher than experimental values, as expected from the limited relaxation time range attainable in the simulations. Deformation proceeds by changes from gauche conformers to nontrans, nongauche, and trans conformers, whereas relaxation mainly allows high‐energy nontrans, nongauche conformers to convert into lower energy trans conformers. Values of the α angle for ring and bonded O? H segments agree with those in the literature. Differences observed for free hydroxyl moieties are discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1601–1625, 2002     

Solid-state 13C NMR characterization of molecular orientation of hot drawn nylon 6

Two-dimensional cross polarization (CP), magic angle spinning (MAS) rotor synchronization NMR spectroscopy has been used to determine quantitatively the molecular orientational distribution function on hot-drawn Nylon 6. Both films and fibers are studied that had been thermally deformed at temperature above T_g, from 60 to 175°C at draw ratios in the range of 1-5.5. In the two-dimensional NMR spectrum, the sidebands that intrinsically originate from the chemical shift anisotropy reveal the degree of molecular orientational order. No preferential orientational order is detected for the sample without thermal deformation, and the highest degree of order is observed for samples which have been hot drawn above T_g at ratios ca. 5. Based on the aggregate model the maximum achievable order parameters are determined. © 1994 John Wiley & Sons, Inc.     

Cluster analysis of molecular simulation trajectories for systems where both conformation and orientation of the sampled states are important

Clustering methods have been widely used to group together similar conformational states from molecular simulations of biomolecules in solution. For applications such as the interaction of a protein with a surface, the orientation of the protein relative to the surface is also an important clustering parameter because of its potential effect on adsorbed‐state bioactivity. This study presents cluster analysis methods that are specifically designed for systems where both molecular orientation and conformation are important, and the methods are demonstrated using test cases of adsorbed proteins for validation. Additionally, because cluster analysis can be a very subjective process, an objective procedure for identifying both the optimal number of clusters and the best clustering algorithm to be applied to analyze a given dataset is presented. The method is demonstrated for several agglomerative hierarchical clustering algorithms used in conjunction with three cluster validation techniques. © 2016 Wiley Periodicals, Inc.     

Fourier transform infrared study of segmental orientation in polymer blends

The effect of the macromolecular plasticizer poly(-methyl--n-propyl--propiolactone), PMPPL, on the orientation of poly(vinyl chloride), PVC, has been studied by FTIR spectroscopy. The addition of PMPPL to PVC does not change significantly the degree of orientation of PVC segments. In blends, PMPPL chains are more oriented when the matrix is richer in PVC but the PMPPL orientation function always remains smaller than that of PVC segments.