An approach to the formation and growth of new phases with application to polymer crystallization: effect of finite size,metastability, and Ostwald's rule of stages

This article aims to link the mainstream subject of chain-folded polymer crystallization with the rather speciality field of extended-chain crystallization, the latter typified by the crystallization of polyethylene (PE) under pressure. Issues of wider generality are also raised for crystal growth, and beyond for phase transformations. The underlying new experimental material comprises the prominent role of metastable phases, specifically the mobile hexagonal phase in polyethylene which can arise in preference to the orthorhombic phase in the phase regime where the latter is the stable regime, and the recognition of thickening growth as a primary growth process, as opposed to the traditionally considered secondary process of thickening. The scheme relies on considerations of crystal size as a thermodynamic variable, namely on melting-point depression, which is, in general, different for different polymorphs. It is shown that under specifiable conditions phase stabilities can invert with size; that is a phase which is metastable for infinite size can become the stable phase when the crystal is sufficiently small. As applied to crystal growth, it follows that a crystal can appear and grow in a phase that is different from that in its state of ultimate stability, maintaining this in a metastable form when it may or may not transform into the ultimate stable state in the course of growth according to circumstances. For polymers this intermediate initial state is one with high-chain mobility capable of thickening growth which in turn ceases (or slows down) upon transformation, when and if such occurs, thus locking in a finite lamellar thickness. The complete situation can be represented by a P, T, 1/l (l crystal thickness) phase-stability diagram which, coupled with kinetic considerations, embodies all recognized modes of crystallization including chain-folded and extended-chain type ones. The task that remains is to assess which applies under given conditions of P and T. A numerical assessment of the most widely explored case of crystallization of PE under atmospheric pressure indicates that there is a strong likelihood (critically dependent on the choice of input parameters) that crystallization may proceed via a metastable, mobile, hexagonal phase, which is transiently stable at the smallest size where the crystal first appears, with potentially profound consequences for the current picture of such crystallization. Crystallization of PE from solution, however, would, by such computations, proceed directly into the final stage of stability, upholding the validity of the existing treatments of chain-folded crystallization. The above treatment, in its wider applicability, provides a previously unsuspected thermodynamic foundation of Ostwald's rule of stages by stating that phase transformation will always start with the phase (polymorph) which is stable down to the smallest size, irrespective of whether this is stable or metastable when fully grown. In the case where the phase transformation is nucleation controlled, a ready connection between the kinetic and thermodynamic considerations presents itself, including previously invoked kinetic explanations of the stage rule. To justify the statement that the crystal size can control the transformation between two polymorphs, a recent result on 1 -4-poly-trans-butadiene is invoked. Furthermore, phase-stability conditions for wedge-shaped geometries are considered, as raised by current experimental material on PE. It is found that inversion of phase stabilities (as compared to the conditions pertaining for parallel-sided systems) can arise, with consequences for our scheme of polymer crystallization and with wider implications for phase transformations in tapering spaces in general. In addition, in two of the Appendices two themes of overall generality (arising from present considerations for polymers) are developed analytically; namely, the competition of nucleation-controlled phase growth of polymorphs as a function of input parameters, and the effect of phase size on the triple point in phase diagrams. The latter case leads, inter alia to the recognition of previously unsuspected singularities, with consequences which are yet to be assessed.     

Fracture mechanics‐based progressive damage modelling of adhesively bonded fibre‐reinforced polymer joints

A quasi‐static progressive damage model for prediction of the fracture behaviour and strength of adhesively bonded fibre‐reinforced polymer joints is introduced in this paper. The model is based on the development of a mixed‐mode failure criterion as a function of a master R‐curve derived from the experimental results obtained from standard fracture mechanics joints. Consequently, the developed failure criterion is crack‐length and mode‐mixity dependent, and it takes into account the contribution of the fibre‐bridging effect. Energy release rate values for adhesively bonded double‐lap joints are obtained by using the virtual crack closure technique method in a finite element model, and the numerically obtained strain energy release rate is compared to the critical strain energy release rate given by the mixed‐mode failure criterion. The entire procedure is implemented in a numerical algorithm, which was successfully used for predicting the strength and R‐curve response of adhesively bonded double‐lap structural joints made of pultruded glass fibre‐reinforced polymers and epoxy adhesives.     

Verformungsverhalten nanostrukturierter HPPMS‐Hartstoffschichten

Elastic‐Plastic Deformation Behavior of Nanostructured HPPMS Hard Coatings Nitride hard coatings deposited via HPPMS (High Power Pulsed Magnetron Sputtering) or HiPIMS (High Power Impulse Magnetron Sputtering) are widely used in tribological applications due to their promising wear and corrosion resistance. During the application, the coated tools or components may be exposed to significant mechanical loads. Therefore, investigations on deformation behavior of the coatings under mechanical loading are of great importance. The objective of the present study was a comprehensive investigation on deformation behavior of nitride hard coatings from the coating system M‐Al‐O‐N (M = Cr, V) using nanoindentation und nanoscratch tests. In this regard, both nanoscale multilayer (nanolaminate) and monolayer coatings were investigated. All the coatings were deposited using HPPMS technology. Contrary to the expectations regarding a brittle behavior of ceramic‐like coatings, the results depict a considerable plastic deformation of the investigated hard coatings. Furthermore, in addition to a high strength, the applied coatings show a high crack resistance under mechanical loading.     

Time dependent voiding mechanisms in polyamide 6 submitted to high stress triaxiality: experimental characterisation and finite element modelling

Double notched round bars made of semi-crystalline polymer polyamide 6 (PA6) were submitted to monotonic tensile and creep tests. The two notches had a root radius of 0.45 mm, which imposes a multiaxial stress state and a state of high triaxiality in the net (minimal) section of the specimens. Tests were carried out until the failure occurred from one of the notches. The other one, unbroken but deformed under steady strain rate or steady load, was inspected using the Synchrotron Radiation Computed Tomography (SRCT) technique. These 3D through thickness inspections allowed the study of microstructural evolution at the peak stress for the monotonic tensile test and at the beginning of the tertiary creep for the creep tests. Cavitation features were assessed with a micrometre resolution within the notched region. Spatial distributions of void volume fraction (\(\mathit{Vf}\)) and void morphology were studied. Voiding mechanisms were similar under steady strain rates and steady loads. The maximum values of \(\mathit{Vf}\) were located between the axis of revolution of the specimens and the notch surface and voids were considered as flat cylinders with a circular basis perpendicular to the loading direction. A model, based on porous plasticity, was used to simulate the mechanical response of this PA6 material under high stress triaxiality. Both macroscopic behaviour (loading curves) and voiding micro-mechanisms (radial distributions of void volume fraction) were accurately predicted using finite element simulations.     

Metamaterial-based graphene thermal emitter

A thermal emitter composed of a frequency-selective surface metamaterial layer and a hexagonal boron nitride-encapsulated graphene filament is demonstrated. The broadband thermal emission of the metamaterial (consisting of ring resonators) was tailored into two discrete bands, and the measured reflection and emission spectra agreed well with the simulation results. The high modulation frequencies that can be obtained in these devices, coupled with their operation in air, confirm their feasibility for use in applications such as gas sensing.

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Use of fuzzy-logic-inspired features to improve bacterialrecognition through classifier fusion

Escherichia coli O157:H7 has been found to cause serious health problems. Traditional methods to identify the organism are quite slow, pulsed-held gel electrophoresis (PFGE) images contain "banding pattern" information which can be used to recognize the bacteria. A fuzzy logic rule-based system is used as a guide to find a good feature set for the recognition of E. coli O157:H7. While the fuzzy rule-based system achieved good recognition, the human inspired features used in the rules were incorporated into a multiple neural network fusion approach which gave excellent separation of the target bacteria. The fuzzy integral was utilized in the fusion of neural networks trained with different feature sets to reach an almost perfect classification rate of E. coli O157:H7 PFGE patterns made available for the experiments.     

Mode-locked laser cavities with a single prism for dispersion compensation

We demonstrate the use of a single prism for adjustable dispersion compensation in a mode-locked laser cavity, instead of the standard approach with a prism pair. A simple model based on the prism-pair configuration is presented to determine the group-velocity dispersion by use of ray optics to trace the wavelength-dependent optical axes through the cavity. We experimentally demonstrated this concept with a passively mode-locked diode-pumped Nd:glass laser producing 200-fs pulses with a 200-mW average output power, using only one intracavity prism. The advantages of such a cavity design are simple alignment, reduced loss, and lossless wavelength tunability This technique can be generalized to other angularly dispersive elements such as prismatic output couplers.     

Capillary HPLC-NMR Coupling: High-Resolution (1)H NMR Spectroscopy in the Nanoliter Scale

Coupling HPLC and NMR is one of the most powerful techniques for simultaneous separation and structural elucidation of unknown compounds in mixtures. To date, however, minimizing the detection volume, as is required when coupling NMR with miniaturized separation techniques, has been accompanied by a dramatic loss in resolution of the NMR spectra. Here, we report on the coupling of gradient capillary HPLC with on-column, high-resolution NMR detection. On-line stopped-flow and static (1)H NMR spectra were acquired with capillary columns of 75-315 μm i.d. With detection over a length of 1.2 cm, cell volumes cover a range of 50-900 nL. An on-line-detected NMR separation of dansylated amino acids was carried out in a 315 μm i.d. fused silica capillary packed to a length of 12 cm with C(18) stationary phase. The low solvent consumption makes the use of fully deuterated solvents economically feasible. NMR spectra with resolution on the order of 3 Hz were obtained using a 50 nL detection cell to measure 1.1 nmol of dansylated γ-aminobutyric acid under static conditions in a 75 μm i.d. capillary.     

Thin-film designs by simulated annealing

With the increasing power of computers, new methods in synthesis of optical multilayer systems have appeared. Among these, the simulated-annealing algorithm has proved its efficiency in several fields of physics. We propose to show its performances in the field of optical multilayer systems through different filter designs.