FROM CRYSTALLINE BLOCK SLIPS TO DOMINANCE OF NETWORK STRETCHING——MECHANISMS OF TENSILE DEFORMATION IN SEMI-CRYSTALLINE POLYMERS

The mechanism of tensile deformation in semi-crystalline polymers was studied based on true stress-strain curvesobtained with the aid of a video-controlled tensile set-up. The deformation is affected by both the crystalline and theamorphous phases. However, the relative weights of the two portions change with the deformation stage. At lowdeformations the coupling and coarse slips of the crystalline blocks dominate the mechanical properties, which allows thesystem to maintain a homogeneous strain distribution in the sample. As the stretching increases, at a critical strain the forcegenerated from entangled fluid portions reaches a critical value to destroy the crystallites. The dominant deformationmechanism then changes into a disaggregation - recrystallization process.

Durable semi-crystalline interphase engineering to stabilize high voltage Ni-rich cathode in dilute ether electrolyte

Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability.However,their oxidation stability has been mostly relying on the high concentration approach,and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte.In this work,we construct a semi-crystalline interfacial layer on the surface of Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2)cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules.Different from traditional brittle crystalline interphases,the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer.Due to this design,the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability(84%capacity retention after 300 cycles).This article provides a solution to address the oxidation instability issue of ether-based electrolytes.

Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.

Dynamic Fracture of a Semi-Crystalline Bio-Based Polymer Pipe: Effect of Temperature

The influence of temperature on the resistance to rapid crack propagation of a semi-crystalline bio-based polymer was studied. The experimental results described in this study allow to initiate a first discussion on the role of viscosity and its link with the fracture behaviour and a heterogeneous microstructure such as the semi-crysalline polymer. Dynamic fracture tests on pipes were carried out. It would appear that a temperature decrease of approximately 40℃ relative to ambient has no significant influence on the average crack propagation velocity (≈0.6cR), fracture energy and surface roughness. On the contrary, crack propagation paths seem to vary with temperature. The difference in fracture behaviour between the amorphous and crystalline phase varies significantly as a function of temperature. The difference between the initiation resistance and the rapid propagation also varies. This difference seems to be significantly reduced by lowering the temperature. The mechanisms of cavitation damage and plastic flow are increasingly limited by the decrease in temperature (and therefore in macromolecular mobility). Crack propagation in the pipe is more extensive and therefore more critical. This is emphasised in particular by the probability of the material to be macro-branched as the temperature decreases.

Fabrication and Characterization of Semi-Crystalline and Amorphous Dielectric Polymer Films for Energy Storage

Dielectric polymer films are energy storage materials that are used in pulse power operations, power electronics and sustainable energy applications. This paper reviews energy storage devices with focus on dielectric film capacitors. Two prominent examples of polymer dielectrics Polyetherimide (PEI) and Poly (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) (THV) have been discussed. Polyetherimide (PEI) is an amorphous polymer recognized for its high-temperature capability, low dielectric loss and high dielectric strength. THV is a semi-crystalline polymer with high dielectric constant, high-temperature capability and charge-discharge efficiency. The primary focus of this paper is to introduce the reader to the fabrication procedures and characterization techniques used in research labs for processing of dielectric polymers. The fabrication and characterization process of both polymers has been discussed in detail to shed the light on experimental process in this area of research.

Fundamental Mechanism of Slow Crack Growth in Semi-Crystalline Polymers under a Constant Load

The purpose is to quantitatively present in a single equation all the factors that affect the failure time by Slow Crack Growth (SCG) in a semi-crystalline polymer (SCP) under a constant load. The fundamental mechanism of fracture is displayed at the molecular level. The rate of fracturing is determined by the Eyring theory of thermal activation. The resulting equation includes the important molecular properties of therein, the length and density of the tie molecules. The underlying microfracture process is the unfolding of the chains in the crystal under the action of the tie molecules.

Self-recoverable semi-crystalline hydrogels with thermomechanics and shape memory performance

Stimuli-responsive hydrogels have become one of the most popular artificial soft materials due to their excellent adaption to complex environments. Thermoresponsive hydrogels triggered by temperature change can be efficiently utilized in many applications. However, these thermoresponsive hydrogels mostly cannot recover their mechanical states under large strain during the process. Herein, we utilize the heterogeneous comb-type polymer network with semicrystalline hydrophobic side chains to design self-recovery semi-crystalline hydrogels. Based on hydrophilic/hydrophobic cooperative complementary interaction and heterogeneous polymer network, hydrogels can be endowed with excellent thermosensitive properties and mechanical performance. The hydrogels exhibit high compressive strength(7.57 MPa) and compressive modulus(1.76 MPa) due to the semi-crystalline domains formed by association of the hydrophobic poly(ε-caprolactone) PCL. The melting-crystalline transition of PCL and elastic polymer network provide the hydrogels excellent thermomechanical performance and self-recovery property. Furthermore, the hydrogels exhibit shape memory behavior, which can be realized by simple process and smart surface patterning. With these excellent properties, our hydrogels can be applied in sensors, flexible devices and scaffolds for tissue engineering.

Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

Three types of semi-cry stalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to(300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2 FBT devices showed a power conversion efficiency of 3.16%,4.40%and 5.65%,respectively,by blending with PC_(71)BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC_(71)BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density(J_(SC)) and open-circuit voltage(V_(Oc)).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71 BM for further optimizing polymer solar cells.

New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature

The stress relaxation of semi-crystalline nylon 1010 cannot be fitted by the Kohlrausch-Williams-Watts formula when the experiments were performed at pre-yielding regime below the glass transition temperature.We study this problem and identify the two-step mechanism of stress relaxation.At short time scale,relaxation is fast,dominated by stress biased thermal fluctuation with a fixed short-range length scale(activation volume).At long time scale,relaxation is slow due to the emergence of a cooperative long-range length scale determined by the stress fluctuation.The cooperative length scale is proportional to the reciprocal of stress and the amplitude of stress fluctuation is the product of stress and activation volume.Based on this two-step mechanism,we propose a new kinetics equation to capture the stress relaxation effectively,where the short time relaxation is described by an Eyring-like local activation and the long-time relaxation is captured by a cooperative excitation process resorting to an extension from the random first order transition theory.Our equation fits the experimental data well and can serve as a model to guide the related experiments of relaxation processes in crystalline solids.

STRUCTURE EVOLUTION OF POLYMER CHAINS FOR NECKING FORMATION IN HIGH-SPEED FIBER SPINNING PROCESS

Finite element method is used to simulate the high-speed melt spinning process, based on the equation system proposed by Doufas et al. Calculation predicts a neck-like deformation, as well as the related profiles of velocity, diameter, temperature, chain orientation, and crystallinity in the fiber spinning process. Considering combined effects on the process such as flow-induced crystallization, viscoelasticity, filament cooling, air drag, inertia, surface tension and gravity, the simulated material flow behaviors are consistent with those observed for semi-crystalline polymers under various spinning conditions, The structure change of polymer coils in the necking region described by the evolution of conformation tensor is also investigated. Based on the relaxation mechanism of macromolecules in flow field different types of morphology change of polymer chains before and in the neck are proposed, giving a complete prospect of structure evolution and crystallization of semi-crystalline polymer in the high speed fiber spinning process.

Controlling and Evaluating the Structure and Morphology of Polymers on Multiple Scales

Crystalline polymers spontaneously form hierarchical structures although the precise manner in which these scales of structure are interconnected especially terms of the formation and evolution of the complete structure remains unclear. We have set out to control these scales of structure by introducing additional components which self-assemble in to nano-scale units which then direct the crystallisation of the polymer matrix. In other words, we first assemble a low concentration top-level structure which is designed to template or direct the sub-sequent crystallisation of the matrix polymer. This top level structure takes on the role of controlling the structure. We have set out to both establish the design principles of such structures and to develop experimental procedures which allow us to follow the formation of such complex hierarchical polymer structures. In particular we focus of the relationships between these different levels of structure and time sequence of events required for the structure to evolve in the targeted manner. In this programme, we have exploited time-resolving small-angle X-ray scattering and electron microscopy together with neutron scattering to probe and quantify the different scales of structure and their evolution. We highlight new neutron scattering instrumentation which we believe have great potential in the growing field of hierarchical structures in polymers. The addition of small quantities of nanoparticles to conventional and sustainable thermoplastics leads to property enhancements with considerable potential in a number of areas Most engineered nano-particles are highly stable and these exist as nano-particles prior to compounding with the polymer resin, they remain as nano- particles during the active use as well as in the subsequent waste and recycling streams. In this work we also explore the potential for constructing nano-particles within the polymer matrix during processing from organic compounds selected to provide nanoparticles which can effectively control the subsequent crystallization process. Typically these nano-particles are rod-like in shape.

Experimental Analysis and Damage Modeling of High-Density Polyethylene under Fatigue Loading

In this study,an experimental analysis for determining the fatigue strength of HDPE-100 under cyclic loading is presented.The curve of cumulative fatigue damage versus number of cycles（D-N） was deduced from stiffness degradation.Based on the three stage damage trend,the remaining fatigue life is numerically predicted by considering a double term power damage accumulation model.This model is found to be accurate,both in modeling the rapid damage growth in the early life and near the end of the fatigue life.Numerical results illustrate that the proposed model is capable of accurately fitting several different sets of experimental data.