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The structural evolution (not only intra-fibrillar but also inter-fibrillar structures) during extension of poly (vinyl alcohol) (PVA) in water at different temperatures are investigated by in-situ small- and wide-angle X-ray scattering (SAXS and WAXS). The stress-strain curves can be defined into four zones with the onset and the end of stress plateau, and the strain hardening point as the zone boundaries. WAXS results show that stretch induces melting of PVA crystal from zones I to III, while SAXS measurements reveal stretch-induced transformation from initial lamella to nanofibrils starts at the onset of zone II, which proceeds via a melting-reconstruction process instead of direct transformation. In zone III, the nanofibrils increase in content and pack periodically with an average inter-fibrillar spacing of about 14–18 nm. Increasing temperature leads to larger inter-fibrillar spacing and more perfect packing of nanofibrils, which may benefit the production of polarizer with homogeneously structural and optical properties. [ABSTRACT FROM AUTHOR]

Recent efforts attempting to in-situ track the polymer film formation during film blowing are summarized. The specially designed film blowing apparatus is firstly introduced, where the air ring is aligned along with the die, and it's capable of installation in the synchrotron beamline (SR-beamline). Later on, detailed structural evolution of different polymeric systems during film blowing, including polyethylene (PE) and poly(butylene adipate-co- butylene terephthalate) (PBAT), are obtained with the assistance of simultaneous acquired Small- and Wide Angle X-ray Scattering (SAXS/WAXS). The transient structure evolution information from oriented polymer melt to final crystalline tubular film clarifies the contribution of the crystallite-based network to final macroscopic performances. Also, the experimental results have shown the influence of intrinsic molecular characteristics and external processing parameters on the formation of stable tubular bubble. Additionally, the post-modification of the blown film, including stretching and surface treatment is also discussed. Current experimental efforts are expected to provide more detailed parameters for mathematical modeling of film blowing, which could help us modify or develop new numerical models. The micro-structural evolution of polymer during film blowing as in-situ characterized by synchrotron radiation X-ray scattering. Image 1 • Feature article focuses on in-situ tracking of structural evolution during Film Blowing. • A new film blowing machine which can be installed in the SR-beamline is designed. • Formation of crystal-based network is only influenced by molecular parameters. • Flow- and temperature-induced crystallization coexist during film blowing. [ABSTRACT FROM AUTHOR]

The copolymerization of ethylene and different α-olefins could result in polyethylene (PE) with different structural topologies, and lead to polyethylene products with different macroscopic performances. Herein, three different polyethylene samples, namely low-density polyethylene (l -PE), metallocene catalyzed ethylene-hexene copolymer (h -PE) and ethylene-octene copolymer (o -PE), were selected as representatives to construct the structure-process-property relationship during film blowing. The detailed crystal-based network evolution during film blowing was first characterized by in-situ synchrotron radiation X-ray scattering. The crystallization process of l -PE film is determined by the coupling effects of temperature and flow, while those of h -PE and o -PE films are dominated by the temperature. Furthermore, the hierarchical crystal structure from the molecular scale to micrometers of final films and segmental dynamics were systematically characterized by multiple ex-situ characterization techniques, i.e. Solid-State NMR, FTIR, SEM. l -PE film shows the crystalline morphology of the row-nucleated structure, whereas h -PE and o -PE show spherulite-like superstructure with better mechanical properties. The current study tentatively constructs the relation of primary chemical structure, microstructural evolution and macroscopic performances of different polyethylene copolymers during film blowing. • Three ethylene/α-olefin copolymers were selected to construct the structure-process-property relationship on the film blowing. • The structural evolution during film blowing was captured by a combination of in-situ SR-SAXS/WAXS and a custom-built film blowing device. • The multi-scale microstructure and dynamics of final films were characterized by ex-situ SAXS/WAXS, FTIR, SEM, and SS NMR. • The mechanical and optical properties of films are well correlated with their structural evolution and microstructure. [ABSTRACT FROM AUTHOR]

Aiming to reveal the effects of mechanical energy and thermal effect on micropore nucleation and growth in oriented high density polyethylene (HDPE) film, stress relaxation after cold stretching was imposed at low and elevated temperature with strain holding constant, respectively, and corresponding structure evolution was tracked by in situ and ex situ small angle X-ray scattering (SAXS). It was found that stress-induced density fluctuation during cold stretching could be completely recovered as soon as the stress was unloaded, which was called as micropore embryo. Mechanical energy release at low temperature can promote micropore nucleation after an induction period. However, the growth of micropore nuclei is inhomogeneous, developing as non-uniform micropores with poor interconnectivity during hot stretching. While during temperature elevation, micropore embryos can be converted into evenly distributed micropores together with formation of fibrils, which can supply growth sites for through pores during hot stretching. Consequently, microporous membranes with narrow micropore size distribution and good permeability could be obtained after the subsequent hot stretching. [ABSTRACT FROM AUTHOR]

The evolution of poly (vinyl alcohol) PVA structure and dichromatic substance induced by uniaxial stretching PVA in the mixed solution with iodine and boric acid (BA) is systematically studied by the combination of in-situ synchrotron radiation small- and wide-angle X-ray scattering (SAXS and WAXD). The experiment is carried out under an orthogonal experimental design for the iodine concentrations of 0.01, 0.2, 1 M, and the BA concentrations of 0.3, 1, and 3 wt%, respectively. We divide the stretch process into three regions, whose boundary is the yield point and strain harden point. The PVA-I 3 - co-crystal generating at high and moderate iodine concentrations is less stable as compared with the PVA crystal, which leads to the earlier decrease of crystallinity at the end of the first region. In the second region, the broken crystal, namely the regular amorphous, is the precursor of the PVA-polyiodide complex. Further increasing the strain, the PVA-I 3 - co-crystals are generated from the one dimension polyiodide surrounded by the PVA chains through a melt-reconstruction process. The adequate BA can make it easy to form the polyiodide at the initial state. Still, the increasing rate of polyiodide is suppressed by further added BA due to the limitation of chain movement by the crosslinking agent. In the final region, the emergence of nanofibril can account for the strain hardening of the film. The evolution of polyiodide and PVA-I 3 - co-crystal revealed by this work gives a better understanding of the polarizer production process, which may guide the resolution of blue leakage of polarizer via an enhancement of the I 3 − in the crystal form during stretching. Image 1 • The structural evolution of dichromatic substance with poly (vinyl alcohol) at different concentrations of boric acid during stretch is investigated by in-situ WAXD and SAXS. • The metastable PVA-I 3 - cocrystal will be easily broken during stretching, which leads to the distinct yield point. • Polyiodide first emerges in the amorphous originated from the broken crystal and then in the highly oriented amorphous during stretching. • The one-dimension polyiodide along with the PVA chain is the precursor of PVA-I 3 - cocrystal. • Dichromatic substance emerges earlier with the increasing of boric acid concentration; however, their final content is less due to the limitation of chain mobility by the crosslinking agent. [ABSTRACT FROM AUTHOR]

The effects of stretching speed on the structural evolutions and mechanical behaviors of hard-elastic polyethylene films are studied with in-situ and ex-situ small-angle X-ray scattering (SAXS), scanning electronic microscope (SEM) and tensile tests in a wide stretching speed range (0.04–4 mm/s). Based on the evolutions of structural parameters extracted from SAXS results and the surface morphologies from SEM experiments, the stretching speed space can be divided into two regions with the boundary of 0.8 mm/s. Stress induced microphase separation of amorphous phase triggers the yielding behavior, which distributes more homogeneously with the increase of stretching speed. In region I, microphase separation tends to develop into cavities at smaller strain due to the thorough relaxation process of molecular chains in amorphous phases, which results in the inhomogeneous deformation during further stretching. In region II, the relaxation of molecular chains is not enough to response to the variation of external tensile field, thus inducing the uniform distribution of the occurrence of microphase separation. Image 1 • Effect of stretching speed on structures and mechanical property was studied. • Stretching speed is of importance in how microphase separation occurs and develops. • The deformation is inhomogeneous at low stretching speed region I. • Plastic deformation occurs earlier at low stretching speed. [ABSTRACT FROM AUTHOR]

Mechanical and structural evolution of poly (vinyl alcohol) (PVA) induced by uniaxial deformation at different concentrations of boric acid is systematically studied with in-situ synchrotron radiation small- and wide-angle X-ray scattering (SAXS and WAXS). The PVA films were stretched uniaxially in the aqueous solution at room temperature with concentrations of boric acid at 0.3 wt%, 1 wt% and 3 wt%, respectively. The stretching process can be divided into three stages through WAXS and SAXS results, whose boundary is the end of the crystallinity platform and the onset of the formation of nanofibrils. In the first stage, the films show elastic stretch with the crystallinity keeping constant and the d -spacing of (101) plane (d 101) decreasing. The unstable crystal breaks up and transfers into amorphous during the second stage so that the force is gradually removed from the unit cell. The connection between the crystal network breaks up in the third stage when the content of boric acid is not sufficient enough. Moreover, increasing the concentration of boric acid leads to the earlier emergence of nanofibrils due to the lower energy barrier induced by entropy decrease, which also results in a reduction of nanofibrils content by limiting the mobility of molecular chain. The results have been applied to establish relationships between the microstructure and the physical characteristics of PVA to help us tune the processing parameters during the practical production. •The structural evolution of poly (vinyl alcohol) at different concentrations of boric acid during stretch were investigated with in-suit WAXS and SAXS. •The addition of adequate boric acid can maintain the connection between the crystal. •Increasing the concentration of boric acid leads to the earlier emergence of nanofibrils. •The boric acid works as the crosslinking agent which limits the mobility of the molecular chain to form more nanofibrils. [ABSTRACT FROM AUTHOR]