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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]

Structural evolutions of cellulose triacetate (CTA) film during uniaxial stretching process at different temperatures were studied by in-situ synchrotron radiation wide-angle X-ray scattering (WAXS) combined with dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results show that four temperature regions can be divided for the CTA film stretching, in which different structural evolutions and deformation mechanisms will be observed. The structural evolutions of CTA film at temperatures between 60 and 125 °C (region I) are seriously influenced by the absorbed moisture, resulting in a large variation of the crystallinity ( χ c ). At temperatures around T g (195 °C), stretch-induced orientations for crystal can be achieved more easily although χ c and crystal size have no large change compared with the flexible-chain semi-crystalline polymers like polyethylene. Interestingly, the CTA film presents various deformation mechanisms including the elongation of amorphous and slipping, formation, destruction and recrystallization of crystals during stretching at different temperatures, which are often observed for the flexible-chain semi-crystalline polymers. These results can provide valuable guidance for the hot-stretching processing and application of CTA retardation film. Image 1 • The structural evolutions of CTA film during stretching were studied by in-situ WAXS. • Four temperature regions with different structural evolutions were observed. • The structural evolution is affected by absorbed moisture at low temperature. • Stretch-induced orientation can be achieved more easily at temperatures around T g. [ABSTRACT FROM AUTHOR]

Abstract The structural evolution of poly (ethylene terephthalate) (PET) with distinct water absorption during uniaxial deformation slightly above glass transition temperature (T g) were investigated by in-situ synchrotron radiation wide angle X-ray scattering (WAXS). Results show that the locally ordered structures are not conducive to stretch-induced crystallization (SIC) although the corresponding entropy is more close to crystals compared to random chains, which is due to the limited chain mobility therein. The "frozen orders" should be destroyed to achieve the critical chain mobility required by SIC even with the presence of water as plasticizer. Unexpectedly, absorption of water does not enhance but suppresses SIC though it does promote the chain mobility, originating from lower stress level with higher water contents. Stress and chain mobility directly correlate with chain stretch and orientation in positive and negative manners, respectively, demonstrating that chain stretch and orientation also play important role in SIC around T g. Graphical abstract Image 10457 Highlights • The structural evolutions of PET samples with different contents of water are investigated with in-situ WAXS. • It is necessary to accumulate sufficient chain mobility for SIC by destroying the frozen orders. • The SIC in PET can be inhibited by water above glass transition temperature. [ABSTRACT FROM AUTHOR]

Lamellar stacks, arranged alternatively with hard crystal and soft amorphous nano-layers, are the basic building units to determine the intrinsic mechanical properties of semi-crystalline polymeric materials. The mechanical instability of hard-elastic isotactic polypropylene (iPP) films with highly parallel lamellar stacks is studied with in-situ synchrotron radiation small- and wide-angle X-ray scattering (SAXS/WAXS) techniques during cyclic tensile deformation. Unexpectedly, the micro-strain, deduced from the relative variation of lamellar periodicity, shows an accelerated increase at the onset of instability and reaches values larger than the corresponding macro-strain after yield, during which no irreversible plastic destruction of crystal is observed. Combining the unpredictable increase of long period and other structural information obtained with in-situ SAXS/WAXS measurements, we propose that stress-induced microphase separation of interlamellar amorphous phase is responsible for the yield behavior and the hyperelasticity of hard-elastic iPP films, which stems from the heterogeneous distribution of tie chain/trapped entanglement in interlamellar amorphous nano-layers. This reversible stress-induced non-equilibrium phase transition of interlamellar amorphous phase is different from current plastic deformation models with crystal destruction in semi-crystalline polymers but in line with the nearly 100% elastic recovery ratio of hard-elastic films. [ABSTRACT FROM AUTHOR]

Combining a homemade uniaxial stretching device and the simultaneous in-situ synchrotron radiation WAXS measurement, the structural evolution during transverse direction (TD) stretching of machine direction (MD) pre-stretched Poly(ethylene terephthalate) (PET) film has been investigated. Current work reveals that increasing the MD pre-stretch before the occurrence of stretch induced crystallization (SIC) can enhance the crystallization and orientation in TD stretching. The concept of parallel chains structures (PCS) cross-linked network is proposed to interpret the rubber-like mechanical behavior. An appropriate stretch ratio window in stretching above the glass transition temperature (T g) is existed, where the PCS cross-linked network before crystallization can be induced by stretching above T g. With the help of the PCS cross-linked network, the chain orientation is retained more effectively under stretching, promoting the formation of subsequent crystallization and crystal cross-linking network. The strain hardening in different pre-stretched samples occurs accompanied by the same crystallinity and various chains orientation. This demonstrates that the strain hardening is determined by the crystal cross-linked network rather than the orientation. Current work supplies a guidance for getting the improved film products of PET with enhanced comprehensive mechanical properties, process stability and higher chain orientation. • The structural evolution in subsequent stretching of pre-stretched Poly(ethylene terephthalate) (PET) film is investigated by the in-situ synchrotron radiation WAXS measurement. • The origin of the novel rubber-like mechanical behavior under the complicated stretching field is better understood by the combination of the in-situ chains orientation, crystallization behavior and mechanical behavior. • The concept of parallel chains structures (PCS) cross-linked network is proposed to interpret the rubber-like mechanical behavior. • The onset of strain hardening corresponds to the formation of the crystal cross-linked network. [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]

Hard-elastic polyethylene (HEPE) cast films are the key intermediate product for producing PE microporous membranes (dry process) used as separators in Lithium battery. The effects of temperature on the deformation mechanisms of HEPE cast films are systematically studied with in-situ synchrotron radiation small- and wide-angle X-ray scattering (SAXS/WAXS) techniques during stretching in a wide temperature range from 25 to 135 °C. The structural evolutions and mechanical behaviors show three distinct features, which contribute to the rough divisions of the temperature space into three regions (I/II/III) with α-I relaxation temperature (T αI) and the onset melting temperature (T onset) as the boundaries. On the basis of the evolutions of the structural parameters like long period (L m), micro-strain (ε m), orientation parameter (f 200), crystallinity (X c), and etc., lamellar separation is the main deformation mode in the linear elastic strain zone. And microphase separation of interlamellar amorphous, lamellar crystal slipping and melt-recrystallization are proposed to determinate the later non-linear mechanical behaviors in the three temperature regions, respectively. The full view of deformation mechanisms in the 2D temperature-strain space aids to deepen the understanding of the nonequilibrium structural evolutions in hard-elastic polyethylene films and guide the manufacture of high-performance microporous membranes with dry process. Image 1 • The structural roadmap of hard-elastic polyethylene films in temperature-strain space was constructed. • The deformation modes depend on the coupled effects of external field and chain mobility. • The microphase separation of interlamellar amorphous dominates in region I. • Plastic deformation like crystal slipping and melt-recrystallization is important in regions II and III. [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]