The effects of temperature on the nonlinear mechanical behaviors of hard-elastic isotactic polypropylene films are systematically studied with in-situ ultrafast synchrotron radiation small-and wide-angle X-ray scattering techniques (SAXS/ WAXS) during uniaxial tensile deformation at temperatures from 30 to 160 °C. Based on the mechanical behaviors and structural evolutions in strain−temperature two-dimensional space, three temperature regions (I, II, and III) are clearly defined with the α relaxation temperature (T α ≈ 80 °C) and the onset of melting temperature (T onset ≈ 135 °C) as boundaries, where different mechanisms dominate the nonlinear deformations after yield. In region I, microstrain in lamellar stacks ε m obtains an accelerated increase after yield and reaches a value significantly larger than corresponding macrostrain ε, during which neither slipping, melting, nor cavitation occurs. We propose stress-induced microphase separation of interlamellar amorphous to be responsible to the hyperelastic behavior in region I. Above T α in region II, due to reduced cohesive strength and enhanced chain mobility, the irreversible reduction of crystallinity and the formation of slender cavities suggest that crystal slipping overwhelms microphase separation and plays the major role in nonlinear deformation, during which chains in lamellar crystals are pulled out and recrystallize into nanofibrillar bridges. In region III above T onset , melting−recrystallization dictates the nonlinear deformation. A schematic roadmap for structural evolution is constructed in strain−temperature space, which may guide the processing of microporous membranes for lithium battery separators as well as other high performance polymer fibers and films.

Stretch-induced crystallization (SIC) and phase transitions of poly­(dimethylsiloxane) (PDMS) have been studied with the in situ synchrotron radiation wide-angle X-ray scattering technique (WAXS) during tensile deformation at temperatures ranging from −45 to −65 °C. The phase transitions during tensile deformation go through different processes at different temperature regions, where four phases are involved in namely oriented amorphous (OA), mesophase, α form, and β form crystals. We found that SIC of the α form can proceed via two different multistage ordering processes with either the mesophase or β form as the structural intermediate. Further cyclic tensile experiments demonstrate that the transition from the β to α form is a reversible process controlled by stress, which is attributed to the different helical pitches in β and α forms. A nonequilibrium phase diagram of SIC and phase transitions are constructed in strain–temperature space, which is of great significance for practical applications of PDMS at low temperature.

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The room-temperature stretching process of polypropylene annealed film with rownucleated crystalline structure was studied by in-situ small-angle X-ray scattering (SAXS) setup and off-line wide-angle X-ray scattering (WAXS), temperature-modulated differential scanning calorimetry (TMDSC) and stress-strain curves testing. The formation process of initial connecting bridges and pores was clarified. For the annealed film, except for the initial lamellae structure, the recrystallized part formed by the melting and crystallization of imperfect crystals during annealing, tie chains connecting the lamellae structure among the amorphous region, secondary crystals from the crystallization of tie chains during annealing and daughter crystals from the special cross-hatched crystalline structure of PP coexist. It was found that 10 % stretching lead to the pronounced increase of long period and the appearance of a few initial connecting bridges. The stretching of daughter crystal and recrystallized part contributed to the formation of initial bridges. At stretching ratio of 30 %, uniform distributed connecting bridges were observed and the stretched film showed maximum structure periodicity. At this stretching ratio, except for the stretching of daughter crystal, the stretching of tie chains and secondary crystals within the amorphous region lead to the formation of more connecting bridges. At higher stretching ratios into the strain-hardening region and beyond the second yield point, except for the stretching of the above mentioned crystalline

Temperature effects on deformation behaviors of extracted ultrahigh molecular weight polyethylene (UHMWPE) precursor fibers are studied with the in situ synchrotron radiation wide-angle X-ray scattering technique (WAXS) during tensile deformation at temperatures from 25 to 130 °C. The structural and mechanical evolution behaviors during tensile deformation can be divided into four temperature regions with boundaries located at temperatures of αI and αII relaxations and the onset of melting, respectively, which reveal that the deformation behaviors of polymer crystals are determined by the interplay between intrinsic structural dynamic or chains mobility and external stress field. Irrespective of temperature, yield and strain-softening proceed via partial melting while crystal slip via cutting crystal planes occurs in the strain-hardening zone. Finally we construct morphological diagrams containing crystallinity, crystal size, and orientation in temperature–strain space, which may serve as a roadmap for UHMWPE fibers processing.

Structural transitions of polyamide 46 (PA46) films during the tensile stretch at temperatures from 37 to 249 °C were studied using in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) and Fourier transform infrared (FTIR) techniques. The structural evolution during the stretch at different temperatures can be roughly divided into three regions. In region I (37 ≤ T < 180 °C), stretch enlarges the d-spacing gap between the (100) and (010/110) planes of α phase (triclinic), which is opposite to that during heating. In region II (180 ≤ T < 230 °C), stretch induces a reverse Brill transition, which is characterized by the single diffraction of γ phase (pseudohexagonal) splitting into two diffractions of α phase, while further increasing the strain drives the two split diffractions to transform to a single broad diffraction. As in situ FTIR measurements reveal the continuously increasing content of trans conformation, we speculate that stretch may induce a new form, which is an intermediate structure close to both α and γ phases (named α′ phase) at large strain. In region III (230 ≤ T ≤ 249 °C), the γ phase may skip the α phase and directly transform into the α′ phase. The nonequilibrium crystal phase diagrams of PA46 were constructed in the strain−temperature space and true stress−temperature space. Current results demonstrate that stretch plays a countereffect of heating on the Brill transition of PA46.

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