A cryo-bulge apparatus for in situ weather balloon crystallization capturing during blowing by synchrotron radiation x-ray scattering.

A cryo-bulge apparatus, which can be directly installed in the synchrotron radiation x-ray scattering beamline, is designed and manufactured. Using the cryo-bulge apparatus, the crystallization of natural rubber during blowing can be captured in situ. For mechanical measurements, the rubber film is tightly clamped at the periphery of a circular window. A low temperature measurement is achieved by the presence of a large iron block, which ensures low temperature variation (<±2 °C in 1 h) during x-ray data acquisition. Since the incident x-ray beam passes through the top-most position of the rubber film, the information obtained by the current equipment is essentially under an equibiaxial deformation mode. Owing to precisely controlled internal pressure and temperature, the crystallization of rubber can be observed in situ by wide-angle x-ray scattering. The onset of crystallization is observed at a temperature T < 0 °C with an internal pressure P > 21 kPa. This suggests that the crystallization of rubber during blowing can occur under the equibiaxial deformation condition at low temperatures. The power scaling law is found to be 0.52%/kPa. The cryo-bulge apparatus is capable of clarifying the microstructural evolution of rubber during multi-dimensional deformation, which can provide guidance for the optimization of a weather balloon.

Reconstructing the mechanical response of polybutadiene rubber based on micro-structural evolution in strain-temperature space: entropic elasticity and strain-induced crystallization as the bridges.

Strain-induced crystallization (SIC) in polybutadiene rubber (BR) was studied by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) over a broad temperature range (-90 °C → 25 °C). Depending on the presence or absence of SIC and quiescent crystallization temperature, three temperature regions are divided. Detailed structural evolution is summarized in the strain-temperature space. Based on this micro-structural evolution information, the macroscopic mechanical response of BR, together with poly(isobutylene-isoprene) rubber (IIR) and natural rubber (NR), is reproduced based on Flory's and Plagge's theories. The origins of the mismatch of calculated and experimental stress-strain curves, especially in the large strain region, are discussed, and are mainly ascribed to the micro-macro connection approach and the network inhomogeneity.

Strain-induced crystal growth and molecular orientation of poly(isobutylene-isoprene) rubber at low temperatures.

With the combination of a low-temperature extension rheometer and in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD), the strain-induced crystallization (SIC) of poly(isobutylene-isoprene) rubber (IIR) was studied in the low-temperature region (-60 °C → 25 °C). The detailed structural evolution of IIR during the SIC is summarized in the strain-temperature space, where three distinct temperature zones are defined. The absence of the SIC in zone I (T > 0 °C) results in the poorest drawability of IIR among all measured temperatures. And with respect to the lowest temperature zone III (-60 °C < T < -50 °C), the SIC still occurs with low ultimate crystallinity (ca. 0.9%). More complicated structural evolution induced by the strain occurs in the intermediate-temperature zone II (-50 °C ≤ T ≤ 0 °C). The orientation ratio of the amorphous part Oa increases monotonically with the increment of the strain, but reaches a platform with Hencky strain ε > ca. 1.8. Meanwhile, the strain-induced crystal growth of IIR is evidenced by the dramatic increment of the lateral crystallite size of (110) and (113) planes. Moreover, the retraction experiment further reveals the network evolutions of IIR: suffering from low ultimate crystallinity (

In situ characterization of strain-induced crystallization of natural rubber by synchrotron radiation wide-angle X-ray diffraction: construction of a crystal network at low temperatures.

Strain-induced crystallization (SIC) of natural rubber (NR) at descending temperatures as low as -60 °C is systematically investigated by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) measurement. The detailed structural evolution of NR during SIC is studied in the strain-temperature space, where up to four regions are defined depending on the SR-WAXD results. In region I, the molecular chains begin to be oriented under tensile loading. The onset of crystallization happens in the very beginning of region II, and the NR crystal acts as a new physical cross-linking point to form a crystal network, namely the series model. The further increment of crystallinity (> ca. 8%) leads to the transition of the crystal network from the series model to the parallel model in region III. The crystal network is finally accomplished in region IV, where the crystallinity remains almost constant. Interestingly, regions III and IV exist only in the intermediate-temperature zone II (-40 °C to -10 °C), which are missing in zones I (-10 °C to 25 °C) and III (-60 °C to -40 °C). This suggests that sufficient crystallinity (χII-III > ca. 8%) is required to form the parallel model. The new crystal network provides a deep understanding of SIC of NR considering the microscopic features, i.e. oriented amorphous component, the onset of crystallization and crystallinity evolution and its correlation with the macroscopic stress-strain curve.