Structural Evolution of PGA Nascent Fiber during Single Low-Temperature and Segmented High-Temperature Hot Stretching

Polyglycolide (PGA) fibers applied as surgical sutures strongly depend on their microstructure. The structural evolution of PGA nascent fibers during single low-temperature stretching and segmented high-temperature stretching was analyzed based on a combination of in situ WAXD/SAXS and DSC measurements. The results indicated that the hot stretching was conducive to the crystal perfection and the local fragmentation and recrystallization of the lamellar crystals may occur under stress induction. The single low-temperature stretching of PGA nascent fibers could be divided into three stages: the stretching of amorphous regions, stretch-induced crystallization and the stretching of crystalline regions. The elongation at break of the fibers can be substantially increased by adopting a segmented stretching method, and the high-temperature stretching can also significantly increase the crystallinity and orientation. The amorphous orientation peak appearing in the low-temperature stretching was gradually converted to crystallization peak during the heating process, which greatly improved the crystallinity and orientation of the fibers. High-temperature stretching compared with low-temperature stretching was more favorable for crystal perfection and structural evolution, where lamellar crystals underwent stress-induced fragmentation recrystallization to transform to fibrous crystals as the strain increased.

The Influence of Ethyl Branch on Formation of Shish-Kebab Crystals in Bimodal Polyethylene under Shear at Low Temperature

Formation of shish-kebab crystals using a bimodal polyethylene system containing high molecular weight(HMW)component with different ethyl branch contents was investigated.In situ small-angle X-ray scattering(SAXS)and wide-angle X-ray diffraction(WAXD)techniques were used to monitor the formation and evolution of shish-kebab structure sheared at low temperature in simple shear mode and low rate.Only the bimodal PE with no branch formed shish-kebab crystals at the shear temperature of 129℃,and the shish length increased with the crystallization time,while bimodal PE with branch has no observable shish under the same conditions.The degree of crystallization for bimodal PE with no branch increased with time up to above 7%,while those with ethyl branch increased continually up to above 23%.Furthermore,bimodal PE's Hermans orientation factor with no branch increased to 0.60,while those with ethyl branch only increased to a value below 0.15.This study indicated that the shish-kebab crystal formed at the low temperature of 129℃is due to the stretch of entangled chains under shear for the bimodal PE with no branch.Only partly oriented lamellar crystals were formed for the bimodal PE with ethyl branch.All the results at the shear temperatures higher,closed to,and lower than the melting point,the modulation of shish crystals formation owing to different mechanisms of the coil-stretch transition and the stretched network by changing shear temperature was achieved in the bimodal PE samples.

A Synchrotron in situ X-ray Study on the Multiple Melting Behaviors of Isomorphous Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)(P(HB-co-HV))with Middle HV Content

The multiple endothermic peaks without observable recrystallization phenomenon of isomorphous poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[P(HB-co-HV)]with the middle HV content of 19.4 mol%and 28.7 mol%were confirmed by differential scanning calorimetry(DSC),and the evolutions of crystal structure and lamellar morphology in the heating and melting process were tracked by in situ synchrotron wide angle X-ray diffraction(WAXD)and small angle X-ray scattering(SAXS)techniques.The emergence of asymmetric features of both the diffraction peaks and scattering curves indicates the coexistence of different lamellar crystals with varied unit cell parameters.Based on the in situ WAXD and SAXS measurements,we calculated the evolutions of the unit cell parameters a and b as well as the long period and lamellar thickness upon heating.The comparative analysis of WAXD and SAXS data confirms that the multiple endothermic peaks of P(HB-co-19.4%HV)and P(HB-co-28.7%HV)result from the melting of different lamellae rather than the melting/recrystallization.The thinner,unstable uniform lamellae with HV counits total inclusion melt first and the thicker,stable sandwich lamellae with HV counits partial inclusion melt last.In addition,the large second melting peak in P(H B-co-19.4%HV),differing from that of samples with HV content of 28.7 mol%and 36.2 mol%,is due to the unique state of HV content leading to a transition of sandwich lamellae to uniform lamellae.The present study establishes the relationship between the different lamellae structure and multiple melting behaviors of isomorphous copolymer.