Huiying Wen

Solvent micro-evaporation and concentration gradient synergistically induced crystallization of poly(L-lactide) and ring banded supra-structures with radial periodic variation of thickness

The crystalline morphology and structure of poly(L-lactide) (PLLA) in a PLLA film–chloroform system were investigated by means of wide angle X-ray diffraction (WAXD), polarized optical microscopy (POM) and atomic force microscopy (AFM). Birefringent and nonbirefringent ring banded supra-structures with radial periodic variation of thickness were obtained, which were induced by micro-evaporation of solvents and concentration gradient of PLLA. The ring banded morphologies consisted of multilayer lamellar crystals, which is a manifestation of alternating ridge and valley bands of periodic variation of thicknesses along the radial direction. The formation of the ring banded supra-structures is associated with diffusion and crystal growth induced periodic variation of concentration gradient, which is attributed to diffusion-related rhythmic growth and the competition between diffusion of polymer segments and growth of crystal lamellae. The mechanism of such banded-ring formation was explored on the basis of rhythmic growth resulting from non-linear diffusion.

Deformation and structure evolution of glassy poly(lactic acid) below the glass transition temperature

Poly(lactic acid) (PLA) is a bio-based and compostable thermoplastic polyester that has rapidly evolved into a competitive commodity material over the last decade. One key bottleneck in expanding the field of application of PLA is the control of its structure and properties. Therefore, in situ investigations under cooling are necessary for understanding the relationship between them. The most intriguing feature of a supercooled liquid is its dramatic rise in viscosity as it is cooled toward the glass transition temperature (Tg) though accompanied by very little change in the structural features observable by typical X-ray experiments. The deformation behaviors and structure evolution of glassy PLA during uniaxially stretching below Tg were investigated in situ by synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques. The stretched samples were measured by differential scanning calorimetry (DSC). The obtained results showed that the deformation and yield stress of glassy PLA are strongly dependent on the stretching temperatures together with the transition from mesophase to mesocrystal and the formation of cavities. With the increase in drawing temperature, the onset of the mesocrystal formation is delayed to a higher strain value, whereas corresponding to the same critical orientation degree of amorphous chains (fam ≈ 0.45). The DSC results indicated that the post-Tg endothermic peak corresponding to the melting of mesocrystal appears and shifts to a higher temperature with increasing stretching temperature, followed by the down-shifts (to a lower temperature) of the exothermic peak of cold crystallization of PLA. The appearance of a small exothermic peak just before the melting peak related to the transition of the α′ to α crystal implies the formation of an α′ crystal during cold crystallization in the drawn PLA samples. The structure evolution of glassy PLA stretched below Tg was discussed in details.

Crystalline structures and crystallization behaviors of poly(L-lactide) in poly(L-lactide)/graphene nanosheet composites

Poly(L-lactide) (PLLA)/graphene nanosheet (GNS) composites and pure PLLA were prepared by the solution blending method. Crystalline structures and crystallization behaviors of PLLA in the composite were investigated by XRD, POM, SAXS, and DSC. It was found that α′ form PLLA formation seemed to be more preferred than α form PLLA formation in PLLA/GNS composites at crystallization temperatures Tcs within the α′–α crystal formation transition region due to the existence of GNSs, resulting in an obvious shift of the α′–α crystal formation transition of PLLA in PLLA/GNSs towards high Tcs compared with that of pure PLLA. At Tcs below α′–α crystal formation transition, the formed α′ crystal turned to be more imperfect due to GNS addition, while at Tcs above α′–α crystal formation transition, the crystal structure of α form PLLA was not affected by GNSs. Further POM observations at high Tcs with only α crystal formed showed that PLLA spherulites were well formed in both PLLA/GNSs and pure PLLA, however with very different crystallization kinetics while isothermally crystallizing at different Tcs. The PLLA crystallization process of PLLA in PLLA/GNSs was accelerated by GNSs with both the nucleation rate and spherulite growth rate increased mainly because of the increasing segmental mobility of PLLA chains due to GNS addition; whereas, GNSs showed no observable influence on the determined zero growth temperature Tzg of α form PLLA and the Tzg was estimated lower than the equilibrium melting point of PLLA, indicating that the crystal growth of PLLA is mediated by a transient mesophase with the transition temperature of Tzg between the mesophase and melt not influenced by GNSs in PLLA. Synchrotron on-line SAXS results revealed that the long periods of PLLA in PLLA/GNS composites isothermally crystallized at different Tcs are much smaller than those in pure PLLA. The GNSs are helpful in forming more perfect recrystallized α form PLLA after the α′ form PLLA is melted with increasing Tcs. The presence of GNSs resulted in imperfect α form PLLA from melt directly when it is isothermally crystallized at different Tcs within the temperature range of α′–α crystal formation transition.

Shear effects on crystalline structures of poly(L-lactide)

The shearing effects of sheared polymer melts on their finally formed crystalline structures of poly(L-lactide) (PLLA) were investigated by means of small angle X-ray scattering (SAXS) and wide angle X-ray diffraction (WAXD). The results of WAXD prove that shear has no effects on the crystal structure of PLLA. The SAXS results demonstrate that both of the long period and the thickness of crystalline lamellae increase with rising shear rates when vertical to the shear direction, but remains constant when being parallel to the shear direction. The structural changes for samples prepared with different shear temperature or under the same shear strain but different shear rate were investigated. The mesophase of polymer melts and shearing effects on their pre-ordered phase turned out to be the key factor affecting the crystal structure of PLLA under different shearing conditions.

Shear effects on crystallization behavior of poly(ethylene-co-octene) copolymers

Crystallization behavior of sheared polymer melts of a series of poly(ethylene-co-octene)s with different octene content was investigated by different scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and synchrotron small-angle X-ray scattering (SR-SAXS) techniques. The DSC results indicated that the hexyl branches content had dramatic effects on the thermal properties and crystallinity of polyethylene. It was also found that shear had no obvious effects on the size of either crystallite or lamellae. However, both crystallite and lamellae were oriented by shearing, especially for the lamellae. All obtained results indicate that the initial states of the polymer melt play an important role in affecting the crystallization behaviors. The difference of the shear-induced crystalline structure evolution and the orientation between crystallite and lamellae support the preordered mesomorphic phase of flexible polymer crystallization process proposed by Strobl.

Synchrotron investigation on the sheared structure evolution of syndiotactic polypropylene crystallization process

The final structure of molten syndiotactic polypropylene (sPP) sheared under different conditions was investigated by synchrotron small-angle x-ray scattering (SAXS) and wide-angle x-ray diffraction (WAXD) techniques to elucidate the shear effects on sPP crystalline structure. The results obtained from the WAXD show that there is no variation on crystalline form but a little difference on the orientation of the 200 reflection. The SAXS data indicate that the lamellar thickness and long period have not been affected by shear but the lamellar orientation is dependent on shear. The experimental data of sPP crystallization from sheared melt may indicate a mesophase structure that is crucial to the shear effects on the final polymer multiscale crystalline structures.

Analysis of structure transition and compatibility of PTT/PC blend without transesterification

Poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends were prepared by solvent mixing to avoid transesterification during high temperature blending. The influences of compositions on the thermal behavior, crystallization morphology and structure of the blends were studied. FTIR results indicated that there was no COO linking to two phenyl groups on each side chain and DSC results supported no transesterification reaction. DSC curves showed that Tc and Tmc increased to maximum range when PC contents were between 7 wt%-15 wt%, however, Tm decreased constantly with the increase of PC contents. It was observed from POM that PTT spherulitic morphology and crystallization kinetics were obviously influenced by the change of PC contents. Structural evolutions during cooling were investigated by SAXS which showed Lc of PTT remained a constant with different PC contents and also fixed during crystallization, nevertheless, it revealed a maximum value of Lnc for sample PTT93. It was concluded that PC chains could be permeated into not only amorphous crystallite structure but also amorphous lamellae structure and 7 wt% PC content was supposed to be the “proper” penetration amount into PTT lamellae structure which led to a maximum capacity of amorphous lamellar layer. Fringedmicelle crystal model was adopted to illustrate semi-crystalline physical structures of the blend in two kinds of component aggregation states.

CRYSTALLIZATION KINETICS OF SYNDIOTACTIC POLYPROPYLENE STUDIED BY TIME-DEPENDENT LIGHT ATTENUATION *

Crystallization kinetics of syndiotactic polypropylene ( sPP) was observed by light attenuation measurements. The initial stages of temperature dependent sPP crystallization fall in the range of Rayleigh scattering and Rayleigh-Debye- Gans scattering. Initial time and growth time of crystallization were obtained, and the trend of crystallization temperature dependent linear attenuation coefficient on the radius and the index of the refraction of the spherulite were evaluated. of polymer crystallization are usually carried out by differential scanning calorimetry or X-ray scattering in the wide- and small-angle range, sometimes also by light scattering, dilatometry or time dependent vibrational spectroscopy. Although based on different properties there is not much difference in the sensitivity of all these methods. Reliable data are only obtained from values of the crystallinity in the range of some percent of the final values. This means that for growing spherulites, which usually reach end sizes in the order of several micrometers, measurements start only at sizes of several hundred nanometers. This, however, is already far away from the initial stages. Nuclei have sizes in the order of several to ten nanometers and these, together with the small hedrites and spherulites existing at the beginning, cannot be observed. To study the objects in these initial stages, one can now use atomic force microscopy (AFM), but this technique has also some shortcomings. Observations by AFM principally refer to the development and growth of spherulites at the free surface of a melt, and conditions here may differ from those in the bulk. In addition, deriving global properties from observations of the development of single objects is sometimes difficult, because a certain selectivity is usually involved. Presently, the work on polymer crystallization has given considerable attention to the possibility that the crystal phase in the final semicrystalline state could be preceded by a transient liquid phase with density different from that of the initial quenched bulk isotropic melt or annealed glassy state. A number of papers have explicitly criticized the spinodal hypothesis and associated experimental studies, favoring the traditional picture of nucleation and growth. Various studies have suggested that the denser transient phase involves chain orientation, and there are good reasons to assume a crystal nucleation and growth which include an intermediate phase in the form of a coverage of the whole volume by a prior mesomorphic phase developing by a mechanism which resembles a spinodal process (7) , or a nucleation into a mesomorphic phase (8) , or the existence of a