In-situ rheo-SAXS (small-angle X-ray scattering) and rheo-WAXD (wide-angle X-ray diffraction) studies were carried out to investigate the nature of shear-induced precursor structures in isotactic ...polypropylene (iPP) melt at 165 °C, near its nominal melting point. Immediately upon the cessation of shear, SAXS patterns clearly showed an evolution of oriented structures in hundreds of angstroms, while the corresponding WAXD patterns did not exhibit any crystal reflections. SAXS patterns at later times showed that the shish-kebab morphology was developed, and the kebabs possessed only a small amount of crystallinity (3%). The combined SAXS and WAXD results indicate that, at the early stages of crystallization, a scaffold (network) of oriented structures is formed. These structures contain (1) primary nuclei (through homogeneous nucleation) that may be crystalline or mesomorphic but having linear connectivity along the flow direction, which form the shish entity, and (2) shish-induced layered crystalline lamellae (kebabs) oriented perpendicularly to the flow direction that have poor lateral connectivity. Subsequent polymer crystallization takes place in the framework of the scaffold, which is probably dominated by the lower molecular weight species. Amounts of the crystalline primary nuclei and the layered crystalline lamellae in the precursor structures were estimated. The results verified, quantitatively for the first time, the well-known concept that minor amounts of linear nuclei induce multiple secondary nucleation sites for the growth of a large quantity of lamellae that grow radially outward from the central core. A mechanistic pathway for the early stages of crystallization in polymer melts under flow is proposed.
Development of shear-induced crystallization precursor structure was studied by in-situ rheo-SAXS (small-angle X-ray scattering) and rheo-WAXD (wide-angle X-ray diffraction) techniques using binary ...polymer blends of high and low molecular weight polyethylenes near their nominal melting temperatures (120 °C). Two low molecular weight polyethylene copolymers, containing 2 mol % hexene, with weight-average molecular weights (M w) of 50 000 (MB-50K) and 100 000 (MB-100K), and polydispersity of about 2, were used as the noncrystallizing matrices. A high molecular weight polyethylene homopolymer with M w of 250 000 (MB-250K) and polydispersity of about 2 was used as the crystallizing minor component. Two series of model blends, MB-50K/MB-250K and MB-100K/MB-250K, each containing weight ratios of 100/0, 97/3, 95/5, and 90/10, were prepared by solution blending to ensure thorough mixing at the molecular level. At the chosen shear conditions (rate = 60 s-1, duration = 5 s, T = 120 °C), while no flow-induced structures were seen in pure MB-50K and MB-100K melts, the blends in both series showed distinct but different shear-induced structures. Results indicate that the high molecular weight component dominates the formation of crystallization precursor structures in the blend under shear, which can act as a template for further crystallization. A “shish-kebab” structure, detected by both SAXS and WAXD, was observed in the MB-100K/MB-250K (90/10) blend, while only a twisted lamellar structure (kebab) was seen in the rest of the blends under the same shear conditions. These findings suggest that the matrix viscosity plays an important role to influence the formation of crystallization precursor structure of the high molecular component under flow. In the MB-100K/MB-250K (90/10) blend, the length of the shish was estimated from the equatorial streak in SAXS, which showed a noticeable decrease with time, while the corresponding scattering intensity was found to increase. The evolution of the shish-kebab structure from SAXS is consistent with the appearance of the (110) peak in WAXD, which can be explained by the coil−stretch transition induced by flow.
In situ synchrotron wide-angle X-ray diffraction (WAXD) was used to monitor crystallization of isotactic polypropylene (i-PP) in the subcooled melt at 140 °C after step shear. The melt was subjected ...to a shear strain of 1430% at three different shear rates (10, 57, and 102 s-1) using a parallel-plate shear apparatus. WAXD results were used to determine the type (α- and β-crystals), orientation, and corresponding mass fractions of i-PP crystals. It was found that formation of oriented α-crystals occurred immediately after application of the shear field. Subsequently, growth of primarily unoriented β-crystals was observed. WAXD patterns clearly showed that β-crystals grew only after the formation of oriented α-crystals in the sheared i-PP melt. The contribution of β-crystals to the total crystalline phase was as high as 65−70% at high shear rates (57 and 102 s-1) and low (20%) at low shear rates (10 s-1), which was attributed to the different amount of surface area of oriented α-crystal cylindrites generated at different shear rates. The growth of β-crystals which is related to the surface area of the oriented α-form crystalline assembly has been proposed earlier. Also, the unoriented nature and fast growth of the β-crystals determined from WAXD experiments provide an explanation for the 2 orders of magnitude increase in the kinetics of crystallization of the unoriented structures, which was previously observed (but not explained) in our crystallization study by small-angle X-ray scattering (SAXS).
Development of orientation‐induced precursor structures (nuclei) prior to crystallization in isotactic polypropylene melt under shear flow was studied by in‐situ synchrotron small‐angle X‐ray ...scattering (SAXS) and rheo‐optical techniques. SAXS patterns at 165°C immediately after shear (rate = 60 s−1, ts = 5 s) showed emergence of equatorial streaks due to oriented structures (microfibrils or shish) parallel to the flow direction and of meridional maxima due to growth of the oriented layer‐like structures (kebabs) perpendicular to the flow. SAXS patterns at later times (t = 60 min after shear) indicated that the induced oriented structures were stable above the nominal melting point of iPP. DSC thermograms of sheared iPP samples confirmed the presence of two populations of crystalline fractions; one at 164°C (corresponding to the normal melting point) and the other at 179°C (corresponding to melting of oriented crystalline structures). Time‐resolved optical micrography of sheared iPP melt (rate = 10 s−1, ts = 60 s, T = 148°C) provided further information on orientation‐induced morphology at the microscopic scale. The optical micrographs showed growth of highly elongated micron size fibril structures (threads) immediately after shear and additional spherulities nucleated on the fibrils at the later stages. Results from SAXS and rheo‐optical studies suggest that a stable scaffold (network) of nuclei, consisting of shear‐induced microfibrillar structures along the flow direction superimposed by layered structures perpendicular to the flow direction, form in polymer melt prior to the occurance of primary crystallization. The scaffold dictates the final morphological features in polymer.
The influence of average molar mass and shear on the crystallization of isotactic polypropylene (iPP) has been studied. The Weissenberg number, a dimensionless parameter consisting of the product of ...the shear rate and a characteristic relaxation time (γ̇0λr), provides a criterion to locate the morphological transition from spherulitic to extended growth. The Weissenberg criterion applies to polymers of high and of low molecular weight. This is attributed to the importance of the initial nucleation process. Comparison of materials of different molar masses and various shear histories is allowed by the introduction of the normalized crystallization time τ, which is the ratio of the experimental time and a characteristic crystallization time λVvmax that needs to be defined from the several possible choices. Rheological and rheooptical experiments furnish the material characteristic relaxation and crystallization time scales, respectively. The time λVvmax, defined with light scattering as the moment at maximum density fluctuation invariant Q η, is chosen here as a characteristic crystallization time scale since it is especially sensitive to the early stages of crystal growth that are responsible for the liquid-to-solid transition. DSC and WAXD have been used to further analyze the effect of shear on the populations of crystalline fractions present in the cooled iPP samples.
Nature of Shear-Induced Primary Nuclei in iPP Melt Somani, Rajesh H.; Yang, Ling; Hsiao, Benjamin S. ...
Journal of macromolecular science. Physics,
01/2003, Letnik:
42, Številka:
3-4
Journal Article, Conference Proceeding
Recenzirano
Although observations of molecular processes in the formation of primary nuclei prior to actual crystallization are beyond the detection limits of current instrumentation, we attempted to probe the ...nature of primary nuclei in sheared isotactic polypropylene (iPP) polymer melt. In situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide angle X-ray diffraction) experiments using synchrotron radiation were carried out to evaluate the effects of an addition of a high molecular weight atactic polypropylene (aPP) (5 wt%), which is compatible with the iPP matrix but does not crystallize, on the evolution of oriented structures in the sheared iPP melt and its crystallization kinetics. It is unlikely that the aPP chain segments can be incorporated into iPP nuclei or crystal; hence, its addition effects, if any, would be seen only in the amorphous melt prior to crystallization. The results showed stonger orientation and improved crystallization kinetics in the iPP/aPP blend compared to pure iPP. Observations that the presence of long chains of an amorphous polymer aid in nucleation and crystallization kinetics of iPP, combined with our previous synchrotron results of sheared iPP melts at high temperature (165°C), lead us to conclude that primary nuclei in iPP most likely consist of liquid-crystalline or mesomorphic bundles of aligned chain segments prior to the formation of crystals.
The nature of polyolefin branch−block copolymers produced using mixed-metallocene catalysts has been further characterized in an attempt to relate polymer microstructure to properties. These ...copolymers were synthesized by incorporating vinyl-terminated, crystallizable macromonomers into amorphous backbones. It was shown that polymer properties depended strongly on the fine details of the polymerization procedure (sequential or ex-situ vs simultaneous or in-situ). Here we present rheological, chromatographic, and thermal data along with polymerization kinetic model simulations to interpret the observed property differences between ex-situ and in-situ produced polymers.
When a polymer blend is heated to within the unstable region of the temperature composition diagram, spinodal decomposition may be observed using small-angle neutron scattering. In the one-phase ...region, scattering has been used to obtain the temperature and composition dependence of the second derivative with respect to composition of the Gibbs free energy of mixing. Correlation of these two types of measurements not only tests the current theories of spinodal decomposition but also provides insight into the molecular parameters controlling domain morphology in phase-separating blends. Results are given for polymethylstyrene-co-acrylonitrile/dPMMA blends. Graphs, photomicrographs, phase diagrams. 39 ref.--AA
Optical and near-infrared Microwave Kinetic Inductance Detectors, or MKIDs are low-temperature detectors with inherent spectral resolution that are able to instantly register individual photons with ...potentially no false counts or readout noise. These properties make MKIDs transformative for exoplanet direct imaging by enabling photon-statistics-based planet-discrimination techniques as well as performing conventional noise-subtraction techniques on shorter timescales. These detectors are in the process of rapid development, and as such, the full extent of their performance enhancing potential has not yet be quantified. MKID Exoplanet Direct Imaging Simulator, or MEDIS, is a general-purpose end-to-end numerical simulator for high-contrast observations with MKIDs. The simulator exploits current optical propagation libraries and augments them with a new MKIDs simulation module to provide a pragmatic model of many of the degradation effects present during the detection process. We use MEDIS to demonstrate how changes in various MKID properties affect the contrast-separation performance when conventional differential imaging techniques are applied to low-flux, short duration observations. We show that to improve performance at close separations will require increasing the maximum count rate or pixel sampling when there is high residual flux after the coronagraph. We predict that taking pixel yield from the value achieved by current instruments of 80% and increasing it to 100% would result in an improvement in contrast of a factor of ∼4 at 3λ/D and ∼8 at 6λ/D. Achieving better contrast performance in this low flux regime would then require exploiting the information encoded in the photon arrival time statistics.
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