Crystallization and melting of isotactic polypropylene crystallized from quiescent melt and stress‐induced localized melt

Temperature dependency of crystalline lamellar thickness during crystallization and subsequent melting in isotactic polypropylene crystallized from both quiescent molten state and stress‐induced localized melt was investigated using small angle X‐ray scattering technique. Both cases yield well‐defined crystallization lines where inverse lamellar thickness is linearly dependent on crystallization temperature with the stretching‐induced crystallization line shifted slightly to smaller thickness direction than the isothermal crystallization one indicating both crystallization processes being mediated a mesomorphic phase. However, crystallites obtained via different routes (quiescent melt or stress‐induced localized melt) show different melting behaviors. The one from isothermal crystallization melted directly without significant changing in lamellar thickness yielding well‐defined melting line whereas stress‐induced crystallites followed a recrystallization line. Such results can be associated with the different extent of stabilization of crystallites obtained through different crystallization routes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 957–963     

Size and shape of Nafion particles in water after high‐temperature treatment

Perfluorosulfonic acid ionomers have been widely used as proton‐conducting materials in polymer‐electrolyte membrane fuel cells and their dispersions in polar solvents are used to prepare proton‐conducting membranes as well as catalyst layers. While it has been known that the dispersed particles become monodisperse after heating to 230 °C or above, their size and shape have not been fully characterized yet. Cryogenic transmission electron microscopy images and small‐angle X‐ray scattering profiles of the dilute aqueous dispersions before and after heating to 240 °C have clearly shown that rod‐like particles became significantly shorter cylinders without changing their radii. Particle length distributions were lognormal and average molar mass and dispersity after heating to 240 °C were consistent with the values from size exclusion chromatography. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 813–818     

Nanocavitation around a crack tip in a soft nanocomposite: A scanning microbeam small angle X‐ray scattering study

We explore nanocavitation around the crack tip region in a styrene‐butadiene random copolymer filled with typical carbon black (CB) particles used in the rubber industry for toughening the rubber. Using quasistatic loading conditions and a highly collimated X‐ray microbeam scanned around the crack tip, we demonstrate the existence of a damage zone consisting of nanovoids in a filled elastomer matrix. The existence of voids near the crack tip is demonstrated by a significant increase of the scattering invariant Q/Q₀ in front of both fatigued and fresh cracks. The size of the zone where cavities are present critically depends on the macroscopic strain ε_m, the loading history, and the maximum energy release rate G applied to accommodate the crack. Our findings show that nanovoiding occurs before fracture in typical CB‐filled elastomers and that realistic crack propagation models for such elastomers should take into account a certain level of compressibility near the crack tip. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 422–429     

Template–polymer commensurability and directed self‐assembly block copolymer lithography

Block copolymer directed self‐assembly (BCP) with chemical epitaxy is a promising lithographic solution for patterning features with critical dimensions under 20 nm. In this work, we study the extent to which lamellae‐forming poly(styrene‐b‐methyl methacrylate) can be directed with chemical contrast patterns when the pitch of the block copolymer is slightly compressed or stretched compared to the equilibrium pitch observed in unpatterned films. Critical dimension small angle X‐ray scattering complemented with SEM analysis was used to quantify the shape and roughness of the line/space features. It was found that the BCP was more lenient to pitch compression than to pitch stretching, tolerating at least 4.9% pitch compression, but only 2.5% pitch stretching before disrupting into dislocation or disclination defects. The more tolerant range of pitch compression is explained by considering the change in free energy with template mismatch, which suggests a larger penalty for pitch stretching than compressing. Additionally, the effect of width mismatch between chemical contrast pattern and BCP is considered for two different pattern transfer techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 595–603     

Flexible transparent fluorinated nanohybrid with innovative heat‐resistance property—new technology proposal for fabrication of transparent materials using “crystalline” polymer

A new technology for the production of transparent material, using a “crystalline” polymer, is proposed in this study. In addition, a heat‐resistant transparent flexible plastic film with a high hydrophobic surface and a thermal decomposition temperature near 400 °C was created. Partially fluorinated crystalline polymer with switchboard‐type lamellae results high transparency as a consequence of the formation of a high‐density amorphous structure based on high‐temperature drawing just below the melting point at 250 °C. Melt‐compounding with montmorillonite modified by the long‐chain quaternary phosphonium with high coverage induces formation of a nanohybrid that retains transparency and also results in an increase in the thermal degradation temperature by over 50 °C. Through this technology, which results in heat‐resistance, transparency, and flexibility, the nano‐micro‐millimeter structures of solid‐state polymers are hierarchically controlled, which enables the creation of new materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1674–1690     

Fully exfoliated layered silicate epoxy nanocomposites

Fully exfoliated layered silicate epoxy nanocomposites are reported in this article. The processing route that resulted in these fully exfoliated layered silicate epoxies is based on a combination of high‐shear mixing in the presence of acetone and ultrasonication. Homomogeneous and random dispersion of the individual silicate nanolayers in the epoxy is confirmed through transmission electron microscopy images spanning low to high magnification as well as by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3981–3986, 2004     

Effect of selected structural parameters of styrene–butadiene block copolymers on their compatibilization efficiency in polystyrene/polybutadiene blends

The effects of the block length and block number of linear styrene–butadiene (S–B) block copolymers on their compatibilization efficiency in blending polystyrene with polybutadiene were studied. For this purpose, two sets of model S–B copolymers and both homopolymers were prepared by anionic polymerization. Diblocks, triblocks, or pentablocks of S–B copolymers were blended with these homopolymers, and the structures and some end‐use properties of the blends were determined. The supramolecular structure (determined by small‐angle X‐ray scattering), morphology (determined by transmission and scanning electron microscopy), and stress‐transfer characteristics (impact and tensile strengths) of the blends were chosen as criteria for the compatibilization efficiency of the copolymers used. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2612–2623, 2002     

Micro‐phase‐separation behavior of amphiphilic polyurethanes involving poly(ethylene oxide) and poly(tetramethylene oxide)

The temperature dependence of thermal, morphological, and rheological properties of amphiphilic polyurethanes was examined with differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), rheological measurements, and Fourier transform infrared spectroscopy. Multiblock (MPU) and triblock (TPU) polyurethanes were synthesized with two crystallizable segments—poly(ethylene oxide) (PEO) as a hydrophilic block and poly(tetramethylene oxide) (PTMO) as a hydrophobic block. DSC and WAXS measurements demonstrated that the microphase of MPUs in the solid state is dominantly affected by the PEO crystalline phase. However, high‐order peaks were not observed in the SAXS measurements because the crystallization of the PEO segments in MPUs was retarded by poor sequence regularity. The microphase in the melt state was induced by the hydrogen bonding between the N? H group of hexamethylene diisocyanate linkers and the ether oxygen of PEO or PTMO blocks. As the temperature increased, the smaller micro‐phase‐separated domains were merged into the larger domains, and the liquidlike ordering was eventually disrupted because of the weakening hydrogen bonding. However, the fully homogeneous state of an MPU with a molar ratio of 5/5 PEO/PTMO (MPU55) was not confirmed even at much higher temperatures with both SAXS and rheological measurements. However, the SAXS patterns of TPU showed weak but broad second‐order peaks below the melting temperature of the PEO block. Compared with MPU55, the ordering of the TPU crystalline lamellar stacks was enhanced because of the high sequence regularity and the low hydrogen‐bonding density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2365–2374, 2003     

Nanostructure evolution in a poly(ether ester) elastomer during drawing and the displacement of hard domains from lamellae

A poly(ether ester) thermoplastic elastomer with a soft block content of 50 wt % has been studied with synchrotron small‐angle X‐ray scattering (SAXS) during strain/relaxation cycles. The rigid nodes of the elastic network are not the hard domains themselves but instead are ordered three‐dimensional assemblies of several hard domains. At a critical elongation, single hard domains are disrupted and dislocated from these assemblies in a peculiar manner. In the ultimate structure, remaining pairs of hard domains form (semi)elastic nodes. The complex two‐dimensional SAXS patterns indicate stacks from tilted lamellae that are destroyed when the sample is strained to double its initial length. With multidimensional chord distribution function analysis, the complex nanostructure and its evolution in the draw experiment have been analyzed. The fundamental hard domains are not lamellae but cylinders (5 nm × 8 nm) arranged on a lattice at cylindrical coordinates (r₁₂, r₃), which are given by the intersections of r₃(r₁₂) = ±1.5r₁₂ ± 13nmn, n being a natural number. A semielastic component is made from hard domains forming other lamellar assemblies, which are characterized by n = 3/2. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1947–1954, 2003     

Analysis of small-angle scattering of suspensions of organically modified montmorillonite: Implications to phase behavior of polymer nanocomposites

A generalized model for scattering from a collection of independent (isolated) stacks of layers enabled predictions of and parameterized fits to small-angle X-ray scattering from layered silicate dispersions. From this fundamental development, example investigations that use small-angle scattering to examine the structure of organically modified montmorillonite dispersions in toluene and toluene–acetone blends provided detailed information on the distribution of the stacks (relative concentrations, K and fraction of individual layers, χ) and characteristics of the intercalated crystallite (mean number of layers per stack, 〈N〉; layer repeat distance, D; and fractional stack disorder, δ). The analysis initially supported correlations with discotic phase behavior, which provides concise definitions for various morphologies (exfoliated, intercalated, and mixed). Finally, examination of the deviations between the scattering model and the experiment provided insights for improved experimental technique, more complete utilization of the scattering data, a sound basis for real-time observations, insight into inconsistencies between scattering and microscopy, and minimization of incorrect or overinterpretation of data. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3214–3236, 2003