Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers.

Advanced fibers revolutionized structural materials in the second half of the 20th century. However, all high-strength fibers developed to date are brittle. Recently, pioneering simultaneous ultrahigh strength and toughness were discovered in fine (<250 nm) individual electrospun polymer nanofibers (NFs). This highly desirable combination of properties was attributed to high macromolecular chain alignment coupled with low crystallinity. Quantitative analysis of the degree of preferred chain orientation will be crucial for control of NF mechanical properties. However, quantification of supramolecular nanoarchitecture in NFs with low crystallinity in the ultrafine diameter range is highly challenging. Here, we discuss the applicability of traditional as well as emerging methods for quantification of polymer chain orientation in nanoscale one-dimensional samples. Advantages and limitations of different techniques are critically evaluated on experimental examples. It is shown that straightforward application of some of the techniques to sub-wavelength-diameter NFs can lead to severe quantitative and even qualitative artifacts. Sources of such size-related artifacts, stemming from instrumental, materials, and geometric phenomena at the nanoscale, are analyzed on the example of polarized Raman method but are relevant to other spectroscopic techniques. A proposed modified, artifact-free method is demonstrated. Outstanding issues and their proposed solutions are discussed. The results provide guidance for accurate nanofiber characterization to improve fundamental understanding and accelerate development of nanofibers and related nanostructured materials produced by electrospinning or other methods. We expect that the discussion in this review will also be useful to studies of many biological systems that exhibit nanofilamentary architectures and combinations of high strength and toughness.

Optimizing depth resolution in confocal Raman microscopy: a comparison of metallurgical, dry corrected, and oil immersion objectives.

Spherical aberration is probably the most important factor limiting the practical performance of a confocal Raman microscope. This paper suggests some simple samples that can be readily fabricated in any laboratory to test the performance of a confocal Raman microscope under realistic operating conditions (i.e., a deeply buried interface, rather than the often-selected alternative of a bare silicon wafer or a thin film in air). The samples chosen were silicon wafers buried beneath transparent polymeric or glass overlayers, and a polymer laminate buried beneath a cover glass. These samples were used to compare the performance of three types of objectives (metallurgical, oil immersion, and dry corrected) in terms of depth resolution and signal throughput. The oil immersion objective gave the best depth resolution and intensity, followed by a dry corrected (60x, 0.9 numerical aperture) objective. The 100x metallurgical objective was the worst choice, with degradations of approximately 5x and 8x in the depth resolution and signal from a silicon wafer, comparing a bare wafer with one buried under a 150 microm cover glass. In particular, the high signal level obtained makes the immersion objective an attractive choice. Results from the buried laminate were even more impressive; a 30x improvement in spectral contrast was obtained using the oil immersion objective to analyze a thin (19 microm) coating on a PET substrate, buried beneath a 150 microm cover glass, compared with the metallurgical objective.

Novel mesoporous mixed Nb-M (M = V, Mo, and Sb) oxides for oxidative dehydrogenation of propane.

Novel thermally stable mesoporous mixed metal Nb-M (M = V, Mo and Sb) oxides were synthesized in the presence of a nonionic Pluronic P123 surfactant. These oxides displayed promising pore structures and chemical compositions for selective oxidative functionalization of propane: high surface areas (up to 200 m2/g), large pore sizes (5-14 nm), and high pore volumes (up to 0.46 cm3/g). The oxidative dehydrogenation of propane to propylene over mesoporous mixed metal Nb-M oxides employed as a probe reaction suggested that the M component was dispersed as the molecular surface species and also formed a solid solution with NbOx in the inorganic walls of these mesoporous mixed metal oxides.