Nanomechanical bending behavior and elastic modulus of silver nanowires (65–140nm∅) suspended across silicon microchannels were investigated using digital pulsed force mode (DPFM) atomic force microscopy through coincident imaging and force profiling. Deflection profiles analyzed off-line demonstrate the role of bending nanowire shape and symmetry in experimentally determining boundary conditions, eliminating the need to rely on isolated midpoint bending measurements and the usual assumptions for supported-end behavior. Elastic moduli for as-prepared silver nanowires ranged from 80.4±5.3to96.4±12.8GPa, which met or exceeded the literature values for bulk silver. The calculated moduli were based on classic modeling, both with one-dimensional analytical solutions and three-dimensional finite element analysis. Modeling results indicate that the classic models are accurate as long as the boundary conditions are not arbitrarily assumed but directly confirmed by data analysis. DPFM also facilitated the experimental determination of sample gauge lengths from images and bending profiles.
An in-depth analysis of the chemical functionality in HCl-doped polyaniline (PANI) nanopowders is discussed through interpretations of x-ray photoelectron spectra. The distinctions between three PANI sample types, produced under varied synthesis conditions, are compared on the basis correlations between newly collected electron spectra for chemical analysis (or also x-ray photoelectron spectroscopy) and electromagnetic (EM) shielding effectiveness (SE) within two frequency bands (100–1500 MHz and ∼2–14 GHz). The findings are discussed with reference to previous data analysis of electrical conductivities and Raman and UV-vis spectra analyzed from replicates of the same PANI nanopowders, where only the 8–12 GHz range for SE was tested. They further corroborate previous results for limited-solvent conditions that enhance EM shielding. The three nanopowder types show distinctive differences in polaron, bipolaron, and polar lattice contributions. The collective findings describe the chemical connections between controlling and, most importantly, limiting the available solvent for polymerization with simultaneously doping and how it is that the newly developed solvent-limited approach for HCl-PANI nanopowders provides better shielding than traditionally solvent-rich methods by having more extended and perhaps even faster polaron delocalization than other PANI-based products. The maximum oxidation (50%) and doping (49%) levels obtained in the solvent-free nanopowders also produced the highest SE values of 37.3 ± 3.7 dB (MHz band) and 68.6 ± 4.6 dB (GHz band).
Probing the specific hydrogen-bonding behavior of thermoplastic poly-urethane (TPU) blends using vibrational spectroscopies remains the sin qua non for understanding the link between hydrogen-bonding and phasesegregation behavior. However, current literature holds to more traditional univariate approaches when studying the morphologically interesting normal molecular vibrations of TPUs. In the present study, multivariate analysis, including principal component analysis (PCA) and principal component regression (PCR), is used to scrutinize the relevant Raman bands acquired from a binary mixture of analogous TPU copolymer blends. Considering the near identical behavior of selected spectral regions, PCA was capable of isolating linear and nonlinear composition-dependent trends on PC-scores plots. From here, the PC scores, extracted from wavelengths comprising the carbonyl stretching region (1681–1764 cm−1), CH2 deformations (1380–1500 cm−1), aromatic stretch from the hard segment (1617 cm−1), and amide II mixed band (1540 cm−1), were used to explicitly predict the mole fraction of hard segment present in each blend using PCR. Spectral preprocessing, wavelength selection, and variable scaling were major factors in PCR accurately predicting the weight fraction of each copolymer in spite of the clearly evident, blend-specific spectroscopic behavior.