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Nanoindentation was performed on amorphous silicon nitride films of different thicknesses deposited on gallium arsenide (GaAs) (001) substrates using a conical indenter. Both “pop-in” and ‘pop-out’ were observed from the load-displacement curves when the indentation load exceeded a critical value. Pop-in occurring during loading is associated with plane-slip in the GaAs substrate, and pop-out during unloading is attributed to the interfacial delamination between the film and the substrate. Finite element modeling (FEM) was used to analyze the stress evolution during unloading. The FEM results showed that the stress at the interface evolved from compressive to tensile status during the withdrawal of indentation load, and the interfacial debonding was induced at a critical tensile stress, which is consistent with the pop-out observed. A deformation model for interpreting the pop-in and pop-out events is thereby proposed.
The probability for amorphous silicon (a-Si) to phase transform under indentation testing is statistically determined as a function of annealing temperature from the probability of a pop-out event occurring on the unloading curve. Raman microspectroscopy is used to confirm that the presence of a pop-out event during indentation is a clear signature that a-Si undergoes phase transformation. The probability for such a phase transformation increases with annealing temperature and reaches 100% at a temperature of 340 °C, a temperature well before the temperature where the average bond-angle distortion is fully minimized. This suggests that multiple processes are occurring during full relaxation.
Nano-structured graphene has recently attracted extraordinary attention due to its potential use as an electronic or spintronic material. We investigated the electrical conductivities of antidot and Ar-sputtered graphene samples under a magnetic field in terms of the carrier density. Antidot samples exhibit conductivity that is well explained by charged impurity scattering, which is associated with intravalley scattering. This suggestion is supported by the low intensity of the Raman D band, which is related to intervalley scattering induced by structural defects. In contrast, Ar-sputtered samples show a strong D band and conductivity that is affected by defect scattering. The difference in the main scattering mechanism between the two types of samples appears as Shubnikov-de Haas oscillations at high magnetic fields, which are observed in antidot samples but not in Ar-sputtered samples. Furthermore, an analysis of weak localization effects in both samples at low fields reveals that intra- and intervalley scatterings play significant roles in antidot and Ar-sputtered samples, respectively.
We have investigated the microstructure, the quasistatic and high-rate mechanical properties of magnesium (Mg)-based metal-matrix composites (MMCs) reinforced with nanoparticles, also termed as metal-matrix nanocomposites (MMNCs), in this case reinforced with nanoparticles of β-phase silicon carbide (β-SiC) the volume fraction ranging from 5 to 15 vol%. The yield and the ultimate strength increase with reinforcement volume fraction up to 10 vol% nanoparticles. MMCs with micrometer-sized SiC particles have higher yield strength than their MMNC counterparts, whereas the ultimate strength shows the opposing trend, suggesting greater strain hardening in the MMNCs. Transmission electron microscopy shows that the average interparticle distance decreases with increasing SiC vol%. Recrystallization was reported as completed during sintering at 575 °C [R.D. Doherty et al., Mater. Sci. Eng. A, 238, 219 (1997)], but dislocations might be generated due to thermal expansion mismatch of Mg/SiC during cooling. The majority of Mg-grains below 20 nm remain around the nanoparticles. As such a reverse volume fraction effect takes place in 15 vol% nanoparticle-reinforced MMNCs, which off sets the strengthening advantage induced by the nanoparticles.
“Nanostructured” germanium (Ge; also known as “voided,” “porous,” “nanoporous,” “cratered,” and “honeycomb” Ge) created via ion beam modification has been studied for many years. This work reviews the progress made in studying and characterizing the nanostructured morphology, particularly via the use of experimental techniques such as scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. Specifically, the empirical observations of the structural evolution of Ge as a function of ion beam modification conditions are discussed with added emphasis placed on quantification of the microstructure. The experimental observations and microstructure quantification are further discussed in terms of the implications for proposed formation mechanisms of the nanostructured morphology. Potential uses of the nanostructured morphology in chemical sensor and energy storage applications and suggested future lines of research to further the fundamental understanding of nanostructuring in Ge using ion beam modification are also presented.
We have prepared stable ultrafine narrow dispersed copper nanoparticles (Cu-NPs) using a facile chemical reduction technique below room temperature (300 K), without any template. X-ray diffraction and high-resolution transmission electron microscopy studies reveal the growth of highly crystalline Cu-NPs with an average diameter of 2.2 nm. Interestingly, these Cu-NPs demonstrate both interband electronic transitions along with usual surface plasmon resonance, a unique phenomenon previously unobserved in any noble metal nanoparticles. These Cu-NPs do not get oxidized easily and could be suitable candidates for different optical devices, heat transfer liquids, and biological applications.
Nickel-yttrium nanocrystalline alloys with an as-milled grain size of approximately 6.5 nm were synthesized using high-energy cryogenic mechanical alloying. The microstructural changes due to annealing were characterized using x-ray line broadening, microhardness, focused ion beam channeling contrast imaging, and transmission electron microscopy. Experiments demonstrated that increasing yttrium content led to stabilization of the nanocrystalline grain size at elevated homologous annealing temperatures. Additionally, it was found that inadvertent contamination with nitrogen during the milling process caused the formation of yttrium nitride (YN) precipitates, which, in turn, resulted in an additional nonlinear hardening effect beyond the expected hardening due to grain-size reduction. Results reveal that kinetic pinning by YN particles is effective in retaining a nanostructure to relatively high temperatures.
The structures of γ- and δ-K4P2O7 are solved by X-ray powder diffraction (conventional laboratory X-ray and synchrotron data, respectively), both in hexagonal symmetry (aγ = 5.9645(3) Å, cγ = 14.4972(8) Å, Vγ = 446.64(4) Å3 at 300 °C, Zγ = 2, space group P63/mmc; aδ = 10.211 45(7) Å, cδ = 42.6958(4) Å, Vδ = 3855.59(7) Å3 at room temperature, Zδ = 18, space group P61) with cell–supercell relations $a_\delta \approx a_\gamma \sqrt{3}$ and cδ ≈ 3 cγ. In the experimental conditions, the expected β/γ transition previously announced at 486 °C is not observed; the γ-form is stable at least up to the maximum temperature of our measurements (700 °C). In the γ-form, similar to the orthorhombic form of Na4P2O7, idealized, the pyrophosphate group is in eclipsed conformation, the K+ cations occupying three different coordinations. In the δδ-form, two of the three different [P2O7]4− groups are staggered and one eclipsed, the K+ cations occupying 12 independent sites.
Eighty specimens of cellulosic materials were analyzed over a period of several years to study the diffraction characteristics resulting from polymorphism, crystallinity, and chemical substitution. The aim of the study was to produce and verify the quality of reference data useful for the diffraction analyses of cellulosic materials. These reference data can be used for material identification, polymorphism, and crystallinity measurements. Overall 13 new references have been characterized for publication in the Powder Diffraction File (PDF) and several others are in the process of publication.
Chitin is a natural polysaccharide found in many diverse phyla and almost always occurs in association with protein. In this study the chitin polymer is characterized by X-ray diffraction from its naturally occurring unprocessed state through various steps used in the purification procedure. In addition, the effect of different treatments on the final product is examined. These studies show that native chitin has a characteristic diffraction pattern that is not altered by the mild treatments used to isolate relatively pure chitin. Chitins prepared from different sources exhibit the same characteristic diffraction pattern. In addition, chitin films prepared using non-degrading solvents retain most of the characteristic patterns. De-acylation of chitin to produce chitosan results in large changes to the diffraction pattern. To a very limited extent features present in the diffraction pattern of native chitin can be recovered by re-acylation of chitosan.
The stereoselective synthesis of 7-fluoro-2-exo-(2-methylpropen-1-yl)-2,3,4,5-tetrahydro-1,4-epoxybenzo[b]azepine was developed by intramolecular 1,3-dipolar cycloaddition of the nitrone derived from the corresponding 2-allyl-4-fluoro-N-(3-methylbut-2-enyl)aniline. The X-ray powder diffraction (XRPD) pattern for the new compound was analyzed and found to crystallize in a monoclinic system with space group P21/m (No. 11) and refined unit-cell parameters a = 11.655(5) Å, b = 5.850(2) Å, c = 18.314(4) Å, β = 104.27(3) and V = 1210.1 (6) Å3.