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We describe the synthesis of nitrides of iridium and palladium using the laser-heated diamond anvil cell. We have used the in situ techniques of x-ray powder diffraction and Raman scattering to characterize these compounds and have compared our experimental findings where possible to the results of first-principles theoretical calculations. We suggest that palladium nitride is isostructural with pyrite, while iridium nitride has a monoclinic symmetry and is isostructural with baddeleyite.
We report a novel finding of slither propagation of shear bands on the fracture surface of a Cu47.5Zr47.5Al5 bulk metallic glass (BMG). The nanoscale heterogeneities in the as-cast state are aggregated along shear bands with irregular morphology. Such heterogeneities create a fluctuating stress field during shear band propagation leading to a slither propagation mode. The slither propagation of 10 to 15 nm wide shear bands is effective to improve both the plasticity and the “work-hardening-like” behavior of BMGs if the size, the morphology, and the elastic properties of the heterogeneities are intimately intercalated during solidification.
ZnO grown on α-Al2O3(0001) generally possesses an orientation such that α-Al2O3(0001) is parallel to ZnO(0001) and two in-plane domains nucleate, so that α-Al2O3[11¯20] is parallel to ZnO[11¯20] and/or α-Al2O3[11¯20] is parallel to ZnO[10¯10]. In this paper, we report a new growth mode for ZnO grown on α-Al2O3(0001) using metalorganic chemical vapor deposition (MOCVD). We find that α-Al2O3[11¯20] is parallel to ZnO[10¯10], but the (0001) plane of ZnO is tilted relative to the (0001) plane of α-Al2O3 such that ZnO(0001) is almost parallel to the α-Al2O3(¯1104) plane. This orientation reduces the extent of lattice mismatch. The interface between ZnO and α-Al2O3 is abrupt and possesses periodic dislocations.
Molybdenum polyoxometalate (PMo)/silica mesoporous composite thin films, which can be applied as multifunctional materials for photochromic and electrochemical applications, were prepared by impregnating PMo into amino-functionalized mesoporous silica thin films. The composite thin films possess excellent reversible photochromic properties and change from colorless to blue under ultraviolet (UV) irradiation. It is shown in the study that intervalence charge transfer and ligand-to-metal charge transfer are the main reasons for photochromism. After UV irradiation, the charge transfer occurs by the reduction of heteropolyanions accompanying the formation of heteropolyblues with multivalence Mo (+6, +5), and the bleaching process of composite thin films is closely related to the presence of oxygen. Moreover, the composite thin films deposited on the indium tin oxide (ITO) substrate can be used as the electrode and have many advantages, including simple fabrication, fast response, and good stability. The modified ITO electrode retains the electrochemical properties of PMo, can catalyze the electroreduction of the BrO3−, and may be used as the current sensor for the BrO3−.
A diamondlike carbon (DLC) thin film was deposited onto a stainless steel substrate using a plasma-enhanced chemical vapor deposition (PECVD) process. Nanoindentation, coupled with focused-ion-beam (FIB) milling, was used to investigate contact-induced deformation and fracture in this coating system. Following initial elastic contact between the coating and the indenter and apparent plastic yield of the substrate, pop-ins were observed in the load–displacement curve, indicative of coating fracture. However, FIB cross-sectional images of indentations revealed the presence of ring, radial, and lateral cracks at loads much lower than the critical load for the first observed pop-ins. Finite element modeling was used, and the properties of the substrate and the film were calibrated by fitting the simulated load–displacement curves to experimental data. Then, based upon the experimental observations of damage evolution in this coating system, the stress distributions relevant to initiate ring, radial, and lateral cracks in the coating were ascertained. Furthermore, the effects of substrate yield stress and coating residual stress on the formation of these cracks were investigated.
Surface modification of the elastomer polydimethylsiloxane (PDMS) by exposure to oxygen plasma for four minutes creates a thin, stiff film. In this study, the thickness and mechanical properties of this surface-modified layer were determined. Using the phase image capabilities of a tapping-mode atomic force microscope (AFM), the surface-modified region was distinguished from the bulk PDMS; specifically, it suggested a graded surface layer to a depth of about 200 nm. Load-displacement data for elastic indentation using a compliant AFM cantilever was analyzed as a plate bending on an elastic foundation to determine the elastic modulus of the surface (37 MPa). An applied uniaxial strain generated a series of parallel nanocracks with spacing on the order of a few microns. Numerical analyses of this cracking phenomenon showed that the depth of these cracks was in the range of 300–600 nm and that the surface layer was extremely brittle, with toughness in the range of 0.1– 0.3 J/m2.
The effect of changes in poly(acrylic acid) (PAA) conformation on removal of Si3N4 film was investigated. PAA was used as a passivation agent by adsorption on an Si3N4 film in shallow-trench isolation chemical–mechanical planarization (STI CMP). Adsorption behavior of PAA on the Si3N4 film and the conformation transition were determined by adsorption isotherms and force measurements using atomic force microscopy (AFM) as a function of ionic strength. AFM results revealed that, as ionic strength increases, the repulsive force between the negatively charged carboxylate groups along the backbone of PAA is reduced due to counterion screening and to the changes of PAA conformation from a stretched to a coiled configuration. At high ionic strength, the coiled conformation of PAA formed a dense passivation layer on the Si3N4 film, which led to suppression of the removal rate of Si3N4 film from 72 to 61 Å/min in the STI CMP process.
The strain rate dependence of freestanding, nanocrystalline gold films was evaluated by a microtensile technique with applied strain rates on the order of 10−4 to 10−6 s−1. Film thickness ranged from 0.25 to 1.00 μm with corresponding grain sizes of 40 to 100 nm. The plastic properties were found to be particularly sensitive to strain rate, film thickness, and grain size, while the elastic property remained relatively unchanged. The thinner films exhibited significant strain rate sensitivity, while the thicker film exhibited only marginal changes. Hall–Petch boundary hardening was observed and dominated plastic flow at larger strain rates, while diffusion-controlled deformation mechanisms appeared to be activated with increasing influence as strain rate decreased. Analysis of dislocation-based and grain-boundary diffusion-related creep suggested that the films were likely experiencing power-law creep as the dominant deformation mechanism in this grain size regime at lower strain rates.
The presence of low-molecular-weight by-products is a major problem in poly[2-hydroxethyl methacrylate (HEMA)-silica] hybrids prepared using sol-gel synthesis. Low-molecular-weight by-products have a detrimental effect on the optical transparency, and mechanical and storage properties of poly(HEMA-silica) hybrids. To solve this problem, a new sol-gel synthesis procedure was developed to prepare organic–inorganic hybrids. Glycidyl methacrylate (GMA) was used as a comonomer to form poly(HEMA-GMA-silica) (PHGS) hybrids. In addition to forming a copolymer, GMA has two more functions. It facilitates the removal of almost all of the low-molecular-weight by-product molecules formed during sol-gel synthesis and also prevents further condensation of free silanol groups during the polymerization, storage, and use. The mechanical properties of PHGS hybrids were evaluated by using compression testing. The mechanical properties of PHGS hybrids were higher compared to Plexiglas G poly(methyl methacrylate), and the hybrids can be synthesized with reproducible mechanical properties.
In this study, we report the growth of metallic tungsten nanowires induced by alloy catalysts (Fe–Ni) at a temperature of 850 °C. The synthesized tungsten nanowires have bottom diameters of 100 to 400 nm and tip diameters of <80 nm, and show a well-defined single-crystalline structure. The formation of the (Fe,Ni)-catalyzed W nanowires should be controlled by the vapor–solid–solid mechanism, rather than the traditional vapor–liquid–solid mechanism, because the growth temperature is significantly below the lowest eutectic temperature (1455 °C) of the Fe–Ni–W ternary system. Our study demonstrates the feasibility of synthesizing metallic nanowires via metal-catalyzed methods, which may be extended to the synthesis of some other metallic nanowires.
Electrodeposited Ag film was explored as a potential interfacial barrier to Bi segregation for suppressing the interfacial embrittlement of Cu/SnBi interconnects. The presence of Ag film introduced Ag3Sn intermetallic layer at the interface, which effectively prevented Bi from reaching the Cu/intermetallic interface. When the persistent slip bands (PSBs) in the Cu single crystal were driven to impinge the Cu/Cu3Sn interface, interfacial cracking was averted and instead superceded by cracking of intermetallic compounds (IMCs) at the interface.
A technique of phase identification from the characteristics of electronic structures is established by Auger electron spectroscopy. GaN epilayers in wurtzite and zinc-blende polytypes are used for practical investigations. Auger spectra show phase-dependent energetic shifts and peak intensity variations. Simulation of theoretical spectra reveals the substantial correlation of the Auger line shape with the bonding electronic states. This approach demonstrates the correspondence between electronic structure and atomic structure and hence provides criteria for phase identification.
The effects of salient testing parameters on four-point adhesion measurements of thin-film structures on silicon substrates were systematically studied. These included specimen geometry, applied displacement rate, and load point separation. Measured fracture energy values, Gc, were observed to increase as the ratio of applied moment arm to specimen thickness was decreased beyond a value of ∼4, particularly for specimens with Gc > 5 J/m2. Testing parameters that affect the steady-state crack velocity were also found to affect reported Gc values. The resulting trends in Gc values are shown to be related to loading-point friction and environmentally assisted cracking effects. Good practice testing guidelines are suggested to improve the accuracy and precision of four-point bend measurements.
Despite the importance of the prior-β grain structure in determining the properties of titanium-based alloys, there are few published studies on methods of controlling the size of these grains in commercial alloys. The existing research raises questions about the relative importance of solute elements in grain-refining mechanisms, particularly the common alloying elements of aluminum and vanadium. The effect of these elements was investigated by producing a series of castings in a nonconsumable arc-melting furnace, and the results were interpreted with the aid of available phase-diagram information and solute-based models of grain refinement. A small reduction in grain size was obtained with increasing solute additions; however, this was not expected from the theoretical analysis. Possible reasons for this discrepancy are discussed.
Polyvinylidene difluoride fibers and composite fibers with Ni–Zn ferrite nanoparticles and rutile nanoparticles were prepared by electrospinning dimethyl formamide (DMF) solutions. To prevent agglomeration, the ferrite nanoparticles were coated with silica, allowing the formation of a stable ferrofluid in DMF as well as the formation of homogeneous fibers. The rutile nanoparticles could be spun with a uniform distribution within the fiber without silica coating. The effects of various solution properties (viscosity and solids loading for composite fibers) and processing parameters (flow rate and voltage) on fiber morphology and diameter were studied to identify a processing window that resulted in the formation of smooth, defect-free fibers. Of the variables examined, fiber diameter was found to be the most strongly dependent on the viscosity of the electrospinning solution. Infrared spectroscopy revealed that the inclusion of well-dispersed nanoparticles in the electrospun fibers enhanced the presence of the ferroelectric phase in the composite fibers.
The microstructural evolution and piezoelectric properties of lead-free ceramics (0.98-x)(Na0.5Bi0.5)TiO3–x(Na0.5K0.5)NbO3–0.02BaTiO3 (0 ⩽ x ⩽ 0.98, abbreviated as (0.98-x)NBT–xNKN–0.02BT) were investigated. The effects of the amount of NKN on the crystal structure, microstructural evolution, and piezoelectric properties were examined. The 0.93NBT–0.05NKN–0.02BT ceramics having a lower NKN content gave good performances with piezoelectric properties of d33 = 140 pC/N and kp = 21%, because of the soft additive Nb5+ ions at the B sites. However, a paraelectric cubic phase was observed in the wide range of compositions between x = 0.1 and x = 0.9. At a higher NKN content of x > 0.9, a morphotropic phase boundary (MPB) between the tetragonal and orthorhombic phases was found in the 0.015NBT–0.965NKN–0.02BT ceramics, and the piezoelectric properties were enhanced (d33 = 135 pC/N, kp = 29%). The piezoelectric properties of this system were closely related to its crystal structure.
Silicon nanoporous pillar array (Si-NPA) is a silicon hierarchical structure with regularly patterned surface morphology. Through a heterogeneous reaction process, zinc sulfide nanocrystallites (nc-ZnS) were grown onto Si-NPA and a unique heterostructure of ZnS/Si-NPA was obtained. The formation of wurtzite nc-ZnS was proved by x-ray diffraction, and the average grain size was evaluated to be ∼18 nm. X-ray photoelectron spectroscopy disclosed that as-grown nc-ZnS was well separated from Si-NPA by a SiO2 thin layer of ∼1.3 nm. The photoluminescence (PL) spectrum of ZnS/Si-NPA showed that in addition to the two red PL bands peaked at ∼648 and ∼705 nm observed in Si-NPA, three other PL bands peaked at ∼365, ∼418, and ∼472 nm were observed and attributed to the PL from nc-ZnS. It was also demonstrated that as-prepared ZnS/Si-NPA heterostructure could exhibit good rectification characteristic featured by a high forward current density of ∼75 mA/cm2 at 2 V and high reverse breakdown voltage of ∼10 V. Our results indicated that ZnS/Si-NPA might be a valuable heterostructure nanosystem to be further probed for achieving enhanced optical and electrical properties.
Nanocrystalline SrTiO3 particle/polymer composite film was synthesized from a titanium–organic film and strontium ion in aqueous solution by applying a direct current (dc) field. The titanium–organic precursor was synthesized from acetylacetone-modified titanium isopropoxide and a methacrylate derivative. Ultraviolet treatment of the titanium–organic film decreased the leaching of Ti moieties from the precursor film during dc treatment. Crystalline SrTiO3 particles were formed in the precursor films on stainless-steel substrates under a dc field above 40 °C without a high-temperature process. The size of SrTiO3 particles increased with increasing reaction temperature from 40 to 50 °C at 3.0 V/cm. SrTiO3 particles also increased in size with increasing reaction time from 35 to 60 min at 3.0 V/cm and at 50 °C. SrTiO3 particle/polymer films were synthesized on stainless-steel substrates at 3.0 V/cm and 50 °C for 60 min.
Bulk samples of an ultrafine-grained tungsten–tantalum composite alloy have been synthesized by consolidating mechanically milled composite powders. The grain growth during densification is limited due to the submicron-scale layering of the individual metals in the composite particles and the relatively low sintering temperature (1300 °C). The ultrafine microstructure of the high-density (∼99% theoretical density) samples leads to a high yield stress of ∼3 GPa under quasi-static uniaxial compression. A tendency for Ta-rich solid-solution formation during densification was observed, and the high-temperature phase equilibria in the composite powders were examined further using high-energy x-ray diffraction at temperatures up to 1300 °C.
Hollow capsules have been intensively investigated due to their high capacity of encapsulating large quantities of guest molecules, making them promising candidate materials for various encapsulation applications. In this work, CaCO3 hollow capsules were successfully synthesized via an emulsion route. The interior hollow structure of the capsules was confirmed by using scanning electron microscopy and transmission electron microscopy (TEM). The vaterite polymorph of the as-synthesized CaCO3 capsules was determined by using x-ray diffraction, high-resolution TEM, and Fourier transform infrared spectroscopy. A self-assembly model was proposed to explain the formation mechanism of the vaterite capsules. By adjusting experimental parameters such as the internal solution amount and the surfactant amount of the double-emulsion system, the average capsule size could be adjusted accordingly. However, the increase in capsule size was at a compensation of size-uniformity degradation. The capsule size uniformity was then further optimized by increasing the magnetic stirring rate. The resultant vaterite capsules demonstrated biodegradability behavior after immersion in phosphate-buffered saline solution, leading to their promising applications in the area of controlled drug delivery.