MRS Online Proceedings Library (OPL)

Raman spectroscopy is a technique widely used to study the vibrational modes of carbon nanotubes. The low-frequency Radial Breathing Modes (RBMs) are frequently used to characterize carbon nanotube samples. We report a Raman spectroscopic study on the strain-induced intensity variations of the RBMs of Single-Wall Carbon Nanotubes (SWNTs) in epoxy/SWNT composites. The RBM intensities have been found to vary significantly over a range of strain between -0.3% and 0.7%. The trend (increase or decrease) as well as the magnitudes of the intensity variation depends on the nanotube diameter and its chirality. Using tight-binding calculations, we have shown that these intensity variations can be explained entirely by resonance theory. Electronic density of states calculations confirm that the energy separation between the Van Hove singularities shifts with strain. The nanotubes are thus moved closer or further away from resonance, causing the intensity variations. It is demonstrated that through the use of resonance theory, a tentative chirality can be assigned to each type of SWNT from knowledge of its RBM position and the effect of strain upon the RBM intensity, thus determining its entire structure.

The crystallization behavior of polymers in nanocomposites with inorganic fillers (montmorillonite layered silicate, MMT) is reviewed. Various different polymers are comparatively discussed [poly(vinyl alcohol) (PVA), polypropylene (PP), syndiotactic-polystyrene (sPS), and poly(ethylene oxide) (PEO)] representing three types of filler/matrix interactions: strong specific interactions (PVA/MMT), weak/negligible interactions (sPS and PP/o-MMT), and “unfavorable” (PEO/MMT). In the case of PVA/MMT, crystallization of PVA is strongly promoted by MMT, also stabilizing a new crystal form not found in bulk PVA. For sPS and PP/o-MMT, crystallization is only moderately affected, exhibiting traces of simple heterogeneous nucleation and mostly bulk-like crystal structures, with very small traces on non-bulk crystals. For PEO, crystallization is impeded near the MMT surfaces, due to coordination of the surface cations to the PEO. In all cases smaller spherulite sizes develop when filler is added, independent of the size of the bulk polymer spherulites, whereas the crystallization temperature changes reflect the strength of the polymer/surface interactions.

The residual microstrains in cryomilled Ni powders, processed under various cryomilling conditions, are measured by XRD and analyzed using a single line approximation (SLA) method. The results show that the average residual microstrains are in the range of 2×10-3 ∼ 6×10-3, and the residual microstrain on the (200) plane is higher than those on the other planes by 33 %. The measured microstrain is proposed to evolve from the introduction of N as impurity atoms in Ni lattice may be attributed to the evolution of the residual microstrain. The N atoms tend to stay in the octahedral sites of Ni, and the diameter of N atom is larger than that of the octahedral site of Ni by 48 %. Accordingly, a lattice strain field is expected around interstitial N atoms that are located at octahedral sites. By comparing the crystal structure around the octahedral site of Ni with that of Ni3N structure, the lattice strains are estimated to be in the range of 5 ∼ 15 %. The results show that the (200) plane has the lattice strains that are two times higher than those in other planes, and this is argued to be the reason for the measured anisotropy of residual microstrain in Ni after cryomilling.

Ceramic coatings can provide an ideal protection for MEMS (MicroElectroMechanical Systems) structures while imposing a great challenge in processing a prime, reliant coating due to their inherent brittleness and defects formed during processing. In an attempt to compensate for the weakness of the ceramic coating, we have developed a low-temperature solution precursor process to create strain-tolerant, protective bilayer coating consisting of an integrated ceramic-organic hybrid material. The top ceramic coating offers an inert, protective layer whereas the underlying nanometer scale self-assembled organic coating provides compliance for the overlying hard coating. Together, these bilayers minimize mechanical and thermal stresses. In addition, organic self-assembled monolayers(SAM) act as a ‘template’ by forming a proper surface functionality for the subsequent growth of hard ceramic coatings. Molecular level understanding of the microstructure and micromechanics involved in the synthesis and processing of the coating is systematically studied by a variety of characterization techniques such as XRD, AFM, SEM/EDS and nanoindentation. This work is also complemented by numerical simulation to provide a clearer understanding of the stress development in the ceramic coating and its interfacial properties.

We report the results of a study of adsorption of small molecules on the surface of buckminsterfullerene, C60. The pressure dependence of the Raman spectrum was investigated over the range 0–10 GPa in methanol-water mixtures that were used as the pressure transmitting fluid (PTF) in a diamond anvil cell. It is found that the spectral shift and its pressure derivative are sensitive to both the applied pressure and to the composition of the PTF. These observations are consistent with an explanation that involves preferential adsorption onto the surface of the C60. In particular, the notion of C60 collapse needs not be invoked to explain the observations.

Testing methods are reviewed that can be applied to the small sample sizes which result from many of the processing routes for preparation of nanocrystalline materials. These include the measurement of elastic properties on small samples; hardness, with emphasis on nanoindentation methods; the miniaturized disk bend test (MDBT); the automated ball indentation test (ABI); the shear punch test; and the use of subsize compression and tensile samples.

This contribution presents challenges to control the microstructure in nano-structured materials via a relatively new approach, i.e. using a so-called nanocluster source. An important aspect is that the cluster size distribution is monodisperse and that the kinetic energy of the clusters during deposition can be varied. Interestingly the clusters are grown in extreme non-equilibrium conditions, which allow obtaining metastable structures of metals and alloys. Because one avoids the effects of nucleation and growth on a specific substrate one may tailor the properties of the films by choosing the appropriate preparation conditions.

We report the results of first-principles calculations showing that boron can form a wide variety of metastable planar and tubular forms with unusual electronic and mechanical properties. The preferred planar structure is a buckled triangular lattice that breaks the threefold ground state degeneracy of the flat triangular plane. When the plane is rolled into a tube, the ground state degeneracy leads to a strong chirality dependence of the binding energy and elastic response, an unusual property that is not found in carbon nanotubes. The achiral (n, 0) tubes derive their structure from the flat triangular plane. The achiral (n, n) boron nanotubes arise from the buckled plane, and have large cohesive energies and novel structures as a result.

Ultrathin polymer films have been deposited on both multi-wall and aligned carbon nanotubes using a plasma polymerization treatment. TEM experimental results showed that a thin film of polystyrene layer (several nanometers) was uniformly deposited on the surfaces of the nanotubes including inner wall surfaces of the multi-wall nanotubes. The coated multi-wall nanotubes were mixed in polymer solutions for studying the effects of plasma coating on dispersion. It was found that the dispersion of multi-wall carbon nanotubes in polystyrene composite was significantly improved. The deposition mechanisms and the effects of plasma treatment parameters are discussed.

The microstructural evolution in a nanostructured Al-Mg alloy fabricated by cryogenic mechanical alloying (cryomilling), was investigated using transmission electron microscopy (TEM). Nanostructured Al-Mg powders were first synthesized by a mechanical alloying under liquid nitrogen media (cryomilling), and the powders were subsequently degassed, hot isostatically pressed, and extruded into a full dense, bulk form. The results showed that Si containing phases and (Fe,Ni)Al intermetallics existed in as-extruded Al-Mg alloy. In addition, the extrusion temperature has a strong influence on the formation of microstructural anisotropy. A lower extrusion temperature yields a microstructure that is more anisotropic relative to that present at the higher extrusion temperature. More specifically, at the lower temperature, the nano-sized Al grains have a tendency to rotate towards the <111> direction, along the extrusion direction.

This study applies NMR, SRA, MIP, SEM and electric resistance tests to examine the microstructure of the composite materials of nano concrete. The test results show that owing to the pozzolanic reaction activated by the nanopowders, the CaOH2 content within the composite materials is decreasing, filling the capillary and gel pores. This way, the microstructure of the composite materials is transformed in its arrangement, which makes concrete much more well-mixed and densified, enhancing the compressive strength. The permeability is cut down as well. In conclusion, it ends in much better durability.

We perform atomistic simulations to compute bending of freestanding nanoscale thin Si film induced by strained Ge islands. We show that a larger Ge dome island can induce smaller bending than a smaller hut island and explain the surprising experimental observation for growth of Ge islands on patterned silicon-on-insulator substrate (SOI) with Si template layer thinned down to nanometer scale. This counterintuitive bending behavior is caused by strain sharing between the film and the ultra thin substrate.

Near nanoscale fine particles including vanadium dioxide (VO2) and zinc oxide (ZnO) were incorporated into matrix materials (tin and polymer adhesives). A number of mechanical damping tests were conducted on the prepared composite materials at frequency ranges of 0 − 2 kHz and over a broad temperature range. The mechanical vibration test results showed that VO2 and ZnO gave significantly higher negative-stiffness (or damping) at approximately 68 °C (155 F) and 29 °C (85 F). For example, approximately 15% and 12% damping values were achieved at first and second resonance frequencies, respectively, which can potentially prevent vibration on the materials. This significant improvement on the damping of the nanocomposite material may be because of the ferroelasticity, viscoelasticity and/or interfacial sliding at those particular temperatures. It was also observed the etching of substrate surfaces improved adhesion and contributed consistent results to vibration testing reproducibility. Thus, it is concluded that nanocomposite existing damping properties can be an important method to achieve large damping responses over a broad temperature range.

The microstructural characteristics and mechanical behavior at room temperature of a nanostructured Al-Mg alloy, with grain sizes of approximately 100 nm, manufactured by a cryomilling process were investigated in the present study. The results reveal an asymmetry of yield strength between tension and compression. On the basis of the mechanical behavior results it appears that the presence of a few micron inclusions may have a negative effect on tensile behavior of the cryomilled nanostructured Al-Mg alloy.

During processes of mechanical alloying the characteristic structural length scales of an alloy, including the phase domain size and the crystallite grain size, decrease gradually to a nanocrystalline or even amorphous final state. This method therefore allows a unique avenue to explore the structure-property relationship over several orders of magnitude in length scale. In this work we have considered an ideal equiatomic Ti-Zr system deformed through multiple cold-rolling passes to refine the structural length scales into the nanometer range. The variation of the hardness of the system with decreasing length scale is discussed in terms of traditional Hall-Petch scaling, chemical mixing and the phase evolution of the system, as well as other possible contributions to the hardness variations during processing.

Quantized high-frequency (∼1016 Hz) correlated longitudinal electron excitations (plasmons) generated in the energy-loss range 0–50 eV by fast electrons passing through any solid enable one to probe various states of matter. Their energy, Ep, is directly related to the density of valence electrons, thus allowing determination of solid-state properties that are governed by ground-state densities. Universal features and scaling in relations between Ep and the cohesive energy per atomic volume, bonding electron density and elastic constants have been established. The resulting correlations follow the universal binding energy relationship, thus providing new insights into the fundamental nature of structure-property relationships. They allow direct in situ determination of local material properties in an analytical electron microscope, as illustrated by examples utilizing Al- and Ti-based structural alloys.

The creep resistance of the directionally solidified ceramic eutectic of Al2O3/c-ZrO2(Y2O3) was studied in the temperature range of 1200–1520°C both experimentally and by mechanistic dislocation models. The creep of the eutectic in its growth direction exhibits an initial transient that is attributed to stress relaxation in the c-ZrO2(Y2O3) phase, but otherwise in steady state shows many of the same characteristics of creep in sapphire single crystals with c-axis orientation. The creep strain rate of the eutectic has stress exponents in the range of 4.5–5.0 and a temperature dependence suggesting a rate mechanism governed by oxygen ion diffusion in the Al2O3. A detailed dislocation model of the creep rate indicates that much of the nano-scale encapsulated c-ZrO2(Y2O3) is too small to deform by creep so that the major contribution to the recorded creep strain is derived from the diffusion-controlled climb of pyramidal edge dislocations in the Al2O3 phase. The evidence suggests that the climbing dislocations in Al2O3 must repeatly circumvent the c-ZrO2(Y2O3) domains acting as dispersoids resulting in the stress exponents larger than 3. The creep model is in very good agreement with the experiments.

We deposited multilayer Nanocrystalline Diamond (NCD) thin films on Ti-6Al-4V substrates that were machined to imitate the shapes of the condyle and fossa of the temporomandibular joint (TMJ). We performed low stress wear assessment experiments on condyle/fossa pairs mounted in a custom-built mandibular movement simulator (MMS) for 5 x 105 loaded cycles at 1.2 Hz, which is equivalent to 4.4 years of clinical use. Analysis of wear surfaces on the control and the NCD-coated pairs indicated that no film delamination occurred on the NCD-coated condyle/fossa couple and that wear damage was extensive on the uncoated condyle/fossa pair. The high stress wear tests performed using the Ortho-POD machine at loads of 80 and 165 N showed that loss of film on the condyle specimens occurred after 3300 and 341 cycles, respectively. A subsequent evaluation of the influence of condyle curvature on wear by articulating a multilayer condyle/disk pair at a load of 50 N and 250 000 cycles at 1.2 Hz, showed that film delamination on the condyle occurred after 12500 cycles and no loss of film was observed on the disk after 250 000 cycles of articulation. Our results show that the observed lower film lifetimes on the condyles at high stresses are not related to intrinsic stresses in the film but probably due to lower film adhesion on the curved surfaces of the condyle.

High molecular weight polyaniline / multi-walled carbon nanotube composite films were fabricated using solution processing. Composite films with various weight percentages of multiwalled carbon nanotubes were fabricated. Physical properties of these composites were analyzed by thermogravimetric analysis, tensile testing, and scanning electron microscopy. These results indicate that the addition of multiwalled nanotubes to polyaniline significantly enhances the mechanical properties of the films. In addition, metal–semiconductor (composite) (MS) contact devices were fabricated, and it was observed that the current level in the films increased with increasing multiwalled nanotube content. Furthermore, it was observed that polyaniline containing one weight percent of carbon nanotubes appears to be the most promising composition for applications in organic electronic devices.

Carbon films deposited by filtered cathodic arc show a high compressive stress which limits their thickness because of delamination. We study three methods of relieving the stress in these films. We first determine the dependence of the stress on DC bias up to bias voltages of 1200V and show that the formula of Davis provides a good fit to the data including the stress maximum in the region of 150–200V and the progressive decrease in stress at higher voltages. In the second method, plasma immersion ion implantation (PIII) was used to create multilayer of alternating high density, high stress (PIII on) films and lower density, low stress (PIII off) films. This method enabled thicker structures to be produced. In the third method we made multilayers using amorphous silicon and carbon layers. Annealing of these layers showed that the stress could be reduced to very low values because of the ability of the silicon layers to absorb compressive stress by contracting after the annealing step. The microstructural effects of PIII were studied by transmission and scanning electron microscopy.