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 mechanical properties of sputter-deposited NiTi shape memory alloy thin films ranging in thickness from 35 nm to 10 μm were examined using nanoindentation and atomic force microscopy (AFM). Indents made in films as thin as 150 nm showed partial shape recovery upon heating, although film thickness was found to have a marked effect on the results. A modified spherical cavity model is used to describe the findings, which suggest that the substrate tends block the shape memory effect as film thickness decreases below a threshold level which is specific to applied load. This has the net effect of decreasing the indent recovery below the critical film thickness. The fact that the spherical cavity model predicts the critical film thickness at which the shape memory effect is blocked indicates that the increased recovery of nanoscale indentations is due to a suppression of plastic processes rather than an enhancement of shape memory processes.

Accurate neutron powder diffraction experiments at D20, ILL Grenoble, allowed to monitor the reconstructive tetragonal to monoclinic phase transition as a function of the size of zirconia nanoparticles. In the nanocrystals, both phases are identical to the ones generally observed in micrometric zirconia. Rietveld refinements on these samples point out an increase of the tetragonal fraction and a decrease of the lattice parameters when the size of the particle decreases. An uniaxial strain depending on the grain size is also observed. The phase transition definitely occurs above a threshold crystal size. These results are analysed within the Landau theory and they can be understood as a mechanism of size-dependent phase transition where the primary order parameter is altered by the nanoparticle size.

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.

Phase mixture models describing the mechanical properties of submicrometer grained metals are presented. In this approach, grain boundaries or cell walls are treated as a separate phase. Two cases are considered: the mechanical response of an ultrafine grained material and the process of grain refinement by equal channel angular pressing. Model predictions with regard to the evolution of the microstructure, strength and texture are verified for Cu.

Nanoindentation was used to probe the mechanical response of mesoporous silica films as a function of processing treatment. A contrasted behaviour appears between low temperature processed films which retain the templating agent and are thus little compressible, and high temperature processed films, which are more condensed and also exhibit high porosity. We suggest that the behaviour of the former is dominated by shear flow, at least above a given threshold, while the latter are characterized by a yield strength in compression as is commonly found in porous materials. The response to indentation allows fast qualitative comparison of mechanical responses: in the present work, we show that a fast UV-O3 treatment results in mechanical properties which are undistinguishable from a much more cumbersome high temperature heat treatment.

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.

Fully amorphous and mixed amorphous/crystalline bulky (Fe77+yGa3P9.5-yC4.5B3.5Si2.5)(100-x)/100Fex alloys were prepared varying Fe and Fe-P contents. The effect of the compositional changes on glass forming ability (GFA), stability of the amorphous phase and mechanical properties was studied. When y = 0 and x is enhanced from 0 to 2, the stability of the supercooled liquid region decreases of 10 K. For x = 0 and y = 3.5 the glass forming ability is drastically reduced leading to a mixed structure consisting of bcc-Fe, Fe3(P,C,B) and a small fraction of amorphous phase.

During compression test at room temperature the deformation of fully amorphous samples (y = 0) is dominated by the initiation and propagation of shear bands with consequent nil or small plastic deformation (0.2 % at 3000 MPa) for the alloys with x = 2 and x = 0 respectively. Embrittlement of (Fe77Ga3P9.5C4.5B3.5Si2.5)0.98Fe2 was observed after partial and full devitrification.

A higher Young modulus and a maximum strength of 3300 MPa were shown by the as cast partially crystalline Fe80.5Ga3P6C4.5B3.5Si2.5 alloy; also in this case, no yielding was detected.

Finally, compression tests at high temperature for fully amorphous Fe77Ga3P9.5C4.5B3.5Si2.5 showed inhomogeneous deformation up to 402°C. Homogeneous non-Newtonian plastic deformation was detected at 427°C. Newtonian homogeneous flow at 452°C is limited by the crystallisation of the superliquid and consequent final failure.

The fatigue crack growth rates and fracture toughness of bulk nanocrystalline Al 5083 having a bimodal grain size distribution were investigated. The nanocrystalline powders were prepared by mechanically ball milling spray atomized Al 5083 powders in liquid nitrogen. This nanocrystalline powder was blended with 50 wt% spray atomized large grained Al 5083 powders. The blended powder was then cold pressed, degassed, and extruded into rods. The bimodal Al 5083 thus produced consists of nanocrystalline grain bands and coarse grain bands. While the yield strength of the bimodal Al 5083 is about 25% lower than that of the all nanocrystalline Al 5083, its tensile ductility is almost 50% greater. In addition, the fracture toughness of the bimodal material is about 85% higher than that of the all nanocrystalline counterpart. Fatigue crack growth rates of bimodal Al 5083 are about 30% lower than those of all nanocrystalline Al 5083. The lower fatigue crack growth rates are accompanied by more tortuous crack paths when the crack propagated through the coarse grain regions in the bimodal Al 5083.

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.

A range of multi-wall carbon nanotubes and carbon nanofibres were mixed with a polyamide-12 matrix using a twin-screw microextruder, and the resulting blends used to produce a series of reinforced polymer fibres. The aim was to compare the dispersion and mechanical properties achieved for nanofillers produced by different techniques. A high quality of dispersion was achieved for all the catalytically-grown materials and the greatest improvements in stiffness were observed using aligned, substrate-grown, carbon nanotubes. The use of entangled multi-wall carbon nanotubes led to the most pronounced increase in yield stress. The degrees of polymer and nanofiller alignment and the morphology of the polymer matrix were assessed using X-ray diffraction and calorimetry.

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.

A chemical vapor deposition hydrogen/methane/nitrogen feedgas mixture with unconventionally high methane (15% CH4 by volume) normally used to grow ultra-hard and smooth nanostructured diamond films on Ti-6Al-4V alloy substrates was modified to include diborane (10% B2H6 in hydrogen) for boron-doping. The flow rate for B2H6 was varied to investigate its effect on plasma chemistry, film structure, and mechanical properties. It was found that boron in the plasma can easily be incorporated into diamond films and change the lattice parameter and affect film structure as measured by Raman spectroscopy. Grazing angle x-ray diffraction shows a strong dependence of diamond lattice parameter with diborane flow rate and B2H6:CH4 flow rate ratio. Thermal stability of these films was evaluated by heating in an oxygen environment above 700 °C. Nanoindentation measurements show that the films have high hardness close to that of nanostructured diamond. High film hardness and toughness, combined with good thermal stability and low surface roughness indicate great potential as wear resistant coatings able to withstand high temperature oxidizing environments.

By using elastic continuum model for a spherical body along with the appropriate boundary conditions at the surface of the body, vibrational frequencies of MgO nanoparticles are calculated in the present paper. It is found that the vibrational frequencies corresponding to these eigen values depend strongly on the size of the nano particles and the peaks in the Raman spectra shift to the higher frequencies side as size of the nano particles decreases. We have also investigated the effect of a polymer matrix on the frequencies and Raman shift of MgO nanoparticles. The damping constant is found to vary linearly with the size of nano particles which shows that the mechanical damping is the prominent mechanism in the damping of the acoustic phonon modes.

Production of intermetallic materials in the system TiAl3-X (X = Cr, Mn, Fe) has been achieved by means of mechanical milling and sintering techniques. Spark plasma sintering is used since it reduces time at high temperature and inhibits grain growth. The produced materials have grain sizes in the nano and microscale depending on the material and processing variables. The TiAl3-X alloys are formed mostly by the cubic L12 phase. The average grain size ranges between 30 and 50 nm in the as sintered condition. Aging at elevated temperature has been used to promote grain growth. Compression tests have been performed to evaluate mechanical properties as a function of temperature and grain size. In all cases yield stresses higher that 700 MPa are obtained together with a ductility that depends upon temperature and grain size. No ductility is found for the smallest grains sizes tested (30 nm) at room temperature. Above 673 K, these materials show ductility and additionally they present a quasi superplastic behavior at temperatures higher that 973 K. On the other hand ductility can also be developed in the TiAl3-X alloys by inducing grain growth via annealing. Alloys with grains sizes around 500 nm show high ductility and a large density of microcraks after deformation suggesting that the yield strenght becomes lower than the stress to propagate the cracks. In such materials, a considerably high strength is retained up to 873 K.

In nanostructured metallic multilayers, hardness and strength are greatly enhanced compared to their microstructured counterparts. As layer thickness is decreased, three different regions are frequently observed: the first region shows Hall-Petch behavior; the second region shows an even greater dependence on layer thickness; and the third region exhibits a plateau or softening of hardness and strength. The second and third regions are studied using our discrete dislocation simulation method. This method includes the effects of stress due to lattice mismatch, misfit dislocation substructure, and applied stress on multilayer strength. To do so, we study the propagation of existing threading and interfacial dislocations as the applied stress is increased to the macroyield point. Our results show that in region 2, dislocation propagation is confined to individual layers initially. This “confined layer slip” builds up interfacial content and redistributes stress so that ultimately, the structure can no longer confine slip. The associated macroyield stress in this region depends strongly on layer thickness. In region 3, layers are so thin that confined layer slip is not possible and the macroyield stress reaches a plateau that is independent of layer thickness.

An alternative route to prepare polymer-clay nanocomposites using supercritical carbon dioxide (scCO2) is described. The presence of clay nanoparticles significantly influences the morphology, foaming process and crystallization of a polymer when processed in scCO2. Intercalated structures are successfully produced in the presence of scCO2 even when favorable interactions between the polymer and the clay are not present. The effect of scCO2 on the intercalation process is analyzed for a variety of polymer systems both with modified and unmodified clays. By controlling the hydrophilicity of the polymer and clay systems, specific understanding of the effect of scCO2 on the structure and morphology of the nanocomposites is obtained. Experimental results show significant increases in the clays d-spacings for scCO2-treated samples. This behavior is consistent regardless of the nature of the polymer, showing significant amounts of intercalation even in purely hydrophobic polymers.

This study focuses on the role of chemistry of onium salt(s) used in functionalizing clay and the processing conditions in achieving exfoliated clay vinyl ester nanocomposites. Two different clay treatments were added to vinyl ester resin and three different processing conditions were examined in the formulation of nanocomposite. Through this study, we demonstrate that the degree of exfoliation and dispersion of layered silicate nanocomposite is affected by both processing and the clay chemical treatment. At an organoclay loading of only 3.5wt%, the modulus improved by 20% in partially reactive organoclay system, while the modulus improved by 10% in nonreactive organoclay system compared to that of pristine vinyl ester resin.

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.

A NiCoCrAlY /Al2O3 nanocomposite coating was developed for Inconel 718 substrates to improve thermal barrier coatings (TBC's) based on thermally sprayed NiCoCrAlY and alumina. This intermediate TCE coating was deposited by rf sputtering techniques and was instrumental in increasing the fatigue life of both TBC's and thermal spray instrumentation. Combinatorial chemistry techniques were employed to screen a large number of NiCoCrAlY / Al2O3 compositions to yield an optimal composite coating such that the TCE of the metallic bond coat was matched to the ceramic top coat. The resulting combinatorial libraries were thermally fatigued and the composition of the library with the longest fatigue life was determined by X-ray energy dispersive analysis (EDS). A sputtering target of the optimal composition was fabricated by thermal-spraying a mixture of NiCoCrAlY and alumina to simulate the results from the combinatorial chemistry experiments and form a nanocomposite with the desired properties. The sputtered intermediate TCE coating improved the fatigue life of the TBC's by 160% when compared to as-sprayed TBC's formed on Inconel 718 substrates. When a thermally grown oxide was formed on the surface of NiCoCrAlY bond coated substrates prior to deposition of the intermediate TCE coating, a 200% increase in fatigue life was realized. Techniques for extending the fatigue life of other thermal barrier coating systems using this approach will be discussed.