A novel micro testing machine has been used to perform tensile tests on nanocrystalline Al/Zr microsamples with grain sizes ranging from 10 to 250 nm. The problems associated with testing such small specimens (200μm × 200μm in the gage section) were overcome by using a contact-free interferometrie strain gage (ISDG) and alignment and low friction loading were assured by use of a linear air bearing. The postulated relationship between yield stress and hardness was investigated and will be discussed. The effect of the microstructure and the grain size of the compacts on their mechanical behaviour are also analysed.

Copper-niobium ribbons produced by melt-spinning were compacted by swaging and consolidated using HIPping. Final processing to obtain in-situ composites was done by swaging. The strength of the composite is discussed in terms of the composition and morphology of the niobium phase as evaluated using electron microscopy techniques.

Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Neutron Diffraction (ND) and Mössbauer Spectroscopy (MS) were used to study the nanocrystallization process of Fe73.5Cu1Nb3Si22.5–xBx (x=5, 7, 8, 9 and 12) amorphous alloys. Both the temperature range and the activation energy of Fe(Si) phase precipitation from the amorphous martrix increase with the initial B composition. The initial Si composition influences the mechanism of the nanocrystallization: for the Si rich samples, the beginning of nucleation and growth processes is interface controlled, for the B rich samples it is diffusion controlled. Secondary crystallization from the remaining amorphous is mainly Fe3B and Fe2B, the ratio of Fe3B/Fe2B being dependent on the initial composition too.

Nanocrystalline NiAl has been produced from pre-cast alloys using an electron beam inert gas condensation system. In-situ compaction was carried out at 100 to 300°C under vacuum conditions. Energy dispersive spectroscopy was used to determine chemical composition and homogeneity. Average grain sizes in the range of 4 to 10 nm were found from TEM dark field analyses. A compression-cage fixture was designed to perform disk bend tests. These tests revealed substantial room temperature ductility in nanocrystalline NiAl, while coarse grained NiAl showed no measurable room temperature ductility.

X-ray diffraction (XRD) and differential scanning calorimetry (DSC) have been utilized to investigate the structural evolution of Fe rich Fe-Al alloys during ball milling. It is found that b.c.c. solid solutions can be formed either through ball milling alone or through ball milling together with heat treatment. Thermal diagrams of the milled Fe-Al powders reveal exothermic peaks corresponding to the formation of cc-Fe(Al) solid solution (in both Fe-4wt.%Al and Fe-10wt.%Al) and the formation of FeAl intermetallic compound (in Fe-10wt.%Al). The transformation kinetics of cc-Fe(Al) solid solution in Fe-4wt.%Al were found to follow the Johnson-Mehl-Avrami equation.

The microstructure, mechanical properties, abrasion and wear resistance of WC-Co nanocomposites synthesized by the spray conversion technique by McCandlish, Kear and Kim have been investigated. The binder phase of WC-Co nanocomposites is enriched in W and C, compared to conventional cermets. Small amorphous regions exist in the binder despite the slow cooling after liquid phase sintering. Few dislocations are found in the WC grains. The increased WC content and the amorphous regions modify (i.e. strengthen) the binder phase of the composites. Vickers indentation measurements show a hardness of the nanocomposites reaching 2310 kg/mm2. While the toughness of conventional cermets decreases with increasing hardness, the toughness does not decrease further as the WC grain size decreases from 0.7 to 0.07 μm. but remains constant at 8 MPam1/2. Scratches caused by a diamond indenter are small, commensurate with their hardness. These scratches are ductile, devoid of the grain fracture that is observed with conventional materials. The abrasions resistance of nanocomposites is about double that of conventional materials, although their hardness is larger by 23% only. This is due to the lack of WC grain fragmentation and removal which takes place in conventional cermets. Sliding wear resistance of WC/Co is proportional to their hardness; no additional benefit of nanostructure is obtained. This results from the very small size of adhesive wear events in even large WC grains.

Nanocomposite Ti/Al multilayered thin films have been deposited by magnetron sputtering. These multilayers exhibit interesting structural transitions on reducing the layer thickness of both Ti and Al. Ti transforms from its bulk stable hep structure to fee and Al transforms from fee to hep. The effect of ratio of Ti layer thickness to Al layer thickness on the structural transitions has been investigated for a constant bilayer periodicity of 10 nm by considering three different multilayers: 7.5 nm Ti / 2.5 nm Al, 5 nm Ti / 5 nm Al and 2.5 nm Ti / 7.5 nm Al. The experimental results have been qualitatively explained on the basis of a thermodynamic model. Preliminary experimental results of interfacial reactions in Ti/Al bilayers resulting in the formation of Ti-aluminides are also presented in the paper.

We present atomistic simulations of the crack tip configuration in multilayered Cu-Ni materials. The simulations were carried out using molecular statics and EAM potentials. The atomistic structure of the interface was studied first for a totally coherent structure. Cracks were simulated near a Griffith condition in different possible configurations of the crack plane and front with respect to the axis of the layers. Results show that interface effects predominately control the mechanical behavior of the system studied.

The “polymerizable complex (PC)” technique, a kind of gel technologies, is based on formation of a polyester resin precursor in which various metal ions can be uniformly distributed keeping their initial stoichiometric ratio. The approach allows for the synthesis of multicomponent oxides at reduced temperatures. Feasibility of the PC method is demonstrated for the synthesis of BaTi4O9 at 700–900 °C. BaTi4O9 was subsequently converted to nanocomposite materials by modifying its surface with ultrafine particles of RuO2, and they were used as photocatalysts for decomposition of water into H2 and O2 under irradiation of light from a high-pressure Hg lamp operated at 100 W. High-resolution transmission electron microscopic observations indicates uniform dispersion of spherical RuO2 particles of ∼2 nm in diameter on the host BaTi4O9 surface. The nanocomposite BaTiO9/RuO2 (1 wt % Ru relative to BaTi4O9) material prepared by the PC method at 800 “C showed a photo-catalytic activity ∼3 times higher than that of a material prepared by the conventional ceramic technique at 1100 °C.

The effects of grain size on the phase transformations in nanocrystalline ZrO2-Al2O3 have been experimentally investigated. Compositions from 10 to 50 vol% Al2O3 in ZrO2 were obtained as a hydroxide gel. The powders were then calcined at 600 °C for 17 hours and heat treated at 1100 °C for 24 and 120 hours and at 1200 °C for 2 hours. The phase distribution and grain size were determined using x-ray diffraction and transmission electron microscopy. The initial grain size after calcining was 8–17 nm. It was determined that the critical ZrO2 grain size to avoid the tetragonal to monoclinic phase transformation on cooling from 1100 °C was between 17 and 25 nm. Samples containing 50% Al2O3 maintained a grain size below the critical size for all times and temperatures. The 30% Al2O3 samples showed the same behavior in all but one heat treatment. The remainder of the samples showed significant grain growth and at least partial transformation to the monoclinic phase.

In this paper, we report our experimental results of lead zirconate titanate (PZT) thick-films prepared from the sol-gel derived nanocomposites. Transparent Pb-Zr-Ti-B-Si gels were synthesized from various metal organic precursors. PZT grains with the size of one hundred nanometers were homogeneously grown from the gels in the annealing process. Then PZT thick-films were prepared using the gel-derived glass-ceramic powders with average particle size below 300 nm. Surficial morphology, dielectric and ferroelectric properties of the films were studied. The characteristics of such films are attributed to the nano-sized composite structure of the gel-derived PZT glass-ceramic precursors.

A rapid consolidation technique has been utilized in producing single phase AI2O3 in less than 10 minutes at 1400°C resulting in a grain size less than 500 nm. TiO2 has been added in hopes of obtaining Al2O3/Al2TiO5 nanocomposites in sintering times less than 30 minutes. The sintering process involves resistance heating of a graphite die containing the powder at heating rates of about 10 °C/s. The resistance heating step is preceded by a preparatory step consisting of DC voltage pulses applied across a prepressed powder compact. The retention of the nanostructure is attributed to the rapid heating rate although the possible effect of the DC pulses are also discussed. An Al2O3/Al2TiO5 composite has been produced during a short anneal immediately following sintering of an Al2O3/TiO2 nanocomposite. Substantial grain growth has been observed to occur during the transformation taking the composite to the microcrystalline regime.

“Fish-eye” particles consisting of metal clusters (Ag, Cu) a few nanometers in diameter encapsulated within a thin layer (-1 nm) of silica are produced using aerosol synthesis procedures. We present a method for predicting stable “fish-eye” nanostructures and describe synthesis techniques for producing significant quantities of silica-encapsulated metal nanoparticles.

For many metal/oxide pairs, gas phase formation of oxide encapsulated metal particles is thermodynamically favorable. Using known surface free energies and binary phase diagrams, it is possible to predict whether SiO2-encapsulated metal clusters will form in the gas phase. Two conditions which must be satisfied are: 1) that the surface free energy of the metal is higher than that of Si; and 2) that the metal composition in the particle is greater than the eutectic composition in the metal/Si phase diagram. Ag-SiO2 and Cu-SiO2 are two examples of systems which readily form “fish-eye” structures.

Two types of gas phase cluster sources are used at Purdue for producing encapsulated metal nanoparticles. The Multiple Expansion Cluster Source (MECS) is a well established apparatus which produces small quantities (- 50 mg/hr) of very uniform materials using resistive heating for evaporation. The new Arc Cluster Evaporation Source (ACES) offers much higher production rates (>1 g/hr) using DC arc evaporation. These two cluster sources make possible the study of a unique class of materials.

Optical absorption of nanosized particles in glass was measured. The plasma absorption band was completely spread out for particles below about 1.5 ran in diameter, as also has been found by gold particles in water and a polymer. The growth kinetics suggested growth of spherical particles controlled by diffusion of gold from the matrix to the particles, and a constant number of growing particles, giving a narrow size distribution of particles. For particles below about one ran in diameter (31 gold atoms), the optical absorption was proportional to λ−4, as expected if the absorption results from free electrons in the particles.

In materials that are subject to environmental reactions, one way to increase durability is to decrease the chemical interdiffusion rate. In metal systems, mass transport by diffusion is enhanced – if any change – with finer grained microstructures, because of the greater number of high diffusion interface and boundary paths. In non-metals, increased transport is not necessarily the case, as other mechanisms may control the overall diffusivity. C. Wagner [1] showed the theoretical basis of transport in certain nanocomposite cases based on space charge layers at interfaces.

In an oxide-in-oxide nanocomposite, one can use the tools of bulk analysis to study the near-interface effects on transport. The immiscible pair, TiO2-SiO2, was used as a model system. Nanophase powders (50 and 200 m2/g, respectively) from flame hydrolysis were dispersed with high shear, then freeze-dried and hot-pressed to near theoretical density. Transmission electron microscopy was used to show < 10 nm particles in the composites produced at the time of diffusivity measurement. The rate of change of four-point electrical conductivity in response to a change in oxygen partial pressure was used to estimate chemical diffusivity. The re-equilibration differences between TiO2 diffusivity for bars of about 10 times different square cross-section areas confirmed the interpretation of the conductance rate changes to be the result of bulk interdiffusion.

The interdiffusion rate in the nanoscale dispersoid composites was more than 5 times lower than for same SiO2-fraction composites after coarsening which were like TiO2 with no second-phase. Results are in qualitative agreement with models for impurity segregation to interfaces and for space charge layers near the dispersed nanoparticles.

In order to introduce ferroelectricity into structural ceramics, we synthesized novel ceramic composites containing submicron sized perovskite-type ferroelectrics (ceramic / perovskite-type ferroelectrics nanocomposites). Although perovskite compounds easily react with other ceramics, MgO/BaTiO3 nanocomposites were successfully fabricated using conventional sintering technique. The microstructure of nanocomposites and the phase stability of the dispersed BaTiO3 particulate are discussed.

Thick film resistors are glass/metal oxide nanocomposites used in hybrid microcircuits. These components have a small temperature coefficient of resistance that is useful in systems that experience a wide range of service temperatures. Test samples were produced by printing, drying, and firing resistor pastes in a laboratory process that simulated production conditions. The process parameters of peak firing temperature, time at peak temperature, and probe current were factors in a 23 factorial experiment that measured in-situ resistance (resistance during processing), as-fired resistance, and the temperature coefficients of resistance. As-fired resistance is shown to increase with firing time and temperature. In-situ resistance exhibited a small decrease with increasing firing temperature due to thermally-activated glass conduction at firing temperatures. The temperature coefficient of resistance measurements show that R[T] curve flattens with increasing firing time and temperature. X-ray diffraction revealed Pb-ruthenate, alumina, and Zr-silicate phases to be dispersed in the glass. Transmission electron microscopy in conjunction with energy dispersive x-ray spectroscopy revealed that the conductive phases, Pb- and CuBi-ruthenate particles, increased in size with increasing firing time and temperature. Lattice parameter measurements revealed only a small increase in the ruthenate structure. Resistance changes are attributed to increased separation of the conductive ruthenate particles by coarsening.

Nano-composites allow a materials engineering approach to be exploited to realise specific characteristics in optical thin film ensembles. For example, films can be produced with refractive indices determined by their average composition on the basis of effective medium approximations, so freeing optical designers from the constraints imposed in pure materials. A summary is presented of the progress made in a fundamental study of films based on diverse materials such as fluorides and sulphides, fabricated using molecular beam deposition techniques. The film properties (eg refractive index, surface morphology, environmental stability) are correlated with microstructure (as determined by cross-sectional TEM techniques). The enhanced properties of the films are discussed in relation to the realisation of periodically modulated graded-index structures of the type required for optical filter applications.

Crack/particle interactions in Al2O3/SiC and Al2O3/TiN nanocomposites have been observed by TEM on samples containing cracks produced by Vickers indentations. No significant crack deflection by intragranular SiC particles or microcracking around nanoparticles was found. Intergranular cracks were observed to be deflected into the matrix grains by SiC particles on grain boundaries inclined to the direction of crack propagation. TiN particles were not effective in this way. These features are briefly discussed within the framework of the interfacial fracture energies. These were calculated from interfacial energies, which were determined by the measurement of grain boundary-interface dihedral angles.

The hardness of the recently developed novel superhard nanocrystalline composites exceeds 5000 kg/mm2 (50 GPa) and the elastic modulus 550 GPa. This is due to a special microstructure which is formed when the fraction of the amorphous component reaches the percolation threshold. Experimental data are presented and discussed.