We have examined the effect of excimer laser surface processing and doping with Au on the mechanical, tribological, and bonding properties of MoSx thin films. We find that the effects of processing are manifested primarily in the surface of the films, but that there is also some film-substrate interaction during high fluence processing. The changes are sufficient to dramatically alter the wear life of the films. At low loads, laser processing alone reduces the run-in period and increases wear life. At higher loads, processing reduces wear life, although the run-in period is still short. These results are understood in terms of changes in the hardness of the surface of the films. Laser processing renders deposited films insensitive to high humidity storage. After laser processing, Raman spectroscopy shows changes in bonding to that characteristic of single crystal MoS2. Laser doping with Au results in wear life comparable to or greater than that of unprocessed films even at the highest loads used. Thus, laser doped MoSx films show lower initial friction, comparable wear life, and may exhibit greater environmental stability than as-deposited films.

Aged bricks of AZS and mixed α-β-alumina refractories have been sampled in superstructures of glass making furnaces. α- and β-alumina phases contained in these refractories have been investigated by optical absorption spectroscopy, electron paramagnetic resonance, and electron probe microanalysis. On the side of the brick exposed to the tank atmosphere, β-alumina is the only phase present. The primary corundum grains are transformed into secondary β-alumina under the influence of contaminants from raw materials and oil ashes. The temperature conditions existing in the furnace preclude the formation of β” alumina. The bright blue color of β-alumina originates from the presence of tetrahedral Ni2+ in Al(2) sites, with no evidence for nickel atoms located in the ionic conduction band. By considering the chemical composition of β-alumina, spectroscopic results are consistent with a mutual interaction between divalent and monovalent species during cation diffusion. Indeed, the small divalent cations such as Ni are located in the spinel block and the larger alkali cations play a charge compensation role in the conduction band. As other divalent cations of small ionic radius, nickel hence helps to stabilize β-alumina, which maintains the refractory performance during furnace operation. The spectroscopic evidence of trace amounts of nickel (<100 ppm) in secondary corundum crystals means that this phase formed at the expense of β-alumina inside the high-alumina refractory brick. By considering the diffusion coefficients of Ni2+ in α- and β-alumina, this indicates a fast contamination of the material at an early stage of the furnace history. The formation of a permanent deep layer of primary and secondary corundum has protected the inner part of the refractory brick from further contamination.

The microindenter has proven to be a powerful device in the characterization of the mechanical properties of thin films. The machine has both high resolution in the applied load and penetration depth measurements, as well as the versatility to perform different types of testing. The former provides the capability to deal with extremely thin films, while the latter allows for other mechanical properties, in addition to hardness, to be acquired. Four types of tests, namely indentation, scratch, load relaxation, and indentation fatigue tests can currently be conducted using the microindenter via different operating procedures. Only the scratch and load relaxation techniques will be covered in this paper. In a microscratch test, the normal load, tangential load, scratch length, and acoustic emission are monitored simultaneously during an entire scratch process for the purposes of measuring the critical load and studying the failure mechanisms of the deposited films. The adhesion strength, scratch hardness, fracture toughness, and friction are the mechanical properties which are possible to obtain by using this technique. Results from aluminum, carbon, and zirconia coatings will be discussed. The load relaxation test provides information on the creep properties of the films and results in an empirical constitutive relation between the applied stress and plastic strain rate. The creep properties of DC sputtered Al films will be used as an illustration of this.

Sodium silicates are investigated to enhance the strengths of Bayer process muds and develop structural ceramics without sintering. With an impregnation of sodium silicate from 2% to 10% concentration in red mud, the fracture toughness is enhanced from 0.2 to 0.9 MPa. Compression strengths of 25.1 MPa (3628 psi) have been attained with red mud at 10% silicate concentration. Similar enhancements by a factor of 4 to 5 have been obtained for modulus of rupture and Brinell hardness number. It is shown that these properties do not deteriorate in acidic and neutral environment in water, implying stability to weathering conditions. SEM investigations reveal elongated crystal formation, possibly of aluminum and iron silicates in the aggregate. These crystals act like whiskers enhancing the strength. The process is applicable for development of low-cost construction components.

In this paper, we propose that, depending on their height, ledges on cracks can be efficient sources of dislocations at loadings well below the critical loading for homogeneous emission. Detailed 3-D elastic calculations are presented supporting this proposition. There are two configurations for emission: one which blunts the crack, and one we call a jogging configuration. By our calculations, the blunting configuration should be the more efficient source; however, jogging dislocations are more frequently observed, experimentally. We find that the ledge is only a finite source of dislocations, in the sense that the ledge height decreases as the dislocations are emitted. The atomic configuration at the ledge is composed of finite lengths of real dislocations, which is the reason why such dislocations can be emitted easier than homogeneously produced dislocations. The stresses at the ledge tip produce a cloud of bound dislocations near the ledge, pinned at the ledge ends, so that the ledge crack configuration becomes delocalized. Delocalization of the pileup dislocations in the jogging direction may explain why the jogging dislocations are more frequently seen. Implications for dislocation free zones and ductile transitions are discussed.

We examine the photon emission accompanying rapid crack growth in an unfilled epoxy resin and in the same resin filled with alumina particles. The alumina particles substantially increase the toughness of the material and increase the photon emission intensities at least tenfold. We attribute the increased photon emission in the filled material to high densities of broken bonds near the alumina particles. The photon emission signals from both filled and unfilled materials show nonintegral (fractal) dimensions which are insensitive to the presence of the particles at the level of precision employed. Fractal dimension measurements of the fracture surfaces are likewise relatively insensitive to the presence of the filler, despite marked variations in apparent surface roughness. The photon emission signals were examined for the presence of chaos. Computations of the correlation exponent of Grassberger and Procaccia indicate that the photon emission fluctuations are not noise-like in character, and suggest deterministic chaos. Lyapunov exponent estimates on photon emission signals confirm the presence of chaotic processes. X-ray photoelectron spectroscopy and electron microscopy of the fracture surface indicate very little interfacial failure; i.e., fracture proceeds predominantly through the epoxy matrix in both filled and unfilled materials. Consequently, the character of the polymer matrix dominates the fracture process and therefore determines the fractal nature of the surface and the chaotic nature of the photon emission intensities in each material.

The high temperature equilibrium conductivity (950 °C–1050 °C) of congruent LiNbO3 can be resolved into two components: an electronic portion that is dependent on the oxygen partial pressure and an ionic portion that is pressure independent. It is shown that the two components can be obtained from an analysis of the total equilibrium conductivity measured as a function of oxygen partial pressure. The ionic transport number (fractional ionic conductivity) thus obtained is compared with that obtained from an oxygen concentration cell measurement. The two techniques are found to be in excellent agreement, confirming the experimental validity of the defect chemistry method. From the temperature dependence of the ionic conductivity, the activation energy (138 kJ/mol [1.43 eV]) for the ionic transport is obtained. The results are in good agreement with the value previously obtained for the oxygen chemical diffusivity.

Silicone polymers were pyrolyzed to form silicon oxycarbides that contained only silicon, oxygen, and carbon. The starting polymers were mainly methyl trichlorosilane with a small amount of dimethyl dichlorosilane. NMR showed that the polymers had a silicon-oxygen backbone with branching and ring units. When the polymer was heated in hydrogen, toluene and isopropyl alcohol, used in production of the polymer, were given off in the temperature range 150 °C to 500 °C. Substantial decomposition of the polymer itself began only above about 700°by evolution of methane. The network of silicon-oxygen bonds and silicon-carbon bonds did not react and was preserved; the silicon-carbon bonds were linked into the silicon-oxygen network. The silicon oxycarbide was stable above 1000 °C, showing no dimensional changes above this temperature. The interior of the silicon oxycarbide was at very low effective oxygen pressure because oxygen diffused slowly in it. There was also a protective layer of silicon dioxide on the surface of the silicon oxycarbide.

A thorough investigation of the microstructure of single SCS-6 SiC fibers widely used as reinforcements in metal-matrix and ceramic-matrix composites has been made. Various techniques of electron microscopy (EM) including scanning (SEM), conventional transmission (TEM), high resolution (HREM), parallel electron energy loss spectroscopy (PEELS), and scanning Auger microscopy (SAM) have been used to analyze and characterize the microstructure. The fiber is a complicated composite consisting of many different layers of SiC deposited on a carbon core and different carbonaceous coatings covering the SiC layers. The structural and chemical aspects of each layer are characterized and discussed.

Measurements of atomic Na emission accompanying the fracture of sodium trisilicate glass and a soda lime glass in vacuum were made by quadrupole mass spectroscopy and surface ionization techniques. Peak Na° emission intensities occur some 3–6 ms after the fracture event and decay over tens of milliseconds. This behavior is attributed to the diffusion of Na+ ions into a layer of damaged material at the surface where the ions are subsequently neutralized and thermally emitted as Na°. Charge carriers generated during fracture and subsequently trapped at defect sites apparently play important roles in charge compensating Na+ diffusion and in neutralizing Na+. During the first 300 ms following fracture, we also observe intense, short lived (400 μs) bursts in Na° emission which may be associated with catastrophic relaxation of residual stresses. The kinetics of Na emission suggest that the relaxation of newly formed glass surfaces involves rather complex surface physical and chemical processes.

Silicon oxycarbide glass is formed by the pyrolysis of silicone resins and contains only silicon, oxygen, and carbon. The glass remains amorphous in x-ray diffraction to 1400 °C and shows no features in transmission electron micrographs (TEM) after heating to this temperature. After heating at higher temperature (1500–1650 °C) silicon carbide lines develop in x-ray diffraction, and fine crystalline regions of silicon carbide and graphite are found in TEM and electron diffraction. XPS shows that silicon-oxygen bonds in the glass are similar to those in amorphous and crystalline silicates; some silicons are bonded to both oxygen and carbon. Carbon is bonded to either silicon or carbon; there are no carbon-oxygen bonds in the glass. Infrared spectra are consistent with these conclusions and show silicon-oxygen and silicon-carbon vibrations, but none from carbon-oxygen bonds. 29Si-NMR shows evidence for four different bonding groups around silicon. The silicon oxycarbide structure deduced from these results is a random network of silicon-oxygen tetrahedra, with some silicons bonded to one or two carbons substituted for oxygen; these carbons are in turn tetrahedrally bonded to other silicon atoms. There are very small regions of carbon-carbon bonds only, which are not bonded in the network. This “free” carbon colors the glass black. When the glass is heated above 1400 °C this network composite rearranges in tiny regions to graphite and silicon carbide crystals. The density, coefficient of thermal expansion, hardness, elastic modulus, index of refraction, and viscosity of the silicon oxycarbide glasses are all somewhat higher than these properties in vitreous silica, probably because the silicon-carbide bonds in the network of the oxycarbide lead to a tighter, more closely packed structure. The oxycarbide glass is highly stable to temperatures up to 1600 °C and higher, because oxygen and water diffuse slowly in it.

Ultrafine, ternary (Si/C/N) ceramic powders have been produced after CO2 laser initiated reactions between silane and mono- or dimethylamine. Various spectroscopic diagnostics and chemical analyses, including ir spectrophotometry, x-ray photoelectron spectroscopy, and x-ray diffraction analysis have been employed to correlate the parameters involved in gas-phase reactions and the powder final composition.

Novel composite films with a monolayer of organic molecules included between single molecular layers of MoS2 can be prepared with a recently described technique. Styrene-included MoS2, before and after polymerization, is discussed as an example that exhibits interesting properties. The sensitivity to humidity of the styrene-included MoS2 system is monitored in situ with x-ray diffraction where reversible incorporation and removal of water molecules are observed. Films with an anisotropy of electrical conductivity of about 108 are obtained by polymerizing the monomer between the layers.

Researchers using backscattered scanning electron microscopy, along with quantitative image analysis techniques, have clearly demonstrated the existence of a highly porous interfacial region between aggregate particles and the cement paste matrix in ordinary Portland cement concrete. This paper presents the results of a digital-image-based simulation model of this interfacial zone. A dissolution-diffusion-reaction-like cycle of hydrating cement particles is directly simulated using cement particles packed around a simple nonreactive aggregate particle. The model is two-dimensional, as we are comparing to experimental results obtained on two-dimensional images of polished sections. The qualitative features seen experimentally, such as large amounts of porosity and calcium hydroxide in the interfacial zone, are accurately reproduced. A new mechanism, one-sided growth, is proposed, along with the more usual particle-packing ideas, as an explanation of the origin of the characteristic features of the interfacial zone.

Polyvinyltoluene (PVT) latex particles were etched with O2 or CF4/O2 plasma and polystyrene (PS) latex by the O2 plasma. While the effect of these treatments on the surface topology and the specific surface area was minor, the electrokinetic measurements showed a significant change in the surface charge characteristics. The interpretation of the results in terms of a surface complexation model, taking the Stern–Gouy–Chapman structure of the interfacial layer into consideration, yielded the values of the corresponding equilibrium constants, which indicated that the chemical nature and the density of the surface charged groups were altered by plasma attacks.

Constant stress compressive creep studies have been conducted on hot-pressed Si3N4 containing 30 vol. % SiC whiskers and an initial vitreous phase composed of Al2O3, Y2O3, and SiO2. The conditions of temperature and stress were 1470–1670 K and 50–350 MPa, respectively; the atmosphere was purified N2 at 1 atm. Significant changes in the stress exponent and activation energy indicate a change in the controlling creep mechanism at ≍225 MPa and 1570 K. Prolonged annealing in the unstressed condition reduced creep rates but had little effect on the stress exponent values. Transmission and scanning electron microscopy revealed that the break in the stress exponent curves was caused by the removal of the amorphous material at the grain boundary and resulting contacts between Si3N4 grains. The break in the activation energy curves is believed to be similarly related. Analysis of all the data indicates that the composite creeps via grain boundary sliding accommodated by viscous flow at low stresses and temperatures and by diffusion at high stresses and temperatures. The contributions of these two mechanisms varied measurably as a function of stress and temperature. No cavitation was observed. The presence of the SiC whiskers had no observable effect on deformation.

A new approach is proposed to analyze the fracture behavior with crack tip plasticity by the use of three independent measurements: E0 is the energy required per unit length of crack front to prepare the crack just before propagation; the Ef-curve is a plot of the energy required to produce a unit area of fractured surface versus the crack length; and the Ka-curve is a plot of the applied stress intensity factor KIapp versus the crack length. For ABS polymers, the prefracture energy E0 is 33 Jm−1; the Ef-curve is a horizontal line of 5.2 × 104 Jm−2; and the Ka curve has three different regions which depend on the development of the plastic zone during fracture.

Two-step carbonization was found on a polyimide film, Upilex, similar to that observed on another polyimide, Kapton: large weight loss up to about 22 wt. % and linear shrinkage along the film surface to 30% in a narrow temperature range from 500 to 650 °C, and an additional small weight loss and shrinkage in a wide range between 700 and 1000 °C. The yield of carbonization agreed roughly with that calculated by assuming the release of non-carbon atoms as simple species of CO, O2, and N2. A 25 μm Upilex film yielded a relatively high degree of graphitization after heat treatment at 3000 °C: a layered structure under SEM, high magnetoresistance, and a sharp 002 x-ray diffraction peak at a d-spacing of 0.336 nm. The degree of graphitization was lower than for a similar Kapton film, which is attributed to the lack of flatness in the Upilex molecule. A very much lower degree of graphitization was observed for 50 μm Upilex films. This difference is tentatively attributed to constraints that must have influenced the orientation of the Upilex molecules near the surface of the films as they were formed.

Zinc oxide (ZnO) powders were mixed with Polyacrylic Acid (PAA) to form waterless cements. The optimal ZnO/PAA ratio in terms of mechanical strength was found. Also, the role of the relation ZnO to PAA, the curing time, and the strain rate on the final properties of the composites was studied.

Bones are biological structural materials made of dynamically adaptable tissues. They can be considered as complex natural composite materials with load bearing constituents such as osteons and interstitial lamellae cemented with weak bonding materials. In addition, they contain Haversian and Volkmann canals that are functionally needed but are structurally weak. Because of large variation in microstructure, the strength of a bone varies from bone to bone and animal to animal. In this study the applicability of Weibull statistics to fracture strength of bones has been evaluated. The statistics is based on the weakest link theory and has been used successfully for probabilistic design of critical engineering structural components. The analysis shows that the statistics is valid when applied to each type of bone and it differentiates data from different types of bones. The analysis provides an insight in terms of how nature designs its load bearing structures by the process of natural selection.