936 resultados para Fracture mode I parameters
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A whisker is a common name of single crystalline inorganic fibre of small dimensions, typically 0.5-1 μm in diameter and 20-50 μm in length. Whiskers are mainly used as reinforcement of ceramics. This work describes the synthesis and characterisation of new whisker types. Ti0.33Ta0.33Nb0.33CxN1-x, TiB2, B4C, and LaxCe1-xB6 have been prepared by carbothermal vapour–liquid–solid (CTR-VLS) growth mechanisms in the temperature range 900-1800°C, in argon or nitrogen. Generally, carbon and different suitable oxides were used as whisker precursors. The oxides reacted via a carbothermal reduction process. A halogenide salt was added to form gaseous metal halogenides or oxohalogenides and small amount of a transition metal was added to catalyse the whisker growth. In this mechanism, the whisker constituents are dissolved into the catalyst, in liquid phase, which becomes supersaturated. Then a whisker could nucleate and grow out under continuous feed of constituents. The syntheses of TiC, TiB2, and B4C were followed at ordinary synthesis conditions by means of mass spectrometry (MS), thermogravimetry (TG), differential thermal analysis (DTA) and quenching. The main reaction starting temperatures and reaction time for the different mixtures was revealed, and it was found that the temperature inside the crucible during the reactions was up to 100°C below the furnace set-point, due to endothermic nature of the reactions. Quench experiments showed that whiskers were formed already when reaching the temperature plateau, but the yield increased fast with the holding time and reached a maximum after about 20-30 minutes. Growth models for whisker formation have been proposed. Alumina based composites reinforced by (2-5 vol.%) TiCnano and TiNnano and 25 vol.% of carbide, and boride phases (whiskers and particulates of TiC, TiN, TaC, NbC, (Ti,Ta)C, (Ti,Ta,Nb)C, SiC, TiB2 and B4C) have been prepared by a developed aqueous colloidal processing route followed by hot pressing for 90 min at 1700°C, 28 MPa or SPS sintering for 5 minutes at 1200-1600°C and 75 MPa. Vickers indentation measurements showed that the lowest possible sintering temperature is to prefer from mechanical properties point of view. In the TiNnano composites the fracture mode was typically intergranular, while it was transgranular in the SiCnano composites. The whisker and particulate composites have been compared in terms of e.g. microstructure and mechanical properties. Generally, additions of whiskers yielded higher fracture toughness compared to particulates. Composites of commercially available SiC whiskers showed best mechanical properties with a low spread but all the other whisker phases, especially TiB2, exhibited a great potential as reinforcement materials.
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Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.
Design, synthesis and biological evaluation of substituted naphthalene diimides as anticancer agents
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It has been proved that naphthalene diimide (NDI) derivatives display anticancer properties as intercalators and G-quadruplex-binding ligands, leading to DNA damage, senescence and down-regulation of oncogene expression. This thesis deals with the design and synthesis of disubstituted and tetrasubstituted NDI derivatives endowed with anticancer activity, interacting with DNA together with other targets implicated in cancer development. Disubstituted NDI compounds have been designed with the aim to provide potential multitarget directed ligands (MTDLs), in order to create molecules able to simultaneously interact with some of the different targets involved in this pathology. The most active compound, displayed antiproliferative activity in submicromolar range, especially against colon and prostate cancer cell lines, the ability to bind duplex and quadruplex DNA, to inhibit Taq polymerase and telomerase, to trigger caspase activation by a possible oxidative mechanism, to downregulate ERK 2 protein and to inhibit ERKs phosphorylation, without acting directly on microtubules and tubuline. Tetrasubstituted NDI compounds have been designed as G-quadruplex-binding ligands endowed with anticancer activity. In order to improve the cellular uptake of the lead compound, the N-methylpiperazine moiety have been replaced with different aromatic systems and methoxypropyl groups. The most interesting compound was 1d, which was able to interact with the G-quadruplexes both telomeric and in HSP90 promoter region, and it has been co-crystallized with the human telomeric G-quadruplex, to directly verify its ability to bind this kind of structure, and also to investigate its binding mode. All the morpholino substituted compounds show antiproliferative activity in submicromolar values mainly in pancreatic and lung cancer cell lines, and they show an improved biological profile in comparison with that of the lead compound. In conclusion, both these studies, may represent a promising starting point for the development of new interesting molecules useful for the treatment of cancer, underlining the versatility of the NDI scaffold.
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Addressing current limitations of state-of-the-art instrumentation in aerosol research, the aim of this work was to explore and assess the applicability of a novel soft ionization technique, namely flowing atmospheric-pressure afterglow (FAPA), for the mass spectrometric analysis of airborne particulate organic matter. Among other soft ionization methods, the FAPA ionization technique was developed in the last decade during the advent of ambient desorption/ionization mass spectrometry (ADI–MS). Based on a helium glow discharge plasma at atmospheric-pressure, excited helium species and primary reagent ions are generated which exit the discharge region through a capillary electrode, forming the so-called afterglow region where desorption and ionization of the analytes occurs. Commonly, fragmentation of the analytes during ionization is reported to occur only to a minimum extent, predominantly resulting in the formation of quasimolecular ions, i.e. [M+H]+ and [M–H]– in the positive and the negative ion mode, respectively. Thus, identification and detection of signals and their corresponding compounds is facilitated in the acquired mass spectra. The focus of the first part of this study lies on the application, characterization and assessment of FAPA–MS in the offline mode, i.e. desorption and ionization of the analytes from surfaces. Experiments in both positive and negative ion mode revealed ionization patterns for a variety of compound classes comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides, and alkaloids. Besides the always emphasized detection of quasimolecular ions, a broad range of signals for adducts and losses was found. Additionally, the capabilities and limitations of the technique were studied in three proof-of-principle applications. In general, the method showed to be best suited for polar analytes with high volatilities and low molecular weights, ideally containing nitrogen- and/or oxygen functionalities. However, for compounds with low vapor pressures, containing long carbon chains and/or high molecular weights, desorption and ionization is in direct competition with oxidation of the analytes, leading to the formation of adducts and oxidation products which impede a clear signal assignment in the acquired mass spectra. Nonetheless, FAPA–MS showed to be capable of detecting and identifying common limonene oxidation products in secondary OA (SOA) particles on a filter sample and, thus, is considered a suitable method for offline analysis of OA particles. In the second as well as the subsequent parts, FAPA–MS was applied online, i.e. for real time analysis of OA particles suspended in air. Therefore, the acronym AeroFAPA–MS (i.e. Aerosol FAPA–MS) was chosen to refer to this method. After optimization and characterization, the method was used to measure a range of model compounds and to evaluate typical ionization patterns in the positive and the negative ion mode. In addition, results from laboratory studies as well as from a field campaign in Central Europe (F–BEACh 2014) are presented and discussed. During the F–BEACh campaign AeroFAPA–MS was used in combination with complementary MS techniques, giving a comprehensive characterization of the sampled OA particles. For example, several common SOA marker compounds were identified in real time by MSn experiments, indicating that photochemically aged SOA particles were present during the campaign period. Moreover, AeroFAPA–MS was capable of detecting highly oxidized sulfur-containing compounds in the particle phase, presenting the first real-time measurements of this compound class. Further comparisons with data from other aerosol and gas-phase measurements suggest that both particulate sulfate as well as highly oxidized peroxyradicals in the gas phase might play a role during formation of these species. Besides applying AeroFAPA–MS for the analysis of aerosol particles, desorption processes of particles in the afterglow region were investigated in order to gain a more detailed understanding of the method. While during the previous measurements aerosol particles were pre-evaporated prior to AeroFAPA–MS analysis, in this part no external heat source was applied. Particle size distribution measurements before and after the AeroFAPA source revealed that only an interfacial layer of OA particles is desorbed and, thus, chemically characterized. For particles with initial diameters of 112 nm, desorption radii of 2.5–36.6 nm were found at discharge currents of 15–55 mA from these measurements. In addition, the method was applied for the analysis of laboratory-generated core-shell particles in a proof-of-principle study. As expected, predominantly compounds residing in the shell of the particles were desorbed and ionized with increasing probing depths, suggesting that AeroFAPA–MS might represent a promising technique for depth profiling of OA particles in future studies.
Resumo:
AIM: To test in vitro the mechanical resistance, rotational misfit and failure mode of three original implant-abutment connections and to compare them to two connections between non-original abutments connected to one of the original implants. MATERIAL AND METHODS: Three different implants with small diameters (3.3 mm for Straumann Roxolid, 3.5 mm for Nobel Biocare Replace and Astra Tech Osseospeed TX) were connected with individualized titanium abutments. Twelve implants from each system were connected to their original abutments (Straumann CARES, Nobel Biocare Procera, Astra Tech Atlantis). Twenty-four Roxolid implants were connected with non-original abutments using CAD/CAM procedures from the other two manufacturers (12 Nobel Biocare Procera and 12 Astra Tech Atlantis). For the critical bending test, a Zwick/Roell 1475 machine and the Xpert Zwick/Roell software were used. RESULTS: The rotational misfit varied when comparing the different interfaces. The use of non-original grade V titanium abutments on Roxolid implants increased the force needed for deformation. The fracture mode was different with one of the original connections. CONCLUSIONS: Non-original abutments differ in design of the connecting surfaces and material and demonstrate higher rotational misfit. These differences may result in unexpected failure modes.
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The OPERA experiment is searching for νμ → ντ oscillations in appearance mode, i.e., via the direct detection of τ leptons in ντ charged-current interactions. The evidence of νμ → ντ appearance has been previously reported with three ντ candidate events using a sub-sample of data from the 2008–2012 runs. We report here a fourth ντ candidate event, with the τ decaying into a hadron, found after adding the 2012 run events without any muon in the final state to the data sample. Given the number of analyzed events and the low background, νμ → ντ oscillations are established with a significance of 4.2σ.
Resumo:
The OPERA experiment is designed to search for ν μ →ν τ oscillations in appearance mode, i.e., through the direct observation of the τ lepton in ν τ -charged current interactions. The experiment has taken data for five years, since 2008, with the CERN Neutrino to Gran Sasso beam. Previously, two ν τ candidates with a τ decaying into hadrons were observed in a subsample of data of the 2008–2011 runs. Here we report the observation of a third ν τ candidate in the τ − →μ − decay channel coming from the analysis of a subsample of the 2012 run. Taking into account the estimated background, the absence of ν μ →ν τ oscillations is excluded at the 3.4 σ level.
Resumo:
The OPERA experiment was designed to search for νµ → ντ oscillations in appearance mode, i.e. by detecting the τ leptons produced in charged current ντ interactions. The experiment took data from 2008 to 2012 in the CERN Neutrinos to Gran Sasso beam. The observation of the νµ → ντ appearance, achieved with four candidate events in a subsample of the data, was previously reported. In this Letter, a fifth ντ candidate event, found in an enlarged data sample, is described. Together with a further reduction of the expected background, the candidate events detected so far allow us to assess the discovery of νµ → ντ oscillations in appearance mode with a significance larger than 5 σ.
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Helium retention in irradiated tungsten leads to swelling, pore formation, sample exfoliation and embrittlement with deleterious consequences in many applications. In particular, the use of tungsten in future nuclear fusion plants is proposed due to its good refractory properties. However, serious concerns about tungsten survivability stems from the fact that it must withstand severe irradiation conditions. In magnetic fusion as well as in inertial fusion (particularly with direct drive targets), tungsten components will be exposed to low and high energy ion (helium) irradiation, respectively. A common feature is that the most detrimental situations will take place in pulsed mode, i.e., high flux irradiation. There is increasing evidence on a correlation between a high helium flux and an enhancement of detrimental effects on tungsten. Nevertheless, the nature of these effects is not well understood due to the subtleties imposed by the exact temperature profile evolution, ion energy, pulse duration, existence of impurities and simultaneous irradiation with other species. Physically based Kinetic Monte Carlo is the technique of choice to simulate the evolution of radiation-induced damage inside solids in large temporal and space scales. We have used the recently developed code MMonCa (Modular Monte Carlo simulator), presented in this conference for the first time, to study He retention (and in general defect evolution) in tungsten samples irradiated with high intensity helium pulses. The code simulates the interactions among a large variety of defects and impurities (He and C) during the irradiation stage and the subsequent annealing steps. In addition, it allows us to vary the sample temperature to follow the severe thermo-mechanical effects of the pulses. In this work we will describe the helium kinetics for different irradiation conditions. A competition is established between fast helium cluster migration and trapping at large defects, being the temperature a determinant factor. In fact, high temperatures (induced by the pulses) are responsible for large vacancy cluster formation and subsequent additional trapping with respect to low flux irradiation.
Resumo:
Helium retention in irradiated tungsten leads to swelling, pore formation, sample exfoliation and embrittlement with deleterious consequences in many applications. In particular, the use of tungsten in future nuclear fusion plants is proposed due to its good refractory properties. However, serious concerns about tungsten survivability stems from the fact that it must withstand severe irradiation conditions. In magnetic fusion as well as in inertial fusion (particularly with direct drive targets), tungsten components will be exposed to low and high energy ion irradiation (helium), respectively. A common feature is that the most detrimental situations will take place in pulsed mode, i.e., high flux irradiation. There is increasing evidence of a correlation between a high helium flux and an enhancement of detrimental effects on tungsten. Nevertheless, the nature of these effects is not well understood due to the subtleties imposed by the exact temperature profile evolution, ion energy, pulse duration, existence of impurities and simultaneous irradiation with other species. Object Kinetic Monte Carlo is the technique of choice to simulate the evolution of radiation-induced damage inside solids in large temporal and space scales. We have used the recently developed code MMonCa (Modular Monte Carlo simulator), presented at COSIRES 2012 for the first time, to study He retention (and in general defect evolution) in tungsten samples irradiated with high intensity helium pulses. The code simulates the interactions among a large variety of defects and during the irradiation stage and the subsequent annealing steps. The results show that the pulsed mode leads to significantly higher He retention at temperatures higher than 700 K. In this paper we discuss the process of He retention in terms of trap evolution. In addition, we discuss the implications of these findings for inertial fusion.
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The three-dimensional wall-bounded open cavity may be considered as a simplified geometry found in industrial applications such as leading gear or slotted flats on the airplane. Understanding the three-dimensional complex flow structure that surrounds this particular geometry is therefore of major industrial interest. At the light of the remarkable former investigations in this kind of flows, enough evidences suggest that the lateral walls have a great influence on the flow features and hence on their instability modes. Nevertheless, even though there is a large body of literature on cavity flows, most of them are based on the assumption that the flow is two-dimensional and spanwise-periodic. The flow over realistic open cavity should be considered. This thesis presents an investigation of three-dimensional wall-bounded open cavity with geometric ratio 6:2:1. To this aim, three-dimensional Direct Numerical Simulation (DNS) and global linear instability have been performed. Linear instability analysis reveals that the onset of the first instability in this open cavity is around Recr 1080. The three-dimensional shear layer mode with a complex structure is shown to be the most unstable mode. I t is noteworthy that the flow pattern of this high-frequency shear layer mode is similar to the observed unstable oscillations in supercritical unstable case. DNS of the cavity flow carried out at different Reynolds number from steady state until a nonlinear saturated state is obtained. The comparison of time histories of kinetic energy presents a clearly dominant energetic mode which shifts between low-frequency and highfrequency oscillation. A complete flow patterns from subcritical cases to supercritical case has been put in evidence. The flow structure at the supercritical case Re=1100 resembles typical wake-shedding instability oscillations with a lateral motion existed in the subcritical cases. Also, This flow pattern is similar to the observations in experiments. In order to validate the linear instability analysis results, the topology of the composite flow fields reconstructed by linear superposition of a three-dimensional base flow and its leading three-dimensional global eigenmodes has been studied. The instantaneous wall streamlines of those composited flows display distinguish influence region of each eigenmode. Attention has been focused on the leading high-frequency shear layer mode; the composite flow fields have been fully recognized with respect to the downstream wave shedding. The three-dimensional shear layer mode is shown to give rise to a typical wake-shedding instability with a lateral motions occurring downstream which is in good agreement with the experiment results. Moreover, the spanwise-periodic, open cavity with the same length to depth ratio has been also studied. The most unstable linear mode is different from the real three-dimensional cavity flow, because of the existence of the side walls. Structure sensitivity of the unstable global mode is analyzed in the flow control context. The adjoint-based sensitivity analysis has been employed to localized the receptivity region, where the flow is more sensible to momentum forcing and mass injection. Because of the non-normality of the linearized Navier-Stokes equations, the direct and adjoint field has a large spatial separation. The strongest sensitivity region is locate in the upstream lip of the three-dimensional cavity. This numerical finding is in agreement with experimental observations. Finally, a prototype of passive flow control strategy is applied.
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A 10Be/9Be-based chronostratigraphy has been determined for ODP 181, Site 1121 sediment core, recovered from the foot of the Campbell Plateau, Southwest Pacific Ocean. This core was drilled through the Campbell 'skin drift' in ca. 4500 m water depth on the mid-western margin of the extensive Campbell Nodule Field, beneath the flow of the major cold-water Deep Western Boundary Current (DWBC). In the absence of detailed biostratigraphy, beryllium isotopes have provided essential time information to allow palaeo-environmental interpretation to be undertaken on the upper 7 m of the core. Measured 10Be/9Be ratios of sediment, and of ferromanganese nodules entrapped in the sediment, decrease systematically with depth in the core, in accordance with radioactive decay. However, the 10Be/9Be data diverge from ca. 3 m below the seafloor (mbsf) to the top of the core, giving rise to several possible geochronological models. The preferred model assumes that the measured 10Be/9Be ratios of the nodule rims reflect initial 10Be/9Be ratios equivalent to contemporary seawater, and that these can be used to derive the true age of the sediment where the nodules occur. The nodule rim ages can be then used to interpret the sediment 10Be/9Be data, which indicate an overall age to ca. 7 mbsf of ca. 17.5 Ma. The derived chronology is consistent with diatom biostratigraphy, which indicates an age of 2.2-3.6 Ma at 1 mbsf. Calculated sedimentation rates range from 8 to 95 cm m.y.**-1, with an overall rate to 7 mbsf of ca. 39 cm m.y.**-1. The lowest rates generally coincide with the occurrence of entrapped nodules, and reflect periods of increased bottom current flow causing net sediment loss. Growth rates of individual nodules decrease towards the top of the sediment core, similar to the observed decrease in growth rate from core to rim of seafloor nodules from the Campbell Nodule Field. This may be related to an overall increase in the vigour of the DWBC from ca. 10 Ma to the present.
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This study documents two different modes of berm development: (I) vertical growth at spring tides or following significant beach cut due to substantial swash overtopping, and (2) horizontal progradation at neap tides through the formation of a proto-berm located lower and further seaward of the principal berm. Concurrent high-frequency measurements of bed elevation and the associated wave runup distribution reveal the details of each of these berm growth modes. In mode I sediment is eroded from the inner surf and lower swash zone where swash interactions are prevalent. The net transport of this sediment is landward only, resulting in accretion onto the upper beach face and over the berm crest. The final outcome is a steepening of the beach face gradient, a change in the profile shape towards concave and rapid vertical and horizontal growth of the berm. In mode 2 sediment is eroded from the lower two-thirds of the active swash zone during the rising tide and is transported both landward and seaward. On the falling tide sediment is eroded from the inner surf and transported landward to backfill the zone eroded on the rising tide. The net result is relatively slow steepening of the beach face, a change of the profile shape towards convex, and horizontal progradation through the formation of a neap berm. The primary factor determining which mode of berm growth occurs is the presence or absence of swash overtopping at the time of sediment accumulation on the beach face. This depends on the current phase of the spring-neap tide cycle, the wave runup height (and indirectly offshore wave conditions) and the height of the pre-existing berm. A conceptual model for berm morphodynamics is presented, based on sediment transport shape functions measured during the two modes of berm growth. (c) 2006 Elsevier B.V. All rights reserved.
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Fatigue crack initiation and propagation in aluminium butt welds has been investigated. It is shown that the initiation of cracks from both buried defects and. from the weld reinforcement may be quantified by predictive laws based on either linear elastic fracture mechanics, or on Neuber's rule of stress and strain ooncentrations. The former is preferable on the grounds of theoretical models of crack tip plasticity, although either may be used as the basis of an effeotive design criteria against crack initiation. Fatigue lives fol1owing initiation were found to follow predictions based on the integration of a Paris type power law. The effect of residual stresses from the welding operation on both initiation and propagation was accounted for by a Forman type equation. This incorporated the notional stress ratio produced by the residual stresses after various heat treatments. A fracture mechanics analysis was found to be useful in describing the fatigue behaviour of the weldments at increased temperatures up to 300°C. It is pointed out, however, that the complex interaction of residual stresses, frequency, and changes in fracture mode necessitate great caution in the application of any general design criteria against crack initiation and growth at elevated. temperatures.
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Fatigue crack growth behaviour in a 15 wt% SiC particulate reinforced 6061 aluminium alloy has been examined using pre-cracked specimens. Crack initiation and early growth of fatigue cracks in smooth specimens has also been investigated using the technique of periodic replication. The composite contained a bimodal distribution of SiC particle sizes, and detailed attention was paid to interactions between the SiC particles and the growing fatigue-crack tip. At low stress intensity levels, the proportion of coarse SiC particles on the fatigue surfaces was much smaller than that on the metallographic sections, indicating that the fatigue crack tends to run through the matrix avoiding SiC particles. As the stress intensity level increases, the SiC particles ahead of the growing fatigue crack tip are fractured and the fatigue crack then links the fractured particles. The contribution of this monotonic fracture mode resulted in a higher growth rate for the composite than for the unreinforced alloy. An increase in the proportion of cracked, coarse SiC particles on the fatigue surface was observed for specimens tested at a higher stress ratio.