Microstructure and high cycle fatigue fracture surface of a Ti-5Al-5Mo-5V-1Cr-1Fe titanium alloy

Because of the requirements for the damage tolerance and fatigue life of commercial aircraft components, the high cycle fatigue (HCF) properties of Ti–5Al–5Mo–5V–1Cr–1Fe titanium alloy forgings are important. The effects of microstructure types of the α+β titanium alloy on fatigue properties need to be understood. In this paper, by analysing the fracture surfaces of the titanium alloy having four types of microstructure, the effects of microstructure are investigated. The differences of initiation areas and crack propagation among different microstructures were studied. It was found that the area of the initiation region decreases in the order of coarse basketweave, fine basketweave, Widmanstätten, and bimodal microstructure.

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g^-1 at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g^-1 over 300 cycles at the current density of 5.2 A g^-1 (6C).

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection is detected using a position sensitive detector and its output is fed to a lock-in-amplifIer from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

Comment on "Reappraisal of experimental values of third-order elastic constants of some cubic semiconductors and metals"

In a recent paper A. S. Johal and D. J. Dunstan [Phys. Rev. B 73, 024106 (2006)] have applied multivariate linear regression analysis to the published data of the change in ultrasonic velocity with applied stress. The aim is to obtain the best estimates for the third-order elastic constants in cubic materials. From such an analysis they conclude that uniaxial stress data on metals turns out to be nearly useless by itself. The purpose of this comment is to point out that by a proper analysis of uniaxial stress data it is possible to obtain reliable values of third-order elastic constants in cubic metals and alloys. Cu-based shape memory alloys are used as an illustrative example.

On the Tailoring of Magnetic Properties of Fe-Based Alloy Thin Films by Swift Heavy Ion Irradiation and Thermal Annealing

The development of new materials has been the hall mark of human civilization. The quest for making new devices and new materials has prompted humanity to pursue new methods and techniques that eventually has given birth to modern science and technology. With the advent of nanoscience and nanotechnology, scientists are trying hard to tailor materials by varying their size and shape rather than playing with the composition of the material. This, along with the discovery of new and sophisticated imaging tools, has led to the discovery of several new classes of materials like (3D) Graphite, (2D) graphene, (1D) carbon nanotubes, (0D) fullerenes etc. Magnetic materials are in the forefront of applications and have beencontributing their share to remove obsolescence and bring in new devices based on magnetism and magnetic materials. They find applications in various devices such as electromagnets, read heads, sensors, antennas, lubricants etc. Ferromagnetic as well as ferrimagnetic materials have been in use in the form of various devices. Among the ferromagnetic materials iron, cobalt and nickel occupy an important position while various ferrites finds applications in devices ranging from magnetic cores to sensors.

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation. (C) 2003 Elsevier Science B.V. All rights reserved.

Doped sodium aluminium hydrides as hydrogen storage materials: characterizations and mechanistic insights

The dehydriding and rehydriding of sodium aluminium hydride, NaAlR4, is kinetically enhanced and rendered reversible in the solid state upon doping with a small amount of catalyst species, such as titanium, zirconium or tin. The catalyst doped hydrides appear to be good candidates for development as hydrogen carriers for onboard proton exchange membrane (PEM) fuel cells because of their relatively low operation temperatures (120-150 degrees C) and high hydrogen carrying capacities (4-5 wt.%). However, the nature of the active catalyst species and the mechanism of catalytic action are not yet known. In particular, using combinations of Ti and Sri compounds as dopants, a cooperative catalyst effect of the metals Ti and Sn in enhancing the hydrogen uptake and release kinetics is hereby reported. In this paper, characterization techniques including XRD, XPS, TEM, EDS and SEM have been applied on this material. The results suggest that the solid state phase changes during the hydriding and dehydriding processes are assisted through the interaction of a surface catalyst. A mechanism is proposed to explain the catalytic effect of the Sn/Ti double dopants on this hydride.

Adhesive Bonding of Resin Composite to Various Ni-Cr Alloy Surfaces Using Different Metal Conditioners and a Surface Modification System

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of Airborne-Particle Abrasion and Mechanico-Thermal Cycling on the Flexural Strength of Glass Ceramic Fused to Gold or Cobalt-Chromium Alloy

Purpose: To evaluate the effect of airborne-particle abrasion and mechanico-thermal cycling on the flexural strength of a ceramic fused to cobalt-chromium alloy or gold alloy.Materials and Methods: Metallic bars (n = 120) were made (25 mm x 3 mm x 0.5 mm): 60 with gold alloy and 60 with Co-Cr. At the central area of the bars (8 mm x 3 mm), a layer of opaque ceramic and then two layers of glass ceramic (Vita VM13, Vita Zahnfabrick) were fired onto it (thickness: 1 mm). Ten specimens from each alloy group were randomly allocated to a surface treatment [(tungsten bur or air-particle abrasion (APA) with Al(2)O(3) at 10 mm or 20 mm away)] and mechanico-thermal cycling (no cycling or mechanically loaded 20,000 cycles; 10 N distilled water at 37 degrees C and then thermocycled 3000 cycles; 5 degrees C to 55 degrees C, dwell time 30 seconds) combination. Those specimens that did not undergo mechanico-thermal cyclingwere stored inwater (37 degrees C) for 24 hours. Bond strength was measured using a three-point bend test, according to ISO 9693. After the flexural strength test, failure types were noted. The data were analyzed using three factor-ANOVA and Tukey's test (alpha = 0.05).Results: There were no significant differences between the flexural bond strength of gold and Co-Cr groups (42.64 +/- 8.25 and 43.39 +/- 10.89 MPa, respectively). APA 10 and 20 mm away surface treatment (45.86 +/- 9.31 and 46.38 +/- 8.89 MPa, respectively) had similar mean flexural strength values, and both had significantly higher bond strength than tungsten bur treatment (36.81 +/- 7.60 MPa). Mechanico-thermal cycling decreased the mean flexural strength values significantly for all six alloy-surface treatment combinations tested when compared to the control groups. The failure type was adhesive in the metal/ceramic interface for specimens surface treated only with the tungsten bur, and mixed for specimens surface treated with APA 10 and 20 mm.Conclusions: Considering the levels adopted in this study, the alloy did not affect the bond strength; APA with Al(2)O(3) at 10 and 20 mm improved the flexural bond strength between ceramics and alloys used, and the mechanico-thermal cycling of metal-ceramic specimens resulted in a decrease of bond strength.

Composite materials design, manufacture and evaluation

Fibre-Reinforced-Plastics are composite materials composed by thin fibres with high mechanical properties, made to work together with a cohesive plastic matrix. The huge advantages of fibre reinforced plastics over traditional materials are their high specific mechanical properties i.e. high stiffness and strength to weight ratios. This kind of composite materials is the most disruptive innovation in the structural materials field seen in recent years and the areas of potential application are still many. However, there are few aspects which limit their growth: on the one hand the information available about their properties and long term behaviour is still scarce, especially if compared with traditional materials for which there has been developed an extended database through years of use and research. On the other hand, the technologies of production are still not as developed as the ones available to form plastics, metals and other traditional materials. A third aspect is that the new properties presented by these materials e.g. their anisotropy, difficult the design of components. This thesis will provide several case-studies with advancements regarding the three limitations mentioned. In particular, the long term mechanical properties have been studied through an experimental analysis of the impact of seawater on GFRP. Regarding production methods, the pre-impregnated cured in autoclave process was considered: a rapid tooling method to produce moulds will be presented, and a study about the production of thick components. Also, two liquid composite moulding methods will be presented, with a case-study regarding a large component with sandwich structure that was produced with the Vacuum-Assisted-Resin-Infusion method, and a case-study regarding a thick con-rod beam that was produced with the Resin-Transfer-Moulding process. The final case-study will analyse the loads acting during the use of a particular sportive component, made with FRP layers and a sandwich structure, practical design rules will be provided.

Aminoxyl radicals - pure organic materials with tunable magnetic and sensing properties

Stabile Radikale haben in vielen Bereichen der Chemie, Physik, Biologie und Biomedizin ihren Nutzen unter Beweis gestellt. Gerade im letzten Jahrzehnt erlebte diese Substanzklasse vor allem wegen den Anwendungsmöglichkeiten von Nitroxiden als Red-Ox-Sensoren oder magnetischen Materialen ein erneutes Interesse. Das erste Kapitel beschäftigt sich mit der grundlegenden Theorie zur Entwicklung magnetischer Materialien. Des Weiteren sollen anhand einiger Beispiele Radikale im Komplex mit paragmagnetischen Metallen, Biradikale und Polyradikale beschrieben werden. rnrnIm zweiten Kapitel soll auf die Synthese von Hybrid Fluorophore-Nitrononyl-Nitroxid und Iminonitroxidradiale, sowie ihre Charakterisierung über IR, CV, EPR und Röntgenstrukturanalyse eingegangen werden. Mittels UV/Vis-Spektroskopie soll hierbei eine mögliche Anwendung als Red-Ox-Sensoren festgestellt werden. Hierbei werden über anschließende PL Untersuchungen eben diese Sensoreigenschaften der dargestellten Radikale bestätigt werden. Vielmehr noch soll die Möglichkeit von Pyren-Pyrazol-Nitronyl-Nitroxid als NO-Nachweis erläutert werden.rnrnFortschritte sowohl im Design als auch in der Analyse von magnetischen Materialen auf der Basis von Nitroxiden ist Thema des dritten Kapitels. Über ein klassisches Ullmann-Protokoll wurden verschiedene Nitronyl-Nitroxid und Iminonitroxid Biradiale mit unterschiedlichen π-Brücken zwischen den Radikalzentren synthetisiert. Magnetische Messungen belegen einen relativ starken antiferromagnetischen intramolekularen Austausch für den Großteil der untersuchten Biradikale. Hierbei zeigte sich jedoch eine außergewöhnliche hohe Austausch-Kupplung für 3,3‘-Diazatolandiradikale, die nur über die Existenz von starken intermolekularen Wechselwirkungen beschrieben werden kann. Durch Kombination der Röntgenstrukturanalyse mit DFT Berechnungen konnte im Fall des Tolan verbrückten Diradikals 87c die Intra-Dimer-Kupplung auf Jintra = -8,6 K bestimmt werden. Ein direkter Beweis für eine intermolekulare Anlagerung von Jinter ~- 2K konnte über eine Tieftemperatur AC-Messung von 87c erhalten werden. Bezüglich der magnetischen Messung ist das Nitronyl Biradikal 87c ein vielversprechender Kandidat für einen rein organischen eindimensionalen Quantenmagnet.rnrnAbsicht dieser Untersuchungen ist es zu zeigen, dass über die Kombination verschiedener struktureller Elemente die Sensitivität von Nitroxid basierten Sensoren und die intramolekulare Austauschwechselwirkung in π-konjugierten Spinsystemen so eingestellt werden kann, dass es möglich ist Moleküle mit gezielten Sensor- oder Magneteigenschaften zu entwickeln. rn

Synthesis and investigation of functional polymer materials

Funktionelle Materialien sind in einer Vielzahl von Materialklassen wie Polymeren, Biomaterialien, Gläsern, Metallen, Keramiken und Verbundwerkstoffen anzutreffen. Sie besitzen eine spezifische, intrinsische Funktion, welche auf dem zu Grunde liegenden Design der Verbindung beruht. In dieser Dissertation wurden zwei funktionelle Materialien studiert: ein durch Phosphonatadditive mechanisch verstärktes Epoxidharz und protonenleitende Blockcopolymere, welche Potential für den Einsatz in Brennstoffzellen besitzen. Die Materialien wurden vorranging mittels Festkörper Kernspinresonanzspektroskopie (NMR) untersucht, welche sich besonders für die Untersuchung der lokalen Struktur und Dynamik amorpher Polymere eignet.rnrnPhosphonate sind eine neue Klasse sogenannter molekularer Verstärker, die die mechanischen und thermischen Kennzahlen geeigneter Epoxidharze erhöhen. Es wurde eine Reihe von Phosphonatderivaten synthetisiert um systematische den Effekt der chemischen Struktur und des Aushärteprozesses auf die Eigenschaften eines Modellepoxidharzes zu untersuchen. Die Aufklärung des Verstärkungsmechanismus ergab, dass die Phosphonate währen der thermischen Aushärtung des Epoxidharzes die Aminofunktionalitäten des Härters alkylieren. Dies führt zu der Bildung von homogen verteilten, positiven Ladungen auf der Polymerkette, während negative Phosphonatanionen als Gegenionen wirken. Es konnte gezeigt werden, dass die Struktur des Additivs einen entscheidenden Einfluss auf die Eigenschaften des ausgehärteten Epoxidharzes sowie seine Alterung, d.h. den allmählichen Verlust der Verstärkung, hat.rnrnDes Weiteren wurde eine Serie von sulfonierten Blockcopolymeren synthetisiert. Es handelte sich hierbei um Multiblockcopolyimide, wobei die Polymerketten aus einer alternierenden Sequenz von sulfonierten (hydrophilen) und unsulfonierten (hydrophoben) Blöcken bestanden. Diese Polymere bilden nach einem ‚solvent cast‘ Prozess feste, duktile und transparente Membrane. Sulfonierte Blockcopolymermembrane zeigten im Vergleich mit statistisch sulfonierten Vergleichssubstanzen eine erhöhte Leitfähigkeit, sowie eine erhöhte Wasseraufnahme. Dies wurde auf eine bessere Phasenseparation im Festkörper zurückgeführt. Die Morphologie der Filme war eindeutig anisotrop und stark abhängig von der Blocklänge der Polymere. Durch diverse Festkörper-NMR Methoden konnte gezeigt werden, dass die Protonenmobilität in den Membranen von der betrachteten Längenskala abhängig ist und nicht notwendigerweise mit der makroskopisch beobachteten Leitfähigkeit korreliert.

SOLUTE-DERIVED THERMAL STABILITY OF NANOCRYSTALLINE ALUMINUM AND PROCESSING FACTOR INFLUENCE ON THE FORMATION OF AL6MN QUASICRYSTALS IN MELT-SPINNING

Thermal stability of nanograined metals can be difficult to attain due to the large driving force for grain growth that arises from the significant boundary area constituted by the nanostructure. Kinetic approaches for stabilization of the nanostructure effective at low homologous temperatures often fail at higher homologous temperatures. Thermodynamic approaches for thermal stabilization may offer higher temperature stability. In this research, modest alloying of aluminum with solute (1 at.% Sc, Yb, or Sr) was examined as a means to thermodynamically stabilize a bulk nanostructure at elevated temperatures. After using melt-spinning and ball-milling to create an extended solid-solution and nanostructure with average grain size on the order of 30-45 nm, 1 h annealing treatments at 673 K (0.72 Tm) , 773 K (0.83 Tm) , and 873 K (0.94 Tm) were applied. The alloys remain nanocrystalline (<100 nm) as measured by Warren-Averbach Fourier analysis of x-ray diffraction peaks and direct observation of TEM dark field micrographs, with the efficacy of stabilization: Sr>Yb>Sc. Disappearance of intermetallic phases in the Sr and Yb alloys in the x-ray diffraction spectra are observed to occur coincident with the stabilization after annealing, suggesting that precipitates dissolve and the boundaries are enriched with solute. Melt-spinning has also been shown to be an effective process to produce a class of ordered, but non-periodic crystals called quasicrystals. However, many of the factors related to the creation of the quasicrystals through melt-spinning are not optimized for specific chemistries and alloy systems. In a related but separate aspect of this research, meltspinning was utilized to create metastable quasicrystalline Al6Mn in an α-Al matrix through rapid solidification of Al-8Mn (by mol) and Al-10Mn (by mol) alloys. Wheel speed of the melt-spinning wheel and orifice diameter of the tube reservoir were varied to determine their effect on the resulting volume proportions of the resultant phases using integrated areas of collected x-ray diffraction spectra. The data were then used to extrapolate parameters for the Al-10Mn alloy which consistently produced Al6Mn quasicrystal with almost complete suppression of the equilibrium Al6Mn orthorhombic phase.

Measurements of the Magnetic Permeabilities of the Iron-Manganese Alloy System Prepared by the Methods of Powder Metallurgy

Powder metallurgy is a branch of metallurgy which produces metallic compacts in their final forms by means of pressure and heat-treatment from the pow­ders. The products of powder metallurgy are being used in our daily lives quite often. For example, the tungsten wires in the electric bulbs to the silver-tin fillings of our teeth.

Improvement of Mechanical Properties and Life Extension of High Reliability Structural Components by Laser Shock Processing

Profiting by the increasing availability of laser sources delivering intensities above 109 W/cm2 with pulse energies in the range of several Joules and pulse widths in the range of nanoseconds, laser shock processing (LSP) is being consolidating as an effective technology for the improvement of surface mechanical and corrosion resistance properties of metals and is being developed as a practical process amenable to production engineering. The main acknowledged advantage of the laser shock processing technique consists on its capability of inducing a relatively deep compression residual stresses field into metallic alloy pieces allowing an improved mechanical behaviour, explicitly, the life improvement of the treated specimens against wear, crack growth and stress corrosion cracking. Following a short description of the theoretical/computational and experimental methods developed by the authors for the predictive assessment and experimental implementation of LSP treatments, experimental results on the residual stress profiles and associated surface properties modification successfully reached in typical materials (specifically Al and Ti alloys) under different LSP irradiation conditions are presented. In particular, the analysis of the residual stress profiles obtained under different irradiation parameters and the evaluation of the corresponding induced surface properties as roughness and wear resistance are presented.