Eutectic modification of Al-Si casting alloys

The change of microstructure of eutectic silicon from plate- to coral-like in Al-Si casting alloys is well known for enhancing their ductility. This is achieved by adding low concentrations of a modifying agent. Amongst the elements proposed as modifiers, only strontium, sodium and europium induce a plate-to-coral transition, while others such as ytterbium, only refine the silicon plates. The exact mechanism for the remarkable plate-to-coral change, and the reason why certain elements only refine the structure, is still not completely understood. In this investigation, atom probe tomography and transmission electron microscopy were used to analyze and compare the crystal structure and the distribution of solute atoms in silicon at the atomic level. An unmodified alloy and alloys modified by strontium, sodium, europium and ytterbium were studied. Elements inducing silicon plate-to-coral transition were found to contain nanometer sized clusters at the defects in silicon with stoichiometries corresponding to compounds formed at the ternary eutectic reaction of each system. In contrast ytterbium, that only refines the silicon plates, is unable to form clusters in silicon. It is propose that the formation of clusters of AlSiNa, Al2Si2Sr and Al2Si2Eu at the silicon/liquid interface during solidification restrict silicon growth and increase growth direction diversity. The incorporation of clusters explains the high density of crystallographic defects and the structural modification.Die Zugabe geringer Konzentrationen eines Veredelungselementes in Al-Si-Gusslegierungen führt zu einer für die Duktilität günstigen Morphologieänderung des eutektischen Silizium. Dabei bewirken die Veredelungselemente Strontium, Natrium und Europium einen Übergang von einer platten- zu einer korallenartigen Morphologie, während andere wie Ytterbium nur das Eutektikum verfeinern. Der zu Grunde liegende Mechanismus ist noch nicht vollständig verstanden. In dieser Arbeit wurden mit Hilfe der Atomsondentomographie und der Transmissionselektronenmikroskopie die Kristallstruktur und die Verteilung der im Silizium gelösten Atome auf atomarer Ebene analysiert und verglichen. Eine unveredelte und durch Strontium, Natrium, Europium und Ytterbium veredelte Legierungen wurden untersucht. Es zeigt sich, dass Elemente, die eine korallenartige Morphologie erzeugen (Strontium, Natrium und Europium), nanometergroße Cluster an Defekten in Silizium bilden, deren Stöchiometrien den Verbindungen aus ternären eutektischen Reaktionen des jeweiligen Systems entsprechen. Im Gegensatz dazu werden durch Zusatz von Ytterbium keine Cluster im Silizium gebildet. Es wird gezeigt, dass die Bildung von Clustern aus AlSiNa, Al2Si2Sr und Al2Si2Eu an der Grenzfläche Silizium/Schmelze während der Erstarrung das Siliziumwachstum einschränkt und die Zahl der Wachstumsrichtungen erhöht. Die Einlagerung von Clustern in Silizium erklärt dessen hohe Dichte an kristallographischen Defekten und die Morphologieänderung

Microstructure Evolution and Mechanical Stability of Supersaturated Solid Solution Co-Rich Nanocrystalline Co-Cu Produced by Pulsed Electrodeposition

Thick films of supersaturated solid solution nanocrystalline Co-Cu (28 at.% Cu) were synthesized through the pulsed electrodeposition technique. Microstructural changes of nanocrystalline Co-Cu were intensively studied at various annealing temperatures. Annealing at 300 °C results in a spinodal decomposition within the individual grains, with no grain coarsening. On the other hand, distinct phase separation of Co-Cu is detected at annealing temperatures beyond 400 °C. Static micro-bending tests show that the nanocrystalline Co-Cu alloy exhibits a very high yield strength and ductile behavior, with no crack formation. Static micro-bending tests also reported that a large plastic deformation is observed, but no microstructure change is detected. On the other hand, observation on the fatigue resistance of nanocrystalline Co-Cu shows that grain coarsening is observed after conducting the cyclic micro-bending test

Anharmonicity changes the solid solubility of an alloy at high temperatures

We have developed a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti$_{1-x}$Al$_x$N alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy, corresponding to the true equilibrium state of the system. We demonstrate that the anharmonic contribution and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti$_{1-x}$Al$_x$N alloy, lowering the maximum temperature for the miscibility gap from 6560 K to 2860 K. Our local chemical composition measurements on thermally aged Ti$_{0.5}$Al$_{0.5}$N alloys agree with the calculated phase diagram.Comment: 4 pages, 5 figures, supplementary materia

Growth and thermal stability of TiN/ZrAlN: Effect of internal interfaces

Wear resistant hard films comprised of cubic transition metal nitride (c-TMN) and metastable c-AlN with coherent interfaces have a confined operating envelope governed by the limited thermal stability of metastable phases. However, equilibrium phases (c-TMN and wurtzite(w)-AlN) forming semicoherent interfaces during film growth offer higher thermal stability. We demonstrate this concept for a model multilayer system with TiN and ZrAlN layers where the latter is a nanocomposite of ZrN- and AlN- rich domains. The interfaces between the domains are tuned by changing the AlN crystal structure by varying the multilayer architecture and growth temperature. The interface energy minimization at higher growth temperature leads to formation of semicoherent interfaces between w-AlN and c-TMN during growth of 15 nm thin layers. Ab initio calculations predict higher thermodynamic stability of semicoherent interfaces between c-TMN and w-AlN than isostructural coherent interfaces between c-TMN and c-AlN. The combination of a stable interface structure and confinement of w-AlN to nm-sized domains by its low solubility in c-TMN in a multilayer, results in films with a stable hardness of 34 GPa even after annealing at 1150 °C.Peer ReviewedPostprint (author's final draft

Atom Probe Tomography investigations on grain boundary segregation in polycrystalline Ti(C,N) and Zr(C,N) CVD coatings

Atom Probe Tomography (APT) was used to obtain a direct evidence of chlor segregation and cobalt diffusion at the grain boundaries (GBs) of polycrystalline coatings deposited by moderate temperature chemical vapor deposition (MT-CVD) on a WC-Co cemented carbide substrate. Reasons behind segregations are discussed, and its effects are correlated to the micromechanical properties of Ti(C,N) and Zr(C,N). It is concluded that chlorine segregation is a relevant factor for explaining the low cohesive strength at the GBs of Ti(C,N) leading to intergranular failure during micro-compression testing, while its absence in Zr(C,N) along with Co diffusion contribute to grain boundary strengthening.Peer ReviewedPreprin

A Detailed Analysis of the Microstructural Changes in the Vicinity of a Crack-Initiating Defect in Additively Manufactured AISI 316L

The fatigue life of metals manufactured via laser-based powder bed fusion (L-PBF) highly depends on process-induced defects. In this context, not only the size and geometry of the defect, but also the properties and the microstructure of the surrounding material volume must be considered. In the presented work, the microstructural changes in the vicinity of a crack-initiating defect in a fatigue specimen produced via L-PBF and made of AISI 316L were analyzed in detail. Xenon plasma focused ion beam (Xe-FIB) technique, scanning electron microscopy (SEM), and electron backscatter diffraction (EBSD) were used to investigate the phase distribution, local misorientations, and grain structure, including the crystallographic orientations. These analyses revealed a fine grain structure in the vicinity of the defect, which is arranged in accordance with the melt pool geometry. Besides pronounced cyclic plastic deformation, a deformation-induced transformation of the initial austenitic phase into α’-martensite was observed. The plastic deformation as well as the phase transformation were more pronounced near the border between the defect and the surrounding material volume. However, the extent of the plastic deformation and the deformation-induced phase transformation varies locally in this border region. Although a beneficial effect of certain grain orientations on the phase transformation and plastic deformability was observed, the microstructural changes found cannot solely be explained by the respective crystallographic orientation. These changes are assumed to further depend on the inhomogeneous distribution of the multiaxial stresses beneath the defect as well as the grain morphology

Eutectic modification by ternary compound cluster formation in Al-Si alloys

Al-alloys with Si as the main alloying element constitute the vast majority of Al castings used commercially today. The eutectic Si microstructure in these alloys can be modified from plate-like to coral-like by the addition of a small amount of a third element to improve ductility and toughness. In this investigation the effects of Eu and Yb are studied and their influence on the microstructure is compared to further understand this modification. The two elements impact the alloy differently, where Eu modifies Si into a coral-like structure while Yb does not. Atom probe tomography shows that Eu is present within the Si phase in the form of ternary compound Al2Si2Eu clusters, while Yb is absent in the Si phase. This indicates that the presence of ternary compound clusters within Si is a necessary condition for the formation of a coral-like structure. A crystallographic orientation relationship between Si and the Al2Si2Eu phase was found, where the following plane normals are parallel: 011Si//0001Al2Si2Eu, 111Si//67¯10Al2Si2Eu and 011Si//67¯10Al2Si2Eu. No crystallographic relationship was found between Si and Al2Si2Yb. The heterogeneous formation of coherent Al2Si2Eu clusters inside the Si-phase is suggested to trigger the modification of the microstructure

Quantification of hydrogen in nanostructured hydrogenated passivating contacts for silicon photovoltaics combining SIMS-APT-TEM : A multiscale correlative approach

Multiscale characterization of the hydrogenation process of silicon solar cell contacts based on c-Si/SiOx/nc-SiCx(p) has been performed by combining dynamic secondary ion mass-spectrometry (D-SIMS), atom probe tomography (APT), and transmission electron microscopy (TEM). These contacts are formed by high-temperature firing, which triggers the crystallization of SiCx, followed by a hydrogenation process to passivate remaining interfacial defects. Due to the difficulty of characterizing hydrogen at the nm-scale, the exact hydrogenation mechanisms have remained elusive. Using a correlative TEM-SIMS-APT analysis, we are able to locate hydrogen trap sites and quantify the hydrogen content. Deuterium (D), a heavier isotope of hydrogen, is used to distinguish hydrogen introduced during hydrogenation from its background signal. D-SIMS is used, due to its high sensitivity, to get an accurate deuterium-to-hydrogen ratio, which is then used to correct deuterium profiles extracted from APT reconstructions. This new methodology to quantify the concentration of trapped hydrogen in nm-scale structures sheds new insights on hydrogen distribution in technologically important photovoltaic materials

Microstructural influence of the thermal behavior of arc deposited TiAlN coatings with high aluminum content

The influence of the microstructure on the thermal behavior of cathodic arc deposited TiAlN coatings was studied as a function of isothermal annealing. Two compositionally similar but structurally different coatings were compared, a Ti0\ub734Al0\ub766N0.96 coating with a fine-grain structure consisting of a mixture of cubic (c) and hexagonal (h) phases, and a Ti0\ub740Al0\ub760N0.94 coating with a coarse-grain structure of cubic phase. By in situ wide-angle synchrotron x-ray scattering, spinodal decomposition was confirmed in both coatings. The increased amount of internal interfaces lowered the decomposition temperature by 50 \ub0C for the dual-phase coating. During the subsequent isothermal anneal at 1000 \ub0C, a transformation from c-AlN to h-AlN took place in both coatings. After 50 min of isothermal annealing, atom probe tomography detected small amounts of Al (∼2 at.%) in the c-TiN rich domains and small amounts of Ti (∼1 at.%) in the h-AlN rich domains of the coarse-grained single-phase Ti0\ub740Al0\ub760N0.94 coating. Similarly, at the same conditions, the fine-grained dual-phase Ti0\ub734Al0\ub766N0.96 coating exhibits a higher Al content (∼5 at.%) in the c-TiN rich domains and higher Ti content (∼15 at.%) in the h-AlN rich domains. The study shows that the thermal stability of TiAlN is affected by the microstructure and that it can be used to tune the reaction pathway of decomposition favorably

Lattice Vibrations Change the Solid Solubility of an Alloy at High Temperatures

We develop a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti_(1−x)Al_xN alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy corresponding to the true equilibrium state of the system. We demonstrate that the vibrational contribution including anharmonicity and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti_(1−x)Al_xN alloy, lowering the maximum temperature for the miscibility gap from 6560 to 2860 K. Our local chemical composition measurements on thermally aged Ti_(0.5)Al_(0.5)N alloys agree with the calculated phase diagram