Serrated Plastic Flow During Nanoindentation in Nd-Based Bulk Metallic Glasses

The microstructure of Nd_{60}Al_{10}Ni_{10}Cu_{20-x}Fex (x = 0, 5, 7, 10, 15, 20) alloys can change from homogeneous phase to a composite structure consisting of amorphous phase plus clusters or nanocrystals by adjusting the Fe content. The effect of microstructure on the plastic deformation behavior in this alloy system is studied by using nanoindentation. The alloys with homogeneous amorphous structure exhibit pronounced flow serrations during the loading process of nanoindentation. The addition of Fe changes the plastic deformation behavior remarkablely. No flow serration is observed in the alloys with high Fe content for the indentation depth of 500 nm. The mechanism for the change of plastic serrated flow behavior is discussed.

Deformation and fracture of impulsively loaded sandwich panels

Light metal sandwich panel structures with cellular cores have attracted interest for multifunctional applications which exploit their high bend strength and impact energy absorption. This concept has been explored here using a model 6061-T6 aluminum alloy system fabricated by friction stir weld joining extruded sandwich panels with a triangular corrugated core. Micro-hardness and miniature tensile coupon testing revealed that friction stir welding reduced the strength and ductility in the welds and a narrow heat affected zone on either side of the weld by approximately 30%. Square, edge clamped sandwich panels and solid plates of equal mass per unit area were subjected to localized impulsive loading by the impact of explosively accelerated, water saturated, sand shells. The hydrodynamic load and impulse applied by the sand were gradually increased by reducing the stand-off distance between the test charge and panel surfaces. The sandwich panels suffered global bending and stretching, and localized core crushing. As the pressure applied by the sand increased, face sheet fracture by a combination of tensile stretching and shear-off occurred first at the two clamped edges of the panels that were parallel with the corrugation and weld direction. The plane of these fractures always lay within the heat affected zone of the longitudinal welds. For the most intensively loaded panels additional cracks occurred at the other clamped boundaries and in the center of the panel. To investigate the dynamic deformation and fracture processes, a particle-based method has been used to simulate the impulsive loading of the panels. This has been combined with a finite element analysis utilizing a modified Johnson-Cook constitutive relation and a Cockcroft-Latham fracture criterion that accounted for local variation in material properties. The fully coupled simulation approach enabled the relationships between the soil-explosive test charge design, panel geometry, spatially varying material properties and the panel's deformation and dynamic failure responses to be explored. This comprehensive study reveals the existence of a strong instability in the loading that results from changes in sand particle reflection during dynamic evolution of the panel's surface topology. Significant fluid-structure interaction effects are also discovered at the sample sides and corners due to changes of the sand reflection angle by the edge clamping system. © 2012 Elsevier Ltd. All rights reserved.

镁-锌-稀土系合金的组织和性能研究

　　制备了Mg-4.5wt%Zn-1～5wt%RE系合金（RE元素包括轻稀土：La、Ce、Nd、Sm；重稀土：Gd和Y），研究了铸态和热处理态合金的组织和性能。（1）适量的稀土元素均可细化合金晶粒，其中轻稀土元素的细化效果好于重稀土元素；（2）含轻稀土元素合金中的析出相主要为(Mg,Zn)17RE2和Mg4Zn7，而含重稀土元素的合金中的析出相主要为MgZnxREy(Mg3Zn6RE, Mg3RE2Zn3)和Mg4Zn7；（3）加入稀土元素后，合金的强度提高；稀土含量相同时，含轻稀土元素的强化效果较好。Mg-4.5Zn-1Ce合金具有最高的强度。T5处理态合金的抗拉强度、屈服强度和伸长率分别为236 MPa、111 MPa和15.8%，T6处理态合金分别为233 MPa、131 MPa和8.9%。强度提高的主要原因是合金中生成了大量的纳米级Mg4Zn7强化相，以及晶界沉淀相的连续性降低；（4）含重稀土元素合金的时效硬化效果高于含轻稀土元素的合金，经T6处理后，含重稀土元素合金的断裂强度和屈服强度均提高，而含轻稀土元素合金只有屈服强度提高。 　　研究了挤压变形Mg-4.5Zn-1Ce合金的组织和性能。473 K时效后峰值态合金具有较高抗拉强度和屈服强度，其值分别为291 MPa和239 MPa，比铸态分别提提高了55 MPa和128 MPa。高强度产生的原因是合金中生成了大量棒状和点状混合结构的纳米级Mg4Zn7强化相和晶粒的细化。 　　应用Edge-to-edge匹配模型成功预测了MgZn2/α-Mg体系中的位相关系，扩大了该模型的应用范围。并对模型进行了改进，主要体现在：1)确定匹配方向的平面上所有原子的中心位置需在平面上；2）匹配方向之间可任意配对。应用优化后的模型预测了Mg17Al12/α-Mg体系中的位相关系，预测结果与实验结果的吻合率为4/6，好于原模型预测的吻合率4/8。另外，使用优化后的模型，成功的预测出了理想的Burgers位相关系，从而证实了该位相关系是确实存在的，而不是near Burgers位相关系测定的误差。使用优化后的模型还成功的解释了该合金体系中稀土元素的晶粒细化机制和沉淀强化机制。

Fabrication and characterisation of semiconductor nanowires and metal interconnects

One-dimensional semiconductor nanowires are considered to be promising materials for future nanoelectronic applications. However, before these nanowires can be integrated into such applications, a thorough understanding of their growth behaviour is necessary. In particular, methods that allow the control over nanowire growth are deemed especially important as it is these methods that will enable the control of nanowire dimensions such as length and diameter (high aspect ratios). The production of nanowires with high-aspect ratios is vital in order to take advantage of the unique properties experienced at the nanoscale, thus allowing us to maximise their use in devices. Additionally, the development of low-resistivity interconnects is desirable in order to connect such nanowires in multi-nanowire components. Consequently, this thesis aims to discuss the synthesis and characterisation of germanium (Ge) nanowires and platinum (Pt) interconnects. Particular emphasis is placed on manipulating the nanowire growth kinetics to produce high aspect ratio structures. The discussion of Pt interconnects focuses on the development of low-resistivity devices and the electrical and structural analysis of those devices. Chapter 1 reviews the most critical aspects of Ge nanowire growth which must be understood before they can be integrated into future nanodevices. These features include the synthetic methods employed to grow Ge nanowires, the kinetic and thermodynamic aspects of their growth and nanowire morphology control. Chapter 2 outlines the experimental methods used to synthesise and characterise Ge nanowires as well as the methods used to fabricate and analyse Pt interconnects. Chapter 3 discusses the control of Ge nanowire growth kinetics via the manipulation of the supersaturation of Ge in the Au/Ge binary alloy system. This is accomplished through the use of bi-layer films, which pre-form Au/Ge alloy catalysts before the introduction of the Ge precursor. The growth from these catalysts is then compared with Ge nanowire growth from standard elemental Au seeds. Nanowires grown from pre-formed Au/Ge alloy seeds demonstrate longer lengths and higher growth rates than those grown from standard Au seeds. In-situ TEM heating on the Au/Ge bi-layer films is used to support the growth characteristics observed. Chapter 4 extends the work of chapter 3 by utilising Au/Ag/Ge tri-layer films to enhance the growth rates and lengths of Ge nanowires. These nanowires are grown from Au/Ag/Ge ternary alloy catalysts. Once again, the supersaturation is influenced, only this time it is through the simultaneous manipulation of both the solute concentration and equilibrium concentration of Ge in the Au/Ag/Ge ternary alloy system. The introduction of Ag to the Au/Ge binary alloy lowers the equilibrium concentration, thus increasing the nanowire growth rate and length. Nanowires with uniform diameters were obtained via synthesis from AuxAg1-x alloy nanoparticles. Manifestation of the Gibbs-Thomson effect, resulting from the dependence of the mean nanowire length as a function of diameter, was observed for all of the nanowires grown from the AuxAg1-x nanoparticles. Finally, in-situ TEM heating was used to support the nanowire growth characteristics. Chapter 5 details the fabrication and characterisation of Pt interconnects deposited by electron beam induced deposition of two different precursors. The fabrication is conducted inside a dual beam FIB. The electrical and structural characteristics of interconnects deposited from a standard organometallic precursor and a novel carbon-free precursor are compared. The electrical performance of the carbon-free interconnects is shown to be superior to that of the organometallic devices and this is correlated to the structural composition of both interconnects via in-situ TEM heating and HAADF-STEM analysis. Annealing of the interconnects is carried out under two different atmospheres in order to reduce the electrical resistivity even further. Finally, chapter 6 presents some important conclusions and summarises each of the previous chapters.

The Effect of Antimony Substitution on the Magnetic and Structural Properties of Fe0.75–xSi0.25Sbx Alloys

The results of the investigation of the magnetic and structural properties of the alloy system Fe0.75–xSi0.25Sbx, where x = 0, 0.05, 0.1, 0.15, 0.2, and 0.25 synthesized by mechanical alloying followed by heat treatment are described. The x-ray diffraction reveals that all samples crystallize in the DO3-type cubic phase structure. Substituting Fe by Sb led to a de-crease in the lattice constant and the unit cell volume. The magnetic properties are investigated by vibrating sample magnetometer and show that all the samples are ferromagnetically ordered at room temperature. The Curie temperature is found to decrease linearly from (850 ± 5) K for the parent alloy to (620 ± 5) K for the alloyith x = 0.25. The satura-tion magnetizations at room temperature and at 100 K are found to decrease with increasing the antimony concentration. The above results indicate that Sb dissolves in the cubic structure of this alloy system.

Re-examination of the effect of NbC precipitation on shape memory in Fe-Mn-Si-based alloys

Current literature pertaining to the shape memory effect in the Fe–Mn–Si-based system is critically discussed. It is argued that the
enhanced shape memory previously attributed to NbC precipitation is mainly due to the associated thermo-mechanical treatments.
It is concluded that the thermo-mechanical processing of the alloy is the dominant factor that determines the shape memory effect in
this alloy system.

The use of Fe-30% Ni and Fe-30% Ni-Nb alloys as model systems for studying the microstructural evolution during the hot deformation of austenite

The development of physically-based models of microstructural evolution during thermomechanical processing of metallic materials requires knowledge of the internal state variable data, such as microstructure, texture, and dislocation substructure characteristics, over a range of processing conditions. This is a particular problem for steels, where transformation of the austenite to a variety of transformation products eradicates the hot deformed microstructure. This article reports on a model Fe-30wt% Ni-based alloy, which retains a stable austenitic structure at room temperature, and has, therefore, been used to model the development of austenite microstructure during hot deformation of conventional low carbon-manganese steels. It also provides an excellent model alloy system for microalloy additions. Evolution of the microstructure and crystallographic texture was characterized in detail using optical microscopy, X-ray diffraction (XRD), SEM, EBSD, and TEM. The dislocation substructure has been quantified as a function of crystallographic texture component for a variety of deformation conditions for the Fe-30% Ni-based alloy. An extension to this study, as the use of a microalloyed Fe-30% Ni-Nb alloy in which the strain induced precipitation mechanism was studied directly. The work has shown that precipitation can occur at a much finer scale and higher number density than hitherto considered, but that pipe diffusion leads to rapid coarsening. The implications of this for model development are discussed.

Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography

We report on the characterization of grain boundary (GB) segregation in an Fe-28Mn-0.3C (wt.%) twinning-induced plasticity (TWIP) steel. After recrystallization of this steel for 24 h at 700 °C, ∼50% general grain boundaries (GBs) and ∼35% Σ3 annealing twin boundaries were observed (others were high-order Σ and low-angle GBs). The segregation of B, C and P and traces of Si and Cu were detected at the general GB by atom probe tomography (APT) and quantified using ladder diagrams. In the case of the Σ3 coherent annealing twin, it was necessary to first locate the position of the boundary by density analysis of the atom probe data, then small amounts of B, Si and P segregation and, surprisingly, depletion of C were detected. The concentration of Mn was constant across the interface for both boundary types. The depletion of C at the annealing twin is explained by a local change in the stacking sequence at the boundary, creating a local hexagonal close-packed structure with low C solubility. This finding raises the question of whether segregation/depletion also occurs at Σ3 deformation twin boundaries in high-Mn TWIP steels. Consequently, a previously published APT dataset of the Fe-22Mn-0.6C alloy system, containing a high density of deformation twins due to 30% tensile deformation at room temperature, was reinvestigated using the same analysis routine as for the annealing twin. Although crystallographically identical to the annealing twin, no evidence of segregation or depletion was found at the deformation twins, owing to the lack of mobility of solutes during twin formation at room temperature.

Comparative study of the microstructures and mechanical properties of direct laser fabricated and arc-melted AlxCoCrFeNi high entropy alloys

High entropy alloys (HEA) are a relatively new metal alloy system that have promising potential in high temperature applications. These multi-component alloys are typically produced by arc-melting, requiring several remelts to achieve chemical homogeneity. Direct laser fabrication (DLF) is a rapid prototyping technique, which produces complex components from alloy powder by selectively melting micron-sized powder in successive layers. However, studies of the fabrication of complex alloys from simple elemental powder blends are sparse. In this study, DLF was employed to fabricate bulk samples of three alloys based on the AlxCoCrFeNi HEA system, where x was 0.3, 0.6 and 0.85M fraction of Al. This produced FCC, FCC/BCC and BCC crystal structures, respectively. Corresponding alloys were also produced by arc-melting, and all microstructures were characterised and compared longitudinal and transverse to the build/solidification direction by x-ray diffraction, glow discharge optical emission spectroscopy and scanning electron microscopy (EDX and EBSD). Strong similarities were observed between the single phase FCC and BCC alloys produced by both techniques, however the FCC/BCC structures differed significantly. This has been attributed to a difference in the solidification rate and thermal gradient in the melt pool between the two different techniques. Room temperature compression testing showed very similar mechanical behaviour and properties for the two different processing routes. DLF was concluded to be a successful technique to manufacture bulk HEA[U+05F3]s.

Influência da convecção termossolutal na transição colunar/equiaxial em ligas Al-Si sob condições unidirecionais e transitórias de extração de calor

A relação entre macroestrutura e propriedades mecânicas de um material tem sido objeto de intensa investigação pois o tamanho dos grãos, a orientação cristalina e a distribuição dos mesmos exercem influência direta no comportamento mecânico dos produtos acabados. Assim, o entendimento dos fatores que influenciam a formação das zonas estruturais coquilhada, colunar e equiaxial nos materiais fundidos como, por exemplo, o sistema de liga, composição da liga, temperatura de vazamento, temperatura do molde, material do molde, coeficientes de transferência de calor na interface metal/molde, taxa de resfriamento, gradientes térmicos, dimensão da peça, presença de convecção no líquido, transporte de soluto, etc é de fundamental importância para a melhoria da eficiência do processo de fundição envolvido. Com base no conhecimento dos princípios termofísicos em que essas zonas são formadas, é possível manipular de forma bastante razoável a estrutura dos produtos fundidos e, conseqüentemente, as propriedades mecânicas dos mesmos. Tendo como principal foco a análise da mudança da zona colunar para a equiaxial, este trabalho apresenta um estudo teórico-experimental sobre a transição colunar/equiaxial (TCE) das ligas hipoeutéticas Al- 3%Si, Al-7%Si Al-9%Si solidificadas unidirecionalmente em um dispositivo horizontal refrigerado a água sob condições transientes de fluxo de calor. A condição de contato térmico na superfície de extração de calor foi padronizada como sendo polida. Os perfis térmicos foram medidos em diferentes posições do lingote e os dados foram armazenados automaticamente. Um método numérico é utilizado na determinação de variáveis térmicas de solidificação como coeficientes de transferência de calor na interface metal/molde (h_i), velocidades das isotermas liquidus (V_L), gradientes térmicos (G_L) e taxas de resfriamento (T_R) que influenciam diretamente a referida transição estrutural. Os resultados teóricos e experimentais apresentaram boa concordância. Um estudo comparativo entre os resultados obtidos neste trabalho e valores propostos na literatura para analisar a TCE durante a solidificação unidirecional vertical ascendente sob condições transientes de extração de calor das ligas investigadas, também é apresentado.

Analysis of transport properties of mechanically alloyed [Pb1-xSnxTe]

The work described in this thesis had two objectives. The first objective was to develop a physically based computational model that could be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. The second objective was to determine how the secondary phase inclusions observed in Pb1-xSnxTe alloys made by consolidating mechanically alloyed elemental powders impact the ability of the material to harvest waste heat and generate electricity in the 400 K to 700 K temperature range. The motivation for this work was that though the promise of this alloy as an unusually efficient thermoelectric power generator material in the 400 K to 700 K range had been demonstrated in the literature, methods to reproducibly control and subsequently optimize the materials thermoelectric figure of merit remain elusive. Mechanical alloying, though not typically used to fabricate these alloys, is a potential method for cost-effectively engineering these properties. Given that there are deviations from crystalline perfection in mechanically alloyed material such as secondary phase inclusions, the question arises as to whether these defects are detrimental to thermoelectric function or alternatively, whether they enhance thermoelectric function of the alloy. The hypothesis formed at the onset of this work was that the small secondary phase SnO2 inclusions observed to be present in the mechanically alloyed Pb1-xSnxTe would increase the thermoelectric figure of merit of the material over the temperature range of interest. It was proposed that the increase in the figure of merit would arise because the inclusions in the material would not reduce the electrical conductivity to as great an extent as the thermal conductivity. If this were to be true, then the experimentally measured electronic conductivity in mechanically alloyed Pb1-xSnxTe alloys that have these inclusions would not be less than that expected in alloys without these inclusions while the portion of the thermal conductivity that is not due to charge carriers (the lattice thermal conductivity) would be less than what would be expected from alloys that do not have these inclusions. Furthermore, it would be possible to approximate the observed changes in the electrical and thermal transport properties using existing physical models for the scattering of electrons and phonons by small inclusions. The approach taken to investigate this hypothesis was to first experimentally characterize the mobile carrier concentration at room temperature along with the extent and type of secondary phase inclusions present in a series of three mechanically alloyed Pb1-xSnxTe alloys with different Sn content. Second, the physically based computational model was developed. This model was used to determine what the electronic conductivity, Seebeck coefficient, total thermal conductivity, and the portion of the thermal conductivity not due to mobile charge carriers would be in these particular Pb1-xSnxTe alloys if there were to be no secondary phase inclusions. Third, the electronic conductivity, Seebeck coefficient and total thermal conductivity was experimentally measured for these three alloys with inclusions present at elevated temperatures. The model predictions for electrical conductivity and Seebeck coefficient were directly compared to the experimental elevated temperature electrical transport measurements. The computational model was then used to extract the lattice thermal conductivity from the experimentally measured total thermal conductivity. This lattice thermal conductivity was then compared to what would be expected from the alloys in the absence of secondary phase inclusions. Secondary phase inclusions were determined by X-ray diffraction analysis to be present in all three alloys to a varying extent. The inclusions were found not to significantly degrade electrical conductivity at temperatures above ~ 400 K in these alloys, though they do dramatically impact electronic mobility at room temperature. It is shown that, at temperatures above ~ 400 K, electrons are scattered predominantly by optical and acoustical phonons rather than by an alloy scattering mechanism or the inclusions. The experimental electrical conductivity and Seebeck coefficient data at elevated temperatures were found to be within ~ 10 % of what would be expected for material without inclusions. The inclusions were not found to reduce the lattice thermal conductivity at elevated temperatures. The experimentally measured thermal conductivity data was found to be consistent with the lattice thermal conductivity that would arise due to two scattering processes: Phonon phonon scattering (Umklapp scattering) and the scattering of phonons by the disorder induced by the formation of a PbTe-SnTe solid solution (alloy scattering). As opposed to the case in electrical transport, the alloy scattering mechanism in thermal transport is shown to be a significant contributor to the total thermal resistance. An estimation of the extent to which the mean free time between phonon scattering events would be reduced due to the presence of the inclusions is consistent with the above analysis of the experimental data. The first important result of this work was the development of an experimentally validated, physically based computational model that can be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. This model will be critical in future work as a tool to first determine what the highest thermoelectric figure of merit one can expect from this alloy system at a given temperature and, second, as a tool to determine the optimum Sn content and doping level to achieve this figure of merit. The second important result of this work is the determination that the secondary phase inclusions that were observed to be present in the Pb1-xSnxTe made by mechanical alloying do not keep the material from having the same electrical and thermal transport that would be expected from “perfect" single crystal material at elevated temperatures. The analytical approach described in this work will be critical in future investigations to predict how changing the size, type, and volume fraction of secondary phase inclusions can be used to impact thermal and electrical transport in this materials system.

Age Hardening of Silver-Platinum Alloys

The alloy system selected for study was the binary alloy of platinum and silver. An examination of the various silver alloy diagrams revealed that of several possible alloys, the silver platinum was the most suit­able with regard to solubility.

Microstructure control in Sn-0.7mass%Cu alloys

Soldering alloys based oft the Sn-Cu alloy system are amongst the most favourable lead-free alternatives due to a range of attractive properties. Trace additions of Ni have been found to significantly improve the soldering characteristics of these alloys (reduced bridging etc.). This paper examines the mechanisms underlying the improvement in soldering properties of Sn-0.7 mass%Cu eutectic alloys modified with concentrations of Ni ranging front 0 to 1000 ppm. The alloys were investigated by thermal analysis during solidification, as well as optical/SEM microanalyses of fully solidified samples anti samples quenched during solidification. It is concluded that Ni additions dramatically alter the nucleation patterns and solidification behaviour of the Sn-Cu6Sn5 eutectic anti that these changes are related to the superior soldering characteristics of the Ni-modified Sn-0.7 mass%Cu alloys.

Heterogeneous nucleation of Mg-Al alloys

Grain size is one of the most important microstructural characteristics determining the mechanical properties and therefore the service performance of polycrystalline materials. Heterogeneous nucleation involves the addition or in situ formation of potent nuclei in the system to promote nucleation events, leading to a fine grain structure. This paper reports experimental results using graphite and SiC as potential grain refining agents to form in situ nuclei for Mg in Mg-Al alloys, and demonstrates the key role of Al4C3 in grain refilling this important alloy system. This insight will contribute to the design and development of the most cost effective, eco-friendly grain refining agents for Mg-Al alloys. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.