Three different B-site additives, Mg1/3Nb2/3, Zr4+, and Cu1/2W1/2, were added to BNT ceramics in varying concentrations. These were abbreviated as BNMN, BNZ, and BNCW, respectively. The compositions were calcined to form a perovskite structure, ground to a fine powder, pressed into tablets and sintered to form dense ceramics. XRD analysis confirmed the formation of the perovskite phase. The electro-mechanical properties of the ceramics were evaluated. There were improvements in the low-field room temperature dielectric constant of 30% with 25% BNMN, 13% with 10% BNZ, and 16% with 2% BNCW. Higher concentrations of the additives degraded the dielectric performance. The conductivity of the BNT ceramics was reduced with very small concentrations (0.25 to 0.5%) of each of the additives. This reduction was maintained at the higher concentrations of the additives, which allowed for higher electric fields to be applied during both the poling process and the strain measurements. Improvements of approximately 30% in the d33 values were found at concentrations of 0.5% of each of the additives, but higher concentrations of the additives degraded the d33 values. The coercive field was affected by the additions to BNT. Increasing concentrations of BNMN reduced the coercive field in bipolar strain measurements. This was accompanied by a reduction in the remanent strain. Small additions (0.5 to 1.5%) of BNZ resulted in an increase in the coercive field by about 12%, followed by a 25% decrease at 5% BNZ. The remanent strain followed the same pattern. All concentrations of BNCW studied reduced the coercive field by about 12%. The remanent strain increased by 25% at 0.5% BNCW, and decreased by 42% at 2.5% BNCW. The electro-mechanical results for the BNMN and BNZ additives were compared to the behaviours of their lead-based counterparts, PMN and PZ. There was no consistent trend in the response of the electromechanical properties to the additions between the current lead-free and the lead-based systems. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2008-10-03 15:13:24.791

The prime objective of this dissertation is to design, synthesize and characterize lead-free piezoelectric based magnetostrictive components based magnetoelectric (ME) composites that exhibit self-bias characteristics and high amplitude of ME coupling. The secondary goal of this thesis was to lay down the foundation for nanoscale and flexible magnetoelectric devices. Self-biased ME effect was investigated in lead-free three-phase laminate composites. This effect is characterized by non-zero remanent ME responses at zero magnetic bias field (Hbias). It was revealed that the self-biased ME effects can be observed in three-phase laminate composites consisting of piezoelectric material and two dissimilar magnetostrictive materials. On applying Hbias to the laminates in bending mode configuration, the ME responses were found to exhibit hysteretic behaviors with remanent ME responses. The shape of hysteretic ME response could be controlled by adjusting the magnetic interactions and piezoelectric properties. Further, converse magnetoelectric (CME) responses in bending-mode three-phase laminates exhibited hysteretic behaviors with similar magnitudes during Hbias sweep as it was generated directly by applying ac voltage (Vac) without any external Hbias. Lead-free (1 - x) [0.948 K0.5Na0.5NbO3 - 0.052 LiSbO3] - x Ni0.8Zn0.2Fe2O4 (KNNLS-NZF) compositions were synthesized for optimizing ME properties of particulate composites. Island-matrix microstructure was developed to improve the magnitude of ME coupling effect by overcoming the problems found in conventional particulate composites. The structure lead to improvement of ME coefficient with maximum magnitude of 20.14 mV/cm ae as well as decrease of optimum Hbias of < 500 Oe in the composition of 0.7 KNNLS - 0.3 NZF particulate composites. Room-temperature ME phase diagram of (1 - x) BaTiO3 - x BiFeO3 materials (BT - x BFO, x = 0.025 - 1.0) was investigated for designing compositions suitable for thin film devices. The BT - x BFO compositions in narrow range of x = 0.71 - 0.8 were found to exhibit good piezoelectric, dielectric and magnetic properties simultaneously. The room temperature ME coefficient was found to be maximum with high magnitude of 0.87 mV/cmOe in the optimized composition of x = 0.725.This composition was found to consist of local monoclinic distortions with average rhombohedral symmetry as confirmed by detailed structural analysis through Raman spectroscopy and atomic pair distribution functions (PDFs). MnFe2O4 (MFO)-Ni core-shell nanoparticles were synthesized and characterized for developing tunable devices such as memristor. The MFO nanoparticles synthesized by solvothermal method exhibited diameter of 200 nm, mean primary particle size of 15 nm, high saturation magnetization of 74 emu/g and coercivity of 89 Oe. Ni encapsulation on MFO nanoparticles was performed by aqueous ionic coating method. Ni shells with uniform thickness of 1 nm were coated on MFO nanoparticles by this method. In order to develop future nanoscale dual phase energy harvesters and magnetic field sensors, vertically-aligned piezoelectric nanorods were synthesized. In the initial attempt, Pb(Zr0.52Ti0.48)O3 (PZT) was used to verify the feasibility of developing one dimensional (1D) piezoelectric nanostructures with controlled diameter and height. For the 1D nanostructure, well-ordered anodic aluminum oxide (AAO) templates were prepared by two step aluminum anodizing. The PZT nanorods were synthesized by vacuum infiltration of PZT precursor solutions and exhibited uniform diameter of 90 nm and aspect ratio of 10 with vertical in respect to the Pt-Si substrate. The piezo-response of PZT nanorods showed good magnitude owing to the reduced clamping effect from the substrate. Attempt towards the development of flexible tunable devices that possess magnetic field sensing and actuation ability was made in the later part of the thesis. The electroactive polymeric actuators in the form of Polypyrrole (PPy) / Au / Polyvinylidene fluoride (PVDF) / Au / Polypyrrole (PPy) were synthesized and the process flow was optimized. Pore size and thickness of PVDF layer was adjusted by changing the solvent, viscosity and drying temperature. Different types of electrolyte solutions were investigated to improve the strain and response time. The actuators exhibited high deflection of 90 % with fast response of 50% deflection per second. Dual-functional structure in the form of  PPy-MFO / Au / PVDF / Au / PPy-MFO was developed by PPy polymerization including MFO nanoparticles via cyclovoltammetric method. / Ph. D.

The addition of lead to the copper alloys increase the machinability of thework material (without reference here to environmental factors) and reduces the overall production cost of the components at different stages, despite copper being expensive, which makes a challenging task to replace lead. Since lead is dangerous to human health. Many materials are considered to replace lead in brass and silicon is one of the alternative. This thesis characterizes the lead and the lead free brass's surfacemetallurgy for a certain cutting data. The study includes identification of alteredmaterial zones (AMZ) defined by the plastic deformation, hardness alterationsand grain distributions.The study results include the analysis of deformed subsurface region andcomparison exemplifying differences between the two materials under twodifferent studies. / Lead free brass

Este trabalho visou estudar o efeito dos parâmetros microestruturais da liga de latão 60/40 isenta de chumbo, com enfoque na observação da influência de 4 diferentes frações volumétricas e morfologias da fase &#946 nos aspectos de usinabilidade. Os resultados foram comparados com duas referências comerciais de ligas de latão, sendo uma de corte livre com adição de chumbo, e outra de latão 70/30 isenta de fase &#946. Esta comparação foi feita por meio dos ensaios de caracterização microestrutural, ensaios mecânicos de dureza Vickers, tração uniaxial e ensaios de usinabilidade. Na avaliação da usinabilidade foram estudadas as morfologias macro e microestrutural dos cavacos, rugosidade final das peças usinadas, medição das forças de corte e análise da vida útil da ferramenta. Esta comparação de desempenho em usinabilidade busca viabilizar a gradativa substituição das ligas de latão com chumbo por ligas isentas de metais pesados, preenchendo uma demanda crescente de mercado por este tipo de produto. A fase &#946 exerce uma importante influência na redução das forças de corte e rugosidade, além do fato de que o efeito térmico cumpre um papel importante no comportamento em usinagem dos latões, evidenciado pela alteração das frações volumétricas das fases µ e &#946 no cavaco analisado, a qual é associada a uma transformação de ordem-desordem. / This work presents a study of microstructural features of lead-free 60/40 brasses on their machinability, which was focused on the observation of four different volumetric fractions and morphologies of &#946 phase. Two commercial brasses were used as base materials: a free cutting brass with lead and a 70/30 brass without &#946 phase, respectively. These materials were manufactured through hot extruded, cold worked and heat treated rods of these three different alloys, and submitted a microstructure analysis, and mechanical characterization by Vickers hardness and a uniaxial tensile test. Machinability tests were conducted to evaluate the morphology and microstructure of the chips and the final roughness of the workpieces, cutting forces and tool wear test. The results help to evaluate the feasibility of substitution of the leaded brasses for brasses without heavy metals, filling a growing demand for this product in the industry. The &#946 phase has a strong influence on cutting forces and roughness reduction as well as the thermal effect plays an important role in the volume fraction of µ and &#946 phases of the analyzed chip, which was related to the presence of &#946 phase and an order-disorder transformation.

In July 2006, the legislation of RoHS(The Restriction of the use of the Hazardous Substances in Electrical and Electronic Equipment) is fully implemented in EU. Although the major industries have response and preparedness for lead-free products, but they have no complete solution for using lead-free solder paste to replacing tin-lead solder paste. Therefore, two major issues arose in the surface mount process which are the cost increasing and the reliability decreasing of electronic products caused by higher reflow temperature. In addition to these two issue, surface mount of LED is also faced with the problem of attenuating of light intensity of LED due to the increasing of reflow temperature. After years, the companies of solder paste product and surface mount technology accumulate a lot of processing experience and they have certain yield on reflow process of LED. In order to keep competitiveness and market share, the know-how is treated as confidential. By working with about 10 professional surface mount manufacturers, it is interesting to note that solder paste and oven temperature curve used by each manufacturer are not actually the same. By adopting the experiences of cooperation with several professional surface mount manufacturers through experiments, the purpose of this thesis is to find the optimal reflow process parameters such that the light intensity loss of the LED caused by lead-free reflow process can be reduced as much as possible. By using Taguchi method and the executed experiments , the optimal parameter-combination have found efficiently from the four parameters: the peak of reflow temperature, the peak temperature of residence time, the brand of solder and the pre-baking time of LED. The results showed that the peak reflow temperature has the greatest influence among the selected four parameters and the following is the peak temperature residence time. The light intensity loss can be reduced up to 4-9% by adopting the obtained optimal parameters.

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The interfacial reactions of Sn-Zn and Sn-Zn-Al solder balls with Au/Ni surface finish under aging at 150¢J were investigated. With microstructure evolution, quantitative analysis, elemental distribution by X-ray color mapping from an electron probe microanalyzer (EPMA), the reaction procedure of phase transformation was proposed. During the reflow, Au dissolved into the solder balls and reacted with Zn to form £^-Au3Zn7. As aging time increased, £^-Au3Zn7 transformed to £^3-AuZn4. Finally, Zn precipitated near the Au-Zn intermetallic compound. On the other hand, Zn reacted with the Ni layer and formed Ni5Zn21. But the Al-Au-Zn IMC formed at the interface of Sn-Zn-Al solder balls, the reaction of Ni with Zn was inhibited. Even though the aging time increased to 50 days, no Ni5Zn21 was observed. The Joule effect was more apparent than the electromigration in the biased solder balls. First of all, the new phase (Au, Ni)Zn4 was proposed in the biased condition and in 175¢Jaging. Secondly, the thickness of the Ni5Zn21 IMC were the same between the anode and the cathode. Finally, We directly measure the temperature of the biased solder balls which was up to 173¢J.

Solder joints are the most fragile parts in electronic package. The properties of joints made of lead-free material are harder and crisper than those of lead-contained material. They tend to break due to dynamic loading by absorbing the impact energy and result in malfunction. Thus, how to improve the reliability of contact joints made of lead-free material in dynamic loading has become an important topic for research. This work is based on JEDEC Standard JESD22 - B111 ¡§Board Level Drop Test Method of Components for Handheld Electronic Products,¡¨ and JESD22 ¡V B110 ¡§Subassembly Mechanical Shock¡¨. The setup of drop test apparatuses was used to conduct dropping tests with the impact of acceleration 1500 G, in order to acquire the reliability of SnAgCu, SnCu, and SnAg alloy, which would be compared with 63Sn37Pb. The specimens would be red-dyed for an analysis under SEM to examine the distribution of the breakage. The results were analyzed by Weibull distribution to predict Mean Time to Failure (MTTF), it is revealed that MTTF of solder joints made of Sn0.7Cu, Sn2.6Ag0.5Cu, and Sn3.0Ag0.5Cu (MTTF=355.32, 295.82, 289.54 cycles respectively) are longer than that made of 63Sn37Pb (MTTF=152.52 cycles). Notably, MTTF of alloy Sn0.7Cu is 2.3 times of solder joints of SnPb. Alloy Sn3.0Ag0.5Cu has the shortest MTTF among the three, which is also 1.89 times of alloy SnPb. That is to say, under impact of 1500G, solder joints made of Sn0.7Cu, Sn2.6Ag0.5Cu, and Sn3.0Ag0.5Cu possess greater resistance to shock than alloy 63Sn37Pb, which is in common by used at present. In addition, the breakage of solder joints mainly generated on Intermetallic Compound (IMC) and around the four corners, distributed from the periphery to the central area. Especially, those on the corners receive greater stresses due to edge effect.

With electronic packaging towards the development of lead free process, the research on the portable electronic devices subject to impact load is emphasized gradually. At present, for drop test and cyclic bending test, most of the failure modes lie on the modes of "fracturing in IMC layer" or "fracturing on IMC/solder boundary". The purpose of this work is to use 3D numerical analysis software ANSYS/LS_DYNA, that were found out a proper numerical model, to further analyze the impact fracture of lead-free solder. From the numerical results, the strain rate of solder joint ranges from 103 s-1 to 104 s-1 under an impact velocity of 2 m/s. At this strain rate, the mechanical properties of solder joint could be effectively investigated. When IMC strength is smaller than 300MPa, the main failure mode is fracturing of IMC; whilst, IMC strength is greater than 300MPa, the failure mode becomes fracturing of bulk solder, but the failure mode of fracturing of IMC and a partial solder requires a model with more fine meshes to simulate. Different velocities did not affect the numerical results significantly, because the material parameters of a solder ball is strongly dependent on strain rate. Also, we found that the impact test in reality does not present a shear-dominant mode alone even when the impact angle is 0¢X. While using simulation to carry out the dynamic experiment, it can be observed that the course of solder joint suffering the damage provides a good reference and contrast for the experimental work in the future.

With the electronic packaging towards the rapid development of lead free process, the related research on the portable electronic devices subject to impact load is emphasized urgently. At present, the failure modes of fracturing in IMC layer and fracturing on IMC/solder boundary are mostly encountered due to drop test and cyclic bending test respectively. The purpose of this work is to use 3D numerical analysis software ANSYS/LS_DYNA, that were found to be a suitable numerical model for further analyzing the impact fracture of lead-free solder. The relationship between simulation and ball impact test system was compared and the effects of variable parameters on solder balls subjected to impact loading was investigated. Also, the transient deformation and fracturing of solder joints subjected to the impact load were studied numerically and experimentally. Then, the transient response and the failure modes of the solder joint due to impact load were predicted by varied strain rate tests. From the numerical results, the strain rate mechanical properties of solder joint due to high can be effectively obtained. The difference of IMC strength caused three kinds of failure modes of the solder ball, however the failure mode of fracturing in IMC and a party of solder requires a model to simulate with more refined meshes. Different velocities affected the numerical results significantly. The higher the velocity of impact test applied, the lower the impact loading received. That is mainly attributed to the material parameters adopted of a solder ball is strongly dependent on the strain rate considered. Also, it is found that the impact test in reality does not result in a shear-dominant failure mode. While using dynamic simulation instead of the experiment, the damage process of solder joint can be observed. That provides a good reference and contrast for the experimental work in the future.