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Thesis advisor: Zhifeng Ren / Solid state cooling and power generation based on thermoelectric principles are regarded as one of the technologies with the potential of solving the current energy crisis. Thermoelectric devices could be widely used in waste heat recovery, small scale power generation and refrigeration. It has no moving parts and is environmental friendly. The limitation to its application is due to its low efficiency. Most of the current commercialized thermoelectric materials have figure of merit (ZT) around 1. To be comparable with kitchen refrigerator, ZT is required at room temperature. Skutterudites have emerged as member of the novel materials, which potentially have a higher ZT. In the dissertation, my investigation will be focused on the optimization of CoSb₃ &ndash based skutterudites. Starting with Co and Sb elements, CoSb₃ will form through a high energy ball mill. Unfortunately, even after 20 hours, only a small percentage of the powders have transformed in into CoSb₃. Then the powders will be compacted into bulk samples by DC-controlled hot press. CoSb₃ single phase will form after press. Characterization of the structure and thermoelectric properties will be presented with details. The effects of synthesis conditions on thermoelectric properties of skutterudites were studied and discussed. Several possible methods of improving the ZT of N type skutterudites were applied. The highest obtained ZT thus far is about 1.2 from Yb doped CoSb₃. For a group of samples with nominal composition Yb_xCo₄Sb₁₂, the increased Yb concentration in our samples not only enhanced the power factor due to electron doping effect but also decreased the thermal conductivity due to a stronger rattling effect. In addition, the increased grain boundary density per unit volume due to the small grains in our bulk skutterudite materials may have also helped to enhance the phonon scattering and thus to reduce the thermal conductivity. Single and double doping methods with different combinations were also tried. So far, none of them have surpassed ZT of 1.2. Mixing different materials with Yb_0.35Co₄Sb₁₂ so far to increase the phonon scattering was also performed. No dramatic thermal conductivity reduction was observed. Small amounts of Fe/Mn substitution on Co sites will decrease the power factor to undesired degrees. Some results with Nd filled P type sample will be briefly introduced. P type samples are also obtained through substitution on Sb site. Preliminary work on preparing the electrode for CoSb₃ will be presented in the dissertation. CoSi₂ has low resistivity, and a similar coefficient of thermal expansion (CTE) as of doped CoSb₃. It is good electrode candidate. DC controlled hot press is used to make the contact. Thermal stability of the contact was tested. Small cracks will form in the contact area, further improvement is necessary. Finally, my previous work on ZnO nanowire growth is briefly introduced. Large throughput of ZnO nanowire could be obtained with NaCl as the support to promote the conversion of Zn powder to ZnO. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

An experimental ball-milling study was performed to compare the deagglomeration behavior and the evolution of the particle size distribution with increasing milling time of two relatively coarse WC powders used for the production of cemented carbide cutting tools. The WC-powders were found to have distinctly different particle size distributions and particle morphologies prior to milling. Lab-scale WC samples were made using a range of different process parameters and milling times. These were then analysed by means of microscopy, laser light scattering, gas adsorption BET analysis and X-ray powder diffraction, XRD, to attain particle size distribution, specific surface area and a mean crystal size, respectively. The results suggested a linear relation between log(particle size) and log(milling time) between 10 and 80 hours milling. The viscosity was shown to have a minor effect on the milling efficiency. Both the number of collisions of milling balls per unit time as well as the kinetic energy of the milling ball affected the size reduction; more collisions or higher energy resulted in a higher milling efficiency. The evaluation of the effect of the process parameters on milling efficiency was facilitated by the use of simple scaling factors. For example, all milling curves for samples with different WC amounts coincided when rescaling the milling time using a scaling factor based on the weight of the WC and milling balls. The same scaling factor could be used with success for rescaling the results from different trials obtained with laser light scattering, gas adsorption and XRD. The results of this work are useful for future work on modeling of the milling process which should lead to more accurate predictions of the outcome of milling unit operations.

Silicon nanoparticles (SiNPs) are regarded as a promising alternative of traditional II-VI quantum dots in the field of bio-applications due to their photoluminescence and bio-compatibility. <br>Chapter 1 reviews various synthetic routes and applications of SiNPs. <br>Chapter 2 describes the mechanochemical synthesis of photoluminescent SiNPs with an organic ligand shell through reactive high energy ball milling (RHEBM). The morphology and size distribution of as-prepared SiNPs were determined by TEM. The bonding modes of the ligand shell including their mole fractions were investigated based on NMR and FTIR spectra of the as-prepared SiNPs.<br>Chapter 3 introduces the removal of the iron impurities, which were introduced into the SiNPs product from the milling media, stainless steel, by a physical method (GPC) and a chemical method (washing by HCl aqueous solution). The effect of the iron impurities to the optical properties of SiNPs is discussed.<br>Chapter 4 exhibits the surface functionalization of SiNPs with various functional groups through thiol-ene click reactions of vinyl-terminated SiNPs with various thiols. In addition, SiNP nanoclusters and DNA-conjugated SiNPs were prepared through thiol-ene click reactions of vinyl-terminated SiNPs with a tetrathiol-terminated crosslinker and a thiol-functionalized DNA, respectively<br>Chapter 5 is a miscellaneous chapter which includes the preparation of SiNPs through RHEBM of silicon wafers with 2,3-dimethyl-1,3-butadiene, and the effect of UV irradiation at 254 nm to the chemical structures and optical properties of SiNPs. / acase@tulane.edu

Size reduction processes, particularly fine grinding systems, in mineral processing and cement production plants constitute a great portion of energy consumption and operating costs. Therefore, the grinding systems should be designed properly and operated under optimum conditions to achieve productive and cost effective operations. The use of simulation based on kinetic mathematical models of grinding has proven useful in this respect. The kinetic models contain two essential parameters, namely, breakage rate and breakage distribution functions, that are to be determined experimentally, and preferably in laboratory, or by back-calculation from the mill product size distribution for a given feed size distribution. Experimental determination of the breakage parameters has been mostly carried out in laboratory batch mills using one-size-fraction material. The breakage rate parameter is obtained from the disappearance rate of this one-size-fraction material, while the breakage distribution parameters are estimated from the short-time grinding of the same material. Such laboratory methods using one-size fraction material, however, are not truly representative of industrial continuous mill operations where the mill contents have a distribution of particle sizes. There is evidence in the literature that the size distribution of the mill contents affects the breakage parameters. This thesis study was undertaken with the main purpose of investigating the effect of the size distribution of the mill hold-up on the brekage parameters of quartz and calcite minerals in lockedcycle dry grinding experiments. The locked-cycle and one-size-fraction experiments were performed in the Bond ball mill instrumented with a torque-measuring device. Different closing screen sizes were used in the locked-cycle work to produce different size distributions of the mill hold-up, and the operating conditions were changed in the one-size-fraction experiments to obtain different power draws. Particle breakage parameters were assessed for these changing conditions. Prior to the experiments related to the main purpose of the study, preliminary experiments were conducted for two reasons: (i) to find the power draw of the Bond mill in relation to the operating conditions with the intention of eliminating the use of costly torque-measuring devices by others / and (ii) to find the most accurate estimation method of breakage distribution functions among the three existing methods, namely, the &ldquo / zero-order production of fines&rdquo / method, the BII method, and the G-H method. The G-H method was found to be more appropriate for the current study. The locked-cycle grinding experiments revealed that the breakage rate function of coarse fractions increased with increasing proportion of fines in the mill hold-up. Breakage distribution functions were found to be environment-dependent and non-normalizable by size in one-size-fraction and locked cycle grinding experiments. It was concluded that the cumulative basis breakage rate function could sufficiently represent the breakage characteristics of the two studied materials in a wide range of operating conditions. Therefore, it would be more appropriate to evaluate the breakage characteristics of materials ground in ball mills by linearized form of the size-discretized batch grinding equation using single parameter instead of dealing with two parameters which may not be independent of each other.

The main objective in this study is to compare breakage parameters of narrow size fractions of cement clinker taken from the product end and feed end of industrial-scale high pressure grinding rolls (HPGR) in order to assess whether the breakage parameters of clinker broken in HPGR are improved or not. For this purpose, drop weight tests were applied to six narrow size fractions above 3.35 mm, and batch grinding tests were applied to three narrow size fractions below 3.35 mm. It was found that the breakage probabilities of coarse sizes and breakage rates in fine sizes were higher in the HPGR product. This indicated that clinker broken by HPGR contained weaker particles due to cracks and damage imparted. However, no significant weakening was observed for the -19.0+12.7 mm HPGR product. Although HPGR product was found to be weaker than HPGR feed, fragment size distribution of HPGR product did not seem to be finer than that of the HPGR feed at a given loading condition in either the drop weight test or batch grinding test. Also, drop weight tests on HPGR product and HPGR feed showed that the breakage distribution functions of coarse sizes depended on particle size and impact energy (J). Batch grinding tests showed that the specific breakage rates of HPGR product and HPGR feed were non-linear which could be represented with a fast initial breakage rate and a subsequent slow breakage rate. The fast breakage rates of each size fraction of HPGR product were higher than HPGR feed due to cracks induced in clinker by HPGR. However, subsequent slow breakage rates of HPGR product were close to those of HPGR feed due to elimination of cracks and disappearance of weaker particles. Besides, the variation in breakage rates of HPGR product and HPGR feed with ball size and particle size also showed an abnormal breakage zone where ball sizes were insufficient to effectively fracture the coarse particles. Breakage distribution functions of fine sizes of HPGR product and HPGR feed were non-normalizable and depended on particle size to be ground. However, batch grinding of -2.36+1.7 mm and -1.7+1.18 mm HPGR feed yielded the same breakage pattern.

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We have designed and engineered bi-catalyst magnesium hydride composites with superior sorption performance to that of ball milled magnesium hydride catalyzed with the individual baseline catalysts. We have examined the effect of single-walled carbon nanotube (SWCNT)-metallic nanoparticle additions on the hydrogen desorption behavior of MgH2 after high-energy co-milling. We showed the synergy between SWCNT's and metallic nanoparticles in catalyzing the sorption of magnesium hydride. The optimum microstructure for sorption, obtained after 1 h of co-milling, consists of highly defective SWCNTs in intimate contact with metallic nanoparticles and with the hydride. This microstructure is optimum, presumably because of the dense and uniform coverage of the defective SWCNTs on the MgH2 surface. Cryo-stage transmission electron microscopy (TEM) analysis of the hydride powders revealed that they are nanocrystalline and in some cases multiply twinned. Since defects are an integral component of hydride-to-metal phase transformations, such analysis sheds new insight regarding the fundamental microstructural origins of the sorption enhancement due to mechanical milling. The nanocomposite shows markedly improved cycling as well. Activation energy analysis demonstrates that any catalytic effect due to the metallic nanoparticles is lost during cycling. Improved cycling performance is instead achieved as a result of the carbon allotropes preventing MgH2 particle agglomeration and sintering. The nanocomposite received over 100 sorption cycles with fairly minor kinetic degradation. We investigated the catalytic effect of Fe + Ti bi-metallic catalyst on the desorption kinetics of magnesium hydride. Sub-micron dimensions for MgH2 particles and excellent nanoscale catalyst dispersion was achieved by high-energy milling. The composites containing Fe shows DSC desorption temperature of 170 °C lower than as-received MgH2 powder, which makes it suitable to be cycled at relatively low temperature of 250 °C. The low cycling temperature also prevents the formation of Mg2FeH6. The ternary Mg-Fe-Ti composite shows best performance when compared to baseline ball milled magnesium hydride with only one catalytic addition. With a very high BET surface area it also shows much less degradation during cycling. The synergy between Fe and Ti is demonstrated through use of TEM and by carefully measuring the activation energies of the baseline and the ternary composites. / Materials Engineering

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