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In this study, various techniques of hydrometallurgy and ultrasound-assisted solvent extraction were used to recover the platinum group metals (PGM¡¦s) from a composite sample of honeycomb-type autocatalysts. After they were removed from the converter casings, the autocatalyst substrates were first crushed and then ground by a ball mill. The recovery procedures employed are shown as follows: (1) dissolve PGM¡¦s from ground spent autocatalyst by aqua regia leaching; (2) separate PGM¡¦s from base metals in the aqua regia leachate by metal cementation using zinc powder so that PGM¡¦s can be precipitated out; (3) the PGM¡¦s precipitate was first dissolved by aqua regia, then proceed to remove nitrate and hydrochloride within. The residue was further dissolved in hydrochloride acid as a preparation step for solvent extraction; (4) the PGM¡¦s pregnant solution of hydrochloride acid was treated by solvent extraction and stripping to separate and purify each component of PGM¡¦s. Effects of ultrasound agitation on the efficiency of solvent extraction was also evaluated in this work. Results of aqua regia leaching experiments have shown that the quantity of dissolved PGM¡¦s increased as the solid-to-liquid ratio decreased. The maximum dissolved quantity of PGM¡¦s could be obtained by a 3-hr leaching time. At this stage, the PGM¡¦s recoveries are 80-90% for platinum and rhodium and greater than 99% for palladium. The result of a preliminary test has indicated that acetic acid can not effectively separate the PGM¡¦s and base metals. Thus, the method of cementation by zinc powder was employed to separate PGM¡¦s from base metals. Before cementation, the aqua regia leachate was diluted and pH-adjusted to greater than 2. In so doing, an almost complete cementation (>99%) could be obtained by the least quantity of zinc powder. In addition, the base metals occurred with the PGM¡¦s precipitate have been minimized except lead and zinc. While palladium was extracted by di-n-octyl sulfide (DOS), ultrasound assistance has rendered a complete extraction within a few minutes. At this stage, the extraction efficiency was found to be independent of the HCl concentration. It was found that platinum and rhodium were not extracted by DOS. When platinum was extracted by tri-n-octylamine (TOA) and assisted by ultrasound, rhodium will be extracted at the HCl concentration higher than 4M. Thus, TOA is not an effective chemical for selective extraction of platinum. TOA was then replaced by tributyl phosphate (TBP). Experimental results have indicated that the extraction of platinum using TBP was affected by the HCl concentration. The best result was obtained when the HCl concentration was 5M. Extraction by TBP was found to be fast. It took only 20-30 seconds to reach the equilibrium even with no ultrasound assistance. But multi-stage extractions are generally required to extract platinum completely. Rhodium was found to be not extracted by TBP. After palladium and platinum were extracted, only rhodium was remained in the reffinate. In summary, solvent extraction using DOS and TBP has made it possible to separate palladium, platinum, and rhodium effectively. In the palladium stripping solution almost no base metals was determined. However, zinc and lead were found in the platinum stripping solution and the rhodium-containing raffinate. These base metals should be removed to achieve a better purity for each precious metal. The TCLP (i.e., a leaching test for toxicity) result of the autocatalyst substrate after aqua regia leaching has found to be non-hazardous. However, several streams of wastewater and acid gas generated in the recovery process should be properly managed to avoid the secondary pollution.

The acidification has been a known problem in Sweden for several decades. Sulphurous compounds, spread from the British Isles and the European continent led to a decrease in the pH-value of the rain that fell over Sweden. Since the acidification was discovered in the 1960s, active measures against the sulphurous deposition have been undertaken. The sulphurous deposition has decreased by 90 %, and the problem was for some time considered under control, until recently when a new era of the acidification may have started. Due to the increased demand of renewable energy, and Sweden’s potential to use biomass instead of fossil fuels, whole tree harvesting has been more utilized. Studies indicate that the forest soils are depleted in base cations in a faster rate when whole tree harvesting is performed compared to regular stem harvesting. Mass balance calculations and simulations indicate that an increased bio uptake of base cations due to whole tree harvesting leads to an increased biological acidification. However, although many studies agree that the impact of the whole tree harvest on the base cation supply of the soils is significant, long running Swedish experiments indicate that the difference between whole tree harvesting and regular stem harvesting diminishes over time. After a 40 year period, the difference in base cation supply between whole tree harvested soils and stem harvested soils are small. The reason for this could be different processes that reallocate base cations from different pools, which are not usually studied. The aim has been to investigate and evaluate different chemical extraction methods (Aqua Regia, HCl, EDTA, BaCl2, NH4OAc and water) capability to extract the base cations calcium, potassium, magnesium and sodium from four different Swedish forest soils and what this means for our understanding of how much base cations a soil contains. The extractions indicated that there is a statistical significant difference between the methods ability to extract base cations. Generally Aqua Regia was the most potent method, followed by HCl, EDTA, BaCl2, NH4OAc and water in decreasing order of effectiveness to extract the base cations. Linear correlations were found between EDTA, BaCl2 and NH4OAc. The internationally widely used method NH4OAc was considered to be at risk of underestimating the amount of base cations in the soil. / Försurningsproblematiken har länge varit ett känt problem i Sverige. Svavelhaltiga föroreningar som spreds från de brittiska öarna och den europeiska kontinenten ledde till att pH-värdet i regnet som föll över Sverige sjönk. Sedan upptäckten på 60-talet har aktiva åtgärder vidtagits mot utsläppen vilket har lett till en minskning av de försurande föroreningarna med 90 %. På grund av den stora utsläppsreduktionen som skett ansågs försurningsproblematiken vara under kontroll, tills nyligen då en ny etapp av för- surningen kan ha påbörjats. På grund av den ökande efterfrågan av förnyelsebar energi, i kombination med Sveriges stora skogstillgångar, har helträdsskörd av träd blivit alltmer nyttjad. Studier visar att markens baskatjonförråd utarmas i större utsträckning av helträdsskörd, då även grenar, rötter och toppar tas om hand jämfört med vanlig stamskörd då endast stammen tas med från skogen. Massbalanssimuleringar antyder att ett ökat bioupptag av baskatjoner på grund av helträdsskörd leder till en ökad biologisk försurning. Trots att många studier är överens om helträdsskördens inverkan på markens innehåll av baskatjoner visar lång- liggande försök i Sverige att skillnaderna mellan uttag av hela träd och stamved minskar med tiden. Efter en period på 40 år återstår endast små skillnader mellan avverknings- metoderna. Orsakerna till varför mätningarna och massbalansberäkningarna och simuleringarna inte stämmer överens kan vara många, t.ex. att det finns processer som kan omfördela baskatjoner från de som vanligtvis studeras. Syftet har varit att undersöka och utvärdera olika kemiska extraktionsmetoders (Aqua Regia, HCl, EDTA, BaCl2, NH4OAc och vatten) förmåga att extrahera baskatjonerna kalcium, kalium, magnesium och natrium från fyra olika skogsjordar i Sverige och vad resultaten betyder för vår uppfattning av mängden baskatjoner i marken. Extraktionerna visade att en statistiskt signifikant skillnad fanns mellan metodernas förmåga att extrahera de olika baskatjonerna. Generellt var Aqua Regia den metod som extraherade den största mängden baskatjoner, HCl, EDTA, BaCl2, NH4OAc och vatten följde i fallande ordning efter förmåga att extrahera baskatjonerna. Linjära korrelationer mellan EDTA, BaCl2 och NH4OAc upptäcktes. Den internationellt ofta använda metodiken för att extrahera baskatjoner, NH4OAc, ansågs riskera att underskatta mängden baskatjoner i marken.

As the integration scale of transistors/devices in a chip/system keeps increasing, effective cooling has become more and more important in microelectronics. To address the thermal dissipation issue, one important solution is to develop thermal interface materials with higher performance. Carbon nanotubes, given their high intrinsic thermal and mechanical properties, and their high thermal and chemical stabilities, have received extensive attention from both academia and industry as a candidate for high-performance thermal interface materials. The thesis is devoted to addressing some challenges related to the potential application of carbon nanotubes as thermal interface materials in microelectronics. These challenges include: 1) controlled synthesis of vertically aligned carbon nanotubes on various bulk substrates via chemical vapor deposition and the fundamental understanding involved; 2) development of a scalable annealing process to improve the intrinsic properties of synthesized carbon nanotubes; 3) development of a state-of-art assembling process to effectively implement high-quality vertically aligned carbon nanotubes into a flip-chip assembly; 4) a reliable thermal measurement of intrinsic thermal transport property of vertically aligned carbon nanotube films; 5) improvement of interfacial thermal transport between carbon nanotubes and other materials. The major achievements are summarized. 1. Based on the fundamental understanding of catalytic chemical vapor deposition processes and the growth mechanism of carbon nanotube, fast synthesis of high-quality vertically aligned carbon nanotubes on various bulk substrates (e.g., copper, quartz, silicon, aluminum oxide, etc.) has been successfully achieved. The synthesis of vertically aligned carbon nanotubes on the bulk copper substrate by the thermal chemical vapor deposition process has set a world record. In order to functionalize the synthesized carbon nanotubes while maintaining their good vertical alignment, an in situ functionalization process has for the first time been demonstrated. The in situ functionalization renders the vertically aligned carbon nanotubes a proper chemical reactivity for forming chemical bonding with other substrate materials such as gold and silicon. 2. An ultrafast microwave annealing process has been developed to reduce the defect density in vertically aligned carbon nanotubes. Raman and thermogravimetric analyses have shown a distinct defect reduction in the CNTs annealed in microwave for 3 min. Fibers spun from the as-annealed CNTs, in comparison with those from the pristine CNTs, show increases of ~35% and ~65%, respectively, in tensile strength (~0.8 GPa) and modulus (~90 GPa) during tensile testing; an ~20% improvement in electrical conductivity (~80000 S m⁻¹) was also reported. The mechanism of the microwave response of CNTs was discussed. Such an microwave annealing process has been extended to the preparation of reduced graphene oxide. 3. Based on the fundamental understanding of interfacial thermal transport and surface chemistry of metals and carbon nanotubes, two major transfer/assembling processes have been developed: molecular bonding and metal bonding. Effective improvement of the interfacial thermal transport has been achieved by the interfacial bonding. 4. The thermal diffusivity of vertically aligned carbon nanotube (VACNT, multi-walled) films was measured by a laser flash technique, and shown to be ~30 mm² s⁻¹ along the tube-alignment direction. The calculated thermal conductivities of the VACNT film and the individual CNTs are ~27 and ~540 W m⁻¹ K⁻¹, respectively. The technique was verified to be reliable although a proper sampling procedure is critical. A systematic parametric study of the effects of defects, buckling, tip-to-tip contacts, packing density, and tube-tube interaction on the thermal diffusivity was carried out. Defects and buckling decreased the thermal diffusivity dramatically. An increased packing density was beneficial in increasing the collective thermal conductivity of the VACNT film; however, the increased tube-tube interaction in dense VACNT films decreased the thermal conductivity of the individual CNTs. The tip-to-tip contact resistance was shown to be ~1×10⁻⁷ m² K W⁻¹. The study will shed light on the potential application of VACNTs as thermal interface materials in microelectronic packaging. 5. A combined process of in situ functionalization and microwave curing has been developed to effective enhance the interface between carbon nanotubes and the epoxy matrix. Effective medium theory has been used to analyze the interfacial thermal resistance between carbon nanotubes and polymer matrix, and that between graphite nanoplatlets and polymer matrix.