两种催化裂化催化剂载体的矿物学特性研究－高岭土和酸活化水黑云母

通过对贵州大方高岭土（GZK-1）、苏州高岭土（JSK）、新疆伊宁高岭土（XJK-6）和新疆尉犁水黑云母及其酸活化处理样矿物学特征的系统研究，得出如下讨论：（1）GZK-1、JSK、和XJK-6的微活指数依次为 29%, 13%和0%，在微活指数上埃洛石＞高岭石＞地开石；（2）高岭土的微活指数仅与杂质铁(Fe_2O_3+FeO)的含量有一定的正相关关系；（3）高岭土的微活指数与其孔体积和比表面积有正相关关系；（4）高岭土的微活指数主要与矿物成分有关，其结构羟基的特性是活性的根源；（5）XJK-6的比表面积小(9 m~2/g)、孔体积小(0.026 ml/g)、大孔多、热稳定性好、几乎无活性；（6）在一定的实验条件下，可获得即具大的比表面积、孔径和孔体积，又尽可能保持原有晶体结构的酸活化产物；（7）活化样品中K_2O、Fe_2O_3、MgO的含量可指示其比表面积的变化；（8）水黑云母含金云母晶层的矿物晶体结构决定了其比蛭石晶层耐酸腐蚀，在较为苛刻的条件下金云母晶层仍然保持；（9）酸活化产物的特点：结构中含一定量的镁；Na_2O含量低，K_2O的含量高；比表面积大(130 m~2/g)；孔体积高(0.119 ml/g)，中孔多；微活指数低 (4.7%).

地幔柱与岩浆成矿-峨嵋山大火成岩省地震波速层物相解释及典型PGE矿床成岩成矿机制研究

地幔柱概念在19世纪60至70年代就被提出，但是由于板块构造理论在解释地球上岩浆活动的分布规律时取得了空前的成功，在当时这一理论是被排斥的。板块边界概念可以解释地球上绝大部分的岩浆产出，但在解释板内岩浆的成因时往往显得力不从心，尽管这些岩浆的体积只占地球岩浆总量的2％。地幔柱理论模型发展到现在得到不同学科的支持。地质学、地球化学、地球物理学、古生物学、比较行星学、实验岩石学等等都提供了直接或间接的证据，证明地幔柱几乎存在整个地：质历史时期。当前地幔柱理论中在地球化学领域有两大研究热点：高钦低钦玄武岩的起源以及地幔柱中是否存在循环俯冲洋壳物质。完全解决这些问题才可能深入系统地建立地慢柱成矿作用模型。现在已经建立了一些矿床类型与地慢柱作用的联系：如现在认为赋存在金伯利岩中的金刚石矿床的形成与地慢柱作用密不可分，一些岩浆硫化物矿床和岩浆氧化物矿床很显然是地慢柱岩浆作用形成的，如西伯利亚火成岩省的Noril'sk-Talnakh铜镍铂族元素矿床以及KeweenawaJI大陆裂谷体系的Dultlth杂岩体的Cu-Ni矿床。另外还有赋存在大型基性一超基性层状岩体中的PGE、Ni和cu矿床，如Great Dyke和布什维尔德杂岩体。一些超大型热液矿床也与地慢柱有可能的联系（Pirajno，2000）：如270oMa形成的超大型Kidd Creek火山成因块状硫化物矿床（Bleeker et al.，1 999；Wynan et al.，1999）和南澳大利亚1600Ma形成的超大型olymPicD翻矿床。本文的研究工作包含两方面内容：通过热力学计算峨眉山玄武岩在深部的结晶分异，对峨眉山大火成岩省的岩浆量分布和岩浆氧化物矿床（华Ti磁铁矿矿床）的分布以及下地壳高波速层的物相进行理论解释；对峨眉山大火成岩省金宝山PGE典型矿床进行成岩成矿的地球化学研究，预测整个大火成岩省的岩浆硫化物矿床产出位置。大多数峨眉山玄武岩的 MgO＜7％，Ni为4-232ppm，它们是原始岩浆结晶分异后的产物。峨眉山玄武岩省下地壳和上地幔之间存在厚度为：8-25km1，P彼速为7.1-7.8km／s的附加层（高地震波速层）。滇西地区出露的洲套第三纪富碱斑岩，地球化学和同位素研究表明斑岩的岩浆源是来自“壳一慢混合层”，源区的形成时代为220-25Ma，与峨眉山玄武岩的形成时代一致。所以有理由认为该附加层是由峨眉山玄武岩在此结晶分异形成的。与地慢柱有关的洋岛Hawaii、Marquesas Islands；海底高原Oniong Java、大陆火山岩省ColumbiaRiver Plateaus地震彼研究都表明在上地慢顶部有一高速附加层，Farnetani etal.（1996）的研歼表明高速附加层是由来自地幔柱的岩浆在此结晶分异形成的。玄武岩是一种混合的部分熔融产物，是不同成分的地幔橄榄岩在不同的压力下熔出的。这种降压熔融高温高压实验是做不到的。熔出的熔体成分是温度、压力及橄榄岩成分（源区）的函数，形成的岩浆是一个多压熔融的集合体。热力学计算能够较为精确地计算出生成的岩浆成分和约束岩浆产生的过程。岩浆的结晶分异也是同样的情形，尤其是分离结晶过程，实验岩石学是很精确难模拟其过程的。热力学计算使用的MELTS程序，MELTS适用范围很广，适用于模拟岩石熔融生成岩浆和岩浆的冷却结晶。现今峨眉山大火成岩省的地壳厚度为40恤，这被认为是后期褶皱加厚的缘故。根据峨眉山玄武岩中辉石斑晶成分和玄武岩本身成分计算出分异结晶的压力为6kb，那么当时的地壳厚度约为20km：选择氧逸度为QFM，这一氧逸度范围认为是大多数大陆溢流玄武岩结晶分异时的氧化还原环境。热力学计算结果通过峨眉山玄武岩成分进行约束和验证。Al2O3、NaZO＋K 20、CaO与MgO计算的演化趋势线与实际观察的演化符合较好，橄榄石和斜方辉石的结晶使得CaO随着MgO的降低而增高；当单斜辉石成为液相线矿物时，cao也随着Mgo的降低而降低了。单斜辉石在岩浆演化到MgO＝10．3％时成为液相线矿物。整个计算过程中斜长石未成为液相线矿物，这与大多数玄武岩不具有Eu异常是一致的，并月＿Al2O3随着MgO的减小单调增加也说明了这点。不过大多数峨眉山玄武岩常含有斜长石斑晶，这是低压下结晶分异的结果。由于斜长石密度小，所有很难与高铁玄武岩分离。整个计算的难点也是创新点是波速计算。通过分离的堆晶矿物组合中各种矿物的成分和质量分数计算的附加层波速比观察值高，不过堆积岩体常常会有残留岩浆存在矿物晶粒间，这样会降低岩石的压缩波速。大型基性一超基性岩体常常会残留有或者捕获5-30％的岩浆。假定两个高波速附加层分别捕获7叭，和巧％的残留岩浆，计算的结果就大体等于观察值。热力学和质量平衡计算研究表明：高地震波速层为橄榄辉石岩一辉石岩的巨型侵入岩体；峨眉山中岩区的岩浆量最大也符合含V-Ti磁铁矿矿床只产在中岩区，如太和、白马、攀枝花、红格等岩体；西岩区的岩浆量最小表明几乎没有可能在西岩区形成有规模的V-Ti磁铁矿矿床，实际观察仅仅只见到数量少而小的岩体；东岩区下地壳厚达20灿1的高波速层暗示东岩区上地壳的侵入岩体积也应该具有相当规模，应该是V－Ti磁铁矿矿床成矿区。目前在东岩区很少发现与峨眉山玄武岩有关的岩浆矿床的主要原因是：东岩区的剥蚀深度不够，没有可观的侵入岩体出露，而中岩区侵入岩都侵入在元古代地层中。按照质量平衡的计算方法，最保守的估算整个峨眉地慢柱岩浆事件产生的岩浆量为8.9*106km3，上地壳峨眉山玄武岩和侵入岩体积为3.9*106km3。如果按照初始覆盖面积5x106km2计算（与西伯利亚暗色岩初始覆盖面积相当），喷发高峰期为2Ma，计算的喷发速率为3.9km3／year。这并不亚于西伯利亚暗色岩的喷发速率4km3／year。这对于研究峨眉山大火成岩浆事件与二叠·三叠交界或end-QuadaluPian生物灭绝之间的可能联系具有重要意义。本文另一方面的研究工作是：首先系统地介绍了岩浆硫化物矿床的基本原理，然后通过金宝山PGE矿床实例研究，提出金宝山岩体成岩模式，并且对整个峨眉山大火成岩省的岩浆硫化物矿床产出位置进行理论预测。详细地球化学研究表明金宝山镁铁一超镁铁岩是峨眉山大火成岩省古老火山岩浆房的残留物。岩体主要由底部超镁铁岩和上部镁铁岩组成，两种岩石的质量大致相同。根据超镁铁岩的矿物组合计算的成岩时的氧逸度较高，热力学方法计算的成岩压力为2kb左右。超镁铁岩的包嵌结构和铁铁岩的微晶一细晶结构说明超镁铁岩为镁铁岩结晶的矿物堆积形成的。镁铁一超镁铁岩的蚀变程度不同以及Sc、Sr、Eu等元素在两类岩石中的不同特征指示了整个成岩过程。金宝山岩体的原始岩浆 MgO=8％说明高镁玄武岩并不是形成PGE矿床的必要条件。金宝山的成岩模式是：在火山喷发前，岩浆侵位时橄榄石和少量铬尖晶石先结晶，沉淀在岩浆房底部；随后结晶的是斜方辉石和斜长石，斜方辉石也沉淀在岩浆房底部，斜长石由于密度较小集中中岩浆房上部，岩浆房的中部是：少量的斜长石小斑晶。由于斜方辉石和斜长石的结晶，这样岩浆中的Sc、Sr和Eu就会亏损，也是岩浆房底部堆积岩的原始捕获岩浆。火山喷发后，由于压力的突然降低，岩浆房底部的堆晶会发生再熔融，几乎消耗掉所有的斜方辉石，橄榄石也呈熔蚀状浑圆形态，重新熔融的斜方辉石导致超镁铁岩中残留岩浆比原始捕获岩浆更加富Sc，这种岩浆由于富MgO和在快速冷却的环境下同时结晶，最终形成光性方位一致的单刹辉石。喷发后岩浆房空间的剩余导致围岩-灰岩进入，造成岩浆房中剩余岩浆强烈的碳酸盐化。峨眉山玄武岩Cr-Mg#的相关关系定义一条正常玄武岩演化线。大多数这些玄武岩的Ni也保持了这种演化关系，其中低钦玄武岩和过渡型高钦玄武岩Ni-Mg＃相关关系远离了正常演化线，这些玄武岩的Cu-Mg#相关关系也有类似的情形。峨眉山低钦和过渡类型高钦玄武岩Ni和 Cu的非正常亏损，表明它们在地表下经历了硫饱和事件。金宝山岩浆硫化物矿床成岩模型的建立，为在整个大火成岩省寻找岩浆硫化物矿床提供了一种新认识。低钦和过渡型高钦玄武岩的古老火山口下部是岩浆硫化物矿床的所在地。

龙溪软玉的矿物学研究

龙溪玉是除新疆软玉、台湾软玉之外的中国三大软玉之一。本文采取以宏观到微观再到亚微观逐步深入的工作方法，在地质产状、物质成分、物理性质、谱学特征、显微——亚显微组构等方面对龙溪玉进行了基础矿物学。矿物物理学和成因矿物学或岩石学的综合性研究。最后，提出了龙溪玉形成的过程机理和成因模式。龙溪玉是多相变质作用过程中热力场和应力场交相变化的动热变质作用的产物，反映了早期的变质结晶作用，构造期的变形作用及其后的恢复，重结晶作用和退变质作用的复杂结合。文中并对Cao－Mgo－Sio_2－H_2o－Co_2五元五相热力学多体系通过构筑拓扑相图的方法深入探讨含玉体透闪片岩在区域进变质作用过程中形成的温压条件，估讨为550－600℃。4－5干巴，而变形作用与退变质作用过程中的温温压条件则明显低于这个数值范围。

广西贺县龙水金矿床的同位素地球化学研究及成因探讨

广西贺县龙水金矿位于湘桂稳定区，桂粤交界山脉的北段，博白-茶陵深断裂的西侧，区内广泛发育加里东期到燕山期的花岗岩，出露的基底地层主要为震旦系到寒武系。本文主要研究龙水金矿II号矿化带。该带位于寒武系水口群清溪亚群和大宁花岗闪长岩体的接触带附近，围岩为寒武系的碳质板岩，矿脉为硫化物石英脉，主要有黄铁矿、方铅矿、闪锌矿和石英等矿物。金矿化与硫化物密切相关。主要的金矿物为银金矿，少许自然金。确定金矿床的成矿年龄一直是个比较刺手的问题。本文选择矿脉中信为是成矿期的石英作为Rb-Sr等时年龄测定的对象，是基于其纯净和其中的原生气液包体基本可代表成矿热液的特征。结果表明其Rb-Sr等时年龄为120.5Ma，并认为此年龄代表了成矿年龄。有石英Rb-Sr等时线的~(87)Sr/~(86)Sr初始比为0.732089, 与矿脉中碳酸相加矿物的Sr同位素比值（约为0.7337-0.7402）一起，表明Sr应是来自地壳的富Rb盐矿物的Sr源区。另外，为了与围岩的蚀变年龄对比，测定了近矿围岩的Rb、Sr同位素组成，结果形成两条等时线，年龄分别为245.9 Ma和173.6 Ma，表明成矿以前至少发生了两次地质事件，导致了Sr同位素的均一化。这两次地质事件分别与华南的东吴运动及燕山运动第一幕相对应。矿石Pb同位素的~(206)Pb/~(204)Pb、 ~(207)Pb/~(204)Pb 和~(208)Pb/~(204)Pb 分别在18.4-18.9、15.6-16.1和38.4-39.6的范围内，并在~(207)Pb/~(204)Pb vs ~(206)Pb/~(204)Pb坐标图上呈现出斜率为1左右的线性排布。只有个别数据点要以得出依据Doe模式的模式年龄，约为200 Ma。在Zart,am Pb构造模式中，矿石Pb同位素数据大部分位于上地壳Pb线以上，呈现出富放射性成因Pb的特征。为了解释异常Pb的成因，本文进行了定量计算。结果表明矿石Pb为古老的存留地壳Pb与少地幔源Pb的混合，即矿石Pb同位素经历了这样的演化过程：在39-29.8亿年间由地幔分异出的地壳 Pb，未参与壳幔循环作用，一直到燕山期，与少量幔源Pb混合，并加入成矿。混合μ值为9.85-10.22。矿石的地质情况及矿石Pb同位素的Δα-Δβ-Δγ示踪结果均支持这一结论。本文初次研究了脉石英中的U、Pb同位素组成。脉石英中Ｕ含量很低。Pb同位素组成基本可以划分为两组，一组为与方铅矿数据近似的普通Pb组成，另一组则较富放射性成因Pb，并向围岩的Pb同位素组成漂移，可能是随着热液的演化和大气降水的加入，受围岩Pb的影响所致。矿脉中硫化物样品的S同位素比值（加权平均为0.16‰）和碳酸盐矿物样品的C同位素比值（在-0.1～-4.1‰的范围内），表明其应为内生来源。根据脉石英的气液包体均一温度（180-250 ），计算与脉石英存在0同位素平衡的热液的同位素的同位素组成，结果为1.2～-4.8‰，表明有大气降水的参与。石英气液包体水溶液为弱碱性，其成分分析表明其中K_2O/Na_2和CaO/MgO（分别根据K~+/Na~+和Ca~(2+)/Mg~(2+)的换算）与围岩相差很大。另外，矿石中微量元素主要为Au、A2g、Cu、Pb、Zn、Co、Ni、Mo、Bi、Ga、As、Sb、和Hg，而围岩中微量元素则主要为Cu、Ni、Mn、V、Zr、Ti、Cr和Ba。因此，热液中成矿元素主要不是来自围岩。黄铁矿的Co/Ni、S/Se/的比值可以指示热液化的来源。龙水金矿矿脉中黄铁矿的Co/Ni > 1，S/Se < 15000，均在与岩浆作用有关的热液范围内。因此，热液活动应主要与岩浆岩有关。矿石、围岩和花岗闪长岩的稀土配分模式相似，均呈现向右倾斜的V字型，并且类似于太古代后沉积岩。结合Pb、Sr同位素的研究，推测花岗闪长岩的源岩主要为古老的地壳物质。概括起来，龙水金矿床为约120.5 Ma形成的中低温热液矿床；热液中成矿物质主要来自花岗闪长岩。由于围岩与矿床紧密的空间联系及围岩中的高Au含量，围岩可能提供了一部分Au及其他成矿物质。

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO2 have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine. Al-27 and Si-29 MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications. H-1 MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Bronsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO2-modified HY zeolites decreased less, and this result is consistent with that of NH3-TPD, from the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO2 after being modified by the chemical liquid deposition (CLD) method.

In situ study of carbon nanotube formation by C2H2 decomposition on an iron-based catalyst

The properties and formation of nanotubes have been extensively studied, but very few deal with the catalytic production mechanism of nanotubes. Two different techniques, thermogravimetric analysis and UV-Raman, have been applied to analyse the carbon deposition by catalysed decomposition of acetylene over an iron-based catalyst. The nature of the produced carbon materials depends on reaction temperature. Also, TEM allows identification of carbon nanotubes, encapsulated particles, and other nanostructures, while UV-Raman confirms its graphitic and graphite-like nature. (C) 2000 Elsevier Science Ltd. All rights reserved.

Partial oxidation of ethane to syngas over nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide

The catalytic activity, thermal stability and carbon deposition of various modified NiO/gamma-Al2O3 and unmodified NiO/gamma-Al2O3 catalysts were investigated with a flow reactor, XRD, TG and UVRRS analysis. The activity and selectivity of the NiO/gamma-Al2O3 catalyst showed little difference from those of the modified nickel-based catalysts. However, modification with alkali metal oxide (Li, Na, K) and rare earth metal oxide (La, Ce, Y, Sm) can improve the thermal stability of the NiO/gamma-Al2O3 and enhance its ability to suppress carbon deposition during the partial oxidation of ethane (POE). The carbon deposition contains graphite-like species that were detected by UVRRS. The nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide have excellent catalytic activities (C2H6 conversion of similar to 100%, CO selectivity of similar to 94%, 7x 10(4) l/(kg h), 1123 K), good thermal stability and carbon-deposition resistance.

A novel process for converting coalmine-drained methane gas to syngas over nickel-magnesia solid solution catalysts

A novel process is developed in this paper for utilizing the coalmine-drained methane gas that is usually vented straight into the atmosphere in most coalmines worldwide. It is expected that low-cost syngas can be produced by the combined air partial oxidation and CO2 reforming of methane, because this process utilizes directly the methane, air, and carbon dioxide in the coalmine-drained gas without going through the separation step. For this purpose, a nickel-magnesia solid solution catalyst was prepared and its catalytic performance for the proposed process was investigated. It was found that calcination temperature has significant influence on the catalytic performance due to the different extent of solid solution formation in the catalysts. A uniform nickel-magnesia solid solution catalyst exhibits higher stability than the catalysts in which NiO has not completely formed solid solution with MgO. Its catalytic activity and selectivity remain stable during 120 h of reaction. The product H-2/CO ratio is mainly dependent on the feed gas composition. By changing CO2/air ratio of the feed gases, syngas with a H-2/CO ratio between 1 and 1.9 can be obtained. The influences of reaction temperature and nickel loading on the catalytic performance were also investigated. (c) 2004 Elsevier B.V All rights reserved.

Catalytic steam reforming of ethanol to produce hydrogen and acetone

Steam reforming of ethanol over CuO/CeO2 was studied. Acetaldehyde and hydrogen were mainly produced at 260degreesC. At 380degreesC, acetone was the main product, and 2 mol of hydrogen was produced from 1 mol of ethanol. The formation of hydrogen accompanied by the production of acetone was considered to proceed through the following, consecutive reactions: dehydrogenation of ethanol to acetaldehyde. aldol condensation of the acetaldehyde, and the reaction of the aldol with the lattice oxygen [O(s)] on the catalyst to form a surface intermediate, followed by its dehydrogenation and decarboxylation. The overall reaction was expressed by2C(2)H(5)OH + H2O --> CH3COCH3 + CO2 + 4H(2). Ceria played an important role as an oxygen supplier. The addition of MgO to CuO/CeO2 resulted in the production of hydrogen at lower temperatures by accelerating aldol condensation. (C) 2004 Elsevier B.V. All rights reserved.

Controlled growth of uniform silver clusters on HOPG

We have investigated growth of silver clusters on three different, i.e. normally cleaved, thermally oxidized and Ar+ ion sputtered highly oriented pyrolytic graphite (HOPG), surfaces. Scanning tunneling microscopy (STM) observations reveal that uniformly sized and spaced Ag clusters only form on the sputtered surface. Ar+ sputtering introduces relatively uniform surface defects compared to other methods. These defects are found to serve as preferential sites for Ag cluster nucleation, which leads to the formation of uniform clusters. (c) 2005 Elsevier B.V. All rights reserved.

INVESTIGATION OF BUBBLE DYNAMICS AND HEATING DURING FOCUSED ULTRASOUND INSONATION IN TISSUE-MIMICKING MATERIALS

The deposition of ultrasonic energy in tissue can cause tissue damage due to local heating. For pressures above a critical threshold, cavitation will occur in tissue and bubbles will be created. These oscillating bubbles can induce a much larger thermal energy deposition in the local region. Traditionally, clinicians and researchers have not exploited this bubble-enhanced heating since cavitation behavior is erratic and very difficult to control. The present work is an attempt to control and utilize this bubble-enhanced heating. First, by applying appropriate bubble dynamic models, limits on the asymptotic bubble size distribution are obtained for different driving pressures at 1 MHz. The size distributions are bounded by two thresholds: the bubble shape instability threshold and the rectified diffusion threshold. The growth rate of bubbles in this region is also given, and the resulting time evolution of the heating in a given insonation scenario is modeled. In addition, some experimental results have been obtained to investigate the bubble-enhanced heating in an agar and graphite based tissue- mimicking material. Heating as a function of dissolved gas concentrations in the tissue phantom is investigated. Bubble-based contrast agents are introduced to investigate the effect on the bubble-enhanced heating, and to control the initial bubble size distribution. The mechanisms of cavitation-related bubble heating are investigated, and a heating model is established using our understanding of the bubble dynamics. By fitting appropriate bubble densities in the ultrasound field, the peak temperature changes are simulated. The results for required bubble density are given. Finally, a simple bubbly liquid model is presented to estimate the shielding effects which may be important even for low void fraction during high intensity focused ultrasound (HIFU) treatment.

IDENTIFYING AND MONITORING THE ROLES OF CAVITATION IN HEATING FROM HIGH-INTENSITY FOCUSED ULTRASOUND

For high-intensity focused ultrasound (HIFU) to continue to gain acceptance for cancer treatment it is necessary to understand how the applied ultrasound interacts with gas trapped in the tissue. The presence of bubbles in the target location have been thought to be responsible for shielding the incoming pressure and increasing local heat deposition due to the bubble dynamics. We lack adequate tools for monitoring the cavitation process, due to both limited visualization methods and understanding of the underlying physics. The goal of this project was to elucidate the role of inertial cavitation in HIFU exposures in the hope of applying noise diagnostics to monitor cavitation activity and control HIFU-induced cavitation in a beneficial manner. A number of approaches were taken to understand the relationship between inertial cavitation signals, bubble heating, and bubble shielding in agar-graphite tissue phantoms. Passive cavitation detection (PCD) techniques were employed to detect inertial bubble collapses while the temperature was monitored with an embedded thermocouple. Results indicate that the broadband noise amplitude is correlated to bubble-enhanced heating. Monitoring inertial cavitation at multiple positions throughout the focal region demonstrated that bubble activity increased prefocally as it diminished near the focus. Lowering the HIFU duty cycle had the effect of maintaining a more or less constant cavitation signal, suggesting the shielding effect diminished when the bubbles had a chance to dissolve during the HIFU off-time. Modeling the effect of increasing the ambient temperature showed that bubbles do not collapse as violently at higher temperatures due to increased vapor pressure inside the bubble. Our conclusion is that inertial cavitation heating is less effective at higher temperatures and bubble shielding is involved in shifting energy deposition at the focus. The use of a diagnostic ultrasound imaging system as a PCD array was explored. Filtering out the scattered harmonics from the received RF signals resulted in a spatially- resolved inertial cavitation signal, while the amplitude of the harmonics showed a correlation with temperatures approaching the onset of boiling. The result is a new tool for detecting a broader spectrum of bubble activity and thus enhancing HIFU treatment visualization and feedback.

A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Precursor chemistry for oxide related materials

This thesis describes modelling, synthesis, spectroscopic and physical characterisation, as well as application of Magnesium, Calcium and Copper β-diketonate, β-ketoiminate, β-diiminate, Schiff base, amide and fluorenyl compounds. The selected compounds could potentially find application in materials deposition using Atomic Layer Deposition (ALD), MOCVD, CVD and Sol-Gel techniques. Quantum chemical modelling was used as a tool to perform the comprehensive and rapid study of magnesium and calcium precursor molecules in order to predict which of them would be more successful in ALD of metal oxides. Precursor chemistry plays a key role in ALD, since precursors must be volatile, thermally stable, chemisorb on the surface and react rapidly with existing surface groups. This Thesis describes one aspect of this, surface reactivity between ligands and hydroxyl groups, via a gas-phase model with energetics computed at the level of Density Functional Theory (DFT). A number of different synthetic strategies, both aerobic and anaerobic, were investigated for the synthesis of the described metal complexes. These included the use of different metal starting reagents such as, anhydrous and hydrated inorganic metal salts, metal alkyls and Grignard reagents. Some of previously unreported metal complexes of homoleptic and heteroleptic magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, amides and Schiff base type were synthesised and characterised: [Mg(hfpd)2(DipPa)], [Mg(hfpd)2(MapH)2], [Mg(hf-ebp)(THF)2], [Mg(tf-Pap)Cl(THF)2], [Ca(PhNacnac)2], [Cu(tf-Pap)2], [Cu(PhNacnac)2], [Cu(hf-ebp)], [Cu(DipPa)] and [Cu(DipPa)2(4,4’-bypy)]. A comprehensive study on the thermal properties of magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, Schiff base, amide and fluorenyl complexes was performed using TGA and sublimation of selected compounds. Atomic Layer Deposition of MgO using magnesium β-ketoiminate – [bis{(4-N-phenyl)-2-pentonato} magnesium] and β-diketonate - [bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)(THF)magnesium hydrate] was performed on Si(100) substrates at 180°C and 0.2 Torr using O2 plasma.

Probing polarization and dielectric function of molecules with higher order harmonics in scattering-near-field scanning optical microscopy

The idealized system of an atomically flat metallic surface [highly oriented pyrolytic graphite (HOPG)] and an organic monolayer (porphyrin) was used to determine whether the dielectric function and associated properties of thin films can be accessed with scanning-near-field scanning optical microscopy (s-NSOM). Here, we demonstrate the use of harmonics up to fourth order and the polarization dependence of incident light to probe dielectric properties on idealized samples of monolayers of organic molecules on atomically smooth substrates. An analytical treatment of light/sample interaction using the s-NSOM tip was developed in order to quantify the dielectric properties. The theoretical analysis and numerical modeling, as well as experimental data, demonstrate that higher order harmonic scattering can be used to extract the dielectric properties of materials with tens of nanometer spatial resolution. To date, the third harmonic provides the best lateral resolution (∼50 nm) and dielectric constant contrast for a porphyrin film on HOPG. © 2009 American Institute of Physics.