A Study of the Microwave Carbothermic Reduction of Chromite Ore

Microwave reduction testing using activated charcoal as a reducing agent was performed on a sample of Black Thor chromite ore from the Ring of Fire deposit in Northern Ontario. First, a thermodynamic model was constructed for the system. Activity coefficients for several species were found in the literature. The model predicted chromium grades of 61.60% and recoveries of 93.43% for a 15% carbon addition. Next, reduction testing on the chromite ore was performed. Tests were performed at increasing power levels and reduction times. Testing atmospheres used were air, argon, and vacuum. The reduced product had maximum grades of 72.89% and recoveries of 80.37%. These maximum values were obtained in the same test where an argon atmosphere was used, with a carbon addition of 15%, optimal power level of 1200 W (actual 1171 W), and a time of 400 seconds. During this test, 17.53% of the initial mass was lost as gas, a carbon grade of 1.95% was found for the sintered core product. Additional work is recommended to try and purify the sintered core product as well as reduce more of the initial sample. Changing reagent schemes or a two step reduction / separation process could be implemented.

Evolution of a ~2.7 Ga large igneous province: A volcanological, geochemical and geochronological study of the Agnew Greenstone Belt, and new regional correlations for the Kalgoorlie Terrane (Yilgarn Craton, Western Australia)

The thick package of ~2.7 Ga mafic and ultramafic lavas and intrusions preserved among the Neoarchean of the Kalgoorlie Terrene in Western Australia provides valuable insight into geological processes controlling the most prodigious episode of growth and preservation of juvenile continental crust in Earth’s history. Limited exposure of these rocks results in uncertainty about their age, physical and chemical characteristics, and stratigraphic relationships. This in turn prevents confident correlation of regional occurrences of mafic and ultramafic successions (both intrusive and extrusive) and hinders the interpretation of tectonic setting and magmatic evolution. A recent stratigraphic drilling program of the Neoarchean stratigraphy of the Agnew Greenstone Belt in Western Australia has provided continuous exposures through a c. 7 km thick sequence of mafic and ultramafic units. In this study, we present a volcanological, lithogeochemical and chronological study of the Agnew Greenstone Belt, and provide the first pre-2690 Ma regional correlation across the Kalgoorlie Terrane. The Agnew Greenstone Belt records ~30 m.y. of episodic ultramafic-mafic magmatism that includes two cycles, each defined by a komatiite that is overlain by units that become more evolved and contaminated with time. The sequence is divided into nine conformable packages, each consisting of stacked subaqueous lava flows and comagmatic intrusions, as well as two sills without associated extrusions. Lavas, with the exception of intercalations between two units, form a layer-cake stratigraphy and were likely erupted from a system of fissures tapping the same magma source. The komatiites are not contaminated by continental crust ([La/Sm]PM ~0.7) and are of the Al-undepleted Munro-type. Crustal contamination is evident in many units (Songvang Basalt, Never Can Tell Basalt, Redeemer Basalt, and Turrett Dolerite), as judged by [La/Sm]>1, negative Nb and Ti anomalies, and geochemical mixing trends towards felsic contaminants. Crystal fractionation was also significant, with early olivine and chromite (Mg#>65) followed by plagioclase and clinopyroxene removal (Mg<65), and in the most evolved case, titanomagnetite accumulation. Three new TIMS dates on granophyric zones of mafic sills and one ICP-MS date from an interflow felsic tuff are presented and used for regional stratigraphic correlation. Cycle I magmatism began at ~2720 Ma and ended ~2705 Ma, whereas cycle II began ~2705 Ma and ended at 2690.7±1.2 Ma. Regional correlations indicate the western Kalgoorlie Terrane consists of a remarkably similar stratigraphy that can be recognised at Agnew, Ora Banda and Coolgardie, whereas the eastern part of the terrane (e.g., Kambalda Domain) does not include cycle I, but correlates well with cycle II. This research supports an autochthonous model of greenstone formation, in which one large igneous province, represented by two complete cycles, is constructed on sialic crust. New stratigraphic correlations for the Kalgoorlie Terrane indicate that many units can be traced over distances >100 km, which has implications for exploration targeting for stratigraphically hosted ultramafic Ni and VMS deposits.

Gibbs Energy of Formation of Cobalt Divanadium Tetroxide

The Gibbs energy of formation of V2O3-saturated spinel CoV2O4 has been measured in the temperature range 900–1700 K using a solid state galvanic cell, which can be represented as Pt, Co + CoV2O4 + V2O3/(CaO) ZrO2/Co + CoO, Pt. The standard free energy of formation of cobalt vanadite from component oxides can be represented as CoO (rs) + V2O3 (cor) → CoV2O4 (sp), ΔG° = −30,125 − 5.06T (± 150) J mole−1. Cation mixing on crystallographically nonequivalent sites of the spinel is responsible for the decrease in free energy with increasing temperature. A correlation between “second law” entropies of formation of cubic 2–3 spinels from component oxides with rock salt and corundum structures and cation distribution is presented. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that copper vanadite is unstable.

The oxygen potential of the systems Fe+FeCr2O4+ Cr2O3 and Fe+FeV2O4+ V2O3 in the temperature range 750 1600o C

From electromotive force (emf) measurements using solid oxide galvanic cells incorporating ZrOz-CaO and ThOz-YO~.s electrolytes, the chemical potentials of oxygen over the systems Fe + FeCrzO 4 + Cr20 ~ and Fe + FeV204 + V203 were calculated. The values may be represented by the equations: 2Fe(s, I) + Oz(g) + 2Cr2Oa(s) -- 2FeCr204 (s)Akto2 = - 151,400 + 34.7T (• cal= -633,400 + 145.5T(• J (750 to 1536~ A~tO2 = -158,000 + 38.4T(• cal= -661,000 + 160.5T(*1250) J (1536 to 1700~2Fe (s, I) + O2 (g) + 2V203 (s) -- 2FeV204 (s) A/~Oz = - 138,000 + 29.8T(+300) cal= - 577,500 + 124.7T (• J (750 to 1536~A/IO2 = -144,600 + 33.45T(-300) cal = -605,100 + 140.0T(~-1250) J (1536 to 1700~At the oxygen potentials corresponding to Fe + FeCrzO a + Cr203 equilibria, the electronic contribution to the conductivity of ZrO2-CaO electrolyte was found to affect the measured emf. Application of a small 60 cycle A.C. voltage with an amplitude of 50 mv across the cell terminals reduced the time required to attain equilibrium at temperatures between 750 to 9500C by approximately a factor of two. The second law entropy of iron chromite obtained in this study is in good agreement with that calculated from thermal data. The entropies of formation of these spinel phases from the component oxides can be correlated to cation distribution and crystal field theory.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Gibbs free energy of formation of magnesium stannate

he thermodynamic properties of the spinel Mg2SnO4 have been determined by emf measurements on the solid oxide galvanic cell,View the MathML source in the temperature range 600 to 1000°C. The Gibbs' free energy of formation of Mg2SnO4 from the component oxides can be expressed as View the MathML source,View the MathML source These values are in good agreement with the information obtained by Jackson et al. [Earth Planet. Sci. Lett.24, 203 (1974)] on the high pressure decomposition of magnesium stannate into component oxides at different temperatures. The thermodynamic data suggest that the spinel phase is entropy stabilized, and would be unstable below 207 (±25)°C at atmospheric pressure. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that the stannates of nickel and copper(II) are unstable.

Thermodynamic properties of Fe3O4 FeV2O4 and Fe3O4 FeCr2O4 spinel solid solutions

Solid solutions of Fe304-FeV204 and Fe304-FeCr204 were prepared and equilibrated with Pt under controlled streams of CO/CO, gas mixtures at 1673 K. The concentration of Fe in Pt was used to determine the activity of Fe304 in the solid solutions. The activity of the second component was calculated by Gibbshhem integration. From these data, the Gibbs energy of mixing was derived for both systems. The experimental results and theoretical values which are determined from calculated cation distribution compare favorably in the case of vanadite solid solutions but not in the case of chromite solid solutions. The difference is attributed to a heat term arising from lattice distortion due to cation size difference. The positive heat of mixing will give rise to a miscibility gap in the system Fe304-FeCr204 at lower temperatures.

Chromium isotope variations (delta Cr-53/52) in mantle-derived sources and their weathering products: Implications for environmental studies and the evolution of delta Cr-53/52 in the Earth's mantle over geologic time

Here we report chromium isotope compositions, expressed as delta Cr-53/ 52 in per mil (&) relative to NIST 979, measured in selected Cr-rich minerals and rocks formed by the primary magmatic as well as the secondary metamorphic and weathering processes. The main objectives of this study were: (i) to further constrain the isotope composition of the Earth's mantle Cr inventory and its possible variation during geological history, based on the analysis of globally distributed and stratigraphically constrained mantle-derived chromites; and (ii) to investigate the magnitude and systematics of Cr isotope fractionation during oxidative weathering and secondary alteration (i. e., hydration, serpentinization) of the magmatic Cr sources. Specifically, we analyzed delta Cr-53/ 52 in a set of globally distributed mantle-derived chromites (FeMgCr2O4, n = 30) collected from various locations in Europe, Asia, Africa and South America, and our results confirm that a chromite-hosted Earth's mantle Cr inventory is uniform at - 0.079 +/- 0.129& (2SD), which we named here as a ` canonical' mantle d 53/ 52 Cr signature. Furthermore our dataset of stratigraphically constrained chromites, whose crystallization ages cover most of the Earth's geological history, indicate that the bulk Cr isotope composition of the chromite-hosted mantle inventory has remained uniform, within about +/- 0.100&, since at least the Early Archean times (similar to 3500 million years ago, Ma). To investigate the systematics of Cr isotope fractionation associated with alteration processes we analyzed a number of secondary Cr-rich minerals and variably altered ultramafic rocks (i. e., serpentinized harzburgites, lherzolites) that revealed large positive delta Cr-53/ 52 anomalies that are systematically shifted to higher values with an increasing degree of alteration and serpentinization. The degree of aqueous alteration and serpentinization was quantified by the abundances of fluid-mobile (Rb, K) elements, and by the Loss On Ignition (LOI) parameter, which determines the amount of structurally bound water (OH/ H2O) present in secondary hydrated minerals like serpentine. Overall, we observed that altered ultramafic rocks that yielded the highest LOI values, and the lowest amounts of fluid mobile elements, also yielded the heaviest delta Cr-53/ 52 signatures. Therefore, we conclude that secondary alteration (i.e., hydration, serpentinization) of ultramafic rocks in near-surface oxidative environments tend to shift the bulk Cr isotope composition of the weathered products to isotopically heavier values, pointing to a dynamic redox cycling of Cr in the Earth's crustal and near-surface environments. Hence, if validated by future

新疆东昆仑蛇绿岩岩石学、地球化学特征及其大地构造意义

The East Kunlun area of Xinjiang (briefly EKAX) is the western part of broadly speaking East Kunlun orogenic zone. The absence of geological data (especially ophiolites) on this area has constrained our recognition to its geology since many years. Fund by National 305 Item (96-915-06-03), this paper, by choosing the two ophiolite zones (Muztag and Southwestern Margin of Aqikekule Lake ophiolite zones) exposed at EKAX as the studied objects and by the analysis of thin section, electron probe, XRF, ICP-MS, SEM and Sm-Nd isotope, totally and sys ematically dealt with the field geological, petrological, minerological, petrochemical and geochemical characteristics (including trace, rare earth element and Sm-Nd isotope) and the tectonic setting indicated by them for each ophilite zone. Especially, this paper discussed the trace and rare earth element patterns for metamorphic peridotites, their implications and related them to the other components of ophiolite in order to totally disclose ophiolite origins. Besides, this paper also studied the petrological, geochemical and paleobiological characteristics for the cherts coexsisted with the Muztag ophiolite and the tectonic setting indicated by them. Based on these, the author discussed the tectonic evolution from Proterozoic to Permian for this area. For Muztag ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① outcropped along the Muztag-Jingyuhu fault with west-to-east strike, the ophiolite is composed of such three components as metamorphic peridotites, cumulates and volcanic rocks; ② metamophic peridotites consist of such types as lherzolites, serpentinized lherzolites and serpentinites, only pyroxenites is seen of cumulates and volcanic rocks include basalts, basaltic andesites and andesites; ③ mineralogical data on this ophiolite suggest it formed in supra-subduction zone (SSZ)environment, and its mantle wedge is heterogeneous; ④ whole-rock TiO_2 and Al_2O_3 of metamorphic peridotites indicate their original environment with the MORB and SSZ characteristics; ⑤ metamorphic peridotites have depleted LREE and flat REE patterns and volcanic rocks have enriched LREE patterns; ⑥ trace element characteristics of metamorphic peridotites imply that they had undergone Nb and Ta enrichment event after partial melting; ⑦ trace element characteristics of volcanic rocks and their tectonic diagrams show they are formed in the spreading and developed island arc environment with back-arc basin, such as rifted island arc, which is supported by the ε_(Nd)(t) -2.11～+3.44. In summary, the above evidence implies that Muztag ophiolite is formed in SSZ environment, where heterogeneous mantle wedge was metasomatised by the silica-enriched melt from subducted sediments and/or oceanic crust, which makes the mantle wedge enriched again, and this enriched mantle wedge later partially melted to form the volcanic rocks. For Southwestern Margin of Aqikekule Lake ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① it outcropped as tectonic slices along the near west-to-east strike Kunzhong fault and is composed of metamorphic perodotties, cumulates and volcanic rocks, in which, chromites are distributed in the upper part of metamorphic peridotites as pods, or in the lower part of cumulates as near-strata; ② metamorphic peridotites include serpentinites, chromite-bearing serpentinites, thlorite-epidote schists and chromitites, of which, chromitites have nodular and orbicular structure, and cumulates include pyroxenits, serpentinites, chromite-bearing serpentinites, chromites and metamorphically mafic rocks and only basalts are seen in volcanic rocks; ③ Cr# of chromites suggest that they formed in the SSZ and Al_2O_3 and TiO_2 of metamorphic peridotites also suggest SSZ environment; ④metamorphic peridotites have V type and enriched LREE patterns, cumulates have from strongly depleted LREE, flat REE to enriched LREE patterns with universally striking positive Eu anomalies and basalts show flat REE or slight enriched LREE patterns with no Eu anomalies; ⑤ trace element and Sm-Nd isotope characteristics of metamorphic peridotites imply their strikingly heterogeneous mantle character(ε_(Nd)(t)+4.39～+26.20) and later Nb, Ta fertilization; ⑥ trace element characteristics of basalts and their tectonic diagrams show they probably formed in the rifted island arc or back-arc basin enviromnent. In summary, the above evidence shows that this ophiolite formed in the SSZ environment and melts from subudcted plate are joined during its formation. Rare earth element, whole-rock and sedimentary characteristics of cherts with the Muztag ophiolite show that they formed in the continental margin environment with developed back-arc basin, and radiolarias in the cherts indicate that the upper age of Muztag ophiolite is early carboniferous. Based on the accreted wedge models of Professor Li Jiliang for Kunlunshan Mountain and combined with study on the two typical ophiolite profiles of EKAX, the author discussed the tectonic evolution of EKAX from Proterzoic to Permian.

山东莱芜中生代高镁侵入岩及其超镁铁质岩捕掳体的成因研究

In order to know better about the Phanerozoic lithosphere thinning process of Sino-Korea Plate, four Cretaceous intrusion complexes and their ultramafic xenoliths are investigated by this thesis, which are located in Laiwu, Shandong Province, Eastern China, a region far away from plate margin. The four complexes, Kuanshan, Jiaoyu, Jingniushan and Tietonggou, intruded into Archaeozoic granite gneiss and Paleozoic carbonate rocks with scam iron ore at their contact zone. The four complexes can be divided into two magma series, abyssal rocks for the early and hypabyssal rocks for the later. K-Ar dating show that the abyssal rocks intrusion began with 120 ±2 Ma and the hypabyssal rocks intruded about 113 Ma. Abyssal rocks, mainly made up of augite diorites, amphibole diorites and gabbros for the lesser, are chemically characterized with high-Mg (Mg#>0.5) high-K calcalklic rock, which are depleted with Nb, Ta and Ti related to LILE and extremely enriched with Sr and Pb. Comparatively, augite diorites are the most LREE enriched in abyssal rocks, and they show no Eu abnorrnity or weak positive Eu abnormity. Gabbros show the least LREE enrichment with a strong Eu abnormity relatively. In (~(87)Sr/~(86)Sr)_1 -ε Nd(T) diagram, the abyssal rocks show a mixing trend , a rapid change in ε Nd(T) with a relatively small change in (~(87)Sr/~(86)Sr)_1. Low radiogenic Sr and Pb composition with high radiogeic Nd composition indicate that the mixing processes happened in lower crust Melt-rock interactions in lower crust might be the most possible processes to produce these high-Mg and high-K calcalklic magmas. Hypabyssal rocks, mainly made up of granite porphyry and dioritic porphrite, show much higher ε Nd(T) than abyssal rocks. Granite porphyry are distinct with an adakite geochemical characteristics, high (La/Yb)_N, Sr/Y and low Rb/Sr ratio. The adakitic granite porphyry indicates a new lower crust produced by underplating within plate. Ultramafic xenoliths had been found only in augite diorites and amphibole diorites. Field investigations show that ultramafic xenoliths in augite diorites had been inherited from amphibole diorites, so ultramafic xenoliths had been only entrained by hydrous dioritic magma. Ultramafic xenoliths are mainly made up of dunite and harzburgite, orthopyroxenite and bistangite are the lessor. Coarse olivines in dunite often show many chromite exsolution lamellae. Opx in orthopyroxenite often show dense chromite exsolution lamellae. The presence of exsolution minerals indicates that ultramafic xenoliths had cooled before entraining. Metasomatism phenomenons are popular in dunite and harzburgite xenoliths, including two kinds of assemblage, cpx+phlogapite and opx+pl. The first metasomatism assemblage indicates an ancient enrichment. Rb-Sr dating of xenoliths shows that the ancient enrichment happened in 223 ± 7Ma. The second metasomatism assemblage indicates a recent, relatively not deep melt-rock interaction, which might be related with the genesis of the high-Mg high-K calcalklic rocks. Mineralogy and geochemistry indicate that these ultramafic xenoliths might sample the crust-mante transition zone (or the base of lower crust, moho). Investigation of high-Mg intrusions and their ultramafic xenoliths in Laiwu indicate that the thinning processes of Sino-Korea Plate can be divided into two stages. The first stage is lithosphere mantle thinning with crust thickening by underplating in lower crust. The second stage is that the thickened lower crust delaminated into the underlying mantle.

内陆湖沼相和近海沼泽相沉积环境煤中微量元素和矿物的对比研究—以辽宁北票、江西建新和桥头煤研究为例

Using knowledge of geology, geochemistry, coal petrology, mineralogy, by means of a variety of advanced measuring methods such as inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRD), scanning electron microscopy with energy-dispersive spectrometer(SEM-EDS), sequential chemical extract and density fractions, the characteristics of trace elements and minerals in Jurassic Beipiao coal mine under inland limnetic sedimentary environment and in late Permian Jianxin and Qiaotou coal mines under paralic swamp sedimentary environment were studied. Compared with the average concentration in the world bituminous coals, the Beipiao coal was characterized by relatively high contents of Sc, Ti, Cr, Co, Ni, Zn, Se, Sr, Zr, Y, Ba, REE and Th, and lower contents of V, Rb, Cd, Sn, Pb, Bi and U; while the Jianxin coal was relatively enriched in Li, Sc, Ga, Sr, Y, Nb, Sb, Th and U, with low concentration of Be, Co, Ni, Cu, Ge, Zr, Mo, Cd, Cs, Ba, Pb and Bi; and the Qiaotou coal was enriched in Li, Sc, Sr, Nb, Ta, Zr, REE, Hf, Th and U, with low concentration of Be, V, Co, Ni, Cu, Ge, Mo, Cd, Cs, Ba, Tl, Pb and Bi. The concentrations of Ca, Mg and K in Beipiao coal are higher than those in Jianxin coal and Qiaotou coal, while Fe, S and Ti in Beipiao coal are lower than those in Jianxin coal and Qiaotou coal. The proximate analysis of coal samples was carried out, which indicated that Beipiao coal was medium- to high- ash (5.92-60.68%) with low sulphur coal, and Jianxin coal and Qiaotou coal was medium to high ash (8.85-46.33%) with high sulphur. The reflectivity was measured, which explained that Beipiao coal belonged to high volatile bituminous coal, Jianxin coal was low volatile bituminous coal and Qiaotou coal was low volatile anthracite. Quantitative maceral analyses were studied. The characteristics of rare earth elements (REE) were investigated, which showed that the total contents of REE were higher than that of the world's average content. With the increase of coal's metamorphic grade, the total contents of REE decreased from 98.5 X 10"6 of Beipiao coal to 94.2 X 10"6 of Jianxin coal, and to 75.9 X 10"6 of Qiaotou coal, and 5Eu reduced which indicated that the element Eu depleted. The characteristics of REE was controlled by the metamorphic grade of coal. And REE were mainly absorbed in clay minerals in Beipiao coal samples, while in Jianxin and Qiaotou coal mines, REE were primarily related to clay mineral and pyrite. The variation of trace elements in vertical direction of coal seams was studied, and the results showed that different trace elements differed greatly. The correlation between trace elements and ash were determined. Four major trace elements (aluminium-silicates, sulphide, carbonate and phosphate) accounted for the occurrence and distribution of most elements studied were determined. Coal samples were separated by density fraction, which showed that Cr, Cu, Mo and Pb were closely related to inorganic matters mainly distributed in P >2.6 and dropped remarkably in the density fractions P <2.3 . The occurrences of Co, Cr, Ni, As, Se, Mo, U were studied directly and quantitatively using sequential chemical extract with six steps, which showed that Co. Ni, Mo and U were mainly in the form of mineral, and As, Se chiefly in the form of organic state, while Cr mostly in the form of organic state and mineral. Major mineral phases presented in the Beipiao coal were Kaolinite, illite, quartz, calcite, and small amount of siderite, barite. While major mineral phases in Jianxin and Qiaotou coal were pyrite, kaolinite, and small amount of marcasite, rutile, sphalerite. This is the first time that the chromite in the coal was discovered in China, which indicates that Cr occurrence appeared in the form of chromite. The ratio of Sr/Ba, Sr/Ca and V/Ni in Beipiao coal mine under inland limnetic is smaller than that of in Jianxin and Qiaotou coal mines under paralic swamp. The ratio of K/Na and Th/U of Beipiao coal mine is higher than that of Jianxin and Qiaotou coal mine, which proved that Beipiao coal was not affected by sea water and Jianxin and Qiaotou coal were affected by sea water. Trace elements such as Cr, Ni, Mo in minerals were analyzed by SEM-EDS. The factors controlling the enrichment of trace elements can be divided into syngenetic stage factors and epigenetic stage factors.

地球化学样品中铂族元素分析方法的研究-以铬铁矿为例

铂族元素和金银统称为贵金属，他们在石油化工、冶金、能源、地球化学、材料、环境科学、电子、航空航天、生物和医学等诸多领域中有广泛的应用。贵金属分析测试是贵金属研究与应用的必要组成部分，具有非常重要的意义。本文以铂族元素标准样品GPt-5（铬铁矿）为主要研究对象，采用阴离子交换树脂和磅共沉淀分离方法富集铂族元素，探索最佳实验条件：其次考察铂族元素的分离富集过程，探讨磅共沉泞分离富焦铂柞矛青的和理。然后通过碱熔、常压酸溶解-碱熔分解不溶物两种方法分解地质样品，在此基础上建立了电感耦奋寺离子体质谱分析钼族元素的方法，为地质地球化学样品中痕量或超痕量铂族元素含量分析提供了可行的途径，并为分析方法的进一步改进提供理论和方法依据。本文通过实验，得到以下结论：1．碲共沉淀具有操作简单，铂族元素的回收率很高能将铂族元素和贱金属彻底分离等诸多优点，便于广泛运用。2．阴离子交换树脂能很好吸附Au、R、Pd、Os、Ir（W），但对Ru、特别是Rh的回收率很低。通过在上柱前加入 SnCl_2能提高Ru、助的吸附率。3．碱熔分解能力强，操作简单，价格低廉，通过改进的分层碱熔法明显提高了Ru的准确度，对其它铂族元素没有影响；酸浸取结合碱熔对Au、Pt、Pd的分析结果较好，但是对于Ru、．Ir的结果偏低，整个流程较长。4．等离子体质谱法能快捷、精确测试铂族元素，一般用内标标准曲线法测单同位素元素Rh、Au，而用同位素稀释法测其它铂族元素。5．铂族元素经过蹄共沉淀后生成能溶于浓HNO_3和王水的产物，Au主要转化为单质Au，Pt、Pd都形成磅化物。其它铂族元素的富集机理需要进一步深入研究。

Materiais à base de óxidos com estrutura do tipo perovskite e compósitos como ânodos de PCES

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-δ (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27- based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-δ.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Catalytic oxidation of cyclohexane over Cu-Zn-Cr ternary spinel systems

Spinel systems with the composition of Cu 1−x Zn x Cr 2 O 4 [x = 0 CCr, x = 0.25 CZCr-1, x = 0.5 CZCr-2, x = 0.75 CZCr-3 and x = 1 ZCr] were prepared by homogeneous co-precipitation method and were characterized by X-ray diffraction (XRD) and FT-IR spectroscopy. Elemental analysis was done by EDX, and surface area measurements by the BET method. The redox behavior of these catalysts in cyclohexane oxidation at 243 K using TBHP as oxidant was examined. Cyclohexanone was the major product over all catalysts with some cyclohexanol. 69.2% selectivity to cyclohexanol and cyclohexanone at 23% conversion of cyclohexane was realized over zinc chromite spinels in 10 h.