Sedimentology of the Okhotsk Sea

On the basis of two sedimentary records from the central Sea of Okhotsk, we reconstruct the closely coupled glacial/interglacial changes in terrigenous flux, marine productivity, and sea ice coverage over the past 1.1 Myr. The correspondance of our sedimentary records to the China loess grain size record (China loess particle timescale, CHILOPARTS) suggests that environmental changes in both the Sea of Okhotsk area and in SE Asia were closely related via the Siberian atmospheric high-pressure cell. During full glacial times our records point to a strong Siberian High causing northerly wind directions, the extension of the sea ice cover, and a reduced Amur River discharge. Deglacial maxima of terrigenous flux were succeeded by or synchronous to high-productivity events. Marine productivity was strengthened during glacial terminations because of an effective nutrient utilization at times of enhanced water column stratification and high nutrient supply from fluvial runoff and sea ice thawing. During interglacials, SE monsoonal winds prevailed, analogous to today's summer situation of a pronounced Mongolian Heat Low and a strong Hawaiian High. Strong freshwater discharge induced by high precipitation rates in the Amur drainage area and a seasonally reduced and mobile sea ice cover favored marine productivity (although being considerably lower than during the terminations) and a lowered flux of ice-rafted detritus.

Geochemistry and radiogenic isotope ratios of the volcanic sequences from Izu-Bonin Arc, Japan

New radiogenic isotope and trace element data are presented for the volcanic sequences along 600 km of the active Izu-Bonin arc, the Oligocene Izu arc, and their associated rift basins. As with many intra-oceanic island arcs, the Pliocene-Recent Izu-Bonin frontal-arc lavas are highly depleted in Zr, Nb and the rare-earth elements relative to typical mid-ocean ridge basalt (MORB), indicating that the mantle wedge source has undergone a previous episode of melting. Ratios between these elements (such as Nb/Zr and La/Sm), as well as 143Nd/144Nd, do not vary significantly along the length of the frontal-arc. These parameters suggest that each of the arc volcanoes is derived from similar melt fractions of the mantle wedge. However, Ba/Zr, Ba/Rb and 87Sr/86Sr increase along the frontal-arc to the north. This leads us to propose that a variable enrichment in Ba and radiogenic Sr is superimposed on the mantle wedge. Sr-Nd and Pb-Nd isotope variation indicate that both Sr and Pb become more radiogenic after fluid addition. However, Pb isotope ratios do not correlate with increases in Pb concentration or ratios such as Ba/Zr and Nb/Pb. In other words, the Pb isotopic composition of the arc lavas appears to be independent of the amount of Pb introduced by subduction fluids into the mantle source. This buffering of Pb isotopes along the frontal-arc means that the isotopic composition of the lavas is indistinguishable from that of the fluid. Isotopic mixing models presented for the arc are only illustrative of the many plausible combinations of components and quantities. Despite this, we are able to determine that the mantle wedge has isotopic characteristics similar to Indian Ocean MORB, and that the subduction-fluid solute is primarily derived from subducted oceanic basalt with a <2% contribution from subducted sediment. Lavas in the Oligocene Izu arc and fore-arc basin were derived from a mantle wedge of similar composition to the active arc. Despite levels of Pb enrichment comparable to those of the modern arc, the Pb isotopes of the Oligocene volcanics indicate a lower sediment input into the melting region.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

Geochemistry of lower sheeted dike complex samples of ODP Holes 137-504B and 140-504B

Rocks of the lower sheeted dike complex of Hole 504B sampled during Leg 140 were analyzed for major and trace element compositions to investigate the effects of igneous processes and hydrothermal alteration on the compositions of the rocks. The rocks are relatively uniform in composition and similar to the shallower dikes. They are moderately evolved mid-ocean-ridge basalts (MORB) with relatively high MgO (7.9-10 wt%) and Mg# (0.60-0.70), and have unusually low incompatible element contents (TiO2 = 0.42-1.1 wt%, Zr = 23-62 ppm). Discrete compositional intervals in the hole reflect varying degrees of differentiation, and olivine and plagioclase accumulation in the rocks, and may be related to injection of packets of dikes having similar compositions. Systematic depletions of total REE, Zr, Y, TiO2, and P2O5 in centimeter-size patches are most likely attributed to exclusion of highly differentiated, late-stage interstitial liquids from small portions of the rocks. The rocks exhibit increased H2O+ reflecting hydrothermal alteration. Replacement of primary plagioclase by albite and oligoclase led to local gains of Na2O, losses of CaO, and slightly positive Eu anomalies. Some mobility of P2O5 led to minor increases and decreases in P2O5 contents, and some local mobility of Ti may have occurred during alteration of titanomagnetite to titanite. Higher temperatures of alteration in the lower sheeted dikes led to breakdown of pyroxene and sulfide minerals and losses of Zn, Cu, and S to hydrothermal fluids. Later addition of anhydrite to the rocks in microfractures and replacing plagioclase caused local increases in sulfur contents. The lower sheeted dikes are a major source of metals to hydrothermal fluids for the formation of metal sulfide deposits on and within the seafloor.

On the hardness and elastic modulus of bulk metallic glass matrix composites

The influences of the amorphous matrix and crystalline dendrite phases on the hardness and elastic moduli of Zr/Ti-based bulk metallic glass matrix composites have been assessed. While the moduli of the composites correspond to those predicted by the rule of mixtures, the hardness of the composites is similar to that of the matrix, suggesting that the plastic flow in the composites under constrained conditions such as indentation is controlled by the flow resistance of the contiguous matrix. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

On the microstructure-tensile property correlations in bulk metallic glass matrix composites with crystalline dendrites

Bulk metallic glass (BMG) matrix composites with crystalline dendrites as reinforcements exhibit a wide variance in their microstructures (and thus mechanical properties), which in turn can be attributed to the processing route employed, which affects the size and distribution of the dendrites. A critical investigation on the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify ``structure-property'' connections in these materials. This was accomplished by employing four different processing methods-arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat-on composites with two different dendrite volume fractions, V-d. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, lambda, and dendrite size, delta, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite's properties are insensitive to the microstructural length scales when V-d is high (similar to 75%), whereas they become process dependent for relatively lower V-d (similar to 55%). Larger delta in arc-melted and forged specimens result in higher ductility (7-9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer lambda result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Ferroelectric instabilities and enhanced piezoelectric response in Ce modified BaTiO3 lead-free ceramics

The crystal structure, ferroelectric, and piezoelectric behaviors of the Ba(Ti1-xCex)O-3 solid solution have been investigated at close composition intervals in the dilute concentration regime. Ce concentration as low as 2 mol. % induces tetragonal-orthorhombic instability and coexistence of the phases, leading to enhanced high-field strain and direct piezoelectric response. Detailed structural analysis revealed tetragonal + orthorhombic phase coexistence for x = 0.02, orthorhombic for 0.03 <= x <= 0.05, and orthorhombic + rhombohedral for 0.06 <= x <= 0.08. The results suggest that Ce-modified BaTiO3 is a potential lead-free piezoelectric material. (C) 2015 AIP Publishing LLC.

Anodization of sputtered metallic films: The microstructural connection

A simple microstructural rationale for successful anodization of metallic films into ordered oxide nanostructures has been identified. It applies to three of the most commonly studied systems, Zr, Ti and Al films and can be extended to other such oxides. A dense Zone T or II microstructure, in sputtered films, is the most critical ingredient. While T-substrate > 0.3T(melting) Ching is the simplest route, pressure and plasma heating can also be exploited. Such microstructures are also associated with a unique growth stress signature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Zirconocenes as models for homogeneous Ziegler-Natta olefin polymerization catalysts

Using density functional theory, we studied the fundamental steps of olefin polymerization for zwitterionic and cationic Group IV ansa-zirconocenes and a neutral ansa- yttrocene. Complexes [H₂E(C₅H₄)₂ZrMe]ⁿ (n = 0: E = BH₂ (1), BF₂ (2), AlH₂(3); n = +: E = CH₂(4), SiH₂(5)) and H₂Si(C₅H₄)₂YMe were used as computational models. The largest differences among these three classes of compounds were the strength of olefin binding and the stability of the β-agostic alkyl intermediate towards β-hydrogen elimination. We investigated the effect of solvent on the reaction energetics for land 5. We found that in benzene the energetics became very similar except that a higher olefin insertion barrier was calculated for 1. The calculated anion affinity of [CH₃BF₃]^- was weaker towards 1 than 5. The calculated olefin binding depended primarily on the charge of the ansa linker, and the olefin insertion barrier was found to decrease steadily in the following order: [H₂C(C₅H₄)₂ZrMe]⁺ > [F₂B(C₅H₄)₂ZrMe] ≈ [H₂B(C₅H₄)₂ZrMe] > [H₂Si(C₅H₄)₂ZrMe]⁺ > [H₂Al(C₅H₄)₂ZrMe].

We prepared ansa-zirconocene dicarbonyl complexes Me₂ECp₂Zr(CO)₂ (E = Si, C), and t-butyl substituted complexes (t-BuCp)₂Zr(CO)₂, Me₂E(t-BuCp)₂Zr(CO)₂ (E = Si, C), (Me₂Si)₂(t-BuCp)₂Zr(CO)₂ as well as analogous zirconocene complexes. Both the reduction potentials and carbonyl stretching frequencies follow the same order: Me₂SiCp₂ZrCl₂> Me₂CCp₂ZrCl₂> Cp₂ZrCl₂> (Me₂Si)₂Cp₂ZrCl₂. This ordering is a result of both the donating abilities of the cyclopentadienyl substituents and the orientation of the cyclopentadiene rings. Additionally, we prepared a series of analogous cationic zirconocene complexes [LZrOCMe₃][MeB(C₆F₅)₃] (L = CP₂, Me₂SiCp₂, Me₂CCP₂, (Me₂Si)₂Cp₂) and studied the kinetics of anion dissociation. We found that the enthalpy of anion dissociation increased from 10.3 kcal•mol^-1 to 17.6 kcal•mol^-1 as exposure of the zirconium center increased.

We also prepared series of zirconocene complexes bearing 2,2-dimethyl-2-sila-4-pentenyl substituents (and methyl-substituted olefin variants). Methide abstraction with B(C₆F₅) results in reversible coordination of the tethered olefin to the cationic zirconium center. The kinetics of olefin dissociation have been examined using NMR methods, and the effects of ligand variation for unlinked, singly [SiMe₂]-linked and doubly [SiMe₂]-linked bis(cyclopentadienyl) arrangements has been compared (ΔG‡ for olefin dissociation varies from 12.8 to 15.6 kcal•mol^-1). Methide abstraction from 1,2-(SiMe₂)₂(η⁵-C₅H₃)₂Zr(CH₃)-(CH₂CMe₂CH₂CH = CH₂) results in rapid β-allyl elimination with loss of isobutene yielding the allyl cation [{1,2-(SiMe₂)₂(η⁵-C₅H₃)₂Zr(η³-CH₂CH=CH₂)]⁺.

基底对光学薄膜弱吸收测量的影响

对表面热透镜技术测量光学薄膜弱吸收低频调制时不同基底对测量的影响进行了理论分析。用Lambda-900分光光度计测量了K9和石英基底的Ti3O5单层膜的吸收值，将该组样品作为定标片；用表面热透镜装置分别测量了BK7和石英空白基底及HfO2，ZnO两组不同基底不同厚度单层膜样品的吸收。通过分析比较同一工艺条件下镀制的不同基底薄膜样品用与其同种和不同种基底定标片定标测量的结果，表明在低频测量时需要用与测量样品同种基底的定标片定标；不同厚度样品的测量结果表明，在不能严格满足热薄条件时，测量结果需引入修正值。

In vitro anti-HIV and -HSV activity and safety of sodium rutin sulfate as a microbicide candidate

Sodium rutin sulfate (SRS) is a sulfated rutin modified from the natural flavonol glycoside rutin. Here, we investigated its in vitro anti-HIV and -HSV activities and its cytotoxic profile. Fifty percent inhibitory concentration (IC50) values of SRS against HIV-1 X4 virus IIIB, HIV-1 R5 isolates Ada-M and Ba-L were 2.3 +/- 0.2, 4.5 +/- 2.0 and 8.5 +/- 3.8 mu M with a selectivity index (SI) of 563, 575 and 329, respectively. Its IC50 against primary R5 HIV-1 isolate from Yunnan province in China was 13.1 +/- 5.5 mu M, with a Sl of 197. In contrast, unsulfated rutin had no activity against any of the HIV-1 isolates tested. Further study indicated that SRS blocked viral entry and virus-cell fusion likely through interacting with the HIV- I envelope glycoprotein. SRS also demonstrated some activity against human herpes simplex virus (HSV) with an IC50 of 88.3 +/- 0.1 mu M and a Sl of 30. The 50% cytotoxicity concentration (CC50) of SRS was >3.0 mM, as determined in human genital ME 180, HeLa and primary human foreskin fibroblast cells. Minimum inhibitory concentration of SRS for vaginal lactobacilli was >3.0 mM. These results collectively indicate that SRS represents a novel candidate for anti-HIV-1/HSV microbicide development. (C) 2007 Elsevier B.V. All rights reserved.

催化消除NO_x复合氧化物催化剂的研究

氮的氧化物(NOx)是大气中的一种重要的污染物，是酸雨的主要来源，目前氮氧化物的无毒处理已经是国际环保研究中最关键的课题之一。本论文选择了两种复合氧化物：一种是钙钛石结构的含Cu的层状复合氧化物；另一种是以水滑石为前体经焙烧后得的复合氧化物为催化剂对它们的物化性质和对催化消除NOx的活性进行了系统的研究，得到了一些有意义的结果。第一部分：钙钛石型结构的含Cu层状复合氧化物钙钛石复合氧化物由于具有独特的物理化学性质，长期以来一直受到固态物理、固体化学和催化领域的科技工作者的重视。尤其近年来对它们在催化消除NOx反应中的活性的研究引起了催化工作者的极大兴趣，这是由于，一方面，钙钛石类复合氧化物对处理NOx的反应活性比较高，有希望取代贵金属催化剂；另一方面，探讨复合氧化物的固态物理、化学性质与处理NOx反应催化性能的关系，有利于揭示处理NOx反应的催化作用本质，为寻找高效实用的催化剂提供理论依据。本论文系统研究了三个系列含Cu钙钛石型复合氧化物的固态物理化学性质和对NO-CO反应的催化性能，并讨论了二者的关系。主要的工作和结论如下：1) 以La_2CuO_4为模型化合物研究了制备方法对它的性质的影响：用四种制备方法：柠檬酸络合爆炸法，聚乙二醇凝胶法，聚丙烯酰胺凝胶法，DTPA络合法合成了La_2CuO_4。比较了四种方法的特点，和制备方法对La_2Cu0_4的结构的影响，并对所得La_2CuO_4在NO-CO反应中的催化活性的影响进行了研究。结果发现聚乙二醇凝胶法和DTPA络合法有利于形成好的晶形，而聚乙二醇凝胶法和聚丙烯酰胺凝胶法对NO-CO反应有较好的活性，这是由于由不同制备方法得到的样品中的缺陷的种类和含量不I司所致。2) La_(1-x)Ba_xCuO_(3-λ)系列中Ba含量对它的性质的影响：用柠檬酸络合法合成了LaBa_2Cu_3O_(7-λ)，LaBaCu_2O_(5-λ)，La_2BaCu_3O_(7-λ) La_4BaCu_5O_(13-λ)及YBa_2Cu_3O_(7-λ)五种钙钛石结构的复合氧化物。XRD分析表明此系列样品均为层状ABO_3结构（分别为二，三，五层）。用XPS和O_2-TPD对样品中的氧种进行了研究，结果显示样品中存在着两种活性氧种：α氧种和β氧种。在O_2-TPD中低温脱附的是α氧种，它可归属于化学吸附氧与样品中的氧空位的浓度有关。β氧种的脱附温度较高，它归属于晶格氧。利用H_2-TPR和化学分析的手段对样品中的金属离子和活性氧的稳定性进行了表征。结果显示大量的氧空位和Cu~(3+)存在于样品中，并且它们的浓度受Ba离子浓度的影响。此系列样品对CO还原NO的活性研究表明：它们的活性远远高于结构类似的Ln_2CuO_4和Ln_2NiO_4等复合氧化物，在低于300 ℃时N0转化率已接近100％．分析结果表明Cu~(3+)和氧空位对活性起很重要的作用。Ba离子的作用是：一方面使含Cu的ABO_3结构稳定；另一方面使样品更容易吸附NO。3) La_4BaCu_5O_(13-λ)中Mn或C0逐步取代Cu对样品性质的影响合成了两系列分别由Mn或Co逐步取代Cu的样品，XRD分析表明它们仍旧是钙钛石结构。通过XPS，O_2-TPD和化学分析方法对样品中的活性氧种进行了表征，结果表明，当Mn逐步取代Cu离子时，晶格氧增加，而吸附氧开始变化较小，当Mn含量大于Cu含量时，吸附氧迅速减少。在Co取代样品的O_(1s)的XPS谱中，氧种变化较Mn取代的小，这表明Co离子对样品中的氧空位含量的影响较Mn离子的小。氧化还原性能的研究表明当Cu离子被Mn或Co离子部分取代后，Cu离子变得更容易被还原，这表明Cu-M(Mn或CO)之间发生了协同作用，使Cu离子更活泼。当Mn或Co部分取代Cu离子之后，样品对CO还原NO反应的催化活性明显提高，当取代含量达到一定程度时（即X ≥ 3），催化活性迅速降低，这表明Cu离子在反应中起着很重要的作用，经过分析我们认为反应机理如下：Cu~(3+)-O~=-Cu~(3+) + CO → Cu~(2+)-□-Cu~(2+)+CO_2 Cu~(2+)-□-Cu~(2+) → Cu~(3+)-□-Cu~(2+) Cu~(3+)-□-Cu~(2+) + NO~-Cu~(3+)-NO-Cu~(2+) 2Cu~(3+)-NO-Cu~(2+) → 2Cu~(3+)-O~=-Cu~(3+) + N_2 式中□是氧空位，Cu~(3+)-□ 是F心。掺杂部分Mn或Co后，催化活性的提高可以归属于Cu-M之间发生的协同作用使Cu离子更活泼，表征结果表明Cu-Co之间的协同作用较Cu-Mn之间的弱（这可能是由于Co，Cu之间化学性质相似），但掺杂Co的样品的活性较掺杂Mn的要高，同时我们在反应中发现，Co含量较高的样品中反应产物中N_2O比掺杂Mn的样品高出许多，因此我们认为Co离子对反应中反应中间产物N_2O的生成比Mn离子要活性。第二部分以水滑石化合物为前体的复合氧化物水滑石类化合物属于一种阴离子粘土，由带正电荷的金属氧化物／氢氧化物和层间阴离子及水分子组成。以水滑石为母体经焙烧制得的氧化物催化剂用于氧化反应的实例尚不多，且大多用于液相催化反应。最近有文献报道含Co，Cu，Ni水滑石经焙烧后对N_2O分解有很好的活性，但还没有关于此类化合物应用于NO还原和分解的文献报道。我们首次将以水滑石为母体经焙烧制得的尖晶石催化剂用于催化消除NO_x的反应中，考察和表征了变更过渡金属离子时Co-M-Al系列和Mg-M-Al系列催化剂在CO还原NO，NO吸附和NO分解反应中的活性。1) 以Mg-M-Al水滑石为前体的催化剂用共沉淀法合成了一系列Mg-M-Al水滑石（M = Cr，Fe，Mn，Co，Ni，Cu；Mg/M/A1 = 3/1/1）。XRD表征表明所有化合物均为典型的水滑石化合物。通过TG-DTA考察了焙烧对样品的结构和组成的影响。450 ℃焙烧后所有样品的XRD图中仅能发现MgO相，表明过渡金属氧化物均匀地分散在MgO-Al_2O_3中，换句话说，所得样品焙烧后是过渡金属氧化物负载在MgO-Al_2O_3载体上。H_2-TPR研究进一步证实过渡金属氧化物在载体上得到了稳定。此系列样品对C0还原N0反应活性的测定表明Mg-Al-Cu样品表现出远远高于其它样品的活性，而Mg-Al和Mg-Ni-Al在550 ℃以下对反应几乎没有活性，其它样品表现出一定的活性。2) 以Co-M-Al水滑石为前体的催化剂体系经共沉淀法合成了Co-M-Al水滑石（M = 过渡金属），经焙烧后发现样品中有尖晶石相出现。比表面研究表明，在500-700 ℃之间比表面变化较小大约在80m~2/g左右，在更高温度焙烧后比表面迅速下降。此系列样品对NO的吸附性能研究表明Co-Al，C0-Ni-Al，Co-Cr-Al，Co-Fe-Al表现出较高的吸附性能，尤其是Co-Ni-Al在100 ℃对NO表现出100％的吸附；其它样品对NO的吸附较低。用过渡金属离子中d轨道电子在吸附前后的晶体场稳定化能的变化可以很好地解释此系列样品对NO的吸附性能。对NO分解的活性测定表明Co-Ni-A1，Co-Cr-A1和Co-Al表现出了较好的活性，其中Co-Ni-Al的活性最高。其它样品在600 ℃以下几乎没有活性。分析结果表明样品对NO分解有活性的催化剂必须具备两个条件：1：对NO有较好的吸附性能；2: NO分解后产生的氧可以容易的脱附。除Co-Al外，所有样品对CO还原NO表现出很高的活性：在150 ℃即有较高的NO转化率，在180 ℃NO转化率即可达到100％。催化剂的氧化还原性能在反应中起着很重要的作用，H_2-TPR研究发现掺杂其它过渡金属后Co离子的还原温度明显降低，表明Co离子得到了活化。3) 以Co-Cu-Al水滑石为前体的样品用共沉淀法合成了一系列Co/Cu/Al含量不同的水滑石化合物，包括Co/Cu/Al分别为7/1/1，3/1/1及1/1/1和仅含Co或Cu的Co/Al = 3/1，Cu/Al = 3/1等一系列样品。XRD结果表明除Cu-Al外其它样品经焙烧后均出现了尖晶石相。Cu-Al样品经焙烧后出现了CuO相表明样品为CuO负载于Al_2O_3上。NO和CO的TPD研究表明三组份样品对NO和CO的吸附明显高于二组份样品，而且含CO量高的样品对NO和CO的吸附能力更好，表明Co起较强的作用。在三组份样品的NO-TPD脱出物中发现有N_2O和N_2，表明NO在样品表面的吸附为活化吸附。对CO还原NO反应活性的研究表明，三组份样品的活性远远高于二组份样品，且含Co量高的样品活性较高，表明在此系列样品中Co离子起决定性作用，而Cu离子起助催化作用。通过对反应中各组份含量的变化分析，我们认为反应机理如下：CO + O-Cat → CO_2 + □-Cat NO + □-Cat → NO-Cat 2(NO-Cat) → N_2O + O-Cat + □-Cat N_2O + □-Cat → N_2O-Cat N_2_O-Cat → N_2 + O-Cat 2(N_2O-Cat) → N_2 + 2(O-Cat) O-Cat是样品中的晶格氧，在Co-Al中加入其它过渡金属离子使样品中的晶格氧得到活化，因此，催化活性得到提高。用以水滑石为前体，共沉淀法和固相反应法等三种制备方法合成了一系列Co-Cu-Al催化剂，发现以水滑石为前体的样品不论是对NO，CO的吸附性能还是对NO-CO反应的催化活性都远远高于其它方法制备的样品，这可能是由于水滑石可以起到一个模版作用，使Cu, Co离子分散的更均匀，以及使催化剂表面的含氧基团丰富。

伯胺N_(1923)萃取过渡金属离子机理的研究

伯胺由于其特殊的结构（R-NH_2），使它具有和仲、数胺不相同的一些性质。有较强的和矿物酸HX结合形成RNH_3X的能力，从而以离子交换机理萃取金属离子；也可以-NH_2上的氮、氢原子同以高价存在的过渡金属含氧酸以氢键方式相结合；另外，RNH_2也可通过氮原子以配位键形式与一些属于软酸类的过度金属离子形成配合物。通过伯胺萃取金属离子行为的研究，可发现新的萃取体系，扩大我国自行设计的伯胺N_(1923)萃取剂的应用领域，为金属离子的分离提纯工艺提供基本参数。我们实验室过去曾对伯胺N_(1923)萃取稀土（III）、Fe（III）、Zn （II）、Cd（II）、Ag（I）、Sc（III）等的机理进行了比较系统的研究。本工作是在此基础上，进一步完善及扩大N_(1923)对周期表中各族元素的萃取及应用。为此，我们选择了文献尚未报道的Ti（IV）、HgCl_2、Hg(CH_3COO)_2、Cu(CH_3COO)_2为研究对象，对它们的萃取机理进行了较详细的研究。结果表明，自由的N_(1923)或其盐对上述体系具有良好的萃取性能，并初步讨论了N_(1923)在金属离子萃取分离中的应用。一、伯胺N_(1923)萃取HgCl_2的机理 微量汞的萃取及分离对环境保护具有重要的实际意义。我们的研究结果表明，在pH值为3-4.5范围内，即使Cl~-浓度很低时，伯胺N_(1923)也能几乎定量地萃取HgCl_2，其盐酸盐亦能有效地萃取Hg（II），但两者的萃取机理不同。自由伯胺RNH_2可与HgCl_2形成配合物，其萃取机理为：RHN_(2(0)) + HgCl_2 <-> Hg(RNH_2)Cl_(2(0))对伯胺盐，实验证明其机理主要为加合反应，但当Cl~-浓度较高时，则为阴离子交换反应：加合反应：2RNH_3Cl_((0)) + HgCl_2 <-> (RNH_3Cl)_2HgCl_(2(0))交换反应：2RNH_3Cl_((0)) + HgCl_4~(2-) <-> (RNH_3)_2HgCl_(4(0)) + 2Cl~-通过考察温度对配位萃取反应的影响，求得反应的热效应ΔH = -48.82 KJ/mol，并分析了萃合物的IR、NMR谱。二、伯胺N_(1923)萃取Hg(CH_3COO)_2的机理 与HgCl_2体系相似，自由伯胺或其盐均能萃取Hg(CH_3COO)_2，萃取机理分别为：RNH_(2(0)) + Hg(CH_3CCO)_2 <-> Hg(RNH_2)(CH_3COO)_(2(0)) (CH_3COONH_3R)_(2(0)) + Hg(CH_3COO)_2 <-> (CH_3COONH_3R)_2Hg(CH_3COO)_(2(0))。在不同的萃取剂浓度下，上述反应的表观平衡常数基本不随萃取剂浓度的变化而改变，其对数值分别为：11.85、8.11。三、伯胺N_(1923)萃取Cu(CH_3COO)_2的机理 水相酸度对萃取反应的影响表明，RNH_2在近中性体系中具有很好的萃取性能，而在乙酸浓度较高的条件下，Cu（II）几乎不被RNH_2所萃取。说明自由伯胺能以配位机理的形式萃取Cu(Oh_3coo)_2，经确定，萃取反应式为：2RNH_(2(0)) + Cu(CH_3COO)_2 <-> Cu(RNH_2)_2(CH_3COO)_(2(0))并对该反应的表观平衡常数及热力学函数进行了计算。通过分析萃合物的IR谱，认为Cu(RNH_2)_2(CH_3COO)_2为平面型四配位的配合物。四、(RNH_3)_2SO_4从硫酸溶液中萃取Ti（IV）的研究 在低酸度（pH：0.84）的H_2SO_4溶液中，伯胺N_(1923)对Ti（IV）具有很强的萃取能力。用化学平衡法确定其反应式为：3(RNH_3)_2SO_(4(0)) + Ti(OH)_3~+ + SO_4~(2-) <-> 2(RNH_3)_3Ti(OH_3)(SO_4)_(2(0))我们用正十二胺代替N_(1923)，合成了上述萃合物的模拟物，经元素分析确定了萃合物的分子式：(RNH_3)_3Ti(OH)_3(SO_4)_2。并较详细地分析了萃合物的NMR、IR谱。变温NMR的结果表明，萃合物中存在两种含有活泼氢的基团，用D_2O交换后的NMR的结果亦证明了这一点。从萃合物的IR谱中，可得到SO_4~(2-)是以单齿配位形式同Ti（IV）相结合的信息。这些结果为所提出的萃取机理提供了直接的证据。并求出了上述萃取反应的表观平衡常数，其对数值为10.15，该值基本不随萃取剂浓度的变化而发生改变。反应的热效应ΔH = 66.49 KJ/mol，由计算得出的ΔG值可知，上述萃取反应有很大的向右进行的趋势。五、伯胺N_(1923)在萃取分离中的应用 为了扩大N_(1923)的应用，通过上述研究，我们对其在萃取分离中的应用进行了讨论，认为在以下几方面有可能得到应用：1、从环境废水中除Hg(II)；2、Hg(II)和Zn(II)、Cd(II)在CH_3COOH体系中的分离；3、CH_3COOH体系中Cu(II)、Co(II)、Ni(II)的萃取分离；4、在较高浓度的H_2SO_4体系中，应用(RNH_3)_2SO_4进行了Ti(IV)-Fe(II)的分离。

通过阴离子转Ziegler-Natta聚合机理转换合成PS-b-EPM

能够作为聚烯烃材料与其它聚合物材料共混增容剂的、含有聚烯烃链段的嵌段共聚物的合成，对于扩大聚烯烃材料的应用，获得性能优良的共混型聚合物材料具有重要意义。烯烃类单体聚合方法单一，而且其通用的聚合方法，Ziegler-Natta聚合，不是令人满意的合成嵌段共聚物的方法。因此，含有聚烯烃链段的嵌段共聚物的合成一直是比较困难的研究课题之一，近年来发展起来的阴离子转Ziegler-Natta聚合方法为合成这类嵌段共聚物开辟了新途径。阴离子转Ziegler-Natta聚合是利用阴离子聚合所得到的活性聚合物及其反离子与过渡金属化合物组成“Ziegler-Natta”催化剂使烯类单体聚合，从而得到含有聚烯烃链段和阴离子聚合物链段的嵌段共聚物的一种新的合成方法。这种结合两种聚合机理的聚合方法能够有效地避免单一机理聚合方法对单体的要求和限制，从而扩大了嵌段共聚物的合成范围。目前，有关阴离子转Ziegler-Natta聚合方法的研究工作尚属于初步阶段，许多基本问题还没有统一的结论。本工作的目的就是对这一聚合方法的聚合规律，特点等基本问题进行初步探讨，为今后这方面工作的开展奠定初步基础。本工作以阴离子转Ziegler-Natta聚合为方法，以PS-EPM嵌段共聚物为合成对象，并通过对产物的组成、分子量、序列分布、温度转变行为及形态的表征，可初步得到以下结论。1、在较低的催化剂浓度下，可使催化效率比较高。在本聚合体系下，最高可达694克EPM段/克Ti。这一数值与一般非载体钛催化体系相比是比较高的。2、在合适的聚合条件下，如聚合时间较短，聚合温度较低，可得到分子量分布较窄的嵌段共聚物，并且基本上不含有非嵌段烯烃共聚物。3、以聚苯乙烯作为阴离子段聚合物，可发生较明显的β-消除反应，使产物中含有难以分离的烯烃共聚物，本工作以几个单元的聚异戊二烯作为聚苯乙烯活性离子的端基，有效地抑制了β-消除反应的发生，得到了比较纯净的PS-EPM嵌段共聚物。5、由阴离子转来的“Ziegler-Natta聚合具有阴离子聚合和Ziegler-Natta聚合的共同特点，是介于阴离子聚合和Ziegler-Natta聚合之间的一种特殊聚合形式；在聚合初期主要呈现阴离子聚合特征随着聚合的进行，逐渐向具有Ziegler-Natta聚合特征的聚合形式过渡。