A hydroxyphenyloxadiazole lithium complex as a highly efficient blue emitter and interface material in organic light-emitting diodes

We synthesized a hydroxyphenyloxadiazole lithium complex (LiOXD) as a blue light-emitting and electron injection/transport material to be used in double-layer organic electroluminescent devices. Devices with the concise configuration of ITO/TPD/LiOXD/Al showed bright blue EL emission centered at 468 nm with a maximum luminance of 2900 cd m(-2). A current efficiency of 3.9 cd A(-1) and power efficiency of 1.1 lm W-1 were obtained. LiOXD was also examined as an interface material. The efficiency of an ITO/NPB/Alq(3)/Al device increased considerably when LiOXD was inserted between Alq(3) and aluminium. The improvement of the device characteristics with LiOXD approached that observed with the dielectric LiF salt.

Novel bis(8-hydroxyquinoline)phenolato-aluminum complexes for organic light-emitting diodes

A novel series of emitting aluminum complexes containing two 8-hydroxyquinoline ligands (q) and a phenolato ligand (p) were synthesized and characterized. Double layer organic light-emitting diodes (OLEDs) were fabricated using these complexes as luminescent layers, and strong electroluminescence (EL) was observed. It was found that their emitting wavelengths were mainly determined by the first ligands (q). Cyclic voltammograms revealed a partially irreversible n-doping process and indicated that these complexes show excellent electron-transporting ability.

Impedance study of (PEO)(10)LiClO4-Al2O3 composite polymer electrolyte with blocking electrodes

A composite solid polymer electrolyte (SPE) of (PEO)(10)LiClO4-Al2O3 was prepared and Pt and stainless steel(SS) blocking electrodes were used for an impedance study. It was found that the semicircle in the high frequency range and the straight line in the low frequency range depend upon different blocking electrodes and polarization potentials applied in the experiments. In the equivalent circuit. two constant phase elements (CPE) have been used instead of the pure geometrical and double layer capacitances. respectively. A theoretical line calculated from their estimated values has a good correlation with the experiment data. Moreover. the equivalent circuit also can be used to explain the impedance properties of Pt and stainless steel (SS) blocking electrodes both in the high and the low frequency ranges. (C) 2001 Elsevier Science Ltd. All rights reserved.

Characterization of multilayer film using electrochemical impedance spectroscopy

A new multilayer film fabricated based on electrostatic attraction in this laboratory was firstly characterized by the electrochemical impedance spectroscopy. The relationship between the charge-transfer resistance and double-layer capacitance with the number of layers was obtained through analyzing the impedance data. It demonstrated that the multilayer film showed a unique structure with the film growth. Compared to other electrochemical methods, the electrochemical impedance spectroscopy was proved to be a very sensitive and useful technique for characterizing the multilayer films.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

The application of the MPB4 theory to the interface between between two immiscible electrolyte solutions .4. The differential capacitance of the water/nitrobenzene interface in the presence of 2:2 electrolyte

We have developed a new theoretical model based on the MPB4 theory to calculate the differential capacitance of the interface of 0.05mol/L MgSO4 in water and 0.1mol/L TBATPB in nitrobenzene. Our results coincide with the experimental values very well. It indicates that our model may describe well the structure of ITIES not only in the presence of 1:1 electrolyte but also in the presence of 2:2 electrolyte.

THE APPLICATION OF THE MPB4 THEORY TO THE INTERFACE BETWEEN 2 IMMISCIBLE ELECTROLYTE-SOLUTIONS .2. THE DIFFERENTIAL CAPACITANCE OF THE WATER 1,2-DICHLOROETHANE INTERFACE

The MPB4 theory is used to calculate the differential capacitance of the interface between LiCl in water and TBATPB in 1,2-dichloroethane at electrolyte concentrations of 0.005, 0.01 and 0.02 M. The effects of the ion size and the image force, and the influence of the electrolyte concentration, the surface charge density and the solvent effect on the inner layer potential drop are considered simultaneously. These effects can be ascribed to the ionic penetration into the opposite solution and ion-ion correlations across the interface. Our results are in better agreement with experimental data than those obtained using Gouy-Chapman theory. This indicates that the MPB4 theory may also describe the structure of the water \1,2-dichloroethane interface provided that the influence of the electrolyte concentration, the surface charge density and the solvent effect on the inner layer potential distribution are included in the calculation. Comparison of the theoretical results with those of the water \nitrobenzene interface shows that the structure of the water \1,2-dichloroethane interface is similar to that of the water \nitrobenzene interface, except that in the former case the inner-layer potential drop is much higher and the effects of the image force and the ion size are more pronounced.

THE APPLICATION OF THE MPB4 THEORY TO THE INTERFACE BETWEEN 2 IMMISCIBLE ELECTROLYTE-SOLUTIONS .1. THE DIFFERENTIAL CAPACITANCE OF THE WATER NITROBENZENE INTERFACE

We use the MPB4 theory to calculate the differential capacitance of the interface between NaBr + water and tetrabutylammoniumtetraphenyl borate (TBATPB) + nitrobenzene at electrolyte concentrations of 0.01 M, 0.02 M and 0.05 M. In addition to the effects

中太平洋海区富钴结壳地球化学特征及成因机制

本文利用ICP-AES、EPMA、X-ray衍射等测试技术以及聚类分析和因子分析等多种数理统计方法，系统地对中太平洋海区富钴结壳的元素地球化学特征、矿物组成和微观组构进行了研究，并探讨了其成因机制，获得以下主要认识： 1中太平洋海区富钴结壳类型多样，均为水成成因，其矿物相主要由锰矿物相、铁矿物相和非金属矿物相组成；富钴结壳壳层发育多种原生和次生构造类型。 2磷酸盐化作用不仅强烈改变富钴结壳元素初始含量，而且造成富钴结壳某些元素间的相关性发生改变，这些敏感型元素对可用于指示富钴结壳是否发生磷酸盐化。在不同水深段内，未磷酸盐化型富钴结壳的主要元素随经向、纬向的变化趋势相似，表明其受水体化学障、表面生产力和物质来源等环境参数控制；而随水深的变化则具有区域一致性，表明水体化学具有区域成层性。 3未磷酸盐化富钴结壳稀土元素含量和轻重稀土分馏程度随水深发生规律变化，这种变化不仅与它们在海洋中的含量和行为有关，也与海洋背景颗粒的吸附有关；铈(Ce)在富钴结壳中基本上呈4价，且动力学因素控制了其富集过程，因此Ce异常不能用于指示富钴结壳形成环境的氧化程度。 4基于富钴结壳微层呈锯齿状且同一微层生长速率不同，提出了富钴结壳在各种基底表面生长以及后继发育过程受固液界面双电层控制的发育模式。在富钴结壳整个发育过程中，经历了从贫氧环境向富氧环境的转变，但微环境则呈富氧-低氧过程的交替。 关键词： 富钴结壳；中太平洋；元素地球化学；界面双电层

Influence of biofilms growth on corrosion potential of metals immersed in seawater

The changes of corrosion potential (E-corr) of metals immersed in seawater were investigated with electrochemical technology and epifluoresence microscopy. In natural seawater, changes of E-corr were determined by the surface corrosion state of the metal. E-corr of passive metals exposed to natural seawater shifted to noble direction for about 150 mV in one day and it didn't change in sterile seawater. The in-situ observation showed that biofilms settled on the surfaces of passive metals when E-corr moved in noble direction. The bacteria number increased on the metal surface according to exponential law and it was in the same way with the ennoblement of E-corr. The attachment of bacteria during the initial period played an important role in the ennoblement of E-corr and it is believed that the carbohydrate and protein in the biofilm are reasons for this phenomenon. The double layer capacitance (C-dl) of passive metals decreased with time when immersed in natural seawater, while remained almost unchanged in sterile seawater. The increased thickness and reduced dielectric constant of C-dl may be reasons.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

软土亚塑性模型与一维非线性固结理论研究

With the great development of Tianjing New Coastal District economy, people need more land to build and live. Land subsidence, which is caused by its special engineering geological conditions, has restricted the further development in the district. Soft soil consolidation is main factor of land subsidence ;thus , on the basis of consolidation theory, the paper make further study on soft soils one-dimension nonlinear consolidation which contains two parts:(1) the nonlinear consolidation of permeability coefficient and compressibility coefficient changing with time and depth, which means real one-dimension nonlinear consolidation;(2) the non-homogeneous consolidation of permeability coefficient and compressibility coefficient only changing with depth. Firstly, nonlinear characteristics of soft soils are elaborated. Hypoplastic theory is introduced to establish a modified soft soils nonlinear constitutive model; the nonlinear governing equation of compressibility coefficient is built, and the nonlinear characteristics of compressibility coefficient are analyzed. Secondly, Considering Load Fluctuation and soil thickness changing ,the consolidation characteristics of single layer is discussed in the paper; meanwhile, on the basis of the Davis and Raymond’s hypothesis and single layer nonlinear consolidation equation, the doubled-layer one-dimension nonlinear consolidation equation is also derived. The solution of the equation is obtained by analytical method, and the consolidation characteristics of doubled-layer soft soil nonlinear theory is also analyzed. Finally, based on assumption that permeability coefficient and compressibility coefficient is varying along depth, single layer soil one-dimension non-homogeneous consolidation differential equation is derived; and the approximate solution is obtained. Furthermore, the single layer non-homogeneous consolidation is extended to double layer non-homogeneous consolidation theory. By using parabolic differential scheme, the matrix equation is established; and the solution of the matrix equation is obtained by chase method. Consolidation characteristics of soil soft single (double) layer non-homogeneous consolidation theory and Terzaghi’s theory are also discussed.

大兴安岭南段中生代火山-侵入杂岩带的双层叠置构造体制兼论滇中武定、易门碳酸质火山岩年代、来源及矿库与找矿研究

These are two parts included in this report. In the first part, the zonation of the complexes in its series, lithofacies, the depth of magma source and chambers is discussed in detailed for the first time based on the new data of petrol-chemistry, isotopes, tectono-magma activity of Mesozoic volcano-plutonic complexes in the southern Great Hinggan Mts. Then, the genetic model of the zonality, double overlapped layer system, is proposed. The main conclusions are presented as follows: The Mesozoic volcanic-plutonic complexes in the southern Great Hinggan were formed by four stages of magma activity on the base of the subduction system formed in late Paleozoic. The Mesozoic magmatic activity began in Meso-Jurassic Epoch, flourished in late Jurassic Epoch, and declined in early Cretaceous Epoch. The complexes consist dominantly of acidic rocks with substantial intermediate rocks and a few mefic ones include the series of calc alkaline, high potassium calc alkaline, shoshonite, and a few alkaline. Most of those rocks are characterized by high potassium. The volcano-plutonic complexes is characterized by zonality, and can be divided mainly into there zones. The west zone, located in northwestern side of gneiss zone in Great Xinggan mountains, are dominated of high potassium basalts and basaltic andesite. The middle zone lies on the southeast side of the Proterozoic gneiss zone, and its southeast margin is along Huangganliang, Wushijiazi, and Baitazi. It composed of dominatly calc-alkaline, high potassium calc-alkaline rocks, deep granite and extrusive rhyolite. The east zone, occurring along Kesheketong Qi-Balinyou Qi-Balinzuo Qi, is dominated of shoshonite. In generally, southeastward from the Proterozoic gneiss zone, the Mesozoic plutons show the zones-mica granitites zone, hornblende-mica granitite zone, mica-hornblende granitite zone; the volcanic rocks also display the zones of calc alkaline-high potassium calc alkaline and shoshonites. In the same space, the late Paleozoic plutons also display the same zonality, which zones are combined of binary granite, granodiorite, quartz diorite and diorite southeast wards from the gneiss. Meso-Jurassic Epoch granite plutons almost distribute in the middle zone on the whole. Whereas late Jurassic Epoch volcanic rocks distribute in the west and east zone. This distribution of the volcano-plutonic complexes reveals that the middle zone was uplifted more intensively then the other zones in Meso-Jurassic and late Jurassic Epoches. Whole rock Rb-Sr isochron ages of the high potassium calc-alkaline volcanic rocks in the west zone, the calc-alkaline and high potassium calc-alkaline granite the middle zone, shoshonite in the east zone are 136Ma, 175Ma and 154Ma, respectively. The alkaline rocks close to the shoshonite zone is 143Ma and 126Ma. The isochron ages are comparable well with the K-Ar ages of the rocks obtained previously by other researchers. The compositions of Sr ans Nd isotopes suggest that the source of Mesozoic volcanic-plutonic complexes in Great Hinggan Mts. is mostly Paleo-Asia oceanic volcanic-sedimentary rocks, which probably was mixed by antiquated gneiss. The tectonic setting for Mesozoic magmatism was subductive continental margin. But this it was not directly formed by present west Pacific subduction. It actully was the re-working of the Paleozoic subduction system( which was formed during the Paleo-Asia ocean shortening) controlled by west Pacific subduction. For this reason, Although Great Hinggan Mts. is far away from west Pacific subduction zone, its volcanic arc still occurred echoing to the volcanic activities of east China, it, but the variation trend of potassium content in volcano-plutonic complexes of Great Hinggan is just reverse to ones of west Pacific. The primitive magmas occurred in the southern Great Hinggan Mts. Include high-potassium calc-alkaline basalt, high potassium calc-alkaline rhyolite, high potassium rhyolite, non-Eu negative anomaly trachy-rhyolite et al. Therefore, all of primitive magmas are either mafic or acid, and most of intermediate rocks occurring in the area are the products of Mesozoic acid magma contaminated by the Paleozoic volcanic- sedimentary rocks. The depth of those primitive magma sources and chambers gradually increase from northwest to southeast. This suggests that Paleozoic subduction still controlled the Mesozoic magmatism. In summary, the lithosphere tectonic system of the southern Great Hinggan Mts. controlling Mesozoic magmatism is a double overlapped layer system developing from Paleozoic subduction system. For this reason, the depth of crust of the southern Great Hinggan Mts. is thicker than that of its two sides, and consequently it causes regional negative gravity abnormity. The second part of this report shows the prolongation of the research work carried on in my doctor's period. Author presents new data about Rb-Sr and Sm-Nd isotopic compositions and ages, geochamical features, genesis mineralogy and ore deposit geology of the volcanic rocks in Kunyang rift. On the base of the substantial work, author presents a prospect of copper bearing magnetite ore deposit. The most important conclusions are as follows: 1. It is proved that all of these carbonatites controlled by a ringing structure system in Wuding-Lufeng basin in the central Yunnan were formed in the Mesoproterozoic period. Two stages could be identified as follows: in the first stage, carbonatitic volcanic rocks, such as lavas(Sm-Nd, 1685Ma), basaltic porphyrite dykes(Sm-Nd, 1645Ma), pyroclastic rocks and volcaniclastic sedimentary rocks, formed in the outer ring; in the second stage, carbonatitic breccias and dykes(Rb-Sr, 1048 Ma) did in the middle ring. The metamorphic age of the carbonatitic lavas (Rb-Sr, 893 Ma) in the outer ring was determined. The magma of carbonatitic volcanic rocks derived mainly form enriched mantle whose basement is depleted mantle that had been metasomated by mantle fluid and contaminated by Archaean lower crust. Carbonatitic spheres were discovered in ore bearing layers in Lishi copper mining in Yimen recently, which formed in calcite carbonatitic magma extrusion. This discovery indicates that the formation of copper ore deposit genesis relates to carbonatitic volcanic activity. The iron and copper ore deposits occurring in carbonatitic volcanic- sedimentary rocks in Kunyang rift results from carbonatitic magmatism. Author calls this kind of ore deposits as subaqueous carbonatitic iron-copper deposit. The magnetic anomaly area in the north of Lishi copper mining in Yimen was a depression more lower than its circumference. Iron and copper ores occurrig on the margin of the magnetic anomaly are volcanic hydrothermal deposit. The magnetic body causing the magnetic anomaly must be magnetite ore. Because the anomaly area is wide, it can be sure that there is a large insidious ore deposit embedding there.

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.

Novel structured emulsions for delivering of food flavours

Flavour release from food is determined by the binding of flavours to other food ingredients and the partition of flavour molecules among different phases. Food emulsions are used as delivery systems for food flavours, and tailored structuring in emulsions provides novel means to better control flavour release. The current study investigated four structured oil-in-water emulsions with structuring in the oil phase, oil-water interface, and water phase. Oil phase structuring was achieved by the formation of monoglyceride (MG) liquid crystals in the oil droplets (MG structured emulsions). Structured interface was created by the adsorption of a whey protein isolate (WPI)-pectin double layer at the interface (multilayer emulsion). Water phase structured emulsions referred to emulsion filled protein gels (EFP gels), where emulsion droplets were embedded in WPI gel network, and emulsions with maltodextrins (MDs) of different dextrose-equivalent (DE) values. Flavour compounds with different physicochemical properties were added into the emulsions, and flavour release (release rate, headspace concentration and air-emulsion partition coefficient) was described by GC headspace analysis. Emulsion structures, including crystalline structure, particle size, emulsion stability, rheology, texture, and microstructures, were characterized using differential scanning calorimetry and X-ray diffraction, light scattering, multisample analytical centrifuge, rheometry, texture analysis, and confocal laser scanning microscopy, respectively. In MG structured emulsions, MG self-assembled into liquid crystalline structures and stable β-form crystals were formed after 3 days of storage at 25 °C. The inclusion of MG crystals allowed tween 20 stabilized emulsions to present viscoelastic properties, and it made WPI stabilized emulsions more sensitive to the change of pH and NaCl concentrations. Flavour compounds in MG structured emulsions had lower initial headspace concentration and air-emulsion partition coefficients than those in unstructured emulsions. Flavour release can be modulated by changing MG content, oil content and oil type. WPI-pectin multilayer emulsions were stable at pH 5.0, 4.0, and 3.0, but they presented extensive creaming when subjected to salt solutions with NaCl ≥ 150 mM and mixed with artificial salivas. Increase of pH from 5.0 to 7.0 resulted in higher headspace concentration but unchanged release rate, and increase of NaCl concentration led to increased headspace concentration and release rate. The study also showed that salivas could trigger higher release of hydrophobic flavours and lower release of hydrophilic flavours. In EFP gels, increases in protein content and oil content contributed to gels with higher storage modulus and force at breaking. Flavour compounds had significantly reduced release rates and air-emulsion partition coefficients in the gels than the corresponding ungelled emulsions, and the reduction was in line with the increase of protein content. Gels with stronger gel network but lower oil content were prepared, and lower or unaffected release rates of the flavours were observed. In emulsions containing maltodextrins, water was frozen at a much lower temperature, and emulsion stability was greatly improved when subjected to freeze-thawing. Among different MDs, MD DE 6 offered the emulsion the highest stability. Flavours had lower air-emulsion partition coefficients in the emulsions with MDs than those in the emulsion without MD. Moreover, the involvement of MDs in the emulsions allowed most flavours had similar release profiles before and after freeze-thaw treatment. The present study provided information about different structured emulsions as delivery systems for flavour compounds, and on how food structure can be designed to modulate flavour release, which could be helpful in the development of functional foods with improved flavour profile.