Surface renewable graphite organosilicate composite electrode containing indium(III) hexacyanoferrate(II/III)

Indium(III) hexacyanoferrate(II/III) (InHCF) supported on graphite powder was prepared using the in situ chemical deposition procedure and subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive graphite organosilicate composite. The composite was used as the electrode material to fabricate a three-dimensional InHCF-modified electrode. InHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The chemically modified electrode can electrocatalyze the oxidation of thiosulfate, and exhibits a good repeatability of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.

Renewable-surface amperometric nitrite sensor based on sol-gel-derived silicomolybdate-methylsilicate-graphite composite material

A new type of silicomolybdate-methylsilicate-graphite composite material was prepared by the sol-gel technique and used for the fabrication of an amperometric nitrite sensor. The silicomolybdic anion acts as a catalyst, the graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry, square-wave voltammetry and chronoamperometry were employed to characterize the sensor. The amperometric nitrite sensor exhibited a series of good properties: high sensitivity (1.771 mu A mmol(-1) dm(3)), a short response time (7 s), remarkable long-term stability and especially reproducibility of surface renewal in the event of electrode surface fouling.

Morphology of conductive blend fibers of polyaniline and polyamide-11

Polyaniline (PANI), a member of the intrinsically conducting polymer (ICPs) family, was blended with polyamide-11 (polyco-aminoundecanoyle) in concentrated sulfuric acid. The above solution was used to spin conductive PANI/polyamide-11 fibers by wet-spinning technology. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were employed to study the two-phase morphology of the conductive PANI/polyamide-11 fibers. The micrographs of the cross-section, the axial section and the surface of the monofilament demonstrated that the two blend components were incompatible. The morphology of PANI in the fibers was of fibrillar form, which was valuable for producing conducting channels. The electrical conductivity of the fibers was from 10(-6) to 10(-1) S/cm with the different PANI fraction and the percolation threshold was about 5 wt.%. By comparing the two blend systems of PANI/Polyamide-11 fibers and carbon black filled poly(ethylene terephthalate) (PET) fibers, it was shown that the morphology of the conductive component had an influence on electrical conductivity, The former had higher conductivity and lower percolation threshold than the latter. (C) 2001 Elsevier Science B.V. All rights reserved.

Sol-gel-derived carbon ceramic electrode containing 9,10-phenanthrenequinone, and its electrocatalytic activity toward iodate

9,10-Phenanthrenequinone (PQ) supported on graphite powder by adsorption was dispersed in propyltrimethoxysilane-derived gels to yield a conductive composite which was used as electrode material to fabricate a PQ-modified carbon ceramic electrode. In this configuration, PQ acts as a catalyst, graphite powder guarantees conductivity by percolation, the silicate provides a rigid porous backbone, and the propyl groups endow hydrophobicity and thus limit the wetting region of the modified electrode. Square-wave voltammetry was exploited to investigate the pH-dependent electrochemical behavior of the composite electrode and an almost Nernstian response was obtained from pH 0.42 to 6.84. Because the chemically modified electrode can electrocatalyze the reduction of iodate in acidic aqueous solution (pH 2.45), it was used as an amperometric sensor for the determination of iodate in table salt. The advantages of the electrode are that it can be polished in the event of surface fouling, it is simple to prepare, has excellent chemical and mechanical stability, and the reproducibility of surface-renewal is good.

Renewable manganous hexacyanoferrate-modified graphite organosilicate composite electrode and its electrocatalytic oxidation of L-cysteine

Manganous hexacyanoferrate (MnHCF) supported on graphite powder was dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite, which was used as electrode material to construct a renewable three-dimensional MnHCF-modifed electrode. MnHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry was exploited to investigate the dependence of electrochemical behavior on supporting electrolytes containing various cations. The chemically modified electrode can electrocatalytically oxidize L-cysteine, and exhibits a distinct advantage of polishing in the event of surface fouling, as well as simple preparation, good chemical and mechanical stability, and good repeatability of surface renewal.

Sol-gel-derived graphite organosilicate composite electrodes bulk-modified with Keggin-type alpha-germanomolybdic acid

A novel inorganic-organic hybrid material incorporating graphite powder and Keggin-type alpha -germanomolybdic acid (GeMo12) in methyltrimethoxysilane-based gels has been produced by the sol-gel technique and used to fabricate a chemically bulk-modified electrode. GeMo12 acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The GeMo12-modified graphite organosilicate composite electrode was characterized by cyclic and square-wave voltammetry. The modified electrode shows a high electrocatalytic activity toward the reduction of bromate, nitrite and hydrogen peroxide in acidic aqueous solution. In addition, the chemically-modified electrode has some distinct advantages over the traditional polyoxometalate-modified electrodes, such as long-term stability and especially repeatability of surface-renewal by simple mechanical polishing.

Structural studies of excimer laser-induced percolative phase transition on polyimide thin film surfaces

The behavior of electrical conductivity for excimer laser irradiated polyimide films in the vicinity of the critical number of laser shots was described by three-dimensional percolative phase transition model. It is: found that electrical conductivity changed more rapidly than that predicted by the percolation model. Thus, the change in microstructure with increasing number of laser shots was analyzed by FT-IR Raman spectrometry and laser desorption time-of-flight mass spectrometry. It is demonstrated that not only the number but also the average size of graphite particles on the irradiated polyimide film surfaces increased with increasing number of laser shots. These results were helpful to better understand the critical change in electrical conductivity on the irradiated polyimide film surfaces. (C) 2001 Elsevier Science B.V. All rights reserved.

Water soluble polyaniline and its blend films prepared by aqueous solution casting

Polyaniline (PAn) was doped with phosphonic acid containing hydrophilic tails. The solubility of the doped PAn in water was controlled by changing the length of hydrophilic chain in the dopant. When poly(ethylene glycol) monomethyl ether (PEGME) with molecular weight M-w = 550 was used as the hydrophilic chain of the dopant, the doped PAn was entirely soluble in water. The film cast from aqueous solution showed good electrochemical redox reversibility, Aqueous solution blending of PAn with poly(ethylene glycol) (PEG, M-w = 20 000) and poly(N-vinyl pyrrolidone) (PVP, M-w = 360 000) was achieved. Percolation threshold of the composite film was lower than 3 wt.%. Electrical conductivity of the composite film was in the range of 10(-1)-10(-5) S cm(-1), depending on molecular weight of the acid and the content of PAn in the composite. (C) 1999 Elsevier Science Ltd. All rights reserved.

Rheological studies on the phase dissolution in a block copolymer

The microphase transition in a styrene-butadiene-styrene triblock copolymer was studied by rheometric mechanical spectroscopy. A high-temperature-melt rheological transition from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure was observed. The transition temperature is determined according to the discontinuity of the rheological properties across the transition region, which agrees well with the results obtained from the small angle X-ray scattering data and the expectation of the random phase approximation theory. Maybe for the first time, microphase dissolution was investigated theologically. The storage modulus (G') and the loss modulus (G '') increase with time during the process. An entanglement fluctuation model based on the segmental density fluctuations is presented to explain the rheological behavior in this dissolution process. (C) 1997 John Wiley & Sons.

Studies on the electrical conductivity of carbon black filled polymers

The conductivity mechanism for a carbon black (CB) filled high-density polyethylene (HDPE) compound was investigated in this work. From the experimental results obtained, it can be seen that the relation between electrical current density (J) and applied voltage across the sample (V) coincides with Simmons's equation (i.e., the electrical resistivity of the compound decreases with the applied voltage, especially at the critical voltage). The minimum electrical resistivity occurs near the glass transition temperature (T-g) of HDPE (198 K). It can be concluded that electron tunneling is an important mechanism and a dominant transport process in the HDPE/CB composite. A new model of carbon black dispersion in the matrix was established, and the resistivity was calculated by using percolation and quantum mechanical theories. (C) 1996 John Wiley & Sons, Inc.

THERMAL AND MECHANICAL-PROPERTIES OF PHENOLPHTHALEIN POLYETHERSULFONE POLY(PHENYLENE SULFIDE) BLENDS

The thermal and mechanical properties of phenolphthalein polyethersulfone/poly(phenylene sulfide) (PES-C/PPS) blends were studied using a differential scanning calorimeter, a dynamic mechanical analyzer, and mechanical characterization. The morphologies of fracture surfaces were observed by scanning electron microscopy. The blends are multiphase systems with strong interaction between the two phases. It is of interest that, although the strength and ductility of PPS are lower than those of PES-C, the addition of PPS can improve markedly the impact strength of PES-C without changing its higher strength. The PPS can also act as a flow aid for PES-C. (C) 1995 John Wiley and Sons, Inc.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.

Metasomatism of the peridotites from southern Mariana fore-arc: Trace element characteristics of clinopyroxene and amphibole

Modal composition and mineral composition of harzburgites from the southern Mariana fore-arc show that they are highly refractory. There are a few modals of clinopyroxene (0.7 vol %) in harzburgites. Two types of amphibole are found in these harzburgites: magnesiohornblende accompanied by clinopyroxene with higher Al2O3 content (> 7%) and lower Mg-#; tremolite around orthopyroxene with lower Al2O3 content (< 2%) and higher Mg-#. Trace element of clinopyroxene and two types of amphibole are analyzed. Primitive mantle-normalised REE patterns for clinopyroxene and magnesio hornblende are very similar and both show HREE enrichment relative to LREE, while magnesiohornblende has higher content of trace element than clinopyroxene. The contents of trace element of tremolite are much lower than those of magnesiohornblende. Clinopyroxene shows enrichment of most of the trace element except HREE and Ti relative to clinopyroxene in abyssal peridotites. Petrology and trace element characteristic of clinopyroxene and two types of amphibole indicate that southern Mariana fore-arc harzburgites underwent two stages of metasomatism. The percolation of a hydrous melt led to mobility of Al, Ca, Fe, Mg, Na, and large amounts of trace element. LILE and LREE can be more active in hydrous melt than HREE and Ti, and the activities of most of the trace element except some of LILE are influenced by temperature and pressure.

埕北断阶带油气运聚动力学研究

The problem of oil and gas migration and accumulation have been investigated for many years in petroleum geology field. However, it is still the most weak link. It is a challenge task to research the question about the dynamics of hydrocarbon migration and accumulation. The research area of this article,Chengbei step-fault zone is the important exploration area of Dagang oil field.The oil distribution is complicated in this area because of abundant faults and rock-reservoir-cap assemblage.In recent years, oil shows is often discovered, but no large-scale pool is found. The most important problem influencing exolore decision is lake of kowning about accumulation process of oil and resources potential. According to the geology characteristic and exolore difficult, the analysis principles of dynamics is used in this paper. The course from source to reservoir is considered as main research line, and relation of valid source rcok, migration dynamic and heterogeneous distribution of carrier is discussed especially in key time. By use of numerial model the couling of migration and passage is realized and dynamic process of oil migration is analysed quantitatively. On the basis of other research about structure and sendiment, basin model is built and parameters are choiced. The author has reconstructed characteristic and distribution of fluid dynamical in main pool-forming time by numerical model. The systems of oil migration and acuumulaiton are divided according to distribution of fluid potential. Furthermore, the scope of valid sourece rock and scale of discharging hydrocarbon is studied in geology history by the method of producting hydrocarbon poential. In carrier research, it is outstanding to analyse the function that fault controls the oil-gas migration and accumulation. According to the mechanism of fault sealing, the paper author puts forward a new quantitative method evaluating fault opening and sealing properties-fault connective probability by using the oil and gas shows in footwall and hangwall reservoir as the index of identifying fault sealing or non-sealing. In this method, many influencing factors are considered synthetically. Then the faut sealing propery of different position in third deimention of faults controlling hydrocarbon acummulation are quantitative evaluated, and it laies a foundation for building compex carrier systems. Ten models of carrier and dynamical are establishe by analysis of matching relation of all kinds of carriers in main pool-forming period. The forming process and distribution of main pathway has been studied quantitatively by Buoyancy-Percolation mode, which can conbine valid source rock, migration dynamical and carrier. On the basis of oil-gas migration and accumulation model, the author computes the loss of hydrocarbon in secondary migration, ahead of cap formation, and the quantity of valueless accumulation according to the stage of migration and accumulation and the losing mechamism. At the same time, resource potential is evaluated in every migration and accumulation system. It shows that the quanlity of middle systems arrive to 5.67×108t, which has a huge explore potential prospect. Finally, according to the result of quantitve analysis above mentioned, the favorable explore aims are forcasted by the way of overlapping migration pathway and valid trap and considering factors of pool-forming. The drilling of actual wells proved that the study result is credible. It would offer strong support to optimize explore project in Chengbei step-fault zone.

渤海湾盆地前第三系构造演化与煤成气成藏研究

The disequilibrium between supply and demand the east part of North China accelerated natural gas exploration in Bohai bay basin. Exploration practice showed that coal-derived gas is important resource. In searching of big to middle scaled coal derived gas field, and realize successive gas supply, the paper carried out integrated study on structural evolution of Pre-Tertiary and evaluation of reservoir forming condition of coal-derived gas. Study work of the paper was based on the following condition: available achievement in this field at present, good understanding of multiphase of tectonic movement. Study work was focused on geological evolution, source rock evaluation and dissection key factors controlling reservoir forming. Based on analysis of seismic data, drilling data, tectonic style of Pre-Tertiary was subdivided, with different tectonic style representing different tectonic process. By means of state of the art, such as analysis of balanced cross section, and erosion restoration, the paper reestablished tectonic history and analyzed basin property during different tectonic phase. Dynamic mechanism for tectonic movement and influence of tectonic evolution on tectonic style were discussed. Study made it clear that tectonic movement is intensive since Mesozoic including 2 phase of compressional movement (at the end of Indo-China movement, and Yanshan movement), 2 phase of extensional movement (middle Yanshan movement, and Himalayan movement), 2 phase of strike slip movement, as well as 2 phase of reversal movement (early Yanshan movement, and early Himalayan movement). As a result, three tectonic provinces with different remnant of strata and different tectonic style took shape. Based on afore mentioned study, the paper pointed out that evolution of Bohai bay basin experienced the following steps: basin of rift valley type (Pt2+3)-craton basin at passive continental margin (∈1－2)-craton basin at active continental margin (∈3- O)-convergent craton basin (C-T1+2)-intracontinental basin (J＋K). Superposition of basins in different stage was discussed. Aimed at tectonic feature of multiple phases, the paper put forward concept model of superposition of tectonic unit, and analyzed its significance on reservoir forming. On basis of the difference among 3 tectonic movements in Mesozoic and Cenozoic, superposition of tectonic unit was classified into the following 3 categories and 6 types: continuous subsidence type (I), subsidence in Mesozoic and uplift for erosion in Cenozoic (II1), repeated subsidence and uplift in Mesozoic and subsidence in Cenozoic (II2), repeated subsidence and uplift in Mesozoic and uplift for erosion in Cenozoic (II3), uplift for erosion in Mesozoic and subsidence in Cenozoic (II4), and continuous uplift (III). Take the organic facies analysis as link, the paper established relationship between sedimentary environment and organic facies, as well as organic facies and organic matter abundance. Combined information of sedimentary environment and logging data, the paper estimated distribution of organic matter abundance. Combined with simulation of secondary hydrocarbon generation, dynamic mechanism of hydrocarbon generation, and thermal history, the paper made static and dynamic evaluation of effective source rock, i.e. Taiyuan formation and Shanxi formation. It is also pointed out that superposition of tectonic unit of type II2, type II4, and type I were the most favorable hydrocarbon generation units. Based on dissection of typical primary coal-derived gas reservoir, including reservoir forming condition and reservoir forming process, the paper pointed out key factors controlling reservoir forming for Carboniferous and Permian System: a. remnant thickness and source rock property were precondition; b. secondary hydrocarbon generation during Himalayan period was key factor; c. tectonic evolution history controlling thermal evolution of source rock was main factor that determine reservoir forming; d. inherited positive structural unit was favorable accumulation direction; e. fault activity and regional caprock determined hydrocarbon accumulation horizon. In the end, the paper established reservoir forming model for different superposition of tectonic units, and pointed out promising exploration belts with 11 of the first class, 5 of the second class and 6 of the third class.