Laser light scattering studies of soluble high-performance polyimides: Solution properties and molar mass distributions

Two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), in CHCl3 at 25 degrees C have been studied using laser light scattering. We found that the z-average radius of gyration ([R(g)]) can be scaled to the weight-average molecular weight (M(w)) as [R(g)] (nm) = 4.95 x 10(-2)M(w)(0.52) and [R(g)] (nm) = 1.25 x 10(-2)M(w)(0.66) respectively for poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), indicating that poly(ODPA/DMMDA) in CHCl3 at 25 degrees C has a more extended chain conformation than poly(BCPOBDA/DMMDA). Using the wormlike chain model approach, we found that the Flory characteristic ratios (C*) of poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA) are similar to 20 and similar to 31, respectively, indicating that both of them have a slightly extended chain conformation in comparison with typical flexible polymer chains, such as polystyrene, whose C-infinity is similar to 10. A combination of the weight-average molar mass (M(w)) with the translational diffusion coefficient distributions (G(D)) has led to D (cm(2)/s) = 3.53 x 10(-4)M(-0.579) and D (cm(2)/s) = 4.30 x 10(-4)M(-0.613) respectively for two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMTA), in CHCl3 at 25 degrees C. Using these two calibrations, we have successfully characterized the molar mass distributions of the two polyimides from their corresponding G(D)s. The exponents of these two calibrations further confirm that both of the polyimides have a slightly extended coil chain conformation in CHCl3. The chain flexibility difference between these two polyimides has also been discussed.

Laser light-scattering study of novel thermoplastics .2. Phenolphthalein poly(ether sulfone) (PES-C)

Five narrowly distributed fractions of phenolphthalein poly(ether sulfone) (PES-C) were studied in CHCl3 by both static and dynamic laser light scattering (LLS) at 25 degrees C. The dynamic LLS showed that the PES-C samples contain some large polymer clusters as in previously studied phenolphthalein poly(ether ketone)(PEK-C). These large clusters can be removed by a 0.1-mu m filter. Our results showed that [R(g)(2)](1/2)(z) = (3.35 +/- 0.13) x 10(-2) M(w)((0.52 +/- 0.03)) and [D] = (2.26 +/- 0.02) x 10(-4)M(w)-((0.54) +/- 0.03)) with [R(g)(2)](1/2)(z), M(w) and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.45 +/- 0.04) x 10(-4)M-((0.55 +/- 0.05)), where D and M correspond to monodisperse species. Using this scaling relationship, we have successfully converted the translational diffusion coefficient distribution into the molecular weight distribution for each of the five PES-C fractional The weight-average molecular weights obtained from dynamic light scattering have a good agreement with that obtained from static laser light-scattering measurements.

Laser light-scattering study of novel thermoplastics .1. Phenolphthalein poly(aryl ether ketone)

Five different molecular weight phenolphthalein poly(aryl ether ketone) (PEK-C) fractions in CHCl3 were studied by static and dynamic laser light scattering(LLS). The dynamic LLS revealed that the PEK-C samples contain some large polymer clusters. These large clusters can be removed by filtering the solution with a 0.1-mu m filter. We found that the persistence length of PEK-C in CHCl3 at 25 degrees C is similar to 2 nm and the Flory characteristic ratio, C-infinity is similar to 25. Our results showed that [R(g)(2)](1/2)(z) = (3.50+/-0.20) x 10(-2)M(w)(0.54+/-0.01) and [D] = (2.37+/-0.05) x 10(-4)M(w)(-0.55+/-0.01), with [R(g)(2)](1/2)(z), M(w), and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.20+/-0.10) x 10(-4)M(-0.555+/-0.015), where D and M correspond to monodisperse species. Using this calibration between D and M,we have determined molecular weight distributions of five PEK-C fractions from their corresponding translational diffusion coefficient distribution.

A study of the dependence of ferrocene diffusion on electrolyte concentration and size in a polymer medium using non-steady-state chronoamperometry

This article describes a quantitative study of the diffusion rate of ferrocene(Fc) dissolved in ploy(ethylene glycol)(PEG) medium containing MClO(4)(M = Li+, Na+, Bu(4)N(+), Hx(4)N(+)). The apparent diffusion coefficient D-app and the active concentration c(a) of Fc were simultaneously measured by using non-steady-state chronoamperometry. The D-app and c(a) of Fc have been estimated in PEG containing different concentrations and sizes of supporting electrolyte, and the dependence of D-app on ferrocene concentrations has been observed. The values of D-app decrease with increasing concentrations of Fc, increasing concentrations of LiClO4 or the ratio (O:Li) and also with 4 decreasing cation radius of the electrolyte. The temperature dependencies conform to a simple free volume model. The concentration and size of the counterion dependencies of the diffusion rate are similar to the behavior of their dependencies of ionic conductivity in polyelectrolyte.

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

THE VISCOSITY BEHAVIOUR OF SEP BLOCK COPOLYMER SOLUTION DURING ITS MICELLIZATION

The viscosities of polystyrene-b-poly (ethylene/propylene) diblock copolymer in mixed solvent of n-octane and benzene were measured. The influences of the constitution of the mixed solvent, temperature and concentration were on the viscosity investigated. During the micellization the solution viscosity increases rapidly. The results are consistent with the study on the micellization by light scattering. The average mass of micelleswas measured and the hydrodynamic radius of gyrations were calculated.

Dielectric response of graded composites having general power-law-graded cylindrical inclusions

The dielectric response of graded composites having general power-law-graded cylindrical inclusions under a uniform applied electric field is investigated. The dielectric profile of the cylindrical inclusions is modeled by the equation epsilon(i)(r)=c(b+r)(k) (where r is the radius of the cylindrical inclusions and c, b and k are parameters). Analytical solutions for the local electrical potentials are derived in terms of hypergeometric functions and the effective dielectric response of the graded composites is predicted in the dilute limit. Moreover, for a simple power-law dielectric profile epsilon(i)(r) = cr(k) and a linear dielectric profile epsilon(i)(r) = c(b + r), analytical expressions of the electrical potentials and the effective dielectric response are derived exactly from our results by taking the limits b -> 0 and k -> 1, respectively. For a higher concentration of inclusions, the effective dielectric response is estimated by an effective-medium approximation. In addition, we have discussed the effective response of graded cylindrical composites with a more complex dielectric profile of inclusion, epsilon(i)(r)=c(b+r)(k)e(beta r). (c) 2005 American Institute of Physics.

A subsurface countercurrent along the east coast of Luzon

A hydrographic section in the region east of Luzon was repeated 14 times during the period from 1986 to 1991. The data revealed the existence of a subsurface countercurrent located on the shoreward side of the Kuroshio with its upper boundary at about 500 m. The countercurrent, which should be called the Luzon Undercurrent (LUG), was only about 50 km wide, which is comparable to the baroclinic radius of deformation. Despite considerable variabilities both in velocity profile and intensity, the LUC appears to be a permanent feature. Over the period of observations, the maximum speed in the LUC calculated from the mean temperature and salinity by assuming geostrophy (relative to 2500 db) was 7 cm s(-1) at about 700 m and its mean geostrophic volume transport was 3.6 Sv (1 Sv = 10(6) m(3) s(-1)). About 28% of this transport was composed of the low-salinity North Pacific Intermediate Water (NPIW) advected to the south along the coast of Luzon. (C) 1997 Elsevier Science Ltd.

油气输导体系研究及应用─以准噶尔盆地东部白家海凸起侏罗系为例

Baijiahai uplift is an important hydrocarbon accumulation belt in eastern Jungger Basin, on which Cainan oilfield and lithologic hydrocarbon reservoir named Cai 43 have been discovered and both of them share the same target formation of Jurassic. However, in the subsequent exploration at this region, several wells that designed for lithologic traps of Jurassic were eventually failed, and that indicates the controlling factors of lithologic reservoir distribution are far more complicated than our previous expectation. This dissertation set the strata of the Jurassic in well Cai 43 region as the target, and based on the integrated analysis of structure evolution、fault sealing ability、simulations of sedimentary microfacies and reservoir beds、distribution analysis of high porosity-high permeability carrier beds、drive forces of hydrocarbons、preferential conduit system and conduit model as well as critical values of the reservoir physical properties for hydrocarbon charging, a special method that different from the conventional way to predict favorable lithologic traps was established. And with this method the controlling factors of the hydrocarbon reservoirs formation are figured out, and further more, the favorable exploration targets are point out. At Baijiahai uplift, fault plays as a crucial factor in the process of the hydrocarbon reservoir formation. In this study, it is found out that the availability of a fault that work as the seal for oil and gas are different. The critical value of the lateral mudstone smear factor (Kssf), which is used to measure the lateral sealing ability of fault, for oil is 3.9 while that for gas is 2.1; and the critical value of vertical sealing factor (F), which similarly a measurement for the vertical sealing ability of fault, for oil is 7.3 while that for gas is 5.1. Dongdaohaizi fault belt that possessed well lateral sealing ability since later Cretaceous have bad vertical sealing ability in later Cretaceous, however, it turns to be well now. Based on the comparison of the physical properties that respectively obtained from electronic log calculating、conventional laboratory rock analysis and the additive-pressure bearing laboratory rock analysis, we established the functions through which the porosity and permeability obtained though conventional method can be converted to the values of the subsurface conditions. With this method, the porosity and permeability of the Jurassic strata at the time of previous Tertiary and that in nowadays are reconstructed respectively, and then the characteristics of the distribution of high porosity-high permeability carrier beds in the evolution processes are determined. With the result of these works, it is found that both well Cai 43 region and Cainan oilfield are located on the preferential conduit direction of hydrocarbon migration. This conclusion is consistent with the result of the fluid potential analysis, in which fluid potential of nowadays and that of later Cretaceous are considered. At the same times, experiment of hydrocarbon injection into the addictive-pressure bearing rock is designed and conducted, from which it is found that, for mid-permeability cores of Jurassic, 0.03MPa is the threshold values for the hydrocarbon charging. And here, the conception of lateral pressure gradient is proposed to describe the lateral driving force for hydrocarbon migration. With this conception, it is found that hydrocarbons largely distributed in the areas where lateral pressure gradient is greater than 0. 03MPa/100m. Analysis of critical physical properties indicated that the value of the critical porosity and critical permeability varied with burial depth, and it is the throat radius of a certain reservoir bed that works as a key factor in controlling hydrocarbon content. Three parameters are proposed to describe the critical physical properties in this dissertation, which composite of effective oil-bearing porosity、effective oil-bearing permeability and preferential flow coefficient. And found that critical physical properties, at least to some extent, control the hydrocarbon distribution of Jurassic in Baijiahai uplift. Synthesize the content discussed above, this dissertation analyzed the key factors i.e., critical physical properties、driving force、conduit system and fluid potential, which controlled the formation of the lithologic reservoir in Baijiahai uplift. In all of which conduit system and fluid potential determined the direction of hydrocarbon migration, and substantially they are critical physical properties of reservoir bed and the lateral pressure gradient that controlled the eventually hydrocarbon distribution. At the same times, sand bodies in the major target formation that are recognized by reservoir bed simulation are appraised, then predict favorite direction of the next step exploration of lithologic reservoir.

电阻率测井反演方法应用研究

Formation resistivity is one of the most important parameters to be evaluated in the evaluation of reservoir. In order to acquire the true value of virginal formation, various types of resistivity logging tools have been developed. However, with the increment of the proved reserves, the thickness of interest pay zone is becoming thinner and thinner, especially in the terrestrial deposit oilfield, so that electrical logging tools, limited by the contradictory requirements of resolution and investigation depth of this kinds of tools, can not provide the true value of the formation resistivity. Therefore, resitivity inversion techniques have been popular in the determination of true formation resistivity based on the improving logging data from new tools. In geophysical inverse problems, non-unique solution is inevitable due to the noisy data and deficient measurement information. I address this problem in my dissertation from three aspects, data acquisition, data processing/inversion and applications of the results/ uncertainty evaluation of the non-unique solution. Some other problems in the traditional inversion methods such as slowness speed of the convergence and the initial-correlation results. Firstly, I deal with the uncertainties in the data to be processed. The combination of micro-spherically focused log (MSFL) and dual laterolog(DLL) is the standard program to determine formation resistivity. During the inversion, the readings of MSFL are regarded as the resistivity of invasion zone of the formation after being corrected. However, the errors can be as large as 30 percent due to mud cake influence even if the rugose borehole effects on the readings of MSFL can be ignored. Furthermore, there still are argues about whether the two logs can be quantitatively used to determine formation resisitivities due to the different measurement principles. Thus, anew type of laterolog tool is designed theoretically. The new tool can provide three curves with different investigation depths and the nearly same resolution. The resolution is about 0.4meter. Secondly, because the popular iterative inversion method based on the least-square estimation can not solve problems more than two parameters simultaneously and the new laterolog logging tool is not applied to practice, my work is focused on two parameters inversion (radius of the invasion and the resistivty of virgin information ) of traditional dual laterolog logging data. An unequal weighted damp factors- revised method is developed to instead of the parameter-revised techniques used in the traditional inversion method. In this new method, the parameter is revised not only dependency on the damp its self but also dependency on the difference between the measurement data and the fitting data in different layers. At least 2 iterative numbers are reduced than the older method, the computation cost of inversion is reduced. The damp least-squares inversion method is the realization of Tikhonov's tradeoff theory on the smooth solution and stability of inversion process. This method is realized through linearity of non-linear inversion problem which must lead to the dependency of solution on the initial value of parameters. Thus, severe debates on efficiency of this kinds of methods are getting popular with the developments of non-linear processing methods. The artificial neural net method is proposed in this dissertation. The database of tool's response to formation parameters is built through the modeling of the laterolog tool and then is used to training the neural nets. A unit model is put forward to simplify the dada space and an additional physical limitation is applied to optimize the net after the cross-validation method is done. Results show that the neural net inversion method could replace the traditional inversion method in a single formation and can be used a method to determine the initial value of the traditional method. No matter what method is developed, the non-uniqueness and uncertainties of the solution could be inevitable. Thus, it is wise to evaluate the non-uniqueness and uncertainties of the solution in the application of inversion results. Bayes theorem provides a way to solve such problems. This method is illustrately discussed in a single formation and achieve plausible results. In the end, the traditional least squares inversion method is used to process raw logging data, the calculated oil saturation increased 20 percent than that not be proceed compared to core analysis.

A study on the dependence of the micro-pore configurations on the volatilization and the burn processes of the organic compounds in the matrix of molten carbonate fuel cells

The micro-pore configurations on the matrix surface were studied by SEM. The matrix of molten carbonate fuel cell (MCFC) performance was also improved by the better coordination between the reasonable radius of the micro-pores and the higher porosity of the cell matrix. The many and complicated micro-pore configurations in the cell matrix promoted the volatilization of the organic additives and the burn of polyvinyl butyral (PVB). The smooth volatilization of the organic additives and the complete burn of PVB were the significant factors for the improved MCFC performance. Oxygen diffusion controlled-burn mechanism of PVB in the cell matrix was proposed. (C) 2002 Published by Elsevier Science Ltd.