The effect of crystallinity on chain mobility and free volume in the amorphous regions of a miscible polycarbonate/polyester blend

Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in T_g and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.     

聚己内酯/硝基纤维素共混体系结晶行为的研究

通过对聚己内酯／硝基纤维素共混体系的热分析、傅立叶变换红外光谱的研究，证实了该共混体系在聚己内酯含量较高时，是一个热力学相容的体系，同时两组分之间存在强的氢键相互作用。在此体系中聚己内酯长成了清晰规整的环带球晶。聚己内酯结晶形态随结晶温度和共混物组成的变化表明，在共混体系中聚己内酯结晶速率与非晶第二组分的扩散速率存在一定的匹配关系，是影响环带球晶形成的重要因素。     

A stream tube model for miscible flow

A simple theoretical model is described for deriving a 1-dimensional equation for the spreading of a tracer in a steady flow at the field scale. The originality of the model is to use a stochastic appoach not in the 3-dimensional space but in the 1-D space of the stream tubes. The simplicity of calculation comes from the local relationship between permeability and velocity in a 1-D flow. The spreading of a tracer front is due to local variations in the cross-sectional area of the stream tubes, which induces randomness in travel time. The derived transport equation is averaged in the main flow direction. It differs from the standard dispersion equation. The roles of time and space variables are exchanged. This result can be explained by using the statistical theory of Continuous Time Random Walk instead of a standard Random Walk. However, the two equations are very close, since their solutions have the same first and second moments. Dispersivity is found to be equal to the product of the correlation length by the variance of the logarithm of permeability, a result similar to Gelhar's macrodispersion.Nomenclature A total cross-section area of the sample - C (resident) concentration of tracer - D,D ^* dispersion coefficient - F flux of tracer - G probability distribution function for permeability in the stream-tube segments - I tracer intensity (mass crossing a surface per unit time) - K permeability - L length of the medium - M number of stream tubes in the medium - N number of segments along a stream tube - P pressure - Q total flow rate in the sample - a length of an elementary stream-tube segment - g probability distribution function for permeability in the space - i, j indices, tube numbers - q flow rate in each stream tube - s variable cross-section area of a stream tube - t, t time - u front velocity - x space variable in the flow direction - small local variation in time - , _t longitudinal, transverse dispersivity - porosity of the porous medium - correlation length in the permeability field - viscosity of the fluid - time for filling an elementary stream tube segment - standard deviation of a stochastic variable - probability distribution of arrival times (Gaussian)     

Optical and Bioelectrochemical Characterization of Water‐Miscible Ionic Liquids Based Composites of Multiwalled Carbon Nanotubes

Acidic treated multiwalled carbon nanotubes (AMWNTs) were ground with water‐miscible room temperature ionic liquids, 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄), and resulted in AMWNTs‐[bmim]BF₄ composite. Its electrical‐ionic conductivity and optical properties were compared with the other two types of carbon materials‐[bmim]BF₄ composites: pyrolytic graphite powder (PGP), pristine multiwalled carbon nanotubes (PMWNTs), through the ac impedance technology and Raman spectroscopy. The impedance data show that AMWNTs‐[bmim]BF₄ composite exhibits the highest conductivity. Raman spectra study exhibits that the [bmim]BF₄ can form gel with PMWNTs and AMWNTs but only form a viscous liquid with PGP. AMWNTs‐[bmim]BF₄ gel modified GC electrode was applied in direct electrochemistry of heme proteins (Hb and HRP) and it catalysis to the reduction of H₂O₂ was investigated.     

Molecular dynamics in a miscible polyester blend

The dynamic mechanical and dielectric spectra of a miscible polyester and polycarbonate blend are investigated with emphasis on the latter technique. It was found that relaxation spectra for the blends from both techniques are broader than those of the constituent homopolymers. This is ascribed to greater intermolecular coupling and concentration fluctuations within the blends. The composition at which the greatest coupling occurs is dependent on the relaxation technique used and is skewed towards the component which shows the highest degree of intermolecular coupling. A number of parameters, such as relaxation time of the polymer molecules in the blend and relaxation strength, are compared as a function of reduced temperature (experimental temperature scaled by the glass transition temperature). Whereas blend behavior is generally intermediate between that of the homopolymers, it appears as though mobility of compositions with low polyester content have a greater relaxation time and possess a higher activation energy when compared to a simple, weighted average of the corresponding homopolymer values. © 1996 John Wiley & Sons, Inc.     

Infrared ellipsometry of interdiffusion in thin films of miscible polymers

A new application of infrared ellipsometry is reported. Specifically, the interdiffusion between thin films of miscible polymers—poly(methyl methacrylate) and poly(vinylidene fluoride)—is detected in a non‐invasive measurement. A novel technique of data analysis for interdiffusion was developed and is described. The validity of the approach is supported by simulations of diffusion in a bilayer. The onset of extensive interdiffusion over a time period of 15 min occurs at a temperature of 160 °C. At a temperature of 190 °C, the data show that complete mixing of a bilayer (850 nm thick) occurs within 30 s, which is consistent with previously reported values of the mutual diffusion coefficient. Infrared ellipsometry is non‐invasive, applicable at elevated temperatures and relatively fast and sensitive. Although, in these measurements, it was unable to determine a concentration profile at the interface, infrared ellipsometry was used successfully to detect when interdiffusion had occurred. Hence, it is a useful means for screening polymer pairs for miscibility. Copyright © 2004 John Wiley & Sons, Ltd.     

Investigating the effect of nanolayered silicates on blend segmental dynamics and minor component relaxation behavior in poly(ethylene oxide)/poly(methyl methacrylate) miscible blends

Polymer–silicate nanocomposites based on poly (ethylene oxide), PEO, poly(methyl methacrylate), PMMA, and sodium montmorillonite clay were fabricated and characterized to investigate the effect of nanolayered silicates on segmental dynamics of PEO/PMMA blends. X‐ray results indicate the formation of an exfoliated morphology in the nanocomposites. At low silicate contents, an enhancement in segmental dynamics of blend nanocomposites and also PEO, minor component in blend, is observed at temperature region below blend glass transition. This result can be attributed to the improvement of the confinement effect of rigid PMMA matrix on the PEO chains by introducing a low amount of layered silicates. On the other hand, at high silicate contents, an enhancement in segmental dynamics of blend nanocomposites and PEO is observed at temperature region above blend glass transition. This behavior could be interpreted based on the reduction of monomeric friction between two polymer components, which can facilitate segmental motions of blend components in nanocomposite systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

SUPERCONVERGENCE OF THE FULL-DISCRETE F.E.M. FOR COMPRESSIBLE MISCIBLE DISPLACEMENT: THE FULL TENSOR CASE

1　ＩｎｔｒｏｄｕｃｔｉｏｎＷｅｓｈａｌｌｃｏｎｓｉｄｅｒｔｈｅｍｏｄｅｌｆｏｒｍｉｓｃｉｂｌｅｄｉｓｐｌａｃｅｍｅｎｔｏｆｏｎｅｃｏｍｐｒｅｓｓｉｂｌｅｆｌｕｉｄｂｙａｎｏｔｈｅｒｉｎａｈｏｒｉｚｏｎｔａｌｒｅｓｅｒｖｏｉｒΩ Ｒ2 ｏｆｕｎｉｔｔｈｉｃｋｎｅｓｓｄｅｓｃｒｉｂｅｄｂｙｔｈｅｎｏｎｌｉｎｅａｒｐａｒａｂｏｌｉｃｓｙｓｔｅｍ[6]ｄ(ｃ) ｐ ｔ+ ·ｕ =ｄ(ｃ) ｐ ｔ- · (ａ(ｃ) ｐ) =ｑ ,(1.1)φ ｃ ｔ+ｂ(ｃ) ｐ ｔ+ｕ· ｃ - · (Ｄ(ｕ) ｃ =(^ｃ -ｃ)ｑ ,(1.2 )ｕ·ν =(Ｄ(ｕ) ｃ-ｃｕ)…     

On the Validity of Darcy's Law for Stable High-Concentration Displacements in Granular Porous Media

Recently, it has been suggested that Darcy's Law might not be applicable for modelling miscible, density-dependent flow in porous media. To investigate this, three sets of careful laboratory column experiments were performed on coarse and medium sands, consisting of upward displacement of water by sodium chloride solutions with concentrations ranging from 5 to 200g/l. Data on salt concentrations and water pressures were collected in horizontal transects along the flow direction. Salt concentration data were also collected in the influent and exit lines. The experimental data were analysed using a simplified approach based on Darcy's Law alone, applied with the assumption of a sharp interface. Darcy's Law was used to estimate porous medium permeability by fitting predictions to experimental data. Consistent estimates of permeability were obtained for each set of experiments. The results indicate that Darcy's Law adequately describes high concentration displacements through saturated coarse- and medium-grained porous media.     

A new description for dispersion

Chang and Slattery (1986) introduced a simplified model for dispersion that contains only two empirical parameters, both of which can be determined in one-dimensional experiments. The traditional model for dispersion (Nikolaevskii, 1959; Scheidegger, 1961; de Josselin de Jong and Bossen, 1961; Bear, 1961a; Peaceman, 1966; Bear, 1972) has three empirical parameters, two of which can be measured in one-dimensional experiments while the third, the transverse dispersivity, must be measured in experiments in which a two-dimensional concentration profile develops. For the common one-dimensional experiment in which the signs of the concentration gradient and of the velocity field are different, the simplified model and the traditional model give identical results. For a one-dimensional experiment in which the signs of the concentration gradient and of the velocity field are at least sometimes the same and for two- and three-dimensional flows, the simplified model of Chang and Slattery (1986) gives results that can differ from those predicted using the traditional model.Only the experimental data of Bear (1961b) and of Yule and Gardner (1978) are sufficiently complete to permit a comparison of the two models. Considering the quality of the experimental data, we can not distinguish between the predicted profiles based upon the simplified model and those based upon the traditional model.