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1.
Molecular transport of haloalkanes into sheets of a polymeric blend of an ethylene–propylene random copolymer and isotactic polypropylene has been studied by a sorption gravimetric technique in the temperature interval of 25–70°C. For all liquids, equilibrium sorption, desorption, resorption, redesorption, and degree of penetrant overshoot have been influenced by the nature of the liquid and the temperature. Diffusion coefficients were calculated from the sorption–desorption kinetic curves using Fick's mathematical relations. The values of diffusion coefficients followed the Arrhenius-type behavior. The temperature-dependent sorption data were analyzed using the van't Hoff relation. The activation parameters for diffusion and heat of sorption data were discussed in terms of the molecular interactions between liquids and the polymer chain segments. The experimental and calculated results are discussed on the basis of the chemical nature of liquids. © 1995 John Wiley & Sons, Inc.  相似文献   

2.
The molecular transport of substituted aromatic solvents through polyurethane/polystyrene (PU/PS, 50/50) semi interpenetrating polymer network has been investigated at 20, 40, and 60°C. Sorption–desorption–resorption–redesorption (S‐D‐RS‐RD) experiments were performed to determine the true value of transport coefficients. Sorption results are obtained by a gravimetric method and diffusion coefficients have been calculated using Fick's equation for the linear data points of time dependent sorption/resorption curves. It was observed that most of the systems follow the Fickian mode of transport. The first order kinetic equation was used to estimate the kinetic rate constant of sorption. Activation parameters for different transport processes were evaluated and the results were used to discuss the polymer–solvent interactions. The concentration profiles at different depths along the thickness of membranes and at different time intervals were computed using Fick's equation under appropriate boundary conditions. The rate of evaporation of liquids has been calculated for desorption and redesorption processes, and these results depend on the volatility of aromatic solvents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 378–390, 2007  相似文献   

3.
A new experimental protocol based on the measurements of sorption (S), desorption (D), resorption (RS), and redesorption (RD) has been used to study the molecular transport of aliphatic alkanes through the miscible blends of an ethylene–propylene random copolymer and an isotactic polypropylene over the temperature interval 25–70°C. Diffusion and activation parameters are evaluated and their dependencies on solvent size, shape, and nature are discussed. Estimated values of the molar mass between chain entanglements, kinetic rate constants, and overshoot index parameters have been influenced by the polymer–solvent interactions. The sorption–diffusion mechanism is found to be of anomalous type. © 1995 John Wiley & Sons, Inc.  相似文献   

4.
ABSTRACT

Solvent sorption and drying performance of engineering polymeric blends of ethylene–propylene random copolymer and isotactic polypropylene in the presence of aromatic liquid: has been studied in the temperature interval 25–70°C. The drying of the polymer is studied from the desorption and redesorption experiments. The present results indicate that the rate of solvent migration and the drying phenomenon is controlled by internal mass transfer of solvent molecules within the polymer matrix. A technique is developed to study the sorption (S) –desorption (D) – resorption (RS)–redesorption (RD) i.e., S–D–RS–RD of the polymer sheets. The S–D–RS–RD experiments are a convenient measure of knowing the continuous weight loss of the polymer during long–term solvent exposure.  相似文献   

5.
The molecular transport characteristics of Santoprene rubber in the presence of n-alkanes, cyclohexane, 2,2,4-trimethylpentane, and 1,2,3,4-tetrahydronaphthalene at 25, 40, 55, and 70°C have been studied using a sorption gravimetric technique. From the sorption and desorption studies, the diffusion coefficients have been calculated and used in the discussion of the transport results. It was observed that these data depend on the size of the penetrants. Furthermore, efforts were made to evaluate the permeation coefficients, molar mass between crosslinks, and the kinetic rate constants. These data showed a systematic dependence on the penetrant size. Activation parameters for the process of diffusion and permeation have been calculated from the temperature dependence of the transport coefficients. © 1995 John Wiley & Sons, Inc.  相似文献   

6.
Sorption/desorption results of halogen‐containing liquids into high‐density polyethylene, linear low‐density polyethylene, very low‐density polyethylene, and polypropylene geomembranes are presented at 25, 50, and 70°C. Sorption results are obtained by a gravimetric method, and diffusion coefficients have been calculated by using Fick's equation from the initial linear portions of the sorption/desorption curves. Swelling of the geomembranes was studied from a measurement of the increase in volume, thickness, and diameter. From a temperature dependence of sorption and diffusion coefficients, the Arrhenius parameters have been calculated. Liquid concentration profiles have been computed using Fick's equation for the appropriate initial and boundary conditions. The results of this study may have relevance in selecting the suitable geomembrane for a specific application in hazardous waste chemical ponds and other similar situations.  相似文献   

7.
H. Kumar 《Polymer》2005,46(18):7140-7155
The sorption-desorption-resorption-redesorption experiments have been conducted to evaluate the transport behaviour of polyethylene glycol (PEG) based polyurethane/polymethyl methacrylate (PU/PMMA, 50/50) semi interpenetrating polymer network (SIPN) with aromatic probe molecules. Molecular migration depends on the nature of the organic solvent, membrane-solvent interaction, temperature, solubility parameter, molecular volume and free volume available within the polymer matrix. The transport parameters like sorption (S), diffusion (D) and permeation (P) coefficients have been calculated for IPN-aromatic probe molecule systems. Sorption and diffusion results measured at different temperatures viz. 20, 40 and 60 °C are found to follow Fickian mechanism. The liquid concentration profiles in the membranes during sorption and resorption processes have been simulated by solving Fick's diffusion equations and by using numerical method. Equilibrium swelling results have been used to measure the molecular mass between cross links, degree of cross linking and cross link density using Flory-Rehner theory. It is found that the mass uptake values decreased with increase in cross link density during polymer-solvent interactions. The estimated Arrhenius activation energy for diffusion (ED) and permeation (EP) are indicative of nature of liquid and their interaction with membrane. Thermodynamic parameters like change in entropy (ΔS) and enthalpy (ΔH) have been calculated using van't Hoffs equation. The rate of evaporation of liquids have been calculated for desorption and redesorption runs, and these results depend on volatility of solvents.  相似文献   

8.
Diffusion coefficients of 1,2-dichloroethane, 1,1,2-trichloroethylene, 1,1,2,2-tetrachloroethane, and carbon tetrachloride into neoprene, SBR, EPDM, NBR, and natural rubber have been obtained from sorption experiments in the temperature interval of 25° to 60°C. Diffusion was found to be dependent on the type and nature of the barrier material in addition to the diffusant size. The mechanism of diffusion appears to follow the anomalous diffusion. Activation energies for diffusion have been estimated and used in the discussion of transport data. Equilibrium sorption data were used to calculate the enthalpy and entropy of sorption for polymer-solvent pairs.  相似文献   

9.
Molecular transport of toluene, methanol, and cyclohexane and their mixtures in Chemraz 505 elastomer has been investigated using gravimetric techniques for short and long time exposure in these solvents. The sorption–desorption results have been used to calculate the diffusion coefficients by solving Fick's equation under appropriate boundary conditions. The dependence of sorption, desorption, diffusion, and permeation on temperature and composition changes was also studied. The results are discussed in terms of possible interactions between Chemraz 505 polymer and the solvent molecules. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43449.  相似文献   

10.
The coefficients of sorption, diffusion, and permeation for five organic esters, three aldehydes, one cyclic ketone, and three substituted aromatic liquids have been calculated for tetrafluoroethylene/propylene copolymer membranes at 30, 40, and 50°C with the sorption–gravimetric technique. With the sorption data, the concentration‐independent diffusion coefficients have been calculated from Fick's diffusion equation. Analytical solutions of Fick's equation under suitable boundary conditions have been obtained so that the liquid concentration profiles in the polymeric membranes at different times and different depths of liquid penetration could be computed. Because of the linearly increasing trend of the diffusion coefficients with temperature, efforts have been made to estimate Arrhenius parameters. Experimental values and the computed quantities have been used to determine the membrane–solvent interactions and to propose suitable applications for the membranes under investigation in various situations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3201–3209, 2003  相似文献   

11.
Solvent sorption and drying performance of engineering polymeric blends of ethylene-propylene random copolymer and isotactic polypropylene in the presence of aromatic liquid: has been studied in the temperature interval 25-70°C. The drying of the polymer is studied from the desorption and redesorption experiments. The present results indicate that the rate of solvent migration and the drying phenomenon is controlled by internal mass transfer of solvent molecules within the polymer matrix. A technique is developed to study the sorption (S) -desorption (D) - resorption (RS)-redesorption (RD) i.e., S-D-RS-RD of the polymer sheets. The S-D-RS-RD experiments are a convenient measure of knowing the continuous weight loss of the polymer during long-term solvent exposure.  相似文献   

12.
Cross-linked copolymers of 2-hydroxyethylmethacrylate/methylmethacrylate HEMA/MMA) with different HEMA contents have been prepared. Water sorption and desorption kinetics have been studied at a temperature of 37°C. The results indicate that the rate controlling step of sorption and desorption is the Fickian diffusion in the swollen polymer. The diffusion coefficient is a function of the water concentration and decreases to zero below a critical value of water content, which depends on the HEMA content.  相似文献   

13.
Molecular transport of organic liquids into Viton fluoropolymers has been investigated by a sorption—desorption gravimetric method. Diffusion coefficients have been calculated from Fick's equation. The sorption—desorption results have been used to calculate the concentration profiles by solving Fick's diffusion equation under suitable boundary conditions. A numerical method based on the finite difference technique was also used to calculate the concentration profiles of liquids as a function of sorption time and thickness of the Viton fluoropolymers. The dependence of sorption, desorption, diffusion, and permeation properties of the liquids on temperature showed a significant effect. The Arrhenius activation parameters have been estimated for diffusion, permeation, and sorption processes. The experimental and calculated results are discussed to study the type and nature of interactions between Viton fluoropolymers and the solvent molecules. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 717–723, 1997  相似文献   

14.
CO2 sorption kinetics of poly(ethylenimine) (PEI)-impregnated MIL-101, γ-alumina, and UVM-7 silica were investigated by the zero-length column technique for the purpose of understanding the effect of amine content, adsorbent porosity, and adsorption temperature on CO2 sorption rates. Each of the adsorbents was impregnated with three different amine contents (20, 35, and 50 wt%) and the effective diffusion time constants were determined at 25°C. For each respective adsorbent, it was found that increasing the amine content results in diminished diffusion rates. Additionally, it was found that the pore size of the support has a profound effect on diffusional kinetics, where microporous MIL-101 yielded substantially slow desorption rates upon amine-functionalization compared to mesoporous γ-alumina. PEI-impregnated UVM-7 silica was further investigated at 50 and 75°C in order to provide insight into the effect of temperature on sorption kinetics. The results indicated that PEI-impregnated UVM-7 exhibited faster sorption kinetics at higher temperatures. Upon desorption, PEI-UVM-7 silica exhibited two distinct regions of mass-transfer control that occur at different sorption times. This is best explained by first the occurrence of surface diffusion followed by diffusion out of the bulky PEI polymer chains. The findings of this study provide novel kinetic characterizations on promising amino-adsorbents for carbon capture applications.  相似文献   

15.
The diffusion and transport of organic solvents through lignin‐filled natural rubber composites have been studied in the temperature range 25–45°C. The diffusion of aromatic solvents through these samples were studied with special reference to the effect of filler concentration, penetrant size, and temperature. Transport coefficients such as diffusion, permeation, and sorption coefficients were estimated. The van't Hoff relationship was used to determine the thermodynamic parameters. The first order kinetic rate constant has been evaluated. A correlation between theoretical and experimental sorption results was evaluated. POLYM. COMPOS., 28:15–22, 2007. © 2007 Society of Plastics Engineers  相似文献   

16.
Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly(l-lactic acid) (PLLA) films at elevated pressures were determined by the gravimetric method, in which the Fick's diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope (SEM) photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.  相似文献   

17.
Analysis of sorption/desorption and diffusion kinetics of ketones and nitriles at 25, 44, and 60°C into three Du Pont's VITON fluoropolymer membranes loaded with different amounts of carbon black has been undertaken by use of a sorption/desorption technique. The transport results are affected by the percent loading of carbon blacks. Diffusion coefficients have been calculated from Fick's equation. These results show a decrease with increasing amount of carbon black. Experimental results have been analyzed by considering swelling of the membranes. Sorption/desorption results have been analyzed from a calculation of the concentration profiles, which are obtained from the analytical solution of Fick's equation. These results have been compared with a numerical solution based on the finite difference method. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 635–647, 1997  相似文献   

18.
Molecular transport of esters, aldehydes, substituted aromatic liquids, and a ketone through a fluoroelastomer (FC‐2120) membrane sample was studied at 30, 40, and 50°C. Sorption results were obtained by using a gravimetric method and concentration‐independent diffusion coefficients were calculated using Fick's diffusion equation. Permeability coefficients were calculated from sorption and diffusion data. Concentration profiles of the liquid penetrants were calculated by solving the Fick's equation under appropriate initial and boundary conditions and these plots are displayed to show the variations in liquid concentrations with reference to the nature of liquids chosen, membrane thickness, as well as the time of polymer immersion in the liquids. Arrhenius activation parameters were also estimated from a temperature dependence of diffusion and sorption coefficients. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 840–847, 2003  相似文献   

19.
Successive desorption experiments of water vapor in poly(methyl methacrylate) (PMMA) were performed at temperatures from 31.0 to 45.0°C. The solubility of water in PMMA was found to be independent of temperature in agreement with literature findings. But the results for diffusion showed stronger dependence on water concentration than those in literature. The diffusion coefficients of water in PMMA became almost independent of temperature at high water concentrations. However, at lower water concentrations, the temperature effect on diffusion was more pronounced. The observed weak temperature dependence of diffusivity at high concentrations is likely due to a high degree of clustering of water molecules found in the PMMA we prepared. Two modified polystyrenes containing 5 and 15 mol %, respectively, 4-hydroxystyrene as comonomer units were blended with PMMA to form hydrogen-bonded polymer blends. Successive desorption experiments of water vapor in the hydrogen-bonded polymer blends were carried out at 31.0°C. The solubility of water in both blends was found to increase with increasing composition of PMMA. The diffusion coefficients for PMMA and its blends increased with increasing concentration of water first, reached a maximum, then decreased with water concentration. When the desorption results were plotted with the previous study of absorption, hysteresis phenomenon of sorption existed in all blend compositions for our experimental time span. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 39–45, 1998  相似文献   

20.
Laboratory test results of sorption/desorption for tetrahydrofuran, tetralin, 1,4-dioxan, methyl acetate, ethyl acetate and butyl acetate into high density polyethylene, linear low density polyethylene, very low density polyethylene and polypropylene geomembranes at 25, 50 and 70 °C are presented. Partition coefficients are calculated from the measured increase in the mass of geomembranes immersed in the liquid of interest, from the initial value until the mass becomes constant. From the initial linear portions of the sorption curves, the diffusion coefficients of liquids into the geomembranes are calculated using the Fick equation. From a temperature dependence of sorption, diffusion and permeation coefficients, the Arrhenius parameters are calculated for each of these processes. Results of the preliminary findings reported here might be useful in the applications of geomembranes in containment facilities. © 1999 Society of Chemical Industry  相似文献   

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