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11.
A fully coupled formulation combining reactive transport and an existing thermo-hydro-mechanical (THM) code is presented.
Special attention has been given to phenomena likely to be encountered in clay barriers used as part of containment systems
of nuclear waste. The types of processes considered include hydrolysis, complex formation, oxidation/reduction reactions,
acid/base reactions, precipitation/dissolution of minerals and cation exchange. Both kinetically-controlled and equilibrium-controlled
reactions have been incorporated. The total analytical concentrations (including precipitated minerals) are adopted as basic
transport variables and chemical equilibrium is achieved by minimizing Gibbs Free Energy. The formulation has been incorporated
in a general purpose computer code capable of performing numerical analysis of engineering problems. A validation exercise
concerning a laboratory experiment involving the heating and hydration of an expansive compacted clay is described. 相似文献
12.
Matthias Heuchel Martin Bhning Ole Hlck Martin R. Siegert Dieter Hofmann 《Journal of Polymer Science.Polymer Physics》2006,44(13):1874-1897
Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO2 gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006 相似文献
13.
Xiao Huang Bishwa Ranjan Nayak Tao Lu Lowe 《Journal of polymer science. Part A, Polymer chemistry》2004,42(20):5054-5066
A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004 相似文献
14.
Sankar Prasad Bhuniya Safikur Rahman Anshul J. Satyanand Mahendrasinh M. Gharia Ashok M. Dave 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1650-1658
Maize starch was modified by allyl chloride adopting an interfacial reaction technique with cetyltrimethyl ammonium bromide as a phase‐transfer catalyst and pyridine as an acid acceptor. The degree of substitution was determined from an increasing carbon content of the modified starch. The percentage of carbon and hydrogen of the allyl‐modified starch was estimated by elemental analysis (C, H, and N), and the product characterization was done through 1H NMR and 13C NMR analyses. The allyl‐modified starch was then copolymerized with methacrylic acid and a combination of methacrylic acid and acrylamide at 50 and 70 °C with potassium persulfate as an initiator. The copolymer thus formed swelled in distilled water after neutralization with sodium carbonate. The percentage of absorption capacity of the hydrogels was determined with distilled water and 0.9% NaCl solution. The highest percentage of absorption, 6500%, was achieved for the developed hydrogel containing allyl starch and acrylic monomer in a 1.7:1 w/w ratio and acrylic monomer, namely, methacrylic acid and acrylamide in a 3.2:1 w/w ratio. The study on biodegradability of the developed hydrogel showed that the hydrogel is degradable in the presence of diastase (amylase). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1650–1658, 2003 相似文献
15.
In this paper we describe the experimental analysis of a novel ion-exchange polymer metal composite (IPMC) actuator under
large external voltage. The experimental analysis is supplemented with a coupled thermodynamic model, which includes mass
transport across the thickness of the polymer actuator, chemical reactions at boundaries, and deformation as a function of
the solvent (water) distribution. In this paper, the case of large electrode potentials (over 1.2 V) has been analyzed experimentally
and theoretically. At these voltage levels, electrochemical reactions take place at both electrodes. These are used in the
framework of overpotential theory to develop boundary conditions for the water transport in the bulk of polymer. The model
is then simplified to a three-component system comprised of a fixed negatively charged polymeric matrix, protons, and free
water molecules within the polymer matrix. Among these species, water molecules are considered to be the dominant species
responsible for the deformation of the IPMC actuators. Experiments conducted at different initial water contents are described
and discussed in the context of the proposed deformation mechanism. Comparison of numerical simulations with experimental
data shows good agreement. 相似文献
16.
The standard view of mechanical adhesive contact is as a competition between a reduction in free energy when surfaces with bonding potential come into contact and an increase in free energy due to elastic deformation that is required to make these surfaces conform. An equilibrium state is defined by an incremental balance between these effects, akin to the Griffith crack growth criterion. In the case of adhesion of biological cells, the molecules that tend to form surface-to-surface bonds are confined to the cell wall but they are mobile within the wall, adding a new phenomenon of direct relevance to adhesive contact. In this article, the process of adhesive contact of an initially curved elastic plate to a flat surface is studied for the case in which the binders that account for adhesion are able to migrate within the plate. This is done by including entropic free energy of the binder distribution in the total free energy of the system. By adopting a constitutive assumption that binders migrate at a speed proportional to the local gradient in chemical potential, the transient growth of an adhesion zone due to binder transport is analyzed. For the case of a plate of very large extent, the problem can be solved in closed form, whereas numerical methods are invoked for the case of a plate of limited extent. Results are presented on the rate of growth of an adhesion zone in terms of system parameters, on the evolution of the distribution of binders and, in the case of a plate of limited extent, on the long-term limiting size of the adhesion zone. 相似文献
17.
This paper is aimed at investigating the effect of the initial water content in a vertisol sample on the whole wetting-drying
process leading the system to a change in volume. In order to do this, an experimental setup was realized and employed with
very thin soil layers wetted from below (“per ascensum”). The results show that the effect of the initial water content on
the swelling-shrinkage process is to shift the corresponding curve e-ϑ towards bigger-smaller values of the humidity but does not seem to affect the dynamics of the process.
The text was submitted by the authors in English. 相似文献
18.
Dilyana Paneva Laetitia Mespouille Nevena Manolova Philippe Dege Iliya Rashkov Philippe Dubois 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5468-5479
Polyelectrolyte complexes (PECs) have been prepared from well‐defined (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2‐acrylamido‐2‐methylpropane sodium sulfonate) (PAMPSNa) after a thorough study of their viscometric properties. The effect of pH and quaternization degree of PDMAEMA on PECs stoichiometry has been examined. PEC‐based materials have been characterized in terms of thermal stability, equilibrium swelling degree, and free/bound water composition. The stoichiometry and swellability of the physically crosslinked hydrogels obtained from fully quaternized PDMAEMA/PAMPSNa complexes do not depend on pH. In contrast, PECs made of non quaternized PDMAEMA and PAMPSNa are highly affected by pH, and could reversibly disintegrate at pH ≥ 9. Partially quaternized PDMAEMA/PAMPSNa PECs exhibit intermediate properties and form stable loose structures in the whole investigated pH range. Finally, stable dispersions of PECs nanoparticles have been successfully produced from dilute solutions of the complementary polyelectrolytes. The nanoparticle average diameter as determined by dynamic light scattering proved to depend on the molar fraction of DMAEMA‐based subunits and on the initial polyelectrolyte concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5468–5479, 2006 相似文献
19.
The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO2 mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO2/g starch–water system at 16 MPa. Moreover, CO2 solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO2 was found to increase with concentration of dissolved CO2, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO2 diffusivity in terms of pressure, temperature, and the concentration of dissolved CO2. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006 相似文献
20.
P. Guenoun M. Delsanti D. Gazeau J.W. Mays D.C. Cook M. Tirrell M. Tirrell L. Auvray 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,1(1):77-86
Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering
and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene)
PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water.
The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting
with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The
order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values
of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found
to be weak.
Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997 相似文献